Recently in Sciences Category

Micro-structure imaging using visibility contrast

Dr. W. Yashiro (University of Tokyo, Japan) and his colleagues recently reported an interesting application of X-ray Talbot interferometry, which usually gives absorption and differential-phase images.  As micro-structures of the sample distort X-ray wave fronts, the research group quantitatively discusses how visibility reduction is caused and influenced.  They also experimentally demonstrate that this new type of experimental method using visibility contrast is feasible for imaging micro-structures, which have been studied by ultra small angle X-ray scattering so far.  For more information, see the paper, "On the origin of visibility contrast in x-ray Talbot interferometry", W. Yashiro et al., Optics Express, 18, 16890 (2010).  For more information on visibility contrast, see the paper, "Hard x-ray dark-field imaging using a grating interferometer", F. Pfeiffer et al., Nature Materials, 7, 134 (2008).

Carbonates of iron-magnesium on the surface of Mars

NASA's Mars Exploration Rover Spirit has obtained some significant data on the detailed chemical composition of the rock exposed on the ground surface of the Columbia Hills of the Gusev crater.  It was found that the rock is a Mg-Fe carbonate (Mc0.62Sd0.25Cc0.11Rh0.02, where Mc = magnesite, Sd = siderite, Cc = calcite, and Rh = rhodochrosite) and a forsteritic olivine (Fo0.72Fa0.28, where Fo = forsterite and Fa = fayalite).  This could suggest extensive aqueous activity under near-neutral pH conditions that would be conducive to habitable environments on early Mars.  On this occasion, in addition to a X-ray spectrometer, a Mossbauer (MB) spectrometer and Miniature Thermal Emission Spectrometer (Mini-TES) greatly contributed to the findings.  For more information, see the paper, "Identification of Carbonate-Rich Outcrops on Mars by the Spirit Rover", R. V. Morris et al., Science 329, 421 (2010).

The recent advent of coherent soft and hard X-ray sources has facilitated the development of imaging techniques that are capable of being inverted to the real space information extremely quickly.  A research group at the SLAC National Accelerator Laboratory, USA, recently developed a novel technique for soft X-rays, based on differential holographic encoding, termed holography with extended reference by autocorrelation linear differential operation (HERALDO).  The technique has achieved superior resolution over other similar lensless techniques, such as X-ray Fourier transform holography, while maintaining the signal-to-noise ratio and algorithmic simplicity.  The spatial resolution was 16 nm, and this was obtained by synthesizing images in the Fourier domain from a single diffraction pattern, which allows resolution improvement beyond the reference fabrication limit.  In addition to the capability of instant high-resolution reconstruction, the technique is found to be robust against data imperfections.  It reduces artifacts arising from the commonly-missing central low-q data.  For more information, see the paper, "High-Resolution X-Ray Lensless Imaging by Differential Holographic Encoding", D. Zhu et al., Phys. Rev. Lett. 105, 043901 (2010).  For more information on the original idea of HERALDO, see the paper, "Holography with extended reference by autocorrelation linear differential operation", M. Guizar-Sicairos and J. R. Fienup, Optics Express, 15, 17592 (2007).
For many years, scientists have argued about the existence of a depletion gap between water and hydrophobic surfaces.  Several recent reports based on high-resolution synchrotron X-ray reflectivity seemed to give a positive conclusion, but they were not in good agreement quantitatively, mainly because the amount being discussed was at experimental resolution.  A research group led by Professor P. Dutta (Northwestern University, Illinois, USA) has recently reported some synchrotron X-ray reflectivity results on the interface between water and self-assembled monolayers.  To enlarge the depletion gap (if any) as much as possible, they chose hydrophobic fluoroalkylsilane, CF3(CF2)5(CH2)2SiCl3 and CF3(CF2)11(CH2)2SiCl3, of which the contact angles were 111 deg and 120 deg, respectively.  It was found that the depleted region width increased with contact angle and exceeded the resolution.  They also concluded that the contribution of its fluctuation to the interface roughness was substantially smaller than has been considered so far.  For more information, see the paper, "How Water Meets a Very Hydrophobic Surface", S. Chattopadhyay et al., Phys. Rev. Lett. 105, 037803 (2010).
X-ray fluorescence has provided new information on the technique known as "sfumato", which Da Vinci and other Renaissance painters used to produce delicate gradations in tones or colors across the canvas.  Dr. P. Walter (Laboratoire du Centre de Recherche et de Restauration des Musees de France, CNRS, France) and his colleagues recently performed quantitative chemical analysis on seven paintings from the Louvre Museum (including the Mona Lisa), by synchrotron X-ray fluorescence at the European Synchrotron Radiation Facility (ESRF).  They were able to clarify how the painter made shadows on faces by the use of layers of glaze or a very thin paint, and by means of the nature of the pigments or additives.   For more information, see the paper, "Revealing the sfumato Technique of Leonardo da Vinci by X-Ray Fluorescence Spectroscopy", L. de Viguerie et al., Angewandte Chemie International Edition (Published Online: Jul 14 2010, DOI: 10.1002/anie.201001116).

Short period, high field undulators can enable short wavelength free electron lasers (FELs) at low beam energy.  A research group led by Professor J. Rosenzweig (University of California, Los Angeles, USA) has recently unveiled a new design based on an approach that utilizes cryogenic materials.  For more information, see the paper, "Short period, high field cryogenic undulator for extreme performance x-ray free electron lasers", F. H. O'Shea et al., Phys. Rev. ST Accel. Beams 13, 070702 (2010).

Soft X-ray resonant diffraction and reflectivity have become one of the most promising tools with which to study magnetic materials. At Diamond Light Source, Oxfordshire, UK, a novel instrument for single crystal diffraction and thin film reflectivity experiments in the soft X-ray regime has been designed and constructed.  It is basically a limited three circle (q, 2q, and c) diffractometer with an additional removable rotation (f), and is equipped with a liquid helium cryostat, and post-scatter polarization analysis.  For more information, see the paper, "RASOR: An advanced instrument for soft x-ray reflectivity and diffraction", T. A. W. Beale et al., Rev. Sci. Instrum. 81, 073904 (2010).

A Brazilian research group recently discussed the thermal influence of soft X-ray free-electron-laser (FEL) pulses on silicon substrate.  Such analysis is important, because the peak power of a single FEL pulse is roughly four orders of magnitude higher than that in conventional synchrotron light facilities.  Their detailed time-evolution analysis indicates that in a worst case scenario, the second pulse could be adversely affected by dynamic thermal distortion induced by the preceding pulse. For more information, see the paper, "Thermoelastic analysis of a silicon surface under x-ray free-electron-laser irradiation", A. R. B. de Castro et al., Rev. Sci. Instrum. 81, 073102 (2010).

What happens when an atom is excited by extremely strong X-ray photons such as an X-ray laser?  A Stanford research group recently published a very exciting report on the ionization of neon  (Z=10) by X-ray laser at the Linac Coherent Light Source (LCLS) housed at the SLAC National Accelerator Laboratory in California, USA.  The laser used in this experiment is extremely powerful (1018 W/cm2, 105 X-ray photons/Å2), and the research group scanned the X-ray photon energy from 800 eV to 2,000 eV, as well as the pulse width from 80 fs to 230 fs.  As the K absorption edge of neon is around 867 eV, below this energy, X-rays can strip some of the eight weakly bound electrons from the outer L shell of the neon atom.  Such a process of peeling electrons from atoms would come as no surprise for readers of X-ray spectrometry.  Above the absorption edge, K shell electrons are preferentially ejected, creating 1s vacancies that are refilled by electrons from the L shell.  Before the relaxation occurs, the remaining K shell electron is even more tightly bound to the neon nucleus than in the ground state.  Therefore, the K absorption edge for the system with a 1s vacancy is higher than usual.  When the research team raised the X-ray photon energy to 993 eV, both electrons from the inner K shell were knocked out, ionizing the atom from the inside out - in other words, coring the atom.  With this "hollow" neon then, a completely empty K shell has been created for the first time by X-ray photons, though similar phenomena may be possible by means of ultra-high temperature plasma, extremely high-energy collision processes etc.  For more information, see the paper, "Femtosecond electronic response of atoms to ultra-intense X-rays", L. Young et al., Nature 466, 56 (2010).  In the same issue, there is an interesting account by Justin Wark, "X-ray laser peels and cores atoms", Nature 466, 35 (2010).

The nature of the hydrogen-bond network in water and ice is one of the most interesting scientific mysteries, as it is still unsolved and always keenly debated.  Professor R. Car (Princeton University, New Jersey, USA) and his colleagues recently published their calculation of the X-ray absorption spectra of water and ice with a many-body approach for electron-hole excitations.  Their calculation reproduces some experimental features, including the effects of temperature change in the liquid.  The spectral difference between the solid and the liquid has been explained by considering short-range order effects, such as the breaking of hydrogen bonds and a non-bonded molecular fraction in the first coordination shell.  For more information, see the paper, "X-Ray Absorption Signatures of the Molecular Environment in Water and Ice", W. Chen et al., Phys. Rev. Lett. 105, 017802 (2010).  For more information on the experimental XAFS spectra of water and ice, see the paper, "The Structure of the First Coordination Shell in Liquid Water", Ph. Wernet et al., Science, 304, 995 (2004).

A research group led by Professor C-U. Ro (Inha University, Korea) has recently reported the combined use of two techniques, attenuated total reflectance FT-IR (ATR-FT-IR) imaging and a quantitative energy-dispersive electron probe X-ray microanalysis, low-Z particle EPMA, for the speciation of mineral particles.  For more information, see the paper, "Speciation of Individual Mineral Particles of Micrometer Size by the Combined Use of Attenuated Total Reflectance-Fourier Transform-Infrared Imaging and Quantitative Energy-Dispersive Electron Probe X-ray Microanalysis Techniques", H-J. Jung et al., Anal. Chem. 82, 6193 (2010).

Laser-based femtosecond X-ray pulse source

A Chinese group led by Professor J. Zhang (President of Shanghai Jiao Tong University) recently published a report on the generation of X-ray pulses of around 3 keV by using an Ar clustering gas jet target (~3mm dia.) and a Ti:sapphire laser (power 800 mJ, pulse width 28 fs, wavelength 800 nm, frequency 10 Hz).  The intensity of the Ar K-shell emissions in the forward direction was found to be around 104 photons/mrad2/pulse.  The group emphasized the significance of laser contrast, which is a ratio of the main pulse and pre-pulse, and found that X-ray flux is reduced by 2 orders of magnitude if the laser pulse contrast decreases from 109 to 107 with constant laser pulse energy. For more information, see the paper, "Intense High-Contrast Femtosecond K-Shell X-Ray Source from Laser-Driven Ar Clusters", L. M. Chen et al., Phys. Rev. Lett. 104, 215004 (2010).

An international team of paleontologists, geochemists and physicists led by Dr. R. A. Wogelius (University of Manchester, UK) recently employed X-ray fluorescence imaging to analyze a 150 million year old fossil of Archaeopteryx, which had dinosaur-like teeth and bird-like feathers.  For many years, it was believed that the fossil contained nothing but bone and rock.  However, the use of a brilliant synchrotron X-ray beam enabled the detection of chemical elements hidden within.  It was found that the fossil still had elemental compositions that were completely different from the embedding geological matrix.  The researchers completed the chemical map of the dinobird for 12 elements for the first time.  Some phosphor and sulfur were found in soft tissue, as well as trace zinc and copper in bone.  The experiment was done at wiggler beam line 6-2 at Stanford Synchrotron Radiation Lightsource (SSRL, California, USA).  For more information, see the paper, "Archaeopteryx feathers and bone chemistry fully revealed via synchrotron imaging", U. Bergmann et al., Proc. Nat. Aca. Sci., 107, 9060 (2010).

X-ray studies on surface ordering in cold liquids

Professor P. Dutta (University of Chicago) and his colleagues recently clarified that the surface density profile acquires layered structures at 0.2 Tc; Tc is the liquid-gas critical temperature.  The present research was for dielectric liquids, pentaphenyl trimethyl trisiloxane, and pentavinyl pentamethyl cyclopentasiloxane. The X-ray reflectivity technique was employed to determine the surface profile experimentally.  The research group had previously found similar phenomena for other liquid dielectric liquids as well as liquid metals.  The present studies could strengthen their series of work.  For more information, see the paper, "Surface order in cold liquids: X-ray reflectivity studies of dielectric liquids and comparison to liquid metals", S. Chattopadhyay et al., Phys. Rev, B81, 184206 (2010).

Dr. C. H. Chen (National Taiwan University, Taiwan) and his colleagues recently published a report on ultra high resolution element mapping.  The research group employed a scanning transmission electron microscope (STEM) with specially enhanced spherical aberration correction.  The beam size was nearly 1 Å.  A silicon drift detector (Bruker XFlash-5030) was employed and set with a solid angle of 0.13 steradian.  The group studied InGaAs/InAlAs superlattices, and discussed the 1.47 Å dumbbell structure using both structural imaging and mapping of characteristic X-rays (In L, Ga K and As K).  For more information, see the paper, "Emergent Chemical Mapping at Atomic-Column Resolution by Energy-Dispersive X-Ray Spectroscopy in an Aberration-Corrected Electron Microscope", M.-W. Chu et al., Phys. Rev. Lett. 104, 196101 (2010).

Efficient XRD analysis of combinatorial libraries

Combinatorial materials synthesis is a promising new way of developing and finding novel functional materials.  By the use of sophisticated thin film technology, it is possible to create compositionally graded samples on the same single substrate.  To analyze this combinatorial library, some novel technique is required.  A UK research group led by Professor K. D. Rogers (Cranfield University, UK) recently reported on high-throughput data collection and analysis using an X-ray diffraction (XRD) probe.  In the research, an extended X-ray beam was used to illuminate the libraries, and a large area detector was used to collect the data.  A new algorithm was employed to analyze the collected data and extract the crystallographic information.  For more information, see the paper, "High Throughput X-ray Diffraction Analysis of Combinatorial Polycrystalline Thin Film Libraries", S. Roncallo et al., Anal. Chem., 82, 4564 (2010).

Coherent X-ray diffraction imaging is one of the hottest research topics in advanced X-ray physics.  The method reconstructs a real-space image from an oversampled diffraction signal by using computer algorithms instead of lenses.  So far, its application has been limited to fairly strong phase objects, mainly due to parasitic scattering from the optics used for limiting the beam.  Korean researchers recently published an interesting report on its application to a nonisolated weak phase object, a one-dimensional trench structure fabricated on a Si substrate.  In their discussion, the authors reported that such work was enabled by employing a special aperture with a very high aspect ratio of nearly 100 made of tantalum (1.7 μm × 2.2 μm aperture with a thickness of 130 μm).  For more information, see the paper, "Coherent hard x-ray diffractive imaging of nonisolated objects confined by an aperture", S. Kim et al., Phys. Rev. B81, 165437 (2010).

A group led by Professor Ch. David (Paul Scherrer Institute, Switzerland) recently developed a synchrotron-based full-field microscope, which can work with hard X-rays, typically 10 keV.  The instrument supports tomographic absorption and phase contrast imaging with a spatial resolution of 144 nm.  The researchers demonstrated phase-contrast 3D imaging of a melanocortin-3 preosteoblast cell.  For more information, see the paper, "Phase-contrast tomography at the nanoscale using hard x rays", M. Stampanoni et al., Phys. Rev. B 81, 140105(R) (2010).

Bragg X-ray Fourier transform holography

Lens-less microscopy is now widely acknowledged to be an elegant solution to the so-called phase problem in X-ray crystallography.  The method is based on the digital retrieval of the phase from the object's coherently diffracted intensity patterns, with the inversion being achieved through the use of time-consuming iterative algorithms.  Fourier transform holography is a similar technique, but is essentially very quick and straightforward.  Dr. V. Chamard (IM2NP, CNRS, Aix-Marseille Universite, France) and her colleagues recently demonstrated 3D imaging of a SiGe nanocrystal with Fourier transform holography.  One unique point of the research is that they employed Bragg geometry, rather than forward scattering geometry, to obtain full 3D information.  The technique requires that a reference crystal is placed near the object crystal to be imaged, and that the two crystals need to have comparable lattice parameters.  They were successful in determining the electron density and the displacement field in 3D without suffering convergence problems, which are often the case with lens-less imaging iterative algorithms.  For more information, see the paper, "Three-Dimensional X-Ray Fourier Transform Holography: The Bragg Case", V. Chamard et al., Phys. Rev. Lett. 104, 165501 (2010).

Dr. M. Giorgetti (University of Bologna and Unita di Ricerca INSTM di Bologna) and his colleagues recently reported the successful application of the chemometric approach to a series of in-situ near edge X-ray absorption spectra of a Cu0.1V2O5 xerogel/Li ion battery.  The research group discusses how the multivariate curve resolution (MCR) technique and also fixed size windows evolving factor analysis (FSWEFA) are useful in determining the number of species and the ratio.  It was found that three different species co-exist during battery charging. For more information, see the paper, "Multivariate Curve Resolution Analysis for Interpretation of Dynamic Cu K-Edge X-ray Absorption Spectroscopy Spectra for a Cu Doped V2O5 Lithium", P. Conti et al., Anal. Chem., Article ASAP (DOI: 10.1021/ac902865h)

A German group at BESSY II recently succeeded in studying the evolution of both the spin (S) and orbital angular (L) momentum of a thin Ni film during ultrafast demagnetization, by means of X-ray magnetic circular dichroism (XMCD).  It was found that both S and L components decrease by irradiating a femtosecond laser pulse, and the time constant is 130±40 fs.  For more information, see the paper, "Femtosecond x-ray absorption spectroscopy of spin and orbital angular momentum in photoexcited Ni films during ultrafast demagnetization", C. Stamm et al., Phys. Rev, B81, 104425 (2010).

There are still many unknown problems related to the structure of amorphous materials, because the X-ray diffraction technique has some limitations in the case of disordered systems.  A research team led by Dr. A. L. Goodwin (Oxford University, UK) recently reported a new elegant general scheme to solve the structure by successfully demonstrating its application to molecular C60, a-Si, and a-SiO2.  The team proposes to employ the information gained in spectroscopic experiments (such as EXAFS, Raman, NMR etc) regarding the number and distribution of atomic environments.  The idea is that such information can be used as a valuable constraint in the refinement of the atomic-scale structures of nanostructured or amorphous materials from the pair distribution function (PDF), which is obtained by Fourier transform of the X-ray diffraction pattern.  Although a conventional reverse Monte Carlo (RMC) approach is not always successful in obtaining the correct structure solution, the team showed that such difficulties can be removed by including the above variance term.  For more information, see the paper, "Structure Determination of Disordered Materials from Diffraction Data", M. J. Cliffe et al., Phys. Rev. Lett. 104, 125501 (2010).
Professor S. Techert (Max-Planck-Institute for Biophysical Chemistry, Goettingen, Germany) and his colleagues have reported on Bragg diffraction experiments with a soft X-ray laser (wavelength 8 nm, pulse width 30 fs, power 4×1011 photons/pulse) from the free electron laser at FLASH, Deutsche Elektronen-Synchrotron (DESY) in Hamburg.  The research group studied Bragg diffraction patterns of single nano-crystal (20 nm×20 nm×20 μm) and powder with grain sizes smaller than 200 nm of silver behenate (AgC22H43O2, chain length 5.8 nm).  So far, many coherent X-ray diffraction studies have been done even with soft X-ray wavelengths, but the present research aims at the analysis of periodic structures that are usually targets of X-ray diffraction with hard X-rays.  They showed an interesting comparison between the single nano crystal and the powder, and also discussed the influence of the extremely high peak power of laser pulses.  For more information, see the paper, "Diffraction Properties of Periodic Lattices under Free Electron Laser Radiation", I. Rajkovic et al., Phys. Rev. Lett. 104, 125503 (2010)

Coherence theory of X-ray and neutron reflectivity

A Dutch neutron research group at Delft University of Technology, Netherlands, recently published a paper describing the extension of their coherence theory on neutron scattering to X-ray reflectivity.  For more information, see the paper, "Coherence approach in neutron, x-ray, and neutron spin-echo reflectometry", V. O. de Haan et al., Phys. Rev. B81, 094112 (2010).

Professor L. J. Allen (University of Melbourne, Australia) and his colleagues have recently demonstrated atomic-resolution chemical mapping in a scanning transmission electron microscope (STEM).  They obtained Sr and Ti images for SrTiO3.  Such images are directly interpretable mainly because the effective ionization interaction is localized.  For more information, see the paper, "Atomic-resolution chemical mapping using energy-dispersive x-ray spectroscopy", A. J. D'Alfonso et al., Phys. Rev. B81, 100101(R) (2010).

Production of coherent soft X-rays in storage ring

With linac-based light sources, the electron beam has a high peak current and small energy spread, and this can be used to drive a seeded single pass free electron laser.  On the other hand, the beams in a storage ring usually have a relatively low current and large energy spread.  To generate ultrashort coherent radiation, the coherent harmonic generation (CHG) technique is a promising candidate.  Dr. D. Xiang (SLAC National Accelerator Laboratory, USA) and Dr. W. Wan (Lawrence Berkeley National Laboratory, USA) have recently proposed a scheme to extend the harmonic number of the CHG technique by an order of magnitude using angular-modulated electron beams in the storage ring.  The technique has the potential of generating femtosecond coherent soft X-ray radiation directly from an infrared seed laser.  For more information, see the paper, "Generating Ultrashort Coherent Soft X-Ray Radiation in Storage Rings Using Angular-Modulated Electron Beams", D. Xiang et al., Phys. Rev. Lett. 104, 084803 (2010).

Accurate X-ray mass attenuation coefficients of zinc

An Australian research group has recently published experimentally obtained X-ray mass attenuation coefficients of zinc for 7.2- 15.2 keV X-rays with an absolute accuracy of 0.044% and 0.197%.  For more information, see the paper, "X-ray mass attenuation coefficients and imaginary components of the atomic form factor of zinc over the energy range of 7.2.15.2 keV", N. A. Rae et al., Phys. Rev. A81, 022904 (2010).

CTR analysis of Rubrene single crystal thin films

Rubrene (5,6,11,12-tetraphenylnaphthacene, C42H28) is a red colored polycyclic aromatic hydrocarbon.  As an organic semiconductor, the most promising application is in organic light-emitting diodes (OLEDs) and organic field-effect transistors, which are the core elements of flexible displays.  Recently, Professor Y. Wakabayashi (Osaka University, Japan) and his colleagues have studied the near surface structure of Rubrene single crystal by crystal truncation rod (CTR) scattering, which gives a modulated profile in the tail of a series of Bragg peaks (0 0 z).  The research group employed coherent Bragg rod analysis (COBRA) rather than conventional curve fitting analysis to determine the electron density profile along the depth.  The analysis has shown that the molecules at the surface are slightly expanded along the surface normal direction, while the second or deeper molecular layers are not affected by the existence of the surface.  Their research can be extended to applications of other similar organic semiconductors.  For more information, see the paper, "Sub-Å Resolution Electron Density Analysis of the Surface of Organic Rubrene Crystals", Y. Wakabayashi et al., Phys. Rev. Lett. 104, 066103 (2010).  For information on COBRA, see, for example, "Direct determination of epitaxial interface structure in Gd2O3 passivation of GaAs", Y. Yacoby et al., Nature Materials 1, 99 (2002).

X-ray nanofocusing by kinoform lenses

Dr. H. Yan (National Synchrotron Light Source II, Brookhaven National Laboratory, USA) has recently reported a comparative study on various kinoform lenses for X-ray nanofocusing.  He employed the geometrical theory, the dynamical diffraction theory, and the beam propagation method, and showed that the geometrical theory becomes invalid.  The influence of the edge diffraction effect from the individual lens element was studied in view of the limit of the focus size.  It was also shown that the length of the lenses can be optimized to reduce the wave field distortion.  For more information, see the paper, "X-ray nanofocusing by kinoform lenses: A comparative study using different modeling approaches", H. Yan, Phys. Rev. B81, 075402 (2010).

MD simulation aids the analysis of local dynamics by EXAFS

Extended X-ray absorption fine-structure (EXAFS) is a powerful tool for the analysis of atomic-scale structure around specific atoms.  In addition to the determination of the atomic distance for the nearest neighboring atoms, it can give some information on the local dynamical properties of crystals.  Recently, Dr. A. Sanson (Universita degli Studi di Verona, Italy) has published the results of the molecular dynamics (MD) simulation in the case of crystalline germanium.  By comparing experimental EXAFS data, he could discuss the radial distribution functions of the first six coordination shells, as well as their parallel and perpendicular mean-square relative displacements as a function of temperature.  For more information, see the paper, "Local dynamical properties of crystalline germanium and their effects in extended x-ray absorption fine structure", A. Sanson, Phys. Rev. B81, 012304 (2010).

Micro XRF analysis of industrial waste

Professor M. A. Castro (Instituto de Ciencia de los Materiales de Sevilla, CSIC-Universidad de Sevilla, Spain) and his colleagues are proposing to employ micro X-ray fluorescence as a feasible and efficient solution to classify waste and also to survey the problems in the production process.  For more information, see the paper, "Application of micro-X-ray fluorescence analysis for the characterization of industrial wastes", M. D. Alba et al., Ind. Eng. Chem. Res., Article ASAP (DOI: 10.1021/ie901716w).

Kβ satellites in EPMA

Argentinian scientists have recently published a paper on the emission of X-rays in the Kβ region of Mg, Al, Si, Sc, Ti, Cr, Fe, Ni, and Zn induced by electron bombardment.  The research includes the KβIII and KβIV spectator hole transitions, the 1s3s quadrupole decay, the Kβ2 and Kβ5 diagram transitions, the structures related to radiative Auger processes, and the Kβ' and Kβ" lines.  For more information, see the paper, "Kβ satellite and forbidden transitions in elements with 12<Z<30 induced by electron impact", S. P. Limandri et al., Phys. Rev. A81, 012504 (2010).

So far, it has been understood that the only way to realize hard-X-ray mirrors with near 100% reflectivity is the use of total external reflection at grazing incidence to a surface.  Dr. Y. V. Shvyd'ko (Argonne National Lab, USA) and his colleagues have recently proposed to use Bragg reflections from synthetic diamond crystal.  They discussed how it shows an unprecedented reflecting power at normal incidence with meV order narrow bandwidths for hard X-rays.  The optics might be a good candidate for X-ray free-electron laser oscillators (X-FELO).  For more information, see the paper, "High-reflectivity high-resolution X-ray crystal optics with diamonds", Y. V. Shvyd'ko et al., Nature Physics, doi:10.1038/nphys1506; published online, 17 January 2010.

A research group led by Professors Y. Takanishi (Kyoto University, Japan) and A. Iida (Photon Factory, KEK, Japan) has recently published its successful investigation into the local layer structure of bent-core liquid crystal, 4-Br-14-O-PIMB, which includes Br atoms.  The group employed a monochromatic X-ray microbeam (3 μm × 4 μm), and observed X-ray scattering from the cell near the Br K absorption edge.  They were able to discover some satellite peaks reflecting the superlattices.  For more information, see the paper, "Microbeam resonant x-ray scattering from bromine-substituted bent-core liquid crystals", Y. Takanishi et al., Phys. Rev. E81, 011701 (2010).

Possibility of downsizing X-ray free electron laser

Laser sources in the hard X-ray region have already become a reality at some free electron laser (FEL) facilities.  However, typical hard X-ray FELs use an accelerator that is several km long to generate a ~10 GeV electron beam with ~kA peak current to drive the FEL.  Dr. D. Xiang (SLAC National Accelerator Laboratory, USA) is proposing an alternative technique to generate an electron beam.  He discusses the possibility of downsizing an X-ray FEL by this method.  In his calculation, a 1.5 Å X-ray FEL with a saturation length within 30 m using a 3.8 GeV electron beam could be feasible.  For more information, see the paper, "Laser assisted emittance exchange: Downsizing the x-ray free electron laser", D. Xiang, Phys. Rev. ST Accel. Beams 13, 010701 (2010).

X-ray Photon Correlation Spectroscopy (XPCS) is a novel technique which reveals the slow dynamics of equilibrium and non-equilibrium processes in condensed matter systems.  A group led by Professor N. P. Balsara (University of California, Berkeley, USA) has recently published research on a polystyrene-polyisoprene block copolymer melt in the vicinity of the order-disorder transition.  The group combined several techniques in addition to XPCS; time-resolved small angle X-ray scattering and rheology.  During their studies of ordering kinetics, it was found that two qualitatively different regimes exist, i.e., shallow and deep quench regimes, respectively.  For more information, see the paper, "Dynamic signatures of microphase separation in a block copolymer melt determined by X-ray photon correlation spectroscopy and rheology", A. J. Patel et al., Macromolecules, Article ASAP (DOI: 10.1021/ma902343m).

Dr. G. J. Havrilla (Los Alamos National Lab., USA; one of the associate editors of X-Ray Spectrometry journal) and his colleague recently published a very interesting report on the analysis of picoliter droplets, which can be now accurately prepared using Hewlett-Packard's extremely sophisticated technology.  The research targets application to analytical science, although the instrument is basically designed for inkjet printing and other similar purposes.  It has been shown that dried deposits of single and multielemental solutions generated in picoliter volumes are able to be used as references for micro X-ray fluorescence.  Evaporation can have a strong influence on extremely small amounts at the picoliter level, but the research group successfully devised the optimal instrumental conditions by monitoring X-ray fluorescence intensity.   For more information, see the paper, "Picoliter droplet deposition using a prototype picoliter pipette: Control parameters and application in micro X-ray fluorescence", U. E. A. Fittschen et al., Anal. Chem., 82, 297 (2010).

Ultimate hard X-ray focusing

For many years, substantial effort has been devoted to developing a good mirror for preparing a small X-ray beam.  Professor K. Yamauchi (Osaka University, Japan) and his colleagues have recently reported the breaking of the 10 nm barrier for hard X-rays.  They employed a combination of two mirrors; the surface of the first mirror is deformable, in order to compensate for figure error of the second mirror.  By such an adaptive optical system, the research group attained a beam size of 7 nm at 20 keV.  The experiments were done at BL29XUL, SPring-8.  For more information, see the papers, "Breaking the 10 nm barrier in hard-X-ray focusing", H. Mimura et al., Nature Physics doi:10.1038/nphys1457; published online: 22 November 2009; corrected online: 2 December 2009.

Kβ/Kα intensity ratio in Cr, Fe and Ni

Dr. I. Han (Ağİbrahim Çeçen University, Turkey) and his colleagues have published a paper on the relationship between the Kβ/Kα X-ray fluorescence intensity ratio and valence-electron configurations.  For more information, see the paper, "Valence-electron configuration of Fe, Cr, and Ni in binary and ternary alloys from Kβ-to-Kα X-ray intensity ratios", I. Han et al., Phys. Rev. A80, 052503 (2009).

Foamlike, cellular structures of the monolayer of organic capped nanoparticles can sometimes be observed on liquid surfaces.  Professor M. K. Sanyal (Saha Institute of Nuclear Physics, India) and his lab members studied the time evolution in the structure and morphology of transferred monolayers of gold-thiol nanoparticles, formed at the air-water interface at different surface pressure, on to a silicon surface.  The research group employed two complementary techniques, X-ray reflectivity and atomic force microscopy (AFM), to see the whole drying-mediated self-assembly of nanoparticles.  For more information, see the paper, "Nanopattern formation in self-assembled monolayers of thiol-capped Au nanocrystals", R. Banerjee et al., Phys. Rev. E80, 056204 (2009).

So far, X-ray microscopy with many types of lens has achieved great success in the observation of biological cells.  In order to extend the limits of spatial resolution and efficiency, X-ray diffraction microscopy (also called coherent X-ray diffraction imaging), which uses coherent X-rays and some image reconstruction algorithms instead of an optical lens system, is now considered as a promising procedure to see whole cells at once and pick out much smaller features, down to around 10 nm or even less.  A research group led by Professor C. Jacobsen (Stony Brook University, USA) recently reported the results for yeast cells with 520 eV soft X-rays at the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory, USA.  Dr. A. Madsen (European Synchrotron Radiation Facility (ESRF), Grenoble, France) and his colleagues observed the cells of the bacteria D. radioduran with 8 keV X-rays.  The advantage of using hard X-rays is the ease of sample handling, and the validity of thin sample approximation for future 3D reconstructions through phasing a diffraction volume.  In both cases, a rapid freezing technique (instead of previously used freeze-drying) was used to avoid the effects of radiation damage from synchrotron X-ray photons.  The Stony Brook group plunged cells in their natural wet state into liquid ethane and maintained them at below -170 oC, leading to the reduction of artifacts due to damage from dehydration, ice crystallization, and radiation.  In the ESRF setup, as absorption in air of 8 keV X rays is small, a nonvacuum environment was implemented for ease of sample handling.  Similar to the system for macromolecular crystallography applications, they based the samples in a continuous cryogenic nitrogen gas jet at around -165 oC.  The spatial resolution was 25 nm and 30-50 nm, for soft and hard X-rays cases, respectively.  For more information, see the papers, "Soft X-ray diffraction microscopy of a frozen hydrated yeast cell", X. Huang et al., Phys. Rev. Lett., 103, 198101 (2009), and "Cryogenic X-ray diffraction microscopy for biological samples", E. Lima et al., Phys. Rev. Lett., 103, 198102 (2009)

Nanometer scale dipole moments in the polarization clusters in BaTiO3 are believed to be thermally excited and thermally relaxed within a picosecond time scale. However, so far, there have been no reports on the direct observation of the dynamics of these dipole moments in such a very short time scale.  The limitation here is mainly due to the low spatial coherence of the X-ray beam, in particular when synchrotron radiation is used as a light source.  Professor K. Namikawa (Tokyo Gakugei Univ, Japan) and his colleagues have recently obtained some interesting results.  To measure the time correlation of speckle intensities, they employed a soft X-ray pulse laser (7 ps in pulse width, 3.5×1010 photons/sec/pulse, 13.9 nm in wavelength, band width 10-4, angular spread 0.5 mrad) at Japan Atomic Energy Agency, Kizugawa, Japan, and a Michelson-type delay pulse generator as well as an X-ray streak camera.  Spatial coherence in their system was estimated at more than 90 %.  The evolution of the relaxation time of the dipole moment near the Curie temperature (TC) was studied.  It was found that the maximum relaxation time (~90 ps) appears at a temperature of 4.5 K above the TC, being coincident with the one where the maximum polarization takes place.  For more information, see the paper, "Direct observation of the critical relaxation of polarization clusters in BaTiO3 using a pulsed X-ray laser technique", K. Namikawa et al., Phys. Rev. Lett., 103, 197401 (2009).
Professors T. Narayanan (ESRF, Grenoble, France), M. Giglio (XFEL, Hamburg, Germany) and their collaborators have recently published an interesting paper on a novel method to map the two-dimensional transverse coherence of an X-ray beam.  The technique uses the dynamical near-field speckles formed by scattering from colloidal particles, which are executing Brownian motions.  It is possible to measure the change of the interference fringes, and consequently the fluctuation of speckles.  It was found that the coherence properties of synchrotron radiation from an undulator source are obtained with high accuracy.  For more information, see the paper, "Probing the transverse coherence of an undulator X-ray beam using Brownian particles", M. D. Alaimo et al., Phys. Rev. Lett., 103, 194805 (2009).

High resolution Ti Kβ" and Kβ2,5 spectra in PIXE

One of the most important applications of X-ray spectroscopy is chemical state analysis.  A research group led by Dr. M. Jaksic (Rudjer Boskovic Institute, Croatia) has recently reported chemical effects observed in high resolution Kβ spectra of Ti oxides and other compounds in the case of 2 MeV proton excitation.  In addition to the determination of the oxidation number by the energy differences between Kβ1,3 and Kβ5, the sum of the relative intensities of Kβ2,5 and Kβ" can give information on the length of chemical bonds.  The influence of self-absorption for thick samples on X-ray spectra is also discussed.  For more information, see the paper, "Chemical effects on the Kβ" and 2,5 X-ray lines of titanium and its compounds", L. Mandic et al., Phys. Rev. A80, 042519 (2009).  Readers might be also interested in the recent synchrotron radiation studies on Ti oxides and other compounds reported by Dr. B. Beckoff's group (PTB, Germany), "Evaluation of high-resolution X-ray absorption and emission spectroscopy for the chemical speciation of binary titanium compounds", F. Reinhardt et al., Anal. Chem. 81, 1770 (2009).

X-ray absorption microscopy is simple, but has low sensitivity in biological samples that are made of light elements.  X-ray phase contrast imaging can provide contrast that is 3 orders of magnitude greater than X-ray absorption.  However, phase contrast imaging has not been that widely used so far mainly because of the unusual requirements of the experimental setup.  Dr. W. Yashiro (The University of Tokyo, Japan) and his colleagues have recently proposed a novel setup that is feasible.  The research group simply added a transmission grating to the setup for conventional X-ray absorption microscopy with a Fresnel Zone Plate (FZP) objective lens.  Because of the self-imaging phenomenon in Talbot effects, a phase difference image can be produced by the transmission grating placed at the downstream of the back focus of the FZP.  The experiment was done at beamline BL20XU, SPring-8.  For more information, see the paper, "Hard-X-Ray Phase-Difference Microscopy Using a Fresnel Zone Plate and a Transmission Grating", W. Yashiro et al., Phys. Rev. Lett. 103, 180801 (2009).

Table-top soft X-ray undulator source

Some readers might remember the news article, "A compact synchrotron light source driven by pulse laser", in X-ray Spectrometry, Vol. 37, No.2 (2008).  The essential point is that a table top pulse laser can be used as an alternative to a linear or circular electron accelerator.  The article above reported the first successful synchrotron radiation generation from laser-plasma-accelerated electrons, but the wavelength was only in the visible to infrared region.  Recently, an international team led by Professors S. Karsch and F. Grunera achieved a new breakthrough.  The team belongs to Munich's Cluster of Excellence "Munich Centre for Advanced Photonics" (MAP), in the Laboratory for Attosecond Physics (LAP) of Ludwig-Maximilians-Universitat (LMU) in Munich and the Max Planck Institute of Quantum Optics (MPQ) in Garching.  In their experiment, the electron accelerator is driven by pulses from a 20 TW (850 mJ in 37 fs) laser system.  Focused into a hydrogen-filled gas cell with a length of 15 mm, the laser pulses produce stable electron beams showing a quasi-monoenergetic energy spectrum with a stable peak in the range of 200-220 MeV and 7 pC of charge in the whole spectrum.  In order to transport the electron beam from the plasma accelerator, the scientists employed a pair of miniature permanent-magnet quadrupole lenses, which have been found to be critical for stability.  The spectrum of their 30cm-long undulator typically consists of a main peak at a wavelength of 18 nm (fundamental), a second peak near 9 nm (second harmonic) and a high-energy cutoff at 7 nm.  For more information, see the paper, "Laser-driven soft-X-ray undulator source", M. Fuchs et al., Nature Physics. 5, 826 (2009).
Professor D. Sparks (University of Delaware, USA) and his colleagues have reported an interesting application of quick X-ray absorption spectrometry to environmental science.  The experiment is basically a continuous monochromator scan (0.3-0.6 sec for each spectrum) at the synchrotron beamline at Brookhaven National Lab.  The main interest here is the initial oxidation rate of As(III) to As(V) by hydrous manganese(IV) oxide, because the toxicity and availability of arsenic to living organisms depends on its oxidation state at the interface to the water.  The research team found that the initial apparent As(III) depletion rate constants are nearly twice as large as those measured with conventional, but much slower techniques.  This indicates the necessity of further studies using such a rapid analytical method.  For more information, see the paper, "Quantification of rapid environmental redox processes with quick-scanning x-ray absorption spectroscopy (Q-XAS)", M. Ginder-Vogel et al., Proc Nat Aca Sci, 106, 16124 (2009).

Geochemical study on As-S system by X-ray spectroscopy

It is known that sulfide sometimes play a significant role in the geochemistry of arsenic under reducing conditions.  So far, it has been assumed that sulfide primarily reduced the solubility and mobility of arsenic by precipitation of arsenic-sulfide minerals, As2S3, but recent studies indicate that under certain conditions, significant concentrations of soluble As-S compounds can exist in sulfidic waters.  Thus, the question is whether they are As(III)-S species ("thioarsenites") or As(V)-S species ("thioarsenates").  A research group led by Dr. B. Planer-Friedrich (University of Bayreuth, Germany) has recently reported that use of X-ray absorption spectroscopy (XANES and EXAFS) can determine the concentration ratio of each species.  The experiment was done at beamline BM20, ESRF.  For more information, see the paper, "Discrimination of Thioarsenites and Thioarsenates by X-ray Absorption Spectroscopy", E. Suess et al., Anal. Chem., Article ASAP (2009), DOI: 10.1021/ac901094b

Theoretical calculation of Cu Kα spectra

Dr. C. T. Chanter and his colleagues have published a paper on the unresolved quantitative discrepancies between experimental and theoretical Cu Kα spectra.  For more information, see the paper, "Theoretical Determination of Characteristic X-Ray Lines and the Copper Kα Spectrum", C. T. Chantler et al., Phys. Rev. Lett. 103, 123002 (2009).

Soft X-ray laser produces 'transparent aluminum'

In the film Star Trek IV (1986), transparent aluminum is used for the exterior portals and windows of spacecraft.  Now transparent aluminum has become a hot topic for real, rather than in science fiction.  An international team, led by Oxford University scientists, has recently reported that a short pulse from the FLASH laser (wavelength 13.5 nm) knocks out a core L-shell electron from every aluminium atom in a 50 nm Al thin film without destroying the metal's crystalline structure.  This rendered the aluminium almost invisible for this wavelength.  This phenomenon is called saturable absorption.  The transient state of aluminium produced in this way is as dense as ordinary matter but can only exist for an extremely short period of time of 40 femtoseconds.  For more information, see the paper, "Turning solid aluminium transparent by intense soft X-ray photoionization", B. Nagler et al., Nature Physics 5, 693 (2009).

Coherent X-rays reveals dynamics of atomic-scale diffusion

So far, diffusion in solids has been investigated by profiling the depth dependence of tracer atoms diffused into the sample.  Although one can obtain the diffusion constant from this, the question is how diffusion takes place on the atomic scale, rather than on the micron scale.  Sometimes quasielastic neutron scattering as well as Mobauer spectroscopy can be used in a very limited number of fortunate cases.  A research group led by Professor G. Vogl (University of Vienna, Austria) recently reported the use of X-ray photon correlation spectroscopy (XPCS) to observe the dynamics of diffusing atoms.  The research was done for intermetallic alloy Cu90Au10, at temperatures of around 540 K, where the system is a substitutional solid solution, that is, the Au atoms statistically occupy sites in the Cu fcc lattice.  The research gives the dynamical behavior of single atoms as a function of their neighborhood, and confirms quantitatively that Au atoms have a tendency to locally order on a certain set of sites in the crystal.  Photon correlation spectroscopy is based on analysis of 'speckle' patterns, which are fine-scale diffraction patterns that appear in the scattering of coherent light from a disordered system.  Speckle patterns are sensitive to the exact spatial arrangement of the disorder.  By observing the intensity fluctuations in the speckle pattern, the characteristic times of fluctuations in the system can be determined.  For more information, see the paper, "Atomic diffusion studied with coherent X-rays", M. Leitner et al., Nature Materials,8, 717 (2009).

When a strong laser beam hits the surface of a material, plasma is produced there, subsequently leading to the emission of a short burst of X-rays.  It is believed that the electrons in the surface plasma are accelerated by the strong electric field of the laser and then penetrate the solid behind. There, they knock out electrons from inner electronic shells, which subsequently undergo inner-shell recombination, leading to characteristic line emissions such as Kα and Kβ spectra.  A research group led by Professor U. Teubner (University of Applied Sciences, Emden, Germany) has reported detailed experimental results on copper and titanium K X-rays.  Particular attention has  been paid to the interplay between the angle of incidence of the laser beam on the target, as well as the influence of prepulses.  For more information, see the paper, "Optimized K x-ray flashes from femtosecond-laser-irradiated foils", W. Lu et al., Phys. Rev. E 80, 026404 (2009).

Solution of phase problem in X-ray crystallography

In X-ray diffraction experiments, one measures the intensity (amplitude) of the diffracted X-rays as a function of position in the reciprocal space, and the information on the phase is always missing.  For many years, this so-called phase problem has been thought as one of the biggest problems in X-ray crystallography.  Professor E. Wolf (University of Rochester, New York) has recently published a very interesting and inspirational paper.  He is famous for several important textbooks on optics and also for his presidency of the Optical Society of America.  The present paper is theoretical, and starts with a criticism of basic understanding of the problem. The author says that trying to measure the phase is rather meaningless.  Almost all scientists assume that the incident X-ray beam is monochromatic in the data analysis, but the author points out that a monochromatic beam is not possible in reality.  Any beam that can be produced in a laboratory is, at best, quasimonochromatic and, therefore, even if both the amplitudes and the phases are given, it is still not possible to solve the problem.  Alternatively, the author proposes the measurement of certain correlation functions, with the use of spatially coherent beams.  While it is extremely important to think about a future strategy regarding the final solution of the phase problem as discussed in the paper, the author makes no mention of the recent significant strides in coherent X-ray scattering.  For more information, see the paper, "Solution of the Phase Problem in the Theory of Structure Determination of Crystals from X-Ray Diffraction Experimentst", E. Wolf, Phys. Rev. Lett. 103, 075501 (2009).

X-ray nanointerferometer

X-ray phase-contrast imaging is extremely powerful for visualizing internal structures with low-Z matrices, which are most likely in bio-medical specimens.  The use of an X-ray interferometer is one of the most promising ways forward for this imaging technology, but resolution has been limited to the micrometer scale so far.  A research group led by Dr. A. Snigirev (European Synchrotron Radiation Facility, Grenoble, France) has recently developed a novel type of X-ray interferometer employing a bilens system with two parallel arrays of compound refractive lenses, each of which creates a diffraction limited beam under coherent illumination.  The energy of the X-rays is 10-20 keV and the material used in the refractive lenses is silicon.  When the two beams overlap, they produce an interference pattern with fringe spacing ranging from tens of nanometers to tens of micrometers.  Readers may notice that the system is similar to the model of a Billet split lens in classical optics (See Fig.7.8, page 263 in "Principle of Optics", M. Born and E. Wolf, 6th Ed, Pergamon Press (1988)).  The use of a modern synchrotron source and this novel optical device thus opens up a new field and could revive old theorems.  Coherent moiré imaging or radiography are promising straightforward applications.  For more information, see the paper, "X-Ray Nanointerferometer Based on Si Refractive Bilenses", A. Snigirev et al., Phys. Rev. Lett., 103, 064801 (2009).

It is well known that the physical properties of semiconductor nanostructures, which have been grown in most cases by the Stranski-Krastanow (SK) mechanism, depend on their size, shape, strain and composition.  In the case of the growth of Ge on Si(001), where the 2D-3D transition is driven by the 4.16% lattice mismatch between Ge and Si, the increase of Ge coverage above a critical thickness of around 4 ML can make coherent islands.  First, square pyramids appear, and then dome-shaped islands are formed.  At about 9 ML, the misfit strain can no longer be accommodated coherently and larger islands called superdomes are present. This raises detailed questions as to dependence on the growth rate, temperature etc.  To provide answers to such questions, in-situ X-ray studies are extremely important.  Professor G. Bauer (Institute of Semiconductor and Solid State Physics, Johannes Kepler University in Linz, Austria) and his colleagues recently performed grazing-incidence small angle X-ray scattering (GISAXS) and diffraction (GID) experiments with a UHV-MBE chamber.  They clarified the kinetics of the growth of Ge superdomes and their facets on Si(001) surfaces, as a function of deposited Ge thickness for different growth temperatures at a low growth rate, by in situ grazing-incidence small-angle x-ray scattering in combination with in situ grazing-incidence x-ray diffraction. At a low growth rate, intermixing is found to be enhanced and superdomes are formed already at lower coverages than previously reported. In addition, the research team observed that at the dome-to-superdome transition, a large amount of material is transferred into dislocated islands, either by dome coalescence or by anomalous coarsening. Once dislocated islands are formed, island coalescence is a rare event and introduction of dislocations is preferred. The superdome growth is thus stabilized by the insertion of dislocations during growth.  For more information, see the paper,   "In situ X-ray scattering study on the evolution of Ge island morphology and relaxation for low growth rate: Advanced transition to superdomes", M.-I. Richard et al., Phys. Rev. B 80, 045313 (2009).

Professor H. Dosch (Director of Deutsches Elektronen-Synchrotron (DESY), Germany) and his colleagues recently published a very interesting paper on the symmetry of disordered systems.  They propose a new technique, X-ray cross correlation analysis (XCCA).  This measures X-ray speckles and is basically an extension of X-ray photon correlation spectroscopy (XPCS).  The samples studied were colloidal glasses, and the research group was able to observe clear symmetries that conventional X-ray diffraction has been unable to extract.  The research group recommends using brilliant coherent X-ray sources, such as X-ray free electron lasers for future research.  For more information, see the paper, "X-ray cross correlation analysis uncovers hidden local symmetries in disordered matter", P. Wochnera et al., Proc Nat Aca Sci, 106, 11511 (2009).

Possibility of atomic inner-shell X-ray laser

Since 1984, laboratory-scale X-ray lasers have been extensively studied.  The shortest wavelength achieved so far is 3.6 nm, with a weak intensity.  On the other hand, X-ray free-electron lasers (XFEL) based on self-amplified spontaneous emission (SASE) from a long undulator in the linear electron accelerator will be available in near future.  The next idea is the use of XFEL to pump a photoionization inner-shell X-ray laser in an atomic gas.  Dr. R. London (Lawrence Livermore National Lab) and a colleague have recently published their theoretical calculations.  For more information, see the paper, "Atomic inner-shell X-ray laser pumped by an x-ray free-electron laser", N. Rohringer et al., Phys. Rev. A 80, 013809 (2009).

Imaging individual objects of several nanometer resolution in space and several femtosecond resolution in time, is now one of the most exciting experiments in X-ray physics.  Over the past decade, coherent X-ray diffraction has overcome a lot of limits in imaging noncrystalline objects at a resolution in the order of X-ray wavelength.  So far, X-ray free electron lasers (or, in the mean time, 3rd generation synchrotron sources) have been considered as a promising source, but the table-top source is no doubt extremely important for many new sciences.  Recently, Dr. H. Merdji (CEA Saclay, France) and his colleagues reported the feasibility of a laser-driven soft X-ray source, which uses the 25th harmonics (32 nm wavelength, 20 fs pulse width) of a Ti:sapphire laser.  They succeeded in observing diffraction patterns from isolated nano-objects with a single 20 fs pulse.  Images were reconstructed with a spatial resolution of 119 nm from the single shot and 62 nm from multiple shots.  For more information, see the paper, "Single-Shot Diffractive Imaging with a Table-Top Femtosecond Soft X-Ray Laser-Harmonics Source", A. Ravasio et al., Phys. Rev. Lett. 103, 028104 (2009).

Dr. P. Glatzel (European Synchrotron Radiation Facility (ESRF), Grenoble, France) and his colleagues recently published an interesting paper reporting systematic studies on both X-ray absorption and Kα emission spectra from sulfur compounds.  The compounds' spectra were compared with quantum chemical calculations using density functional, multiple-scattering, and atomic multiplet theory.  It was found that the near-edge absorption spectra are mainly determined by the geometry of the first coordination sphere in the case of the sulfates and sulfite, while strong orbital hybridization in the case of sulfides results in a much more complex analysis.  On the other hand, the spectral shape of the Kα fluorescence lines shows little influence of the chemical environment, but its energy position is correlated with the valence-shell electron population.  The experiments were done at beamline ID26, ESRF.  The spectrometer used for Kα emission is a combination of a Johansson Si(111) crystal and a CCD camera.  The energy resolution was 0.44 eV for S Kα.  For more information, see the paper, "Electronic Structure of Sulfur Studied by X-ray Absorption and Emission Spectroscopy", R. A. Mori et al., Anal. Chem., Article ASAP, DOI: 10.1021/ac900970z

In January 2006, NASA's Stardust spacecraft brought comet coma particles and interstellar grains from Comet 81P/Wild2.  Synchrotron facilities all over the world have been used for extensive analysis of the chemical composition and crystal structures of the matter.  Recently, Professor L. Vincze (X-ray Microspectroscopy and Imaging Group, Ghent University, Belgium) and his colleagues reported the results of 3D X-ray imaging based on X-ray fluorescence (XRF) tomography.  In the present research, a 200 nm beam was employed, because the typical size of the particles from space was 2 microns.  The measurement consisted of 2D scanning XRF maps for each rotation angle of the sample.  In the XRF spectra, many peaks were found; Ca, Cr, Mn, Fe, Cu, Se etc. For more information, see the paper, "X-ray Fluorescence Nanotomography on Cometary Matter from Comet 81P/Wild2 Returned by Stardust", G. Silversmit et al., Anal. Chem., Article ASAP, DOI: 10.1021/ac900507x  For related work on the same 'star dust' by other groups, for example, see "Chondrulelike Objects in Short-Period Comet 81P/Wild 2", Tomoki Nakamura et al., Science, 321, 1664-1667 (2008) and "Mixing Fraction of Inner Solar System Material in Comet 81P/Wild2", A. J. Westphal et al, The Astrophysical Journal, 694, 18-28 (2009).

Account of Stanford's X-ray laser in Nature Photonics

As reported here previously, in April this year, the first 1.5 Å wavelength laser light was generated at Stanford, USA.  An interesting account of the hard X-ray laser was published in Nature Photonics.  See the article, "Free electron lasers: First light from hard X-ray laser", B. McNeil, Nature Photonics, 3, 375-377 (2009).

 

Confocal X-ray micro fluorescence is a method of 3D analysis, and uses the formation of confocal volume (probing microvolume) defined through the intersection of a focused excitation beam and the sensitive volume of a polycapillary lens placed in front of the detector.  Because of increasing demands, the technique has been widely used at both synchrotron and laboratory sources.  However, some essential problems in quantitative analysis have remained so far.  Dr. A-G. Karydas (Institute of Nuclear Physics, N.C.S.R. "Demokritos", Greece) and his colleagues recently published a paper on the influence of the secondary fluorescence enhancement in this technique.  For more information, see the paper, "Secondary Fluorescence Enhancement in Confocal X-ray Microscopy Analysis", D. Sokaras et al., Anal. Chem., Article ASAP, DOI: 10.1021/ac900688n

Spider silk is a tough yet light material, but recently it has been found that it becomes three times stronger by adding small amounts of metal such as Zn, Ti and Al.  The idea was inspired by research which established that trace metals are frequently found in the toughest parts of some insect bodies.  Bio-materials scientists think that such metals could be incorporated in the protein structures and lead to unusual mechanical properties.  Dr. M. Knez (Max Planck Institute of Microstructure Physics, Halle, Germany) and his colleagues have succeeded in infiltrating Zn, Ti and Al by the application of atomic layer deposition technique.  X-ray fluorescence spectra provided the evidence for them.  For more information, see the paper, "Greatly Increased Toughness of Infiltrated Spider Silk", S-Mo Lee et al., Science, 324, 488-492 (2009).

Grazing-exit micro X-ray fluorescence analysis of plant

Professor K. Tsuji (Osaka City University, Japan) and his colleagues recently reported an interesting application of grazing-exit micro X-ray fluorescence to the analysis of a leaf of Camellia hiemalis.  In their experiments, a polycapillary X-ray lens was used to observe a 30 μm area.  Grazing-exit geometry was employed to enable the observation of the near surface of the plant.  For more information, see the paper, "Grazing Exit Micro X-ray Fluorescence Analysis of a Hazardous Metal Attached to a Plant Leaf Surface Using an X-ray Absorber Method", T. Awane et al., Anal. Chem., 81, 3356-3364 (2009).
At the Photon Factory, KEK, Japan, Dr. T. Okuda (University of Tokyo) and his colleagues have developed a new technique for determining the identity of groups of individual atoms.  Scanning tunneling microscopy (STM) is an existing powerful characterization method, which can detect the atomic positions in real space.  In order to upgrade the STM by giving it the capability to distinguish chemical species, the research group employed synchrotron X-rays, which excite core-level electrons in the sample's atoms.  In this way, secondary electrons can be detected by the STM as they tunnel across the gap.  The important point here is that the tunneling current depends on the chemical species.  Accordingly, the technique provides chemical imaging.  The current spatial resolution is around 10 nm.  In the present research, Fe and Ni L absorption edges were chosen to control the core-level excitation.  The beamline used was BL-13C.  For more information, see the paper, "Nanoscale Chemical Imaging by Scanning Tunneling Microscopy Assisted by Synchrotron Radiation", T. Okuda et al., Phys. Rev. Lett. 102, 105503 (2009)

Influence of coherent length on TXRF and XSW

Dr. A. von Bohlen (Institute for Analytical Sciences, Germany) and his colleagues recently published an interesting paper on the analysis of nanoparticles prepared on the substrate by grazing incidence X-ray Standing Waves (XSW) and Total Reflection X-ray Fluorescence (TXRF).  The influence of coherence length of X-rays from different X-ray sources, the particle form, particle size and distribution are discussed.  For more information, see the paper, "The influence of X-ray coherence length on TXRF and XSW and the characterization of nanoparticles observed under grazing incidence of X-rays", A. von Bohlen et al., J. Anal. At. Spectrom., 2009 (advance article)  DOI: 10.1039/b811178b
A research team from the National Natural History Museum in Paris and the American Museum of Natural History in New York recently analyzed the 3D structure of a 300-million-year-old brain of a relative of sharks and ratfish at the European Synchrotron Radiation Facility (ESRF).  This is the first time that the soft tissue of such an old fossil brain has ever been found, and the sample studied was found in Kansas, United Sates.  The study was performed by combined use of absorption microtomography and a new holotomographic approach, which uses phase-contrasts.  The analysis indicated that the area where the brain-like structure reaches the surface of the sample reveals a high concentration of calcium phosphate, whereas the surrounding matrix is almost pure calcium carbonate. The mineralization of the brain might be due to the presence of bacteria that covered the brain shortly before decay and induced its phosphatization.  For information about the holotomographic approach, see the paper, "Mixed transfer function and transport of intensity approach for phase retrieval in the Fresnel region", P. Guigay et al., Opt Lett., 32, 1617 (2007).  For more information on this research, see the paper, "Skull and brain of a 300-million-year-old chimaeroid fish revealed by synchrotron holotomography", A. Pradela et al., Proceedings of National Academy of Science (published online before print March 9, 2009, doi: 10.1073/pnas.0807047106)

Snap shots of breathing myoglobin

The use of short pulses of extremely bright synchrotron X-rays has opened up a new world.  In Japan, Dr. S. Adachi (KEK, Tsukuba Japan) and his colleagues recently succeeded in recording movies during changes in the molecule structures of myoglobin.  The samples used are frozen myoglobin crystals that had CO (carbon monoxide) stored inside before the start of the experiments.  Even at 100K, irradiating pulsed laser light gave the trigger for the migration of CO molecules.  To see changes in atomic scale, time-resolved X-ray diffraction measurements were performed.  The obtained movie tells us that the CO molecules penetrate into a number of cavities in the crystal and even expand their size.  The research group has obtained an important result suggesting some self-opening mechanism in the ligand migration channel.  For more information, see the paper, "Visualizing breathing motion of internal cavities in concert with ligand migration in myoglobin", A. Tomita et al., Proceedings of National Academy of Science, 106, 2612-2616 (2009) Published online before print February 9, 2009, doi: 10.1073/pnas.0807774106

In classical metallurgy, there exists a very famous rule known as Hume-Rothery's rule, which describes the conditions necessary for the formation of a solid solution from two independent metals.  In order to have a substitutional crystalline solid solution in which the atoms of one element randomly substitute for atoms of another element in a crystal structure, the components must have an atomic size within 15% and electronegativity within 0.4 of each other.  According to this rule, a Ce-Al solid solution cannot be obtained.  Recently, a research team led by Professor H.K. Mao (Carnegie Institution of Washington) and Professor R. Ahuja (Uppsala University) found during high pressure research on the intermetallic compound of Ce3Al that a solid solution is formed in a Ce-Al system.  The differences in radii and electronegativity of Ce and Al were diminished by applying pressure.  Both synchrotron X-ray studies (XRD and X-ray absorption spectroscopy) and ab initio calculations showed the same cause for bringing the two elements closer in radii and electronegativity, resulting in the new alloy phase.  Even after the release of pressure, this substitutional alloy remained.  During in-situ X-ray absorption measurements at the Ce LIII edge, conspicuous changes in the sharpness of the absorption, correlated to delocalization of 4f electrons, were observed.  For more information, see the paper, "Substitutional alloy of Ce and Al", Q-S.Zeng et al., Proceedings of National Academy of Science, 106, 2515-2518 (2009) Published online before print February 2, 2009, doi: 10.1073/pnas.0813328106

Large chemical shift in Eu Lγ emission spectra

Eu is one of the most interesting lanthanides, compounds of which often exhibit remarkable optical, electrical, and magnetic properties.  Therefore, it is extremely important to develop a technique for chemical state analysis.  The X-ray emission spectra of Eu had not been thought to exhibit significant chemical effects.  A research group led by Professor H. Hayashi (Japan Women's Univ) firstly found a large chemical shift (~5 eV) in Eu Lγ4 emission line, depending on the valence state.  They discussed the feasibility of using this as a probe for spin- and valence-selective X-ray absorption fine structure spectroscopy.  For more information, see the paper, "Probe for spin- and valence-selective X-ray absorption fine structure spectroscopy: EuLγ4 emission", H. Hayashi et al., Anal. Chem., 81, 1522 (2009).

X-ray absorption spectroscopy is one of the most powerful probes of molecular structures.  So far, applications have been limited to the steady state and/or quite slowly changing systems.  Recently, Professor M. Chergui (Ecole Polytechnique Federale de Lausanne, (EPFL), Switzerland) and his colleagues reported a very impressive ultrafast X-ray absorption experiment.  There is a large class of Fe(II)-based molecular complexes that show two electronic states closely spaced in energy: a low-spin (LS) singlet and a high-spin (HS) quintet state. They therefore exhibit spin crossover (SCO) behavior, wherein conversion from a LS ground state to a HS excited state (or the reverse) can be induced by small changes in temperature and pressure or by light absorption.  The studies were done for an aqueous solution of [FeII(bpy)3]2+, which serves as a model system for the family of Fe(II)-based SCO complexes.  A 100-mm-thick free-flowing liquid jet of an aqueous solution of 50 mM [FeII(bpy)3]2+ was excited by an intense 400-nm laser pulse (115-fs pulse width, repetition rate 1 kHz), and a tunable femtosecond hard X-ray pulse from the slicing source was used to probe the system in transmission mode at 2 kHz.  The X-ray flux was about 10 photons/pulse at 7 keV.  The time resolution was under 250 fs.  By recording the intensity of a characteristic near edge absorption spectral feature as a function of laser pump/X-ray probe time delay, the very early stages of photo excitation in Fe(II)-based complexes were clarified.  For more information, see the paper, "Femtosecond XANES Study of the Light-Induced Spin Crossover Dynamics in an Iron(II) Complex", Ch. Bressler et al., Science, 323, 489 (2009).

Laser generation in the X-ray region has become realistic because of the construction of free electron laser facilities, which will be available in the near future (Linac Coherent Light Source (LCLS) at Stanford in 2009; European XFEL in 2014).  Another significant route is the extension of existing laser technologies such as high-order harmonic generation (HOHG), particularly from relativistically oscillating plasma mirror-like surfaces.  Professor M. Zepf (Queens University Belfast, UK) and his colleagues recently published an interesting paper showing that it is possible to achieve a near-diffraction-limited focal spot size that is also controllable.  For more information, see the paper, "Diffraction-limited performance and focusing of high harmonics from relativistic plasmas", B. Drome et al., Nature Physics, advanced online publication doi:10.1038/nphys1158

Professor T. Rayment (School of Chemistry, University of Birmingham, UK) and his colleagues have developed a channel-flow cell to study electrochemical reactions on electrodes by time-resolved X-ray absorption spectroscopy.  During the studies with the model system, it was found that a flowing solution is essential to remove any products of beam damage.  For more information, see the paper, "Channel-Flow Cell for X-ray Absorption Spectroelectrochemistry", R. J. K. Wiltshire et al., J. Phys. Chem., C 113, 308 (2009)

Diffractive imaging is a technique for so-called lens-less microscopy, and uses diffraction intensity (image) and phase retrieval calculations rather than focusing systems such as lenses, which are not free from aberrations.  The spatial resolution is basically limited only by the amount of high-angle scattering.  Therefore, the technique has been considered as having the potential to achieve atomic resolution for hard X-rays or other short-wavelength particle beams.  However, so far, the reported results have been still at the level of several nanometers.  Recently, a research group at the University of Illinois, USA proposed a method of improving the resolution.  One of the biggest technical reasons limiting the spatial resolution of diffractive imaging is the difficulty of recording weak coherent scattering signals.  The research group proposes the combined use of low-resolution imaging, which provides the starting phase, real-space constraint, missing information in the central beam and essential marks for aligning the diffraction pattern.  The group used an electron microscope to see a single CdS quantum dot with sub-angstrom resolution and noted that it is possible to use the same procedure in the case of coherent X-ray scattering.  For more information, see the paper, "Sub-angstrom-resolution diffractive imaging of single nanocrystals", W. J. Huang et al., Nature Physics, advanced online publication doi:10.1038/nphys1161

Intracellular chemical imaging of human neuromeranin

Neuromeranin (NM) is a dark colored pigment synthesized within specific catecholamine-producing neurons in the human brain.  It is of uncertain origin and exists as amorphous granules with a heterogeneous structure called NM granules.  At the European Synchrotron Radiation Facility (ESRF) in Grenoble, the microchemical environment of NM in whole neurons from formalin-fixed and paraffin-embedded human substantia nigra sections was recently analyzed.  It was found that concentrations of NM-associated elements increase in the developing brain, and that iron-rich microdomains colocalized with other elements within the pigment.  Furthermore, intracellular speciation of sulfur in NM has revealed the presence of reduced sulfur compounds and various forms of oxidized sulfur compounds which have not previously been reported.  For more information, see the paper, "Intracellular Chemical Imaging of the Developmental Phases of Human Neuromelanin Using Synchrotron X-ray Microspectroscopy", S. Bohic et al., Anal. Chem., Article ASAP, DOI: 10.1021/ac801817k 

Nano-scale chemical imaging of working catalyst

Recent progress in synchrotron X-ray microscopy has opened up extremely attractive applications.  A group led by Professor B. M. Weckhuysen (Utrecht University, The Netherlands) recently watched heterogeneous catalysts in action at high temperature.  Solid catalysts have been widely used in the chemical industry, and accelerate the production of many important compounds.  They are typically composed of nanometre-sized metal or metal oxide particles attached to a solid support with a high surface area.  As complex structural and chemical changes take place during catalytic reactions, direct observation of the reacting catalyst is extremely important.  The team employed X-ray microscopy at the Advanced Light Source, Berkeley, United States, to study the catalytic Fischer-Tropsch reaction where a solid catalyst of iron oxide particles mounted on silica is used to convert carbon monoxide and hydrogen into liquid hydrocarbons that can be used as fuels.  By the use of Fe LII, III and C K absorption edges, scanning transmission X-ray imaging has revealed that during the reaction the iron oxide underwent several transformations; the initial iron oxide (Fe2O3) is converted into another oxide (Fe3O4), before iron silicates (Fe2SiO4) and metallic iron begin to form.  Iron carbides (FexCy) appear in the final stage.  For more information, see the paper, "Nanoscale chemical imaging of a working catalyst by scanning transmission X-ray microscopy", E. de Smit et al., Nature 456, 222-225 (2008).

Calculation of Kα spectra for double ionization case

Professor L. Natarajan (University of Mumbai, India) recently published a paper calculating the energies and electric dipole rates of X-rays from the empty K shells of atoms in the range of Z=12 to 56.  For more information, see the paper, "Relativistic fluorescence yields for hollow atoms in the range 12<Z<56", L. Natarajan, Phys. Rev. A78, 052505 (2008).

X-ray generation by friction of sticky tape

Professor S. Putterman (University of California, Los Angeles, USA) and his colleagues recently demonstrated that simply peeling ordinary sticky tape in a moderate vacuum can generate sufficient X-rays to take an image of a human finger.  The phenomenon has long been known as tribo-luminescence (or mechano-luminescence), but their report (including online video accessible from the Nature News page) has impressed many.  Nanosecond, 100-mW X-ray pulses as well as radio and visible light have been clearly confirmed to be correlated with stick-slip peeling events.  They observed a 15-keV peak in X-ray energy spectra, and attempted to explain it by various models.  For more information, see the paper, "Correlation between nanosecond X-ray flashes and stick-slip friction in peeling tape", C. G. Camara et al., Nature, 455, 1089-1092 (2008), and the news article, "Sticky tape generates X-rays  - How weird is that?", Katharine Sanderson, Nature News, http://www.nature.com/news/2008/081022/full/news.2008.1185.html as well as readers' comments thereon.  A very old and pioneering report describing how peeling tape can be a source of X-rays is "Investigation of electron emission on tearing away highpolymer film from glass in vacuum", V. Karasev et al., Doklady Akademii Nauk SSSR, 88, 777-780 (1953).

Uncertainty in TXRF

Dr. R. Fernandez-Ruiz (Universidad Autonoma de Madrid, Spain) recently published a theoretical paper on the expanded uncertainty associated with TXRF measurements.  For more information, see the paper, "Uncertainty in the Multielemental Quantification by Total-Reflection X-ray Fluorescence: Theoretical and Empirical Approximation", R. Fernandez-Ruiz, Anal. Chem., 80, 8372-8381 (2008).

X-ray fluorescence analysis of rocks from other planets

X-ray fluorescence (XRF) spectra for a number of rock samples from Mars, the Moon, and Mercury have been measured at the Physikalisch-Technische Bundesanstalt (PTB) beamline in the BESSY II electron storage ring.  In the future, both ESA and NASA will send spacecraft to Mercury.  Remote X-ray sensing is planned to obtain chemical composition mapping on the planetary surface.  The present synchrotron XRF spectra will be used as valuable reference for the analysis. For more information, see the paper, "Measuring and Interpreting X-ray Fluorescence from Planetary Surfaces", A. Owens et al., Anal. Chem., 80, 8398-8405 (2008). 

X-ray spectra of shock compression

A research group at Lawrence Livermore National Laboratory recently reported an interesting application of ultrafast X-ray spectrometry to studies on the compression and heating of shocked matter.  Here, the sample is 300 μm thick LiH, which is heated by a 450 J nsec laser, and the X-ray used is Ti Kα X-ray fluorescence (4.51 keV) from Ti foil heated by another pulse laser of 5 psec.  X-ray photons produced at the Ti foil are estimated as a 2 × 1013/pulse.  The energy spectra of X-ray scattering by the LiH sample during compression were taken by a spectrometer consisting of a large curved graphite (HOPG) crystal in van Hamos geometry and an Imaging Plate (IP) detector.  It was found that the X-ray scattering spectrum from shocked LiH shows elastic Rayleigh scattering and inelastic plasmon scattering features.  Whereas earlier in time only elastic scattering was observed, at 7 nsec, a plasmon energy shift of 24 eV was detected.  This indicates the transition to metallic free electron plasma in the solid phase.   For more information, see the paper, "Ultrafast X-ray Thomson Scattering of Shock-Compressed Matter", A. L. Kritcher et al., Science, 322, 69 -71 (2008).
 Professor A. Cupane (University of Palermo, Italy) and his colleagues at the European Synchrotron Radiation Facility (ESRF) recently established a method for structural dynamics.  The technique uses wide-angle X-ray scattering and images proteins in their natural, fast-moving state.  The research group succeeded in capturing the tertiary and quaternary conformational changes of human hemoglobin in close to physiological conditions triggered by laser-induced ligand photolysis.  The time resolution of the observation is in the order of nsec.  The whole process lasts 3 μsec, and the molecule changes from a "relaxed" form that can bond to oxygen, to a "tense" form that squeezes out the oxygen.  They also reported data on optically induced tertiary relaxations of myoglobin and refolding of cytochrome c.  For more information, see the paper, "Tracking the structural dynamics of proteins in solution using time-resolved wide-angle X-ray scattering", M. Cammarata et al., Nature Methods, published online, 21 September 2008, doi:10.1038/nmeth.1255 

X-ray detection of shape changes of catalytic nanoparticles

 It is well known that nanoparticles often enhance catalytic activity.  However, it is still an open question as to whether the metallic or the oxidized state of the particle is the catalytically more active phase.  It is therefore significant to study the oxidation/reduction process of metallic nanoparticles. A group led by Professor H. Dosh (Max-Planck-Institut für Metallforschung, Germany) recently reported on some very interesting XRD and GISAXS studies on the oxygen-induced shape transformation of Rh nanoparticles.  The experiments were done in-situ, during the oxidation/reduction cycle at high temperature.  The group found that shape transformation is driven by the formation of a surface oxide O-Rh-O trilayer, which can stabilize Rh nanoparticles with low-index facets.  For more information, see the paper, "Shape Changes of Supported Rh Nanoparticles During Oxidation and Reduction Cycles", P. Nolte et al., Science, 321, 1654-1658 (2008). 
 X-ray microscopy is continuing to make significant progress in two directions, through the use of advanced X-ray optical elements and through the combined use of coherent X-rays and image analysis.  Currently, the typical spatial resolution available at major synchrotron radiation facilities is the order of tens of nm.  Professor C. Schroer (Technische Universität Dresden, Germany) and his colleagues recently achieved the world record for spatial resolution in X-ray microscopy.  The research group employed the coherent x-ray diffraction imaging technique and observed a single gold nanoparticle (size <100 nm) supported by a Si3N4 membrane with 15.25 keV photons, beam dimensions 100×100 nm2, and flux of more than 1E+8 counts/sec.  The real-space gold image was reconstructed by the hybrid input-output (HIO) method together with the shrink-wrap algorithm.  The resolution of 5 nm was achieved in 600 s exposure time.  The present experiments were done at beamline ID13, ESRF, and a pair of refractive lenses was used to increase the coherent dose density.  For more information, see the paper, "Coherent X-Ray Diffraction Imaging with Nanofocused Illumination", C. G. Schroer et al., Phys. Rev. Lett., 101, 090801 (2008).

Structure of SAM on Au(111)

 

Some of the most well known self-assembled monolayers (SAMs) are alkyl sulfides on gold surfaces.  They have many potential applications in molecular electronics, biosensors, and nanopatterning.  However, there have still been unsolved problems in basic research regarding Au-S interaction.  Recently, Professor A. Morgante (Universita' di Trieste, Italy) and his colleagues published the results of grazing incidence X-ray diffraction and density functional theory-based molecular dynamics simulations for hexanethiol and methylthiol.  The research group demonstrated surface complexes wherein two S atoms are joined by an intermediate Au adatom (RS-Au-SR) for longer chain cases. It was found that the sulfur atoms of the molecules bind at two distinct surface sites, and that the first surface layer contains vacancies as well as gold adatoms that are laterally bound to two sulfur atoms.  Competition between SAM ordering and disordering of interfacial Au atoms takes an important role in the system.  For more information, see the paper, "X-ray Diffraction and Computation Yield the Structure of Alkanethiols on Gold(111)", A. Cossaro et al., Science, 321, 943-946 (2008).

A French research group has reported the application of X-ray fluorescence microscopy to the analysis of macrophages exposed to unpurified and purified single-walled (SW) and multiwalled (MW) carbon nanotubes (CNT).   During this research, elemental mapping at cell level was performed for P, Cl, K, Ca and Fe.  For more information, see the paper, "Carbon Nanotubes in Macrophages: Imaging and Chemical Analysis by X-ray Fluorescence Microscopy", C. Bussy et al., Nano Lett., 8, 2659-2663 (2008).

Synchrotron XRF revealed Van Gogh's hidden painting

It is well-known that Vincent van Gogh (1853-1890) often reused canvases and painted over his older works.  Specialists estimate that about one third of his early paintings conceal other compositions under them.  Recently, an international team led by Professor K. Janssens (University of Antwerp, Belgium) and Dr J. Dik (Delft University of Technology, The Netherlands) successfully applied synchrotron radiation induced X-ray fluorescence spectroscopy to the painting entitled Patch of Grass (painted by Van Gogh in Paris in 1887 and owned by the Kroller-Muller Museum).  The research group recorded X-ray fluorescence intensity maps of several tens of square cm and, in particular, the distribution of Hg and Sb, which corresponds to red and light tones, respectively. In this way, it could analyze an approximate color reconstruction of the flesh tones.  Accordingly, a portrait of a woman was discovered behind the painting.  The measurement was done at DESY in Hamburg, Germany.  For more information, visit the Website, http://www.vangogh.ua.ac.be/, and see the paper, "Visualization of a Lost Painting by Vincent van Gogh Using Synchrotron Radiation Based X-ray Fluorescence Elemental Mapping", J. Dik et al., Anal. Chem., ASAP Article, 10.1021/ac800965g (2008).

3D X-ray image of Ta2O5 nanofoams

Aerogel is a form of nanofoam, an engineered material designed for its high strength-to-weight ratio for application wherever lightness and strength are needed.  Now, the internal structure is within the scope of X-ray analysis.  Lawrence Livermore and Lawrence Berkeley scientists have successfully applied the coherent X-ray diffraction technique to Ta2O5 nanofoam, the density of which is 1.2 % to the bulk, and have reconstructed 3D images to determine its strength and potential new applications.  Combining the obtained structural information with detailed simulations, the research team showed that the blob-and-beam network structure explains why the materials are weaker than expected.  For more information, see the paper, "Three-Dimensional Coherent X-Ray Diffraction Imaging of a Ceramic Nanofoam: Determination of Structural Deformation Mechanisms", A. Barty et al., Phys. Rev. Lett., 101, 055501 (2008). 
Scanning diffraction microscopy, or ptychography, was first developed for the scanning transmission electron microscope (STEM).  In the same way, by using an X-ray nano beam, one can use a STXM.  The X-ray beam is focused onto the sample via a lens, and the transmission is measured.  The image is obtained by plotting the transmission as a function of the sample position, as it is rastered across the beam.  The analysis is straightforward, but its resolution is limited by the beam size.  On the other hand, coherent diffractive imaging (CDI) now reaches resolutions below 10 nm, but the reconstruction procedures are not always easy due to the influences of data quality, sample conditions etc.  A Swiss research group led by Drs. C. David and F. Pfeiffer (Paul Scherrer Institut) recently demonstrated a ptychographic imaging method that bridges the gap between STXM and CDI by measuring complete diffraction patterns at each point of a STXM scan.  The group employed an advanced large-area pixel detector, Pilatus, to obtain the diffraction pattern efficiently.  These diffraction data were then treated with an image reconstruction algorithm developed by the team.  Several tens of thousands of diffraction images were processed to obtain one super-resolution X-ray image.  The algorithm not only reconstructs the sample but also the exact shape of the light probe resulting from the X-ray beam.  The 6.8 keV X-ray beam was focused using a zone plate, and the beam size was 300 nm.  The spatial resolution achieved was about five times higher.  For more information, see the paper, "High-Resolution Scanning X-ray Diffraction Microscopy", P. Thibault et al., Science, 321, 379 - 382 (2008).

3D XRD imaging of corrosion in steel

The corrosion of steel-based mechanical components is said to be responsible for the loss of about 3% of annual global GDP.  Cracks can appear in stainless steel components when stress or strain is combined with a corrosive environment that attacks sensitive grain boundaries.  In nuclear power plants, certain grain boundaries can become sensitive during heat treatments or during fast neutron irradiation.  It is important to observe how these cracks grow in detail, because they have been identified as the primary cause of several critical system failures.  At the European Synchrotron Radiation Facility (ESRF), Grenoble, France, Dr. A. King and his colleagues recently revealed how growing cracks interact with the 3D crystal structure of stainless steel.  The sample was a wire of 0.4 mm in diameter, and 40 keV X-rays were employed.  By using diffraction contrast tomography, the research group could observe the shapes, positions, and orientations of 362 different grains with some 1600 grain boundaries without destroying the sample.  They put the wire into a corrosive liquid, K2S4O6, and applied a load to cause microcracks to grow between the grains.  As the cracks grew, 3D tomographic scans (of 30 minutes each) were made at intervals of between several minutes and two hours to follow the progress of the cracks.  It was found that the cracks grew along the boundaries between the grains.  The technique has enabled visualization of the cracks as they grow and of certain special boundaries that resist cracking.  Information on this method is given in the following papers; "X-ray diffraction contrast tomography: a novel technique for three-dimensional grain mapping of polycrystals. I. Direct beam case", W. Ludwig et al., J. Appl. Crystallogr. 41, 302 (2008) and "II. The combined case", G. Johnson et al., J. Appl. Crystallogr. 41, 310 (2008).  For more information on the present research, see the paper, "Observations of Intergranular Stress Corrosion Cracking in a Grain-Mapped Polycrystal", A. King et al., Science, 321, 382 - 385 (2008).
When X-rays satisfy Bragg's law for a perfect crystal, a significant transparency to X-ray beams is observed.  This is the so-called Bormann effect, and is caused because the X-ray electric field approaches zero amplitude at the crystal planes, corresponding to almost no scattering by atoms.  Recently, Dr. S. P. Collins (Diamond Light Source, United Kingdom) and his colleagues attempted several very interesting experiments - X-ray spectroscopy under the Bormann transmission condition.  The main idea is that the electric quadrupole absorption transitions could be effectively enhanced under conditions of absorption suppression.  The measured sample is gadolinium gallium garnet (Gd3Ga5012) cut parallel to the (100) planes, and some new spectral features were observed in the LI (8,376 eV), LII (7,930 eV) and LIII (7,243 eV) edges for gadolinium, at different temperatures.  They are basically additional peaks on the low energy side, and correspond to an electric quadrupole transition from 2s, 2p1/2 and 2p2/3 to the narrow, half-filled 4f states, respectively.  For more information, see the paper, "Quadrupole transitions revealed by Borrmann spectroscopy", R. F. Pettifer et al., Nature, 454, 196-199 (2008).

Analysis of hyper-accumulating plants

Recently, Professor I. Nakai (Tokyo University of Science, Japan) and his colleagues published a very interesting report on synchrotron X-ray fluorescence analysis of the cadmium hyper-accumulating plant, Arabidopsis halleri ssp. gemmifera.  To investigate the Cd accumulation mechanism, they analyzed the spatial distribution and chemical form of Cd at a cellular level.  At Japanese synchrotron facility, SPring-8, a tiny beam of 3.8 × 1.3 μm2 with 37 keV X-rays was used to see Cd K X-rays.  For more information, see the paper, "Micro X-ray fluorescence imaging and micro X-ray absorption spectroscopy of cadmium hyper-accumulating plant, Arabidopsis halleri ssp. gemmifera, using high-energy synchrotron radiation", N. Fukuda et al., J. Anal. At. Spectrom., 23, 1068-1075 (2008).

X-ray standing wave determines Al occupancy in zeolite

Zeolites are microporous crystalline materials, and in the unit cell, the tetrahedrally coordinated Si and Al atoms occupy the so-called crystallographic T-sites.  In addition to their pore size, Al's occupancy in the specific T-sites is extremely important in catalytic activity.  So far, however, the distribution of Al has remained an unresolved problem.  Recently, Professor J. A. van Bokhoven (ETH Zurich, Switzerland) and his colleagues employed the X-ray standing wave technique to study Al distribution in scolecite (CaAl2Si3O10-3H2O, hydrated calcium aluminum silicate).  They measured the intensity of X-ray fluorescence, Al K, Si K and Ca Kα near the Bragg conditions of (040), (002) and (-402) reflections.  The experiments were done at beamline ID32, ESRF.  For more information, see the paper, "Determining the aluminium occupancy on the active T-sites in zeolites using X-ray standing waves", J. A. van Bokhoven et al., Nature Materials, 7, 551-555 (2008).
Recently, Professor K.-J. Kim (Argonne National Lab., USA) and his colleagues published a very interesting proposal for the world's brightest X-ray source.  In most currently on-going X-ray free electron laser (FEL) projects, self-amplified spontaneous emission (SASE) is employed.  It is known that SASE-FEL creates extremely brilliant, coherent X-ray pulses of 0.1 ps duration.  Due to the low repetition rate, the average brightness is only about 10,000 times compared with existing 3rd generation synchrotron sources.  On the other hand, future X-ray sciences will require other types of X-ray laser source, with an even smaller number of photons in one pulse (to reduce radiation damage to the sample) and with much greater average intensity via a high repetition rate.  In Professor Kim's X-ray source based on a FEL oscillator (X-FELO), a pulse of electrons is carried into an undulator as ordinary FEL, but in order to reflect back the generated X-rays into the undulator entrance, there is an optical cavity consisting of two or more Bragg reflectors with low-Z atoms and with low Debye temperature, such as diamond, beryllium oxide and sapphire crystals.  In the next step, the X-ray photons connect with the next electron bunch and again travel back along the undulator.  This pattern is repeated indefinitely with the X-ray intensity growing each time until equilibrium is reached.  As the spectral bandwidth is extremely narrow, at three to four orders of magnitude finer than those produced by SASE-FEL, the intensity of an individual X-ray pulse from an X-FELO is rather low.  But the average X-ray intensity is higher than that of SASE-FEL.  Over the past 5 years, highly advanced electron beam technologies, which can be used, for example, for a multi-GeV class energy recovery linac (ERL), have become available.  One of the key elements of Professor Kim's idea is combination with ERL.  This is predicted to produce X-ray pulses with 109 photons at a repetition rate of 1-100 MHz.  The pulses are temporarily and transversely coherent, with a rms bandwidth of about 2 meV, and rms pulse length of about 1 ps.  To gain an understanding of the original concept of X-FELO, see the paper, "Proposal for a free electron laser in the X-ray region", R. Colella and A. Luccio, Optical Commun., 50, 41-44 (1984).  For more information on the proposed X-ray source, see the paper, "A Proposal for an X-Ray Free-Electron Laser Oscillator with an Energy-Recovery Linac", K.-J. Kim et al., Phys. Rev. Lett., 100, 244802 (2008).
 The molecular structure of liquid water has been the subject of intense debate for decades.  In 1892, German physicist W. C. Röntgen, who became famous for his discovery of X-rays, published a paper proposing a "mixture model" according to which liquid water consists of two kinds of molecules: a tetrahedral ice-like structure, and another more loosely arranged structure.  In 1933, J. D. Bernal and R. H. Fowler successfully analyzed early X-ray diffraction data on water in terms of a disordered quartz-like structure, and concluded that the unique properties of water are due to the tetrahedral geometry.  Since then, a number of experimental and theoretical studies have been published.  Nevertheless, scientists have not yet captured a clear picture of liquid water.  The debate is far from settled.  Very recently, an international collaborative team led by Dr. A. Nilsson (Stanford Synchrotron Radiation Laboratory) and Professor S. Shin (RIKEN & The University of Tokyo) succeeded in obtaining X-ray spectroscopic evidence to support Röntgen's mixture model.  Thanks to the brilliant synchrotron beamline at the SPring-8, the research group obtained some high resolution oxygen K-edge X-ray emission spectra of liquid water.  The team found that there are two distinct narrow lone-pair derived peaks assigned, respectively, to tetrahedral and strongly distorted hydrogen-bonded species.  For more information, see the paper, "High resolution X-ray emission spectroscopy of liquid water: The observation of two structural motifs", T. Tokushima et al., Chem. Phys. Lett., 460, 387-400 (2008).

Further analysis of silica on Mars

In May 2007, NASA's Mars rover Spirit found that Martian soil has a high concentration of silica.  This is considered as very strong evidence that water could have existed on ancient Mars, because certain hydrothermal reactions are most likely to produce silica.  The discovery was announced in brief at the time (see http://www.nasa.gov/mission_pages/mer/mer-20070521.html), but scientists led by Professor S. Squyres (Cornell University, United States) have now had time to fully analyze the mineral deposits.  In addition to the Miniature Thermal Emission Spectrometer (Mini-TES), the Alpha Particle X-ray Spectrometer (APXS) contributed significantly to the analysis.  Analysis of the elemental composition of the deposits revealed that Si is strongly enriched relative to typical soil, and there are weaker enrichments in Ti, Cr, and Zn.  Other major elements appear to be depleted.  For more information, see the paper, "Detection of Silica-Rich Deposits on Mars", S. W. Squyres et al., Science, 320, 1063 (2008).
Analysis of X-ray and neutron reflectivity is usually done by modeling the scattering length density profile (such as multilayers) of the sample and performing a least square fit to the measured, phaseless reflectivity data.  Professor T. Salditt (Institute for X-ray Physics, Universitat Gottingen) and his colleague recently attempted to extend the inversion technique.  The research group discussed conditions for uniqueness, which are applicable in the kinematic limit (Born approximation), and for the most relevant case of box model profiles with Gaussian roughness.  They also demonstrated that an iterative method to reconstruct the profile based on regularization works well.  For more information, see the paper, "Iterative reconstruction of a refractive-index profile from x-ray or neutron reflectivity measurements", T. Hohage et al., Phys. Rev. E77, 051604 (2008).
Spintronics is now one of the most important keywords in modern sciences and technologies.  The currently employed method for magnetic recording uses electrical current pulses, and there appear to be limitations for extremely high density devices (e.g., G-bit level MRAM).  One of the most promising solutions is the use of spin polarized current in a ferromagnetic medium, which can provide a spin-transfer torque to the magnetization, resulting in its motion.  To develop high-density and very fast devices, it is indispensable to obtain a fundamental understanding of what really takes place there.  Recently, a research group led by Dr. G. Meier (Hamburg University, Germany) succeeded in visualizing spin-torque-induced vortex gyration in micrometer-sized permalloy squares using a 30nm-resolution X-ray microscope at the Advanced Light Source (ALS), Berkeley, United States.  The phases of the gyration in structures with different chirality have been analyzed considering alternating spin-polarized currents and the current's Oersted field.  For more information on the present experiments, see the paper, "Time-Resolved X-Ray Microscopy of Spin-Torque-Induced Magnetic Vortex Gyration", M. Bolte et al., Phys. Rev. Lett., 100, 1701 (2008).

XRD tomography

Progress in nano sciences requires further development of local structural probes, particularly for the study of non-uniform materials.  As material functions are often concerned with heterogeneity and some hierarchical orders of the structures, some kind of zooming from low to high resolution will become crucial in the future.  Furthermore, in addition to two-dimensional (2D) imaging of an object with a lateral resolution determined by the beam size, some depth resolution is important for a better understanding of materials.  So far, X-ray techniques have had several limitations with respect to such points.  Recently, French scientists led by Professor J-L. Hodeau (CNRS, Grenoble, France) have reported an interesting development.  They are trying to combine pencil-beam tomography with X-ray diffraction to examine unidentified phases in nanomaterials and polycrystalline materials.  The experiments were for a high-pressure pellet containing several carbon phases and a heterogeneous powder containing chalcedony and iron pigments.  For more information, see the paper, "Probing the structure of heterogeneous diluted materials by diffraction tomography", P. Bleuet et al., Nature Materials, 7, 468 (2008).

New way to distinguish chirality by X-ray diffraction

X-ray Bragg diffraction can determine crystal structures.  So far, however, distinguishing between right- and left-handed crystals has not been done by ordinary X-ray diffraction.  Japanese scientists led by Professor S. Shin (RIKEN & The University of Tokyo) recently succeeded in revealing the chirality of crystals by measuring Bragg diffraction near the absorption edge, using circular polarization of synchrotron X-rays at the SPring-8.  Reflections only allowed at resonant conditions have been well interpreted for the α-quartz case.  For more information, see the paper, "Right Handed or Left Handed? Forbidden X-Ray Diffraction Reveals Chirality", Y. Tanaka et al., Phys. Rev. Lett., 100, 145502 (2008).

Analysis of trace cadmium in the environment

Cadmium is one of the most ecotoxic metals.  A Spanish and Belgian research group led by Dr. M. Hidalgo (University of Girona, Spain) has recently reported the determination of trace Cd in complex environmental liquid samples.  The method employed is basically a combination of a pre-concentration technique and Cd Kα XRF analysis with a high-energy polarized beam (PANalytical Epsilon 5 with a Gd tube, 100kV-6mA, and a Ge detector).  In order to collect trace Cd effectively, the research group used Aliquat 336 (trademark of Cognis Corp.), which is tricaprylmethylammonium chloride (C25H54ClN), as an extractant.  The typical detection limit is 0.7 μg/L, and the accuracy was investigated by using spiked seawater samples and a synthetic water sample containing, besides Cd, high amounts of other metal pollutants such as Ni, Cu, and Pb.  For more information, see the paper, "High-Energy Polarized-Beam Energy-Dispersive X-ray Fluorescence Analysis Combined with Activated Thin Layers for Cadmium Determination at Trace Levels in Complex Environmental Liquid Samples", E. Margui et al., Anal. Chem., 80, 2357 (2008).

As an X-ray free-electron laser (X-FEL) provides extremely strong pulses, it is necessary to understand the photon-induced damage processes for biological samples.  A research group led by Dr. Chapman (DESY, Germany and Lawrence Livermore National Lab, USA) has discussed how several aspects of existing continuum damage models can be tested during early operation of X-FEL at lower X-ray energies in the range of 0.8-5 keV and low fluences, focusing particularly on macroscopic collective effects such as particle charging, expansion, and average ionization of nanospheres.  For more information, see the paper, "Modeling of the damage dynamics of nanospheres exposed to x-ray free-electron-laser radiation", S. P. Hau-Riege et al., Phys. Rev. E77, 041902 (2008).

It is known that a helical undulator does not generate any higher-order harmonics on the central radiation axis.  As such, off-axis radiation in higher-order harmonics has been considered useless, but so far this problem has not been discussed further.  Professor S. Sasaki and his colleagues (Argonne National Lab, USA) have recently published an interesting paper about this problem.  They found that all the harmonics except the fundamental from a variable polarizing undulator, such as an Advanced Planar Polarized Light Emitter (APPLE) device, are expressed by Laguerre-Gaussian modes carrying orbital angular momentum, when it is phased to deliver circularly polarized radiation.  As the advent of polarized X-ray sources has dramatically expanded the understanding of magnetism, the availability of intense X-ray beams carrying orbital in addition to spin angular momentum could open the door to new condensed matter research via X-ray scattering and spectroscopy methods.  For more information, see the paper, "Proposal for Generating Brilliant X-Ray Beams Carrying Orbital Angular Momentum", S. Sasaki et al., Phys. Rev. Lett., 100, 124801 (2008).

Keyhole coherent diffractive imaging

Recent advances in highly brilliant synchrotron sources including soft X-ray free-electron lasers have ushered in many new methods of microscopy.  Coherent diffractive imaging (CDI) is one of the most promising ways of determining the nanoscale structures of non-crystalline materials.  However, to enable phase determination, the intensity distribution must be sampled at a spacing finer than its Nyquist frequency, which in turn requires the sample to be finite.  In other words, there are some limitations in the sample size.  Recently, an Australian group led by Professor K. A. Nugent (University of Melbourne) proposed a new method, 'keyhole' CDI, which can reconstruct objects of arbitrary size.  In this case, a beam is focused and the object is placed downstream of the focal point so that it is illuminated by a diverging wave.  The geometry looks similar to that of in-line holography, but the requirements placed on the source and detector are different.  The group attempted imaging by visible light and X-rays, and, using the latter, part of an extended object was imaged with a detector-limited resolution of better than 20 nm.  For more information on the present experiments, see the paper, "Keyhole coherent diffractive imaging", B. Abbey et al., Nature Physics, advanced online publication, DOI: 10.1038/nphys896

Determination of beryllium by XRF

Beryllium has exceptional material properties, and because of this, it is an essential element used in the aerospace, computer, electronics, and nuclear industries.  For X-rays, it has been widely used as a window material.  Dr. B. Zawisza (Silesian University, Poland) has recently reported the determination of beryllium by X-rays.  One would think that it is not easy to determine such an extremely light element by XRF.  The novel simple idea is indirect determination of cobalt in the precipitates, [Co(NH3)6][Be2(OH)3(CO3)2(H2O)2]3H2O, fove rmed from hexamminecobalt(III) chloride and ammonium carbonate-EDTA solution.  The detection limit of the proposed method is 0.2 mg of beryllium.  For more information, see the paper, "Determination of Beryllium by Using X-ray Fluorescence Spectrometry", B. Zawisza, Anal. Chem., 80, 1696 (2008).
Fast liquid jets and sprays, which are complex multiphase flow phenomena, have been one of physics' veiled mysteries ever since the pioneering work by Rayleigh in the 19th century (See, W. S. Rayleigh, "On the stability of jets", Proc. Lond. Math. Soc. 4, 10 (1878)).  The main reason is simply that standard microscopy and visible light imaging techniques cannot peer into the dark and murky centers of dense-liquid jets.  Recently, Dr. K. Fezzaa and his colleagues (Argonne National Lab, USA) have succeeded in revealing for the first time the morphology and velocity fields of high-speed and highly turbulent jets generated by a gasoline direct injection system.  The research group employed ultrafast synchrotron-X-ray full-field phase-contrast imaging.  The spatial and time resolutions in the experiments were 5-30 micron and 472 ns, respectively.  For more information on the present experiments, see the paper, "Ultrafast X-ray study of dense-liquid-jet flow dynamics using structure-tracking velocimetry", Y. Wang et al., Nature Physics, advanced online publication, DOI: 10.1038/nphys840

Near-field speckle in coherent X-ray scattering

A coherent X-ray beam produces a speckle pattern when it impinges on a sample.  Usually the size and shape of the speckle do not depend on the sample at all, but a group led by Professor M. Giglio (Universita degli Studi di Milano, Italy) recently found significant effects, observed when the detector is placed in the near field.  Conventional far-field techniques, because of the van Cittert and Zernike theorem, have limitations in the statistical analysis of speckles, but it has now become possible to generate static and dynamic X-ray-scattering data.  In addition, the present technique permits an increase of around four orders of magnitude in beam size and power.  The measurements were done at BM05, European Synchrotron Radiation Facility (ESRF) in Grenoble, France.  The peak energy was 12 keV and the beam size at the sample position was 1 mm × 1 mm.  For more information, see the paper, "X-ray-scattering information obtained from near-field speckle", R. Cerbino et al., Nature Physics, advanced online publication, DOI: 10.1038/nphys837

Lensless X-ray camera for nano materials

A joint research group from the USA and Australia, led by Dr. J. Miao (University of California-Los Angeles) recently published the first results of resonant X-ray diffraction microscopy for element specific imaging of buried structures with a pixel resolution of ~15 nm by exploiting the abrupt change in the scattering cross section near electronic resonances.  They performed nondestructive and quantitative imaging of buried Bi structures inside a Si crystal by directly phasing coherent X-ray diffraction patterns near the Bi-MV edge.  For more information, see the paper, "Nanoscale Imaging of Buried Structures with Elemental Specificity Using Resonant X-Ray Diffraction Microscopy", C. Song et al., Phys. Rev. Lett., 100, 025504 (2008).
A German group led by Dr. B. Kanngiesser (Technische Universitat Berlin) has recently reported the significant extension of 3D micro X-ray fluorescence (XRF) spectroscopy.  Conventional XRF mapping is likely to remain a non-absolute analysis, since it just gives the spatial distribution of elements in the viewing region.  On the other hand, most realistic analytical applications require much greater quantitative imaging of chemical composition, density, thickness of layers etc.  The research group attempted to introduce a reliable quantification procedure, and obtained successful results in the case of stratified material.  For more information, see the paper, "Reconstruction of Thickness and Composition of Stratified Materials by Means of 3D Micro X-ray Fluorescence Spectroscopy", I. Mantouvalou et al., Anal. Chem. ASAP Article, DOI: 10.1021/ac701774d

A compact synchrotron light source driven by pulse laser

Ultrashort X-ray photon pulses are powerful tools for time-resolved studies of molecular and atomic dynamics.  Free electron lasers remain the most promising source.  However, in the future, developing much more compact sources will become significant in widening the field of application.  A group led by Professor D. A. Jaroszynski (University of Strathclyde, UK) has recently reported the first successful combination of a laser-plasma wakefield accelerator, producing 55-75 MeV electron bunches, with an undulator to generate visible synchrotron radiation.  Here, the key would be the laser wakefield accelerator, which produces electron beams with energies from tens of MeV to more than 1 GeV within a few cm, with pulse durations of several fs.  Further improvements, particularly in the energy of electrons, could contribute to the generation of X-ray photons with ultrashort pulse-width as well as extremely high peak power.  For details on laser-plasma wakefield acceleration, see, for example, "Accelerator physics:  Electrons hang ten on laser wake", T. Katsouleas, Nature, 431, 515-516 (2004).  For more information on the present experiments, see the paper, "A compact synchrotron radiation source driven by a laser-plasma wakefield accelerator", H.-P. Schlenvoigt et al., Nature Physics, advanced online publication, DOI: 10.1038/nphys811
The lattice dynamics of materials under high strain is of great interest in materials science.  Japanese scientists led by Professors S. Adachi (KEK, Tsukuba) and S. Koshihara (Tokyo Tech Institute, Tokyo) have recently succeeded in observing the irreversible deformation process of CdS single crystal by single-shot time-resolved Laue diffraction.  The time-resolution here is 100 psec, which is a single-bunch X-ray pulse-width, available at the Photon Factory-Advanced Ring (6.5 GeV).  The data was obtained with various time delays in the order of nsec.  As the observed pattern exhibits six-fold symmetry of the wurtzite structure at 10 ns, corresponding to a shock pressure of 3.92 GPa, i.e., above the threshold pressure of phase transition to a rocksalt structure, they suggest a transient wurtzite structure.  For more information, see the paper, "Shock-induced lattice deformation of CdS single crystal by nanosecond time-resolved Laue diffraction", K. Ichiyanagi et al., Appl. Phys. Lett. 91, 231918 (2007).
For many years, the simultaneous mapping of phases and chemical compositions subjected to extreme conditions has been one of biggest challenges in materials science.  Professor J. M. Howe (Virginia University, USA) and his colleagues have reported the successful study of partially molten Al-Si-Cu-Mg alloy particles, for automobile and aerospace applications, during in situ heating by energy-dispersive X-ray spectroscopy in a transmission electron microscope.  They have discovered some significant results, for instance, Al and Si concentrations change in a complementary and symmetric manner about the solid-liquid interface as a function of temperature.  They also obtained direct evidence for homogeneous nucleation of the Al-rich solid. For more information, see the paper, "In Situ Determination of the Nanoscale Chemistry and Behavior of Solid-Liquid Systems", S. K. Eswaramoorthy et al., Science, 318, 1437-1440 (2007).
At the TOMCAT beamline of the Swiss Light Source at the Paul Scherrer Institute, a phase-contrast X-ray tomographic microscope was recently applied to some very interesting research - the identification and classification of small fossil seeds (0.5~1.8 mm long) of the Early Cretaceous in Portugal and North America.  The conclusion is that these seeds belong to Gnetales and to Bennettitales.  The experiment used a very fast tomography method, the algorithm of which was introduced by Bronnikov, and refined by Gureyev.  For more information, see the paper, "Phase-contrast X-ray microtomography links Cretaceous seeds with Gnetales and Bennettitales", E. M. Friis et al., Nature, 450, 549-552 (2007).

Ultrafast 3D imaging in soft X-ray region

Lensless Fourier transform holography (FTH) is known as an imaging method suitable for high resolution X-ray microscopy with coherent X-rays.  In FTH, there had been a limit on the spatial resolution, mainly because of the contradiction between the requirement on the numerical aperture and the realistic resolving power of high spatial frequency fringes that appeared in the hologram.  Multiplexing, i.e., the use of multiple object and reference signals, can be one promising solution, because it extends the effective field of view.  Recently, a research group led by Professor J. Stöh, a director of Stanford Synchrotron Radiation Laboratory (SSRL), has developed the technique further so that the measurement can be done by a single shot.  Using patterned masks to provide multiple X-ray sources, the team demonstrated the ability to record images simultaneously at different parts of the sample.  3D imaging of ultrafast processes could become a reality if the method is combined with so-called pump-probe experiments.  For more information, see the paper, "Extended field of view soft x-ray Fourier transform holography: toward imaging ultrafast evolution in a single shot", W. F. Schlotter et al., Optics Letters, 32, 3110-3112 (2007).

Reference-free trace element determination by TXRF

Dr. B. Beckhoff (Physikalisch-Technische Bundesanstalt, Berlin, Germany) and his colleagues have successfully performed a reference-free quantitation by total reflection X-ray fluorescence (TXRF) analysis in the soft X-ray region.  So far, element determination by XRF has been usually done with a calibration curve, which requires some reference samples.  However, there have been increasing demands for reference-free analysis, particularly in cases where stable and reliable reference samples are not easily obtained.  The fundamental parameter method, which is one of the most promising ways of performing such reference-free analysis, uses the theoretical XRF intensity expressed by Sherman's equation (or Fujino-Shiraiwa's formula), but appears to be highly dependent on geometrical factors, the spectral distribution of primary X-rays, and atomic fundamental constants etc.  In TXRF, the intensity is affected by additional conditions.  The experiments were done with monochromatic synchrotron radiation, at BESSY II.  The research group has developed a feasible sample chamber specially designed for quantitative XRF.  In addition, several calibrated detector systems have been employed to obtain reliable results.  For more information, see the paper, "Reference-Free Total Reflection X-ray Fluorescence Analysis of Semiconductor Surfaces with Synchrotron Radiation", B. Beckhoff et al., Anal. Chem. 79, 7873 -7882 (2007).
Generally, the structure, composition, and dynamics of the Earth's lower mantle are influenced by the electronic state of iron within minerals at high pressure and temperature.  For instance, if this electronic state leads to a change in the density of minerals, it would alter the travelling velocity of sound waves.  Dr. Jung-Fu Lin (Lawrence Livermore National Laboratory, California, USA) and his colleagues recently determined the spin state of iron in ferropericlase [(Mg0.75,Fe0.25)O] at lower-mantle pressures and temperatures using an X-ray emission spectrometer with in-situ synchrotron X-ray diffraction in a laser-heated diamond cell.  They found that the transition between high and low spin happens at temperatures ranging from 1,900 to 2,300 K and pressures of up to 95 GPa: conditions found between 1,000 and 2,200 km below the surface.  Through integrated absolute difference (IAD) analysis of FeKb spectra, they obtained the ratio of the high-spin to low-spin states in the sample.  An energy shift of 1.6 eV in the main emission peak was interpreted as evidence of the spin transition.  X-ray spectroscopists might find further significant spectral changes, e.g., Kb' satellite, in their data.  For more information, see the paper, "Spin Transition Zone in Earth's Lower Mantle", Jung-Fu Lin et al., Science, 317, 1740-1743 (2007).
X-rays have been used as a tool for probing atomic-scale structures.  Used in combination with pump by laser (usually from the infra red to visible light region), time-resolved X-ray (or soft X-ray) analysis is pushing back the frontiers in the world of materials.  Recently, a further way of performing pump-probe experiments, i.e., an X-ray pump and infra-red probe, has been successfully applied to clarify the dynamics of N2 molecules.  A research team led by Professors H. Kapteyn and M. Murnane (University of Colorado, Boulder, USA) employed 43 eV soft X-rays with ca. 5 fs pulse width, which are laser-generated high-order harmonics, and an intense IR laser pulse (1.5 eV, 30 fs, 1013 W/cm2).  The team found that substantial fragmentation occurs through an electron-shakeup process, in which a second electron is simultaneously excited during the soft X-ray photoionization process.  During fragmentation, the molecular potential seen by the electron changes rapidly from nearly spherically symmetric to a two-center molecular potential.  For more information, see the paper, " Soft X-ray-Driven Femtosecond Molecular Dynamics", E. Gagnon et al., Science, 317, 1374-1378 (2007).

Table-top X-ray diffraction microscopy

The use of coherent X-rays makes it possible to replace lenses by signal processing in X-ray imaging techniques, as demonstrated for the first time in 1999 (See, J. Miao et al., Nature, 400, 342 (1999)).  The current state-of-the-art technique uses radiation produced by a free-electron laser, which, in a single shot, images with a temporal resolution of 25 fs and a spatial resolution of 90 nm.  Very recently, a group led by Professors H. Kapteyn and M. Murnane (University of Colorado, Boulder, USA) has succeeded in performing this kind of measurement in an ordinary laboratory, instead of at a synchrotron facility, using 29 nm soft X-rays generated as 25-31th order harmonics from a 1.3 mJ, 25 fs, Ti:S laser.  The team collected scattering from the sample by means of an X-ray CCD camera.  The spatial resolution of the reconstructed images is 214 nm.  For more information, see the paper, "Lensless Diffractive Imaging Using Tabletop Coherent High-Harmonic Soft-X-Ray Beams", R. L. Sandberg et al., Phys. Rev. Lett. 99, 098103 (2007)
Dr. H. Chapman (Lawrence Livermore National Laboratory, USA) and his colleagues recently published their new imaging technique, which is a new type of X-ray holography, and some successful data obtained at the free electron laser source, FLASH, Hamburg, Germany.  Their technique employs soft X-ray laser pulses which pass through a small hole in a detector mirror, and then encounter a thin, translucent membrane that has been covered with a sample material (140 nm-diameter polystyrene balls) lying just in front of a backing mirror.  In the present case, the X-ray pulse is shorter than the time spent traveling through the sample to the backing mirror and then returning.  The sample is exploded by extremely strong X-ray photons and its size changes in the brief interval that the pulse takes to reflect back.  The time it takes the pulse to return is encoded in the fringe pattern of the X-ray hologram, and this can be read out from the hologram to an accuracy of about one femtosecond.  The spatial resolution is 50 nm in this experiment, but this will be further improved by shorter wavelength laser pulses.  Their newly developed method opens up new opportunities for structure sciences based on holography, interferometry or coherent diffraction, as well as for studies that investigate the femtosecond dynamics of matter in new ways.  It is interesting that the scientists were inspired by Isaac Newton, who noticed in the 18th century that sunlight produced "strange and surprising" light and dark bands on a screen after he had bounced it off a mirror speckled with dust particles.  For more information, see the paper, "Femtosecond time-delay X-ray holography ", H. N. Chapman et al., Nature,. 448, 676-679 (2007).
Electromagnetically induced transparency (EIT) is a coherent optical nonlinearity, and brings dramatic changes in optical properties such as absorption, emission, refraction etc.  The phenomena relate to the quantum mechanical overlapping state created by two different wavelengths of coherent light.  Recently, EIT for X-rays has been theoretically predicted. According to the theory, it is possible to make Ne gas, which is normally opaque, transparent by exposing it to laser light of 800 nm with extremely high flux of 1012 W/cm2.  The scheme could be used for producing ultra-short X-ray pulses.  For more information, see the paper, "Electromagnetically Induced Transparency for X Rays ", C. Buth et al., Phys. Rev. Lett., 98, 253001 (2007).  For more about general EIT, see, for example, "Electromagnetically Induced Transparency.", S. Harris, Physics Today, 50, 36-42 (1997).
Scientists at Argonne National Laboratory and Ames Laboratory, Iowa State University, have recently performed X-ray magnetic circular dichroism (XMCD) measurements of giant magnetocaloric material, Gd5(Ge1-xSix)4.  It was found that germanium becomes magnetic by spin-dependent hybridization between Ge 4p and Gd 5d.  This hybridization can change at the germanium-silicon bond-breaking transition, causing the destruction of magnetic ordering and leading to the giant magnetocaloric effect.  By combining the experimental results with calculations based on density functional theory, it was concluded that the magnetized germanium orbitals act as "magnetic bridges" in mediating the magnetic interactions across the distant gadolinium ions.  For more information, see the paper, "Role of Ge in Bridging Ferromagnetism in the Giant Magnetocaloric Gd5(Ge1-xSix)4 Alloys", D. Haskel et al., Phys. Rev. Lett., 98, 247205 (2007).
A research group at the Japan Atomic Energy Agency (Kizugawa, Japan) has recently developed a novel table-top pulsed X-ray source.  The source employs a Ti:sapphire laser, emitting 70 fs duration 2 TW pulses of 800 nm wavelength at 10 Hz.  The laser beam is focused to the flow of high-density Ar gas.  The source was applied to perform phase contrast imaging.  For more information, see the paper, "Phase-contrast x-ray imaging with intense Ar Ka radiation from femtosecond-laser-driven gas target", L. M. Chen et al., Appl. Phys. Lett. 90, 211501 (2007).
Recently, some very interesting research on magnetic noise from antiferromagnets has been published. Unlike ferromagnets, the characteristics of which have been studied for many years, antiferromagnets have remained a mystery because their internal structure was too fine to be measured.  Their internal order is on the same scale as the wavelength of X-rays, and therefore, X-ray photon correlation spectroscopy, which measures 'speckle' patterns, can give a unique 'fingerprint' of a particular magnetic domain configuration.  It was found that the domain wall motion is thermally activated at temperatures above 100 K, but not so at lower temperatures.  For more information, see the paper, "Direct measurement of antiferromagnetic domain fluctuations", O. G. Shpyrko, et al., Nature 447, 68 (2007).
For many years, the existence of magnetic carbon has remained an enigma.  Previous claims to have solved the mystery were subsequently disproved when it was found that magnetic metals like iron, nickel, etc, were probably present in the carbon samples. Recently,  Dr. Ohldag (Stanford Synchrotron Radiation Laboratory) and his colleagues have shown that pure carbon can be made permanently magnetic at room temperature after carrying out a series of careful measurements including scanning transmission X-ray microscopy, X-ray magnetic circular dichroism (XMCD), PIXE analysis (to check for contamination by magnetic metals), AFM, and MFM etc. The team found that the magnetic order originates only from the carbon p-electron system. For more information, see the paper, p-Electron Ferromagnetism in Metal-Free Carbon Probed by Soft X-Ray Dichroism", H. Ohldag et al., Phys. Rev. Lett., 98,187204 (2007).
Atoms become ions when exposed to extremely intense light.  The process is predicted to occur via tunnelling through the binding potential that is suppressed by the light field near the peaks of its oscillations.  Professor F. Krausz (Max Planck Institute of Quantum Optics in Garching, Germany) and his collaborators recently reported the real-time observation of this most elementary step in strong-field interactions, i.e., light-induced electron tunnelling.  The team used 250-attosecond pulses of UV radiation, and confirmed theoretical predictions about the tunneling process.  It was also found that the process lasted for several hundred attoseconds, depleting atomic-bound states.  This would suggest that the use of tunneling itself is feasible for probing short-lived, transient states of atoms or molecules, e.g., multi-electron excitation (shake-up) and relaxation (cascaded Auger decay) processes etc.  For more information, see the paper, "Attosecond real-time observation of electron tunnelling in atoms", M. Uiberacker et al., Nature, 446, 627 (2007).
It has long been believed that birds can in some way use the natural magnetism of the earth to navigate.  Recently, scientists from the University of Frankfurt employed micro X-ray fluorescence as well as micro XAFS spectroscopy to analyze the skin of the upper beak of homing pigeons.  Within the skin lining, they established the existence of tiny maghemite (g-Fe2O3) and magnetite (Fe3O4) particles (with a ratio of around 9:1) in the dendritic nerve branches that were arranged in a 3D pattern.  According to the research team, this strongly supports the theory that the upper beak of pigeons houses a highly sensitive magneto-receptor that can be used for navigation.  The experiments were done with synchrotron X-rays at HASYLAB in Hamburg, Germany.  For more information, see the paper, "A novel concept of Fe-mineral-based magnetoreception: histological and physicochemical data from the upper beak of homing pigeons", G. Fleissner et al., Naturwissenschaften, published online in mid-March, 2007.
The Sub-Picosecond Pulse Source (SPPS) is a prototype X-ray free electron laser built using the 2-mile-long linear accelerator at Stanford Linear Accelerator Center (SLAC), California, United States.  To date, ultrafast phenomena have been mainly studied with femtosecond lasers operating at ultraviolet to infrared wavelengths; however, these wavelengths are not short enough for structural studies on atomic distances.  Therefore, the emergence of short pulse laser in the hard X-ray region represents a significant challenge.  Recently, at Stanford, an international collaborative team from 20 different institutions succeeded in observing the atomic motion of Bismuth crystal, which, although cubic, has a slight elongation along the diagonal called a Peierls distortion.  The measurements have brought new fundamental insights into the dynamics of the material, which shows very strong coupling between the electronic and ionic structures.  The results could also be used to screen many theoretical calculations made so far.  For more information, see the paper, "Ultrafast Bond Softening in Bismuth: Mapping a Solid's Interatomic Potential with X-rays ", D. M. Fritz et al., Science 315, 633 (2007).
At Brookhaven National Laboratory, United States, researchers have recently found a novel way to generate a very short controllable free electron laser (FEL) pulse, which usually depends on the length of the electron pulse.  The main idea is the use of a Ti:Sapphire laser that combines a 150 femtosecond (FWHM) pulse of light with the much longer electron beam.  This leads to a femtosecond FEL pulse that keeps growing in intensity and shortening in time duration, which is attributed to a phenomenon called superradiance (for details, see, R. H. Dicke, Phys. Rev. 93, 99 (1954)).  The present research is the first to experimentally observe the effects of superradiance in a FEL setup.  The output FEL pulse duration was measured to be as short as 81 femtoseconds, a roughly 50% reduction compared to the input seed laser.  Understanding how to produce these intense, ultrafast pulses of light could help scientists around the world as they begin to construct the next generation of light source facilities.  For more information, see the paper, "Experimental Characterization of Superradiance in a Single-Pass High-Gain Laser-Seeded Free-Electron Laser Amplifier ", T. Watanabe et al., Phys. Rev. Lett. 98, 034802 (2007).

Lensless X-ray microscopy

Professor J. Rodenburg and his colleagues from the University of Sheffield, UK and the Paul Scherrer Institute, Switzerland recently developed a novel X-ray microscope, which is very different from conventional microscopes developed so far, because it does not employ any optics to focus the beams. The lensless technique collects diffraction patterns from several overlapping areas in space, which provides information about how the rays interfere with each other after they have been diffracted through the object.  This interference can then be calculated backwards to what the rays' previous phase changes must have been, giving a complete picture of the structure.  Since this innovative technique relies on a special type of computation (called ptychographical iterative engine (PIE), for details, see H. M. L. Faulkner and J. M. Rodenburg, Phys. Rev. Lett. 93, 023903 (2004)), rather than specific equipment, it could also be used to boost the power of optical and even electron microscopes.  For more information, see the paper, "Hard-X-Ray Lensless Imaging of Extended Objects", J. M. Rodenburg et al., Phys. Rev. Lett. 98, 034801 (2007)
 Platinum is the most efficient electrocatalyst for accelerating chemical reactions in fuel cells for electric vehicles.  However, the reactions that take place during the stop-and-go driving of an electric car cause the platinum to dissolve, which reduces its efficiency as a catalyst.  Recently, a Brookhaven National Lab group led by Dr. R. Adzic found that adding gold clusters to the platinum electrocatalyst is effective in stabilizing and prolonging the life of the electrocatalyst.  The group tested the performance under the oxidizing conditions of the O2 reduction reaction and potential cycling between 0.6 and 1.1 V in over 30,000 cycles, and obtained successful results.  X-ray absorption spectra measured at the Pt LIII edge clearly showed that the Au clusters contribute to protecting the platinum from being oxidized.  The next step of the research is to duplicate the results in real fuel cells.  For more information, see the paper, "Stabilization of Platinum Oxygen-Reduction Electrocatalysts Using Gold Clusters", J. Zhang et al., Science, 315, 220 (2007).

Atomic structure of complex quasicrystals

Icosahedral quasicrystals (i-QCs) are long-range ordered solids that show non-crystallographic symmetries such as five-fold rotations.  Their detailed atomic structures are still far from completely understood, because most stable i-QCs form as ternary alloys suffering from chemical disorder.  Recently, a French-Japanese collaborative team led by Professor A. P. Tsai (Tohoku University, Japan) has succeeded for the first time in obtaining a detailed structure solution for i-YbCd5.7.  Similar to normal crystals, i-QCs exhibit beautiful diffraction patterns, but their lack of periodicity prevents conventional analysis.  However, mathematically, i-QCs can be seen as the projection in 3D of a structure that is periodic in a virtual space of higher dimension.  This resolves the situation because it allows conventional crystallography to be used in the higher-dimensional space.  The obtained result represents an essential starting point for finding the atomic structure of more complex i-QCs.  The team's X-ray experiments were done with synchrotron X-rays at D2AM beamline, ESRF in Grenoble, France.  For more information about the analysis, see the paper, "Atomic structure of the binary icosahedral Yb-Cd quasicrystal", H. Takakura et al., Nature Materials, 6, 58-63 (2007).
In January 2006, the Stardust spacecraft brought back a number of tiny particles from comet Wild 2, which is believed to have originated within a cloud of comets just beyond the orbit of Neptune called the Kuiper Belt.  The particles have been analyzed by X-rays at six synchrotron radiation facilities around the world, ESRF (France), APS (Argonne, USA), SSRL(Stanford, USA), ALS (Berkeley, USA), NSLS (Brookhaven, USA) and SPring-8 (Japan).  The particles from this comet are important because they are believed to be close to the starting material of the solar system, which is now about 4.5 billion years old.  The particles were found to contain a wide variety of minerals and organic materials that look similar to those seen in primitive meteorites found on earth, but the samples also revealed the presence of new materials not previously found in meteorites.  It was also discovered that the samples contained minerals similar to Calcium Aluminum-rich inclusions (CAIs), which can be formed at high temperatures, i.e., in the innermost part of the solar nebula, well inside the orbit of Mercury.  For more information on the Stardust mission, visit http://stardust.jpl.nasa.gov/home/index.html.  Some interesting results have been published as part of a special series of papers in the Dec. 15, 2006, edition of the journal Science.
By combining coherent X-ray scattering with a method of direct phase recovery called over-sampling, lens-free microscopy in the X-ray region becomes a realistic technique. The latest hot topic is the extension of the technique from two to three dimensions.  One of the most promising ways of applying this technique is the recently reported combination of (i) ab initio phase retrieval of 2D coherent diffraction patterns with a guided hybrid input-output algorithm and (ii) 3D image reconstruction with equally sloped tomography.  The scheme was applied to quantitative 3D imaging of a heat-treated GaN particle with each voxel corresponding to 17×17×17 nm3.  The internal GaN-Ga2O3 core shell structure was successfully captured in three dimensions.  For more information about the analysis, see the paper, "Three-Dimensional GaN-Ga2O3 Core Shell Structure Revealed by X-Ray Diffraction Microscopy", J. Miao et al., Phys. Rev. Lett. 97, 215503 (2006).
A group of biologists led by Professor Guerinot (Dartmouth College, USA) has recently clarified that iron is stored in the developing vascular system of the seed of a plant called Arabidopsis.  The group also found that this localization depends on a protein called VIT1, shown to transport iron to the vacuole.  The experiments combined traditional mutant analysis (turning on and off the VIT1 protein) with an X-ray fluorescence micro tomography technique to obtain a map of where iron is stored in the seed.  The results could help in the development of nutrient-rich seed, benefiting both human health and agricultural productivity, because iron deficiency is an area of concern in the issue of human nutrition.  The experiments were done at Beamline X26A, National Synchrotron Light Source (NSLS), Brookhaven, USA.  For more information, see the paper, "Localization of Iron in Arabidopsis Seed Requires the Vacuolar Membrane Transporter VIT1 ", S. A. Kim et al., Science, 314, 1295-1298 (2006).
Sodium saccharinate, NaC7H4NO3SxH2O, listed in most catalogues as a dihydrate (x = 2), has been extensively used as a food additive and has constituted the basic component of the diabetics' diet for about 125 years.  However, due to such factors as the instability of the crystal, the large unit cell and a very complex and heavily disordered structure, scientists have been unable to establish its composition with any certainty, until now.  Dr. P. Naumov (Nat'l Inst for Mater. Sci., Japan) and his collaborators recently succeeded in the first determination of the crystal structure, by using special techniques for preserving unstable crystals during X-ray data collection.  This crystal structure, which has as many as 16 formula units in the asymmetric unit (Z' = 16) as well as one of the largest unit cells, represents one of the most difficult cases for a small molecular species such as the saccharinate ion.  It was found that, instead of being a dehydrate, the crystal is in fact a 1.875 hydrate, because of a structural misfit and the lack of two water molecules per asymmetric unit.  The composition can be best described as Na64(C7H4NO3S)64120H2O.  At a meeting of the Asian Crystallographic Association held in Tsukuba, Japan, Dr. Naumov received the Best Presentation Award.  For more information, see the paper, "Solid-state structure and temperature/evacuation-induced dehydration of sodium saccharinate 1.875 hydrate", P. Naumov et al., Angewandte Chemie, International Edition in English, 44, 1251 (2005).

X-rays reveal how Neanderthal teeth grew

Neanderthals were a species of the Homo genus who inhabited Europe and parts of western Asia approximately 24,000 ~ 350,000 years ago.  It has even been suggested that Neanderthals achieved adulthood faster than modern humans do today. At the European Synchrotron Radiation Facility (ESRF), Grenoble, France, the enamel dentine junction of both a deciduous and a permanent Neanderthal molar tooth (about 130,000 years old) was studied recently by using high-resolution tomography.  It was found that the dental development of Neanderthals was very similar to modern humans.  The permanent molar tooth studied had completed its root growth at about 8.7 years of age, which is typical of many modern human children today.  For more information on the experimental results, see the paper, "How Neanderthal molar teeth grew", R. Macchiarelli et al., Nature, published online 22 November 2006.  For other recent interesting data on Neanderthals, see the paper, "Palaeoanthropology: Return of the last Neanderthal", E. Delson1et al., Nature, 443, 762-763 (2006).
 Professor Weckhuysen (Utrecht University, Netherlands) and his colleagues have recently solved the molecular mechanism for the organic-base-mediated synthesis of zeolites.  AlPO4-5 is a typical zeolite, which can be constructed from aluminium-based tetrahedra (AlO4) and phosphorus-based tetrahedra (PO4).  The research group compared the formation of the chargeless AlPO4-5 framework with the negatively charged framework (known as ZnAPO-34) that is formed by replacing Al3+ in AlPO4-5 with Zn2+.  The former contains one-dimensional channels, but the latter spherical cavities rather than channels.  By employing not only small and wide angle X-ray scattering (SAXS and WAXS), but also X-ray absorption spectroscopy, it was possible to observe in real time both the structural changes in the aluminophosphate gel and the conformational features of the organic base (tetraethylammonium hydroxide) used as a template for the crystallization of zeolite.  The tetraethylammonium ion was found to form a complex with developing zeolite subunits in the gel, adopting a molecular structure close to that found in the final crystal.  This molecular recognition process determines which type of crystal lattice is formed.  The principal point here is that molecular organization takes place before crystallization.  The experiments were done at BM26A, ESRF (Grenoble, France).  For more information, see the paper, "A Combined SAXS/WAXS/XAFS Setup Capable of Observing Concurrent Changes Across the Nano-to-Micrometer Size Range in Inorganic Solid Crystallization Processes", A. M. Beale et al., J. Am. Chem. Soc., 128, 12386 (2006).  Another interesting account can also be found in "Physical chemistry: Porous solids get organized", R. A. van Santen1, Nature, 444, 46 (2006).
A group at the Max Planck Institute led by Professor H. Dosch recently performed detailed studies on the gap between water and a water-repelling surface.  Silicon wafers, functionalized by a self-assembled monolayer of octadecyl-trichlorosilane (OTS), provide strongly hydrophobic substrates.  The main interest here is what happens when water comes onto the OTS layer.  The experiment was not easy, because the liquid water-solid interface is deeply buried in this case.  In this research, X-ray reflectivity measurements using an unusually high-energy beam (72.5 keV) were carried out.  The results indicate the existence of a hydrophobic gap on a molecular scale at the solid-water interface.  For more information, see the paper, "High-resolution in situ X-ray study of the hydrophobic gap at the water-octadecyl-trichlorosilane interface", M. Mezger et al., Proc. Natl. Acad. Sci. USA, published online before print November 20, 2006 
 

Single-shot coherent diffraction imaging using VUV-FEL

At the FLASH free-electron laser facility at DESY in Hamburg, an international team of scientists recently published the first data on diffraction imaging of a non-crystalline sample.  Theoretically, a single X-ray pulse, if it is extremely bright and perfectly coherent, can produce a diffraction pattern from a large macromolecule, a virus or a cell (for example, see, "Potential for biomolecular imaging with femtosecond X-ray pulses",  R. Neutze et al., Nature,  406, 752-757 (2000)).  In the present experiment, the team tested a laser pulse with 25 fs, 41013 W/cm2/pulse, containing 1012 photons at 32 nm wavelength, and obtained a coherent diffraction pattern from a nanostructured non-periodic object before this exploded into a plasma at ca. 60,000 K.  They employed a novel X-ray camera assured of single-photon detection sensitivity by filtering out parasitic scattering and plasma radiation.  For more information, see the paper, "Femtosecond diffractive imaging with a soft-X-ray free-electron laser", H. N. Chapman et al., Nature Physics, published online 12 November 2006.

Combining X-ray reflectometry and microscopy

Argonne National Laboratory researchers in collaboration with Xradia, Inc. have developed a novel X-ray surface topography technique by combining X-ray reflection, which is sensitive to height or depth on a sub nanometer scale, and full-field X-ray microscopy with condenser and objective Fresnel zone plates.  Recent rapid progress in X-ray microscopy now allows scientists to obtain X-ray images with ca. 10 nm spatial resolution.  However, so far, almost all full-filed imaging has employed transmission geometry.  The present research has extended the technique to reflection geometry.  It has become possible to image the distribution of molecular-scale interfacial features directly and non-invasively with full-field imaging. Interfacial phase contrast from elementary defect structures allows direct observation of 0.6-nm-high monomolecular steps at a solid surface.  For more information, see the paper, "Observation of subnanometre-high surface topography with X-ray reflection phase-contrast microscopy", P. Fenter et al., Nature Physics, 2, 700-704 (2006).

X-ray spectroscopy solves mystery of red Pompeii paintings

Artists in ancient Pompeii painted the town red 2,000 years ago with a brilliant crimson pigment made of cinnabar (HgS) that dominated many of the doomed city's wall paintings.  The eruption of the volcano Vesuvius showered the neighbouring towns in pumice and ash, and the Villa Sora, in Torre del Greco, remained buried until just 20 years ago, which is when excavation work started.  In the remains of the house, the distinctive red colour of the wall frescoes has turned black in many places.  The origins of this darkening degradation have not been clearly identified yet and remain a major issue for curators.  At ESRF, by aid of micro X-ray fluorescence and absorption spectroscopy, scientists analyzed red cinnabar paintings coated on a sparry calcite (CaCO3) mortar exhibiting different levels of degradation.  The results indicate two possible degradation mechanisms; formation of HgCl2 and CaSO4 through reaction with NaCl and SO2 from the environment, respectively.  For more information, see the paper, "Blackening of Pompeian Cinnabar Paintings: X-ray Microspectroscopy Analysis", M. Cotte et al., Anal. Chem., 78, 7484-7492, (2006).

3D visualization of plant seed's growth

Scientists from CNRS at the University J. Fourier of Grenoble and from the European Synchrotron Radiation Facility (ESRF) have recently succeeded in constructing 3D pictures of a living plant seed using the holotomography technique with synchrotron light.  This revealed the presence of a network of voids between the cells that may be used for storing the oxygen needed for efficient germination.  For more information, see the paper, "Quantitative phase tomography of Arabidopsis seeds reveals intercellular void network", P. Cloetens et al., Proceedings of the National Academy of Sciences, published online before print September 14, 2006.

In-situ X-ray analysis of working catalysis

Professor Hutchings (Cardiff University, UK) and his colleagues recently published some interesting results on vanadium phosphates (VPOs). VPOs are catalysts used in industry to spur the partial oxidation of n-butane to maleic anhydride, which is then used as a starting material for products such as resins and lubricants.  The research group utilized in-situ powder X-ray diffraction, in addition to laser Raman and electron paramagnetic resonance spectroscopies.  They determined the transformation of VPO phases as a function of temperature and with various reactants and products present over the catalyst.  They concluded that the presence of the reactants rapidly converts w-VOPO4 to d-VOPO4, but that the initial formation of the phase may create V+5 sites associated with increased catalytic activity.  For more information, see the paper, "Chemically Induced Fast Solid-State Transitions of w-VOPO4 in Vanadium Phosphate Catalyst ", M. Conte et al., Science. 313, 1270 (2006).
 Scientists at the Japan Atomic Energy Agency (JAEA) led by Dr W. Utsumi have proved that the formation of bulk metallic glass of elemental Zr and Ti, which was recently reported (see for example, Zhang and Zhao, Nature 430, 332 (2004) and Y. Wang et al., Phys. Rev. Lett. 95, 155501 (2005)) was some sort of phantom.  The experiment basically took the form of X-ray diffraction in high-temperature and high-pressure conditions, but in addition to the normal energy-dispersive detector, the research group employed an in situ angular-dispersive X-ray diffractometer equipped with a 2D detector and X-ray transparent anvils.  The disappearance of all the Bragg peaks in the one-dimensional energy-dispersive data could be taken as evidence of amorphization.  However, the research group found several intense Bragg spots in their angular-dispersive data, even in the exact same conditions where amorphization was reported.  This indicates that Zr and Ti do not form glass, but that the grains grow rapidly.  The experiments were carried out at BL14B1 and BL22XU, SPring-8, Japan.  For more information, see the paper, "Does Bulk Metallic Glass of Elemental Zr and Ti Exist?", T. Hattori et al., Phys. Rev. Lett., 96, 255504 (2006).
Professor P. Pershan (Harvard University, USA) and his colleagues recently found a crystalline monolayer at the surface of the eutectic liquid Au82Si18, at temperatures above the alloy's melting point.  This is unusual for a liquid surface, as the atomic arrangements are ordinarily strongly disordered.  In addition, they found that the gold-silicon eutectic alloy has 7-8 layers near its surface, whereas many metallic liquids typically show only 2-3 distinct atomic layers.  The phenomena are considered as indicative of surface freezing.  The research group employed X-ray reflectivity and grazing incidence X-ray diffraction techniques for the analysis.  For more information, see the paper, "Surface Crystallization in a Liquid AuSi Alloy", Oleg G. Shpyrko et al., Science 313, 77 (2006).
 The appearance of the ultimate X-ray microscope, with atomic-scale resolution and capable of seeing deep inside objects, has long been awaited.  Professor I. Robinson (University College London, UK) and his team recently made a significant step towards realizing this dream, using the technique of coherent X-ray diffraction imaging, the possibility of which was first pointed out by Sayre (Acta Crystallogr. 5, 843 (1952)) but not demonstrated until 1999 by Miao et al (Nature 400, 342 (1999)). They observed the growth of nanometer-sized Pb crystals inside the vacuum chamber.  The results showed that asymmetries in the diffraction pattern can be mapped to deformities, providing a detailed 3-D map of their location in the crystal.  This new method shows that the interior structure of atomic displacements within single nanocrystals can be obtained by direct inversion of the diffraction pattern.  The technique is an attractive alternative to electron microscopy because of the superior penetration of materials of interest by the electromagnetic waves, which are often less damaging to the sample than electrons.  The experiments were done at beamline 34-ID-C at the Advanced Photon Source (APS) in the United States.  For more information, see the paper, "Three-dimensional mapping of a deformation field inside a nanocrystal", Mark A. Pfeifer et al., Nature 442, 63 (2006).
Scientists at North Carolina State University, USA recently published an interesting report on the significance of the anomalously high concentration of local Ge-Ge bonds in amorphous Ge2Sb2Te5, which is commonly used in data storage technologies such as DVD, DVD-RAM etc. The ability to change phases from a crystalline to a non-crystalline state is what allows the DVD to take and hold data.  While the basic properties of this alloy are well known, there are still a lot of unsolved problems: we do not know how the process works on a microscopic level.  The paper indicates that the amorphous phase is an ideal network structure in which the average number of constraints per atom equals the network dimensionality.  For more information, see the paper, ""Application of Bond Constrain Theory to the Switchable Optical Memory Material Ge2Sb2Te5", D. A. Baker et al., Phys. Rev. Lett. 96, 255501 (2006).
A series of very interesting experiments has been performed at beamline ID26 at the European Synchrotron Radiation facility (ESRF), Grenoble, to see how gold nanoparticles catalyze carbon monoxide (CO) with oxygen (O2) into carbon dioxide (CO2).  High-energy resolution X-ray absorption spectroscopy reveals how the oxygen becomes chemically active when bound to the particles.  The reaction took place when the scientists switched from a flow of O2 to one of CO - the O2 bound to the gold reacts with the CO to form CO2.  The technique can be applied to a variety of reactions.  For more information, see the paper, "Activation of Oxygen on Gold/Alumina Catalysts: In Situ High-Energy-Resolution Fluorescence and Time-Resolved X-ray Spectroscopy", Jeroen A. van Bokhoven et al., Angewandte Chemie, published online June 21, 2006.

X-ray observation of plastic deformation

It is well known that a piece of metal deforms in an irreversible or plastic manner when it is bent.  This property is important from the standpoint of the feasibility of forming various types of metallic products as well as toughness as a structural material.  Scientists from Riso National Laboratory, Denmark recently tried taking "snapshots" with hard X-rays.  They observed some extremely interesting phenomena, i.e., the emergence and disappearance of the dislocation structure, which takes place during deformation.  For more information, see the paper, "Formation and Subdivision of Deformation Structures During Plastic Deformation", B. Jakobsen et al., Science 312, 889 (2006).

Focusing of hard X-rays to 30nm scale

Extremely sharp focusing of hard X-rays has been achieved with a device called a Multilayer Laue Lens (MLL), recently developed at Argonne National Laboratory in the United States.  The device consists of a stack of alternating layers of metal and silicon, made by depositing progressively thicker layers.  The main idea is that the structure can work as a linear zone plate for X-rays.  The device has an ability to focus the X-rays with an energy level of 19.5 keV to 30 nm, which is almost the smallest beam size for hard X-rays.  Promising applications for a better X-ray lens would be in full-field and/or scanning probe microscopy.  For more information, see the paper, "Nanometer Linear Focusing of Hard X Rays by a Multilayer Laue Lens", H. C. Kang et al., Phys. Rev. Lett. 96, 127401 (2006)

Synchrotron X-rays unveil nano-world of corrosion

Corrosion detracts some 3% from global GDP.  From a positive point of view, however, chemical attack of metal surfaces may result in surface nano-structures with interesting technological applications such as catalysts and sensors.  Professor H. Dosch (Max Planck Institute) and his colleagues have recently clarified a self-organization process on the surface of Cu3Au(111) single crystal alloy in a sulphuric acid solution, by means of a sophisticated X-ray diffraction technique with the aid of a brilliant synchrotron beam at ESRF, Grenoble, France.  They observed many interesting phenomena. In the initial moments of corrosion, an extremely thin gold-rich layer, which had an unexpected crystalline and well-ordered structure, was formed.  As the corrosion proceeded, this alloy layer was transformed into gold nano-islands of 20 to 1.5 nm.  These islands eventually developed into a porous gold metal layer.  For more information, see the paper, "Initial corrosion observed on the atomic scale", F. U. Renner et al., Nature, 439, 707-710 (2006).
At SPring-8, Harima Japan, Dr. M. Takahasi (Japan Atomic Energy Agency) and his coworkers have recently established a powerful surface X-ray diffraction tool for observing the growth process of semiconductor-like GaAs.  The main feature of the method is the use of multi-energy X-rays, and because of this, it is possible to identify both the atomic arrangements and the type of atoms.  Another significant advantage is the capability of real-time monitoring due to the employment of a brilliant undulator beam.  It was demonstrated that the surface structure called c(4x4), which is observed under certain growth conditions, has dimmers that consist of gallium and arsenic atoms in the top surface layer.  For more information, see the paper, "Element-Specific Surface X-Ray Diffraction Study of GaAs(001)-c(4×4)", M. Takahasi et al., Phys. Rev. Lett. 96, 055506 (2006).
The sketch for View on the Stour near Dedham, painted by Constable in 1822, has been analyzed by X-rays prior to Tate Britain's exhibition, Constable: the Great Landscapes, which opens on 1 June 2006.  The sketch is the 4th of the 6 large River Stour paintings that Constable exhibited at the Royal Academy during 1819-1825.  As with the other River Stour scenes, Constable made a preliminary full-scale compositional sketch in oils when planning the exhibition picture.  The X-ray investigation clearly shows that the sketch originally included two boys fishing by the water's edge and a little girl close to one of the wooden beams marking the edge of a boat-building yard in the foreground.  These figures were then painted out of the sketch by Constable and replaced by two young boys sitting on the edge of the river bank.  In the finished exhibition painting, View on the Stour near Dedham, Constable altered the composition again and did not include the two boys from the sketch.  X-ray analysis has successfully revealed a number of such alterations that are not visible on the surface of the work.  For more information, contact Helen Beeckmans/Patricia O'Connor, Tate Press Office, Millbank, London SW1P 4RG, Phone: +44-20-7887-8730/32, Fax: +44-20-7887-8729, pressoffice@tate.org.uk
Professor E. Ma (Johns Hopkins University, USA) and his colleagues recently succeeded in explaining the atomic packing of metallic glasses, which are of great importance due to their distinctive mechanical and magnetic properties.  The structure is known as 'amorphous' (non-crystalline) and shows no sharp Bragg peaks in the X-ray diffraction pattern.  The research group adopted quite a unique strategy; first, they aimed at obtaining 3D pictures in the short-to-medium range, unlike conventional atomic-level analysis, which looks only at short-range order, and secondly, they did not resort to a predetermined structural model but used reverse Monte Carlo simulations based on experimental X-ray diffraction and absorption data.  One of their key findings was that metallic glass atoms do not arrange themselves in a completely random way. Instead, groups of 7-15 atoms tend to arrange themselves around a central atom, forming 3D shapes called Kasper polyhedra, which join together in unique ways as small nanometer-scale clusters.  For more information, see the paper, "Atomic packing and short-to-medium-range order in metallic glasses", H. W. Sheng et al., Nature, 439, 419-425 (2006).
Generally, relaxor ferroelectrics exhibit a strong polarization dependence on the applied electric field, which so far has been explained by the behavior of the polar nano-regions (PNRs).  Recently, scientists at the U.S. Department of Energy's Brookhaven National Laboratory investigated the short-range polar order of Pb(Zn1/3Nb2/3)O3 (PZN) under an electric field.  X-ray diffuse scattering is very sensitive to local inhomogeneities and the results indicated an unexpected redistribution of PNRs in real space, i.e., the PNR fields preferred to line up perpendicular to the external field instead of aligning with it.  The experiments were done at the beamline X22B at the National Synchrotron Light Source (NSLS, at Brookhaven National Laboratory).  For more information, see the paper, "Electric-field-induced redistribution of polar nano-regions in a relaxor ferroelectric", G. Xu et al., Nature Materials, in the January 15, 2006, online edition.
 
The distribution of ions in solution at an interface is key to the fundamental understanding of electrochemistry as well as to the design of materials and devices such as biomembranes.  So far, classical descriptions of ion distributions, such as the Guoy-Chapman theory (see, G. Gouy, C. R. Acad. Sci. 149, 654 (1910) and D. L. Chapman, Phil. Mag. Ser. 6 25, 475 (1913)), which ignores the details of molecular structure, have been widely used.  Professor M. Schlossman (University of Illinois at Chicago) and his colleagues recently performed very precise X-ray reflectivity measurements to obtain experimentally ion distributions at the interface between solutions (0.01 ~0.08M) of tetrabuytlammonium (TBA) tetraphenylborate (TPB) in nitrobenzene and aqueous TBA bromide.  They found significant deviations from the Guoy-Chapman theory in describing their data. However, on the other hand, molecular dynamics calculations produced potentials that could be used to predict distributions with the Poisson-Boltzmann equation without adjustable parameters.  The experiments were done at the Chemistry and Materials section of the Consortium for Advanced Radiation Sources (ChemMatCARS) beamline 15-ID at the Advanced Photon Source (APS, at Argonne National Laboratory).  For more information, see the paper, "Ion Distributions near a Liquid-Liquid Interface", L. Guangming et al., Science, 311, 216-218 (2006).
Imaging with coherent X-rays at high spatial resolution is a promising technique for obtaining information on the internal structures of non-crystalline specimens.  Researchers at Cornell High Energy Synchrotron Source (CHESS, Cornell University, USA) recently succeeded in extending the Fresnel theory to retrieve phase information needed for a full image reconstruction.  The algorithm gives 3D full field imaging with X-rays.  This new scheme has been developed for coherent X-rays, but the distorted-object concept can be applied to other diffraction and imaging fields such as using visible light, electrons, and neutrons.  The method is particularly important with respect to the utilization of future X-ray sources that have fully coherent photon beams.  Part of their work was published in Phys. Rev. B 72, 033103 (2005).  For more information, visit http://news.chess.cornell.edu/index.html
At the Advanced Photon Source (APS) at Argonne, USA, massive amounts of lead have been detected in bone fragments of 19th Century composer Ludwig von Beethoven (1770-1827), indicating the cause of his years of chronic illness.  The bone fragments, checked by DNA testing to have come from Beethoven's body, were analyzed by micro X-ray florescence.  The findings confirm earlier work done on hair samples.  Furthermore, neither cadmium nor mercury was found within detectable levels this time.  The half life of lead in the human body is about 22 years, and almost 95 percent is captured in the skeletal structure.  For more information, contact Catherine Foster, Phone: +1-630-252-5580, cfoster@anl.gov, http://www.anl.gov
Scientists at the U.S. Department of Energy's Argonne National Laboratory have recently unearthed new clues to making magnets longer lasting and more powerful through element-specific X-ray magnetic circular dichroism (XMCD) measurements.  They have analyzed magnetic moment reversal at each of two inequivalent Nd sites (g and f sites) in a tetragonal single crystal of Nd2Fe14B, which is currently known to be the strongest permanent magnet.  The results provide clear evidence that intrinsic magnetic stability has its atomic origins predominantly at Nd g sites, which exhibit a strong preference for c-axis alignment at ambient temperature and dictate the macroscopic easy-axis direction.  Chemical substitution at Nd f sites, which undermines stability by favoring the xy plane, could enhance intrinsic coercivity.  For more information, contact Catherine Foster (+1-630-252-5580, cfoster@anl.gov) at Argonne, and also see the paper, "Atomic Origin of Magnetocrystalline Anisotropy in Nd2Fe14B", D. Haskel et al., Phys. Rev. Lett., 95, 217207 (2005).
Natural photosynthesis can convert solar energy into chemical energy with almost 100% efficiency.  During photosynthesis, O2 is evolved at a tetra manganese-calcium complex bound to the proteins of photosystem II.  As the details of the mechanism have not been fully understood, artificial solar systems still capture only a minute amount of energy.  Very recently, a German research group has succeeded in providing new insights into the mechanism by means of time-resolved X-ray absorption spectroscopy, which measures Mn K X-ray fluorescence after laser-flash illumination with a time resolution of 10 μs.  The model of the so-called S-cycle treats the manganese complex cycles through five oxidation states, but only four intermediates have been identified experimentally (S0 through S3).  Dioxygen is formed during the transition from S3 to S0, but the expected S4 intermediate in this transition has been elusive.  Real-time X-ray monitoring of photosynthetic O2 production has identified the S4 intermediate and, in contrast to previous proposals, the research group concluded that it is formed by a deprotonation process rather than by electron transfer.  The experiments were done at beamline ID26, European Synchrotron Radiation Facility (ESRF), Grenoble, France.  For more information, see the paper, "Photosynthetic O2 Formation Tracked by Time-Resolved X-ray Experiments", M. Haumann et al., Science, 310, 1019-1021 (2005).
Japanese scientists at Kyoto University have recently found that copper plays a significant role in the formation of toxic dioxin during the incineration of urban waste.  They measured copper K X-ray absorption spectra for fly ash, and investigated the changes in oxidation number when the temperature was controlled near 300 C, where dioxin is sometimes formed.  The data suggest some clear correlation between the existence of cuprous chloride (CuCl) and the formation of dioxin.  The experiments were done at beamline BL01B1, SPring-8, Harima, Japan.  The scientists presented the results at the 41st Annual Conference on X-Ray Chemical Analysis, Japan held at Fukui Institute for Fundamental Chemistry, Kyoto University.  For more information, contact Professor Masaki Takaoka, Kyoto University, phone: +81-75-753-5162, fax: +81-75-753-5170, takaoka@epsehost.env.kyoto-u.ac.jp
 
An international team led by Professor M. Sandström (University of Stockholm) has analyzed the sulfur and iron composition of the wooden timbers of the Mary Rose, a warship of King Henry VIII of England that was wrecked in 1545 and salvaged two decades ago.  Synchrotron X-rays from the Stanford Synchrotron Radiation Laboratory (USA) and the European Synchrotron Radiation Facility (France) were employed.  The experimental results indicate the surviving wood contains two tons of sulfur in different forms, uniformly distributed within the 280-ton hull.  In addition, the Mary Rose contains a great deal of iron from corroded iron bolts, nails and other objects from the ship.  Exposed to oxygen in air, the iron catalyzes the oxidation of sulfur into sulfuric acid. For more information, see the paper, "Sulfur accumulation in the timbers of King Henry VIII's warship Mary Rose: a pathway in the sulfur cycle of conservation concern", M. Sandström et al., Proceedings of the National Academy of Sciences of USA, 102, 14165-14170 (2005).
Control of nano-structures with molecular precision is a key problem in nano sciences and technologies.  While the surface can be readily imaged by scanning probe microscopes, it is not easy to observe buried structures nondestructively.  Dr. O. Sakata and his colleagues recently reported on their success in fabricating Bi nanowires on a Si(001) substrate and their encapsulation in an epitaxially grown crystalline silicon layer.  To explore the buried nanowires, they employed X-ray diffraction (reciprocal-lattice space mapping) with 25.3 keV photons at grazing-incidence geometry (~0.1 deg) using an image plate as a 2D detector.  The results indicate that the nanolines maintain their one-dimensional character and Bi dimerization.  The experiments were carried out at beamline BL13XU, SPring-8, Harima, Japan.  For more information, see the paper, "Encapsulation of atomic-scale Bi wires in epitaxial silicon without loss of structure", O. Sakata et al., Phys. Rev. B 72, 121407(R) (2005).
Some very interesting structural studies have been performed recently at the European Synchrotron Radiation Facility (ESRF), Grenoble, France, on photo-chemically generated, short-lived (<10-6 sec) iodo radicals.  The research team dissolved a molecule of C2H4I2 in liquid methanol and then subjected it to a short laser pulse.  This excited the molecule, which then cooled down while releasing heat into the surrounding liquid.  As a consequence, the temperature rose and the liquid started to expand in response to the increase in temperature.  The absorption of light triggered a chemical reaction, which the researchers studied with picosecond time resolution.  The research team measured the change in shape and composition as early as 100 picoseconds after the initial explosion, then at an interval of 10 nanoseconds, then 1 microsecond and so on.  From these measurements, the team obtained direct structural evidence of the bridged radical (CH2ICH2) in a polar solution.  This transient intermediate has long been hypothesized to explain stereo-chemical control in many association and/or dissociation reactions involving haloalkanes.  For more information, see the paper, "Ultrafast X-ray Diffraction of Transient Molecular Structures in Solution", H. Ihee et al., Science, 309, 1223-1227, (2005).
Professor E. Weber's team at Berkeley, California, US has recently succeeded in finding a new technique to handle metal defects in low-grade silicon, which could dramatically reduce the cost of solar cells. At present, around 90 % of solar cells in the world are made from a refined, highly purified form of silicon. This is because solar cells made from cheaper forms of silicon do not perform well and also because removing impurities is expensive.  The new idea is to manipulate the impurities in a way that reduces their detrimental impact on the solar cell, instead of purifying the material.  The team analyzed how metal contaminants in silicon respond to different types of processing using a synchrotron X-ray microprobe capable of detecting metal clusters as small as 30 nanometers.  In addition to micro-XRF and micro-XAFS, they employed a new method based on a spectrally resolved X-ray-beam-induced current, which generates a map of the minority-carrier diffusion length, revealing the precise impacts of metal impurity clusters on local material performance.  They found that they were able to manipulate the distribution of the metal impurities by varying the cooling rate of the silicon.  When the material is cooled quickly, the metal defects are quickly locked in a scattered distribution. For more information, see the paper, "Engineering metal-impurity nanodefects for low-cost solar cells", T. Buonassisi et al., Nature Materials, 4, 676-679 (2005).
It is known that the colours of many flowers are produced by anthocyanin, which has 6 different types of structure; a cyanidin-type anthocyanin is responsible for the red in roses, while most blue flowers have delphinidin-type anthocyanin.  However, the same cyanidin-type anthocyanin makes roses red but cornflowers blue.  The phenomenon has so far not been entirely explained.  A Japanese group led by Professor K. Takeda (Tokyo Gakugei University, Koganei, Tokyo) recently carried out detailed X-ray analysis and clarified that a complex of six molecules each of anthocyanin and flavone, with one ferric iron, one magnesium and two calcium ions is responsible for the blue in cornflowers.  For more information, see the paper, "Phytochemistry:  Structure of the blue cornflower pigment", M. Shiono et al., Nature, 436, 791 (2005).
The mineral silica (SiO2) is a common substance that is a constituent of all of the planets in our solar system.  At SPring-8, Harima, Japan, Dr. K. Hirose (Tokyo Institute of Technology; Japan Agency for Marine-Earth Science and Technology) and his co-workers recently found that, above 268 GPa and 1800 K, silica exhibits a novel stable high-pressure form with a pyrite-type structure, which is much denser than other known silica phases.  This form of silica could be one of the main constituents of the core of a gas-giant planet such as Uranus or Neptune.  For more information, see the paper, "The Pyrite-Type High-Pressure Form of Silica", Y. Kuwayama et al., Science, 309, 923-925 (2005).
X-ray analysis is a strong tool for speculating on the chemical and physical weathering processes on Mars.  The elemental compositions of the bright dust, dark soil and other soil components collected at different sites on Mars, such as the Gusev crater and Meridiani Planum, have been determined by X-ray fluorescence spectrometers fitted to the Mars Explorer Rovers.  A comparison between the results obtained at both sites generally shows that the bright dust is global in nature and not dominated by the composition of local rocks, and also that the dark soil has the same origin, while other soil components are fairly different.  For more information, see the paper, "An integrated view of the chemistry and mineralogy of martian soils", A. S. Yen et al., Nature, 436, 49-54 (2005).
For many years, great efforts have been made around the world to develop soft and hard X-ray microscopes.  Very recently, scientists at Lawrence Berkeley Laboratory, California, USA, have succeeded in fabricating an extremely high-performance objective lens, i.e., a micro zone plate, which projects a full-field image of the sample.  The spatial resolution is 15 nm or even smaller for synchrotron soft X-rays (150~1800 eV).  The key point is the improvement in electron beam lithography, since the spread due to electron scattering has previously been a big problem when patterning.  The Berkeley team separately drew two different zone-plate patterns and then overlaid them very accurately.  For more information, see the paper, "Soft X-ray microscopy at a spatial resolution better than 15 nm", W. Chao et al., Nature, 435, 1210-1213 (2005).
A joint research group from Russia, the Ukraine and the USA has developed a table-top microscope, consisting of a pulsed extreme ultraviolet (EUV) capillary discharge laser emitting at 46.9 nm, a Schwarzschild condenser, a zone plate objective, and a CCD camera.  To reduce image-degrading effects such as speckle and interference, the team shortened the laser's capillary tube length from 36 to 18 cm to give a low-coherence beam with a pulse energy of around 0.1 mJ.  The spatial resolution is currently 100 nm.  Typical exposure time is 20~70 seconds.  For more information, see the paper, "Reflection mode imaging with nanoscale resolution using a compact extreme ultraviolet laser", F. Brizuela et al., Optics Express, 435, 1210-1213 (2005), http://www.opticsexpress.org/abstract.cfm?URI=OPEX-13-11-3983
Recently, a very old copy of Archimedes' writings, which had been erased, written over and even painted over during the past 1,000 years, has been analyzed by X-ray fluorescence with a sub-micron X-ray beam at Stanford Synchrotron Radiation Laboratory, California, United States.  The palimpsest, which is preserved at Walters Art Museum in Baltimore, is a goatskin parchment on which a 10th-century scribe copied some of Archimedes' manuscripts originally written around 220 B. C.  Later, the ink was erased by being scraped off with a pumice stone.  Further damage was done when forgers painted Byzantine religious images on four pages.  Archaeologists have successfully analyzed much of the 174-page palimpsest by conventional methods using visible and ultraviolet light, but several pages, including those under the paintings, remained obscured.  The main idea behind the work at Stanford is that the ink contains iron pigment, and therefore the analysis is basically the mapping of iron K X-ray fluorescence.  As the ink is only 1-2 microns thick, the use of a sub-micron beam was crucial.  The analysis revealed that the hidden text on two of the pages is about floating bodies and the equilibrium of planes.  Surprisingly, the third page is a previously unknown introduction to Archimedes' Method of Mechanical Theorems.  The main source of the news is an article by Heather Rock Woods, Stanford University,http://news-service.stanford.edu/news/2005/may25/archimedes-052505.html
 For further details, contact Neil Calder, Stanford Linear Accelerator Center, Phone +1-650-926-8707, or Uwe Bergmann, Stanford Synchrotron Radiation Laboratory, Phone +1-650-926-3048, bergmann@SLAC.Stanford.EDU
A joint research group from the Universities of Sheffield and Warwick (both in the United Kingdom) and the European Synchrotron Radiation Facility (ESRF) in Grenoble, France have recently reported an interesting application of a dispersive XAFS (X-ray absorption fine structure) spectrometer, which has no moving parts and is thus inherently more stable than a conventional step-scanning instrument, thereby permitting comparative measurements to be taken rapidly.  The measurements were performed on a FeCo alloy thin film located between the poles of a magnet, which induces a saturating field in the sample.  The magnets were rotated via a stepping motor such that the induced magnetization, causing the strain, lies either along or perpendicular to the X-ray polarization vector.  Transmitted X-ray intensity measurements were made repeatedly at every 90 degree angle between the magnetization vector and the polarization vector.  An entire four-quadrant measurement took about 1s, with repeated measurements accumulated over a 2h period.  The differential absorption spectra obtained in this way can give atomic displacements due to magnetostriction.  The research group demonstrated that it is possible to observe the movement of atoms with a resolution of 0.01 Å i.e., an improvement of 100 times on the previous level.  For further details, see the paper, "Measurement of femtometre-scale atomic displacements by X-ray absorption spectroscopy", R. F. Pettifer et al., Nature, 435, 78-81 (2005).
Projects involving international collaboration are currently under way at the Stanford Linear Accelerator Center, in the U.S., using very bright pulses of X-ray light one thousand times shorter than those typically produced in conventional synchrotron rings.  One of the topics studied very recently concerns melting- how solids transform into liquids on ultra fast time scales.  In the experiment, laser light was used to melt a crystal of InSb, and then ultra-short X-ray pulses were sent to probe the material.  The scattered X-rays provided a glimpse of the first step in the transition from solid to liquid.  It was found that the transition state is governed by inertial dynamics, simply stated by Newton's First Law as: an object in motion continues in motion. For more information, see the paper, "Atomic-Scale Visualization of Inertial Dynamics", A. M. Lindenberg et al., Science, 308, 392-395 (2005).
At beamline ID18, ESRF, scientists studied pieces of hair and skin of Agnès Sorel, who was the beautiful mistress of 15th century French king, Charles VII. Very recently, from X-ray fluorescence spectra, they found that Sorel's remains contained abnormal levels of mercury.  The manner of her death was previously unknown, but incredibly high levels of mercury have been found in her remains.  This finding will give fresh impetus to the search to reveal the the truth behind this historical event.  The source of this news is the web page of ESRF, http://www.esrf.fr/NewsAndEvents/PressReleases/sorel/

Creep damage analysis by synchrotron X-rays

A team of scientists from the Technical University in Vienna, the Technical University in Berlin and the ESRF have combined tomography and diffraction using 80 keV X-rays to observe creep void evolution and the correlation to texture and microstructure development, which are important parameters for understanding the lifetime of components subjected to high temperature loading.  The studies were carried out for a brass alloy, CuZn40Pb2, which contains three phases: -brass, s-brass, and Pb.  They developed a specifically designed creep device in order to avoid artifacts during the tomography, and therefore the path of the incoming and the emerging X-rays over a complete 360 deg turn of the sample is identical.  A tensile load of 25 MPa was applied by using a spring in order to avoid vibrations, and the sample was heated to 375 ºC by an induction-heated loop around the bottom of the sample.  The results reveal that void growth versus time follows an exponential growth law and that the formation of large void volumes coincides with texture evolution and a steady state in the development of dislocation density.  The in-situ determination of void evolution in bulk samples opens up new ways toward the assessment of creep damage to the strength of materials and subsequently towards lifetime predictions of samples and components subject to high temperature loading.  For more information, see the paper, "Simultaneous Tomography and Diffraction Analysis of Creep Damage", A. Pyzalla et al., Science, 308, 92-95 (2005).

X-ray reveals mystery of Antarctic oil painting

X-ray analysis has been applied to a 230-year-old painting by William Hodges, the artist who accompanied Captain James Cook on his second voyage to the Pacific (1772-75).  Recently, it was noticed that the canvas was thicker in some places than in others.  An X-ray subsequently revealed that two icebergs had been painted over and replaced with the lush green foliage of New Zealand, thus proving that Hodges' work is the oldest painting of Antarctica.  The discovery ignited much discussion as to why Hodges erased the icebergs after having survived an extremely hard voyage around the frozen continent.  The main news source is an article by Matt Apuzzo, Associated Press (http://hosted.ap.org/dynamic/fronts/HOME).  For more information about William Hodges's painting, see for example, http://www.nmm.ac.uk/upload/package/30/home.php

Synchrotron microbeam detects trace of tin in rat sperm

A Japanese group is using a brilliant synchrotron microbeam at the SPring-8, Harima, Japan to study the marine pollution problem caused by organic tin compounds, which are known as environmental hormones because of their harmful influence on the endocrine system.  The scientists attempted to determine Sn distribution in the testes of rats exposed to tributyltin chloride, which was orally administered to rats at a dose of 45 x 10-6 mol/kg per day for 3 days.  They employed a 37.5 keV X-ray beam of 3 x 3 micron2 to detect Sn K X-ray fluorescence from the sperm of a seminiferous tubulem, the key point being that measurement can be performed for single cells, thus enabling cell-selective analysis.  For more information, see the paper, "Tin accumulation in spermatozoa of rats exposed to tributyltin chloride by synchrotron radiation X-ray fluorescence (SR-XRF) analysis with microprobe", S. Homma-Takeda et al., Nucl. Instrum. & Methods, B231, 333-337 (2005).

Super conducting devices are promising as high energy-resolution detectors for soft X-ray and/or mass spectrometry.  As the device size is quite small, e.g., several hundred microns squared, arraying has been one of the most important technical targets for enhancing detection efficiency.  So far, it has been difficult to increase the number of arrays, because of the incoming heat problem when connecting wires from devices operated at 0.3 K to electronic circuits at normal temperature.  Dr. M. Ohkubo and his colleagues at the National Institute of Advanced Industrial Science and Technology, Tsukuba, Japan recently succeeded in developing a novel technology using thin co-axis wires of 0.33mm in dia.  They also attached great importance to material selection.  As a result, it has become possible to connect more than 100 arrays, yet the incoming heat is extremely small at 5.4 x 10-6 W. The increase in temperature has effectively been suppressed to 15 mK.  For more information, contact Dr. M. Ohkubo, Phone, +81-29-861-5685, Fax +81-29-861-5730, m.ohkubo@aist.go.jp, http://unit.aist.go.jp/riif/srg/index.htm
Los Alamos National Laboratory scientists, C. Worley, S. S. Wiltshire, T. C. Miller, G. J. Havrilla and V. Majidi, have developed a novel method for detecting fingerprints on surfaces that typically render such prints invisible.  The technique uses micro-X-ray fluorescence (MXRF) and can therefore determine the elements in a fingerprint and obtain a pattern at the same time.  Salts such as sodium chloride and potassium chloride that are excreted in sweat are sometimes present in detectable quantities in human fingerprints.  As the new method might also be able to tell if the person that left the fingerprints also handled something like bomb-making materials, it could potentially be used as a tool in forensic investigation.  For more information, contact Todd Hanson, Phone +1-505-65-2085, tahanson@lanl.gov, http://www.lanl.gov/.
Researchers at the National Cancer Institute (NCI), part of the National Institutes of Health, have found that zinc deficiency in humans is associated with an increased risk of developing esophageal squamous cell carcinoma, an often-fatal form of esophageal cancer numbering about 7,000 cases a year.  The research basically measures the zinc concentration contained in the tissue by means of X-ray fluorescence analysis using synchrotron radiation at Advanced Photon Source, Argonne, USA.  For more details, see the paper, "Zinc concentration in esophageal biopsy specimens measured by X-ray fluorescence and esophageal cancer risk", C.C. Abnet, B. Lai, Y.-L. Qiao, S. Vogt, X.-M. Luo, P.R. Taylor, Z.-W. Dong, S.D. Mark, S.M. Dawsey, J. Nat. Cancer I. 97, 301 (2005).  Information about cancer is available at http://www.cancer.gov or NCI's Cancer Information Service at +1-800-422-6237.

Laser produces coherent 1.3 keV X-ray pulse

An Austrian research group recently succeeded in obtaining highly collimated, spatially coherent X-rays, at a wavelength of about 1 nm and at photon energies extending to 1.3 keV, from high-order harmonic generation in an atomic gas ionized by a 720-nm, 5-fs, 0.2-TW laser pulse.  The beam divergence was evaluated as 0.2 mrad for the spectral range above 200 eV from a knife-edge scan, indicating perfect coherence of the atomic dipoles within a macroscopic volume of diameters of 13μm and 4μm at photon energies of 0.3 keV and 1 keV, respectively.  The beam seems to be diffraction-limited to within a factor of five.  The spectrum of the generated radiation was observed by an energy-dispersive X-ray spectrometer with some filters.  The results are really exciting, because they could detect the copper L-edges (~950 eV)!  One would notice that the energy of photons produced by laser technologies has been increasing every year - the main idea behind this progress is the creation of time-gradient in the driving pulse, which allows some 25% of the helium atoms to be ionized within half a cycle before the pulse peak.  The electrons detached within this time are pushed in the most intense half-cycle back to the atomic core.  For more information, see the paper, "Source of coherent kiloelectronvolt X-rays", J. Seres et al., Nature, 433, 596 (2005).  C. Streli and P. Wobrauschek (Atominstitut der Osterreichischen Universtitaten, Technische Universitat Wien) were the co-authors of this paper.
Scientists at German and American synchrotron facilities have recently reported the significance of lensless imaging in achieving extremely high-spatial resolution.  Although lenses are generally good at obtaining a magnified image of a sample, they also unfortunately introduce aberrations in the image, which ultimately limit the spatial resolution obtainable.  In principle, one can form an image without a lens, by means of a coherent scattering experiment.  The challenge is to solve the so-called phase problem.  The team recently developed a new approach to X-ray holography, realizing a Fourier transform holography geometry by use of a micro- and nanostructured mask.  Special contrast mechanisms can be exploited by resonant soft x-ray scattering and, in the experiment at BESSY, they recorded an image revealing the randomly organized "north" and "south" magnetic regions of a cobalt-platinum film to a spatial resolution of 50 nm, which is 10 times better than that achievable with conventional X-ray focusing optics.  In the future, the technique will be used as a method for ultra-fast stroboscopic imaging on a femtosecond time scale using an X-ray free electron laser such as the Linac Coherent Light Source (LCLS), for example, which is expected to open at Stanford in 2009.  For more information, see the paper, "Lensless imaging of magnetic nanostructures by X-ray spectro-holography", S. Eisebitt et al., Nature, 432, 885-888 (2004).

Imaging atomic motions in materials

The ultra-fast X-ray diffraction technique has now become widely used.  Many experiments using this technique are, in principle, a so-called pump-probe measurement, using a Ti:sapphire laser system (wavelength 800 nm, 1-kHz repetition rate with 5-mJ pulse energy and 45-fs duration) and, for example,  a moving, 20-mm-thick Cu band to generate characteristic X-ray pulses.  Recently, a German group reported the successful imaging of coherent atomic motions in a GaAs/AlGaAs superlattice.  The motions are of great interest and are due to the excitation of electron-hole pairs in the GaAs subband.  Both expansion of the GaAs layers and contrast of the AlGaAs layers were observed, mainly because bonding in the GaAs layers was affected by the excitation.  For more information, see the paper, "Coherent Atomic Motions in a Nanostructure Studied by Femtosecond X-ray Diffraction", M. Bargheer et al., Science, 306, 1771-1773 (2004).

Remote-controlled X-ray spectrometer on surface of Mars

One of the most exciting recent scientific discoveries is that Mars was possibly once wet and salty, suggesting an environment that could serve as a candidate for early life.  The two Mars Rovers, Sprit and Opportunity, have been collecting large amounts of data on the soil, rock and atmosphere by utilizing state-of-the-art analytical instruments including an X-ray spectrometer, which recently determined the major and minor elements of soil and rock samples taken from Meridiani Planum.  For more information, see the paper, "Chemistry of Rocks and Soils at Meridiani Planum from the Alpha Particle X-ray Spectrometer", R. Rieder et al., Science, 306, 1746-1749 (2004).

Ultra short pulses in XUV region

So far, it has been difficult to observe nonlinear responses to an optical field in the extreme ultraviolet (XUV) and soft X-ray regions.  A research group from the University of Tokyo recently succeeded in generating intense isolated XUV pulses (photon energy 27.9 eV) that were shorter than 1 femtosecond through high-harmonic (9th) generation by using a sub-10-femtosecond blue laser (photon energy 3.1 eV) producing a large dipole moment.  For more information, see the paper, "Nonlinear optics in the extreme ultraviolet", T. Sekikawa et al., Nature, 432, 605-608 (2004).
 
Zahi Hawass and his co-workers plan to conduct X-ray analysis of the mummy of King Tutankhamen who ruled Egypt about 3,300 years ago and died while still a teenager.  They will move the mummy from the tomb in the Valley of the Kings in Luxor, where it was discovered in 1922, to the Egyptian Museum in central Cairo by the end of November. Earlier X-ray tests in 1968 revealed bone fragments inside the skull, prompting speculation that the young king was murdered by a blow to the head. However, other evidence suggests death due to illness. This year's experiment is intended to put to rest this mystery by employing a much more powerful X-ray machine donated by Siemens and National Geographic.  The main news source is Reuters (http://www.reuters.com/).  For more information about the mummy, see for example, http://www.thebritishmuseum.ac.uk/mummy/

X-rays revealed that Roman cosmetic used tin oxides

A whitish cream in a small canister, which was recently discovered during archaeological surveys of the remains of a Roman temple in London, has been found to contain SnO2. Archaeologists think the SnO2 was added intentionally, presumably for use as cosmetic.  They believe the unguent was prepared using sophisticated technology: animal fat was heated, possibly with the aim of bleaching it, and the starch was separated by treatment of roots or grains with boiling water, and then white SnO2 , which is readily produced by heating refined tin metal in air, was added.  The non-toxic properties of SnO2 would also have been desirable, because by the second century AD, the dangers of lead were becoming recognized.  XRF and XRD analysis played an important role in the identification of the ancient cosmetic cream.  For more information, see the paper, "Archaeology: Formulation of a Roman cosmetic", R. P. Evershed et al., Nature, 432, 35-36 (2004).
Argonne research group recently published details of their successful application of high-spatial-resolution XRF and XAFS measurements, which they performed in order to make elemental maps and qualitative chemical analyses of single free-floating, or planktonic, and surface-adhered, or biofilm, cells of Pseudomonas fluorescens. The results revealed differences between the planktonic and biofilm cells in terms of morphology, elemental composition and sensitivity to hexavalent chromium, a heavy-metal contaminant and a known carcinogen. The biofilm cells were more tolerant of the contaminant, which damaged or killed the planktonic cells.  The experiments were performed with a 150 nm X-ray beam produced by phase zone plate at the beamline XOR 2-ID, at the Advanced Photon Source (APS), Argonne, USA.  For more information, see the paper, "Elemental and Redox Analysis of Single Bacterial Cells by X-ray Microbeam Analysis", K. M. Kemner et al., Science, 306, 686-687 (2004).

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