Soft X-ray Synchrotron Research Articles

Hydration of Nucleobase as Probed by Electron Emission of Uridine-5′-Mono-Phosphate (UMP) in Aqueous Solution Induced by Nitrogen K-Shell Ionization

To identify the precise early radiation processes of DNA lesions, we measure electron kinetic energy spectra emitted from uridine-5′ monophosphate (UMP) in aqueous solution for the photoionization of the N 1s orbital electron and for the following Auger effect using a monochromatic soft X-ray synchrotron radiation at energies above the nitrogen K-shell ionization threshold. The change of photoelectron spectra for UMP in aqueous solutions at different proton concentrations (pH = 7.5 and 11.3) is ascribed to the chemical shift of the N3 nitrogen atom in uracil moiety of canonical and deprotonated forms. The lowest double ionization potentials for aqueous UMP at different pH obtained from the Auger electron spectra following the N 1s photoionization values show the electrostatic aqueous interaction of uracil moiety of canonical (neutral) and deprotonated (negatively charged) forms with hydrated water molecules.

Synchrotron soft X-ray microscopy and XRF to image Single-walled carbon nanotubes in epithelial cells

Carbon nanotubes (CNTs) have been promoted as nanodevices in the biomedicine areas of diagnosis and therapy. In terms of drug delivery, CNTs could be useful in the case of hydrophobic drugs and multiple co-deliveries of therapeutic and imaging molecules. Epithelial cells, being specialized in absorption and secretion, are the first barrier to overcome. At the same time, several frequent tumors are of epithelial origin (cervix, ovarian, liver). Synchrotron-based imaging and spectroscopic techniques are suitable tools to follow the fate of nanodrugs in epithelial cells. We present an example of multi-microscopy approach combining soft X-ray spectromicroscopy at the TwinMic beamline (Elettra Synchrotron, Trieste, Italy) with light and Scanning Electron (SEM) microscopies. In particular, we show that 2–4 h exposure to SWCNTs is not toxic (no viability changes) to a model of cervical epithelial cells, even though it causes temporary perturbation in the membrane and intracellular structures of exposed cells.

C, N dual-doped ZnO nanofoams: a potential antimicrobial agent, an efficient visible light photocatalyst and SXAS studies.

It is crucial to develop an environmentally friendly and low-cost method to treat industrial effluent that contains soluble dyes and microbes. Most of the photocatalysts have been studied using an external light source that increases the cost of the purification process of effluent. This study focuses on developing efficient solar photocatalytic nanofoams. The controlled growth of ZnO nanofoams (CNZ nanofoams) in a simple method of thermal oxidation using a soft template is reported. Prepared nanofoams are characterized using X-ray diffraction, scanning electon microscopy and synchrotron soft X-ray absorption spectroscopy. By photocatalysis studies under direct sunlight it was found that within 120 min CNZ nanofoams degraded 99% of thedye. In addition, antimicrobial studies of multi-drug-resistant E. Fergusonii isolated from wastewater was carried out. These antimicrobial results showed a good inhibition zone, indicating that prepared nanofoams are both an effective solar photocatalyst and an antimicrobial agent.

Ab Initio Molecular Dynamics Simulations to Interpret the Molecular Fragmentation Induced in Deoxyribose by Synchrotron Soft X-Rays

It has been suggested that core ionization in DNA atoms could induce complex, irreparable damage. Synchrotron soft X-rays have been used to probe the damage induced by such events in thin films of DNA components. In a complementary approach, we investigate the fragmentation dynamics following a carbon or oxygen K-shell ionization in 2-deoxy-D-ribose (DR), a major component in the DNA chain. Core ionization of the sugars hydration layer is also studied. To that aim, we use state-of-the-art ab initio Density Functional Theory-based Molecular Dynamics (MD) simulations. The ultrafast dissociation dynamics of the core ionized molecule, prior Auger decay, is modeled for about 10 fs. We show that the core-ionization of oxygen atoms within DR or its hydration layer may induce proton transfers towards nearby molecules, before Auger decay. In a second step, we model an Auger effect occurring either at the beginning or at the end of the core–hole dynamics. Two electrons are removed from the deepest valence molecular orbitals localized on the initially core-ionized oxygen atom (O*), and this electronic state is propagated by means of Ehrenfest MD. We show an ultrafast dissociation of the DR2+ molecule C-O* bonds, which, in most cases, seems independent of the time at which Auger decay occurs.

Semitransparent Sb2S3 thin film solar cells by ultrasonic spray pyrolysis for use in solar windows.

The integration of photovoltaic (PV) solar energy in zero-energy buildings requires durable and efficient solar windows composed of lightweight and semitransparent thin film solar cells. Inorganic materials with a high optical absorption coefficient, such as Sb2S3 (>105 cm−1 at 450 nm), offer semitransparency, appreciable efficiency, and long-term durability at low cost. Oxide-free throughout the Sb2S3 layer thickness, as confirmed by combined studies of energy dispersive X-ray spectroscopy and synchrotron soft X-ray emission spectroscopy, semitransparent Sb2S3 thin films can be rapidly grown in air by the area-scalable ultrasonic spray pyrolysis method. Integrated into a ITO/TiO2/Sb2S3/P3HT/Au solar cell, a power conversion efficiency (PCE) of 5.5% at air mass 1.5 global (AM1.5G) is achieved, which is a record among spray-deposited Sb2S3 solar cells. An average visible transparency (AVT) of 26% of the back-contact-less ITO/TiO2/Sb2S3 solar cell stack in the wavelength range of 380–740 nm is attained by tuning the Sb2S3 absorber thickness to 100 nm. In scale-up from mm2 to cm2 areas, the Sb2S3 hybrid solar cells show a decrease in efficiency of only 3.2% for an 88 mm2 Sb2S3 solar cell, which retains 70% relative efficiency after one year of non-encapsulated storage. A cell with a PCE of 3.9% at 1 sun shows a PCE of 7.4% at 0.1 sun, attesting to the applicability of these solar cells for light harvesting under cloud cover.

Pristine and oxidised Ag-nanoparticles on free-standing graphene as explored by X-ray photoelectron and Auger spectroscopy

Silver nanoparticles with a mean diameter of 15 nm have been grown on free-standing graphene and explored by soft X-ray synchrotron radiation using the ESCAmicroscopy beamline at Elettra. In particular, the 3d core orbitals and valence band (4d/5 s) of pristine and plasma-oxidised Ag-nanoparticles have been investigated by X-ray photoelectron spectroscopy (XPS), X-ray induced valence band photoemission, and MNN Auger spectroscopy. The X-ray spectra of the pristine Ag-nanoparticles, i.e. XPS, Auger and UPS spectra, are very similar to these of the metallic Ag-bulk film while the spectra of the oxidised Ag-nanoparticles exhibit distinct differences with respect to the oxidised Ag-bulk film. This is inferred from a larger valence band width, an extended valence band photoemission intensity nearly up to the Fermi level of the bulk metal, a smaller two-hole Coulomb correlation energy and a rather bulk-like Auger spectrum. We interpret this as to result from a shell-like composition of the Ag-nanoparticles with a thin passivating oxide layer and an inner metallic core. Moreover, the 3d photoemission peak of the oxidised nanoparticles is shifted to higher binding energy with respect to the bulk oxide peak. This is attributed not only to an XPS chemical shift but also to an additional final state Coulomb charging according to the electrostatic liquid drop model. Comparing the core binding energy shift of Ag-nanoparticles with the electrostatic potential of a spherical compact particle and a flat nanoislands a morphology transformation of the oxidised nanoparticles from 3D to 2D is obvious in the size range 5–15 nm.

Electronic Structure of UTe2 Studied by Photoelectron Spectroscopy

The electronic structure of the unconventional superconductor UTe2 was studied by resonant photoelectron spectroscopy (RPES) and angle-resolved photoelectron spectroscopy (ARPES) with soft X-ray synchrotron radiation. The partial U 5f density of states of UTe2 were imaged by the U 4d–5f RPES and it was found that the U 5f state has an itinerant character, but there exists an incoherent peak due to the strong electron correlation effects. Furthermore, an anomalous admixture of the U 5f states into the Te 5p bands was observed at a higher binding energy, which cannot be explained by band structure calculations. On the other hand, the band structure of UTe2 was obtained by ARPES and its overall band structure were mostly explained by band structure calculations. These results suggest that the U 5f states of UTe2 have itinerant but strongly-correlated nature with enhanced hybridization with the Te 5p states.

Dynamic evolution of Cathode−Electrolyte interface of LiNi0.6Co0.2Mn0.2O2 during the initial Charge−Discharge process

The cathode−electrolyte interface (CEI) is a key factor that affects the electrochemical performance of lithium-ion batteries. However, considerable ambiguity still exists with regard to the composition and properties of the CEI at different potentials during cycling. In this study, we investigate the dynamic evolution behavior of the CEI between the LiNi0.6Co0.2Mn0.2O2 cathode and organic carbonate electrolytes by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), and synchrotron soft X-ray absorption spectroscopy (soft XAS). XPS results reveal the continuous formation and decomposition of the CEI components during the initial charge and discharge process. Lithium alkyl carbonates and lithium fluoride (LiF) form during charging at low voltages, decompose at high voltages, and regenerate during discharging. In addition, soft XAS highlights the formation of electrochemically inactive species on the cathode surface, which generates extra barrier for Li+ diffusion and also decreases active sites for Li+ intercalation. The surface Ni undergoes incomplete oxidation during the charging process and exhibits partial reduction after discharging. These results are consistent with impedance variation in the first cycle and morphology changes on the cathode surface. These findings underscore the value of investigating and regulating the interfacial properties of lithium-ion batteries.

A coincidence velocity map imaging spectrometer for ions and high-energy electrons to study inner-shell photoionization of gas-phase molecules.

We report on the design and performance of a double-sided coincidence velocity map imaging spectrometer optimized for electron-ion and ion-ion coincidence experiments studying inner-shell photoionization of gas-phase molecules with soft X-ray synchrotron radiation. The apparatus employs two microchannel plate detectors equipped with delay-line anodes for coincident, time- and position-resolved detection of photoelectrons and Auger electrons with kinetic energies up to 300 eV on one side of the spectrometer and photoions up to 25 eV per unit charge on the opposite side. We demonstrate its capabilities by measuring valence photoelectrons and ion spectra of neon and nitrogen and by studying channel-resolved photoelectron and Auger spectra along with fragment-ion momentum correlations for chlorine 2p inner-shell ionization of cis- and trans-1,2-dichloroethene.

NOVEL ANALYTICAL STUDY FOR REACTION INTERMEDIATES IN THE PRIMARY RADIATION INTERACTION OF DNA USING A SYNCHROTRON RADIATION-INDUCED LUMINESCENCE SPECTROSCOPY

To identify the precise molecular processes to induce DNA lesions, we attempt a novel spectroscopy of X-ray induced luminescence (XIL) using soft X-ray synchrotron radiation, which is a non-destructive analysis of the reaction intermediates in the elementary reaction pathway of damage induction and self-organized restoration. Using a liquid micro-jet technique to introduce aqueous samples in a vacuum chamber, we measure UV-visible luminescence from nucleotide solution as a function of the soft X-ray energy from the nitrogen to oxygen K-edge region. The XIL intensities for the nucleotide solutions are significantly enhanced in the soft X-ray region (410-530 eV) which is ascribed to the K-shell excitation/ionization of nitrogen atoms in the nucleobases. Furthermore, the XIL spectra do not show any signature of X-ray absorption near-edge structure (XANES) of the nucleobases. This is because the luminescence intensities collected from the integral area of the micro-jet only reflect the quantum yield of luminescence of the absorbed X-ray into UV-visible light irrespective of the absorption cross sections, i.e. of XANES. Thus the present result is the first evidence of luminescence as a result of X-ray absorption of aqueous nucleotides.

Fortune is Unpredictable and Changeable, Especially for Soft X-ray Synchrotron Radiation Researcher

Fortune is Unpredictable and Changeable, Especially for Soft X-ray Synchrotron Radiation Researcher

Grating metrology for X-ray and V-UV synchrotron beamlines at SOLEIL.

Diffraction gratings are key elements of soft X-ray synchrotron beamlines. Besides wavelength dispersion, specific parameters can be tailored to adjust the energy dependent efficiency and focusing, and to correct wavefront aberrations. As key elements of a beamline, any departure from the design values can severely reduce the overall performance. On the other hand, known non-conformities can often be corrected by slight adjustment of the alignment parameters. A careful and accurate metrology is therefore required before installation on the beamline. After presenting what variable line spacing gratings, variable groove depth gratings, and alternate multilayer gratings are, the use of the SOLEIL long trace profiler for the measurement of groove density variation along the surface and of the atomic force microscope for the groove geometry and roughness characterizations will be discussed. A few examples of grating metrology will be presented and analyzed with the help of optical simulations.

Valence and Core-Level X-ray Photoelectron Spectroscopy of a Liquid Ammonia Microjet.

Photoelectron spectroscopy of microjets expanded into vacuum allows access to orbital energies for solute or solvent molecules in the liquid phase. Microjets of water, acetonitrile and alcohols have previously been studied; however, it has been unclear whether jets of low temperature molecular solvents could be realized. Here we demonstrate a stable 20 μm jet of liquid ammonia (−60 °C) in a vacuum, which we use to record both valence and core-level band photoelectron spectra using soft X-ray synchrotron radiation. Significant shifts from isolated ammonia in the gas-phase are observed, as is the liquid-phase photoelectron angular anisotropy. Comparisons with spectra of ammonia in clusters and the solid phase, as well as spectra for water in various phases potentially reveal how hydrogen bonding is reflected in the condensed phase electronic structure.

Cs 吸着バーミキュライトの軟 X 線放射光光電子分光

Cs 吸着バーミキュライトの軟 X 線放射光光電子分光

Normal and resonant Auger spectroscopy of isocyanic acid, HNCO.

In this paper, we investigate HNCO by resonant and nonresonant Auger electron spectroscopy at the K-edges of carbon, nitrogen, and oxygen, employing soft X-ray synchrotron radiation. In comparison with the isosteric but linear CO2 molecule, spectra of the bent HNCO molecule are similar but more complex due to its reduced symmetry, wherein the degeneracy of the π-orbitals is lifted. Resonant Auger electron spectra are presented at different photon energies over the first core-excited 1s → 10a' resonance. All Auger electron spectra are assigned based on ab initio configuration interaction computations combined with the one-center approximation for Auger intensities and moment theory to consider vibrational motion. The calculated spectra were scaled by a newly introduced energy scaling factor, and generally, good agreement is found between experiment and theory for normal as well as resonant Auger electron spectra. A comparison of resonant Auger spectra with nonresonant Auger structures shows a slight broadening as well as a shift of the former spectra between -8 and -9 eV due to the spectating electron. Since HNCO is a small molecule and contains the four most abundant atoms of organic molecules, the reported Auger electron decay spectra will provide a benchmark for further theoretical approaches in the computation of core electron spectra.

Sulfur speciation in growth layers of shell cross section of the long-lived bivalve Margaritifera laevis using synchrotron spectromicroscopy analysis

To reliably utilize the information on growth and environment stored within the hard carbonate shells of long-lived bivalves, it is necessary to accurately count the annual growth lines from their shell cross-sections. In this study, we investigated the relationship between the distribution of minor elements and visual lines in the shell cross-sections of the long-lived mussel Margaritifera laevis collected from the Chitose River in Hokkaido, Japan. The distribution of minor elements, such as sulfur (S), phosphorus (P), strontium (Sr), magnesium (Mg), and sodium (Na), in a cross-section of the umbo was determined by X-ray fluorescence analysis using synchrotron soft X-ray radiation. The chemical properties of S and P were analyzed in-situ using soft X-ray photoabsorption spectroscopy, and the chemical form dependence of S distribution was determined by speciation mapping. In addition, the annual and disturbance lines were visualized by staining shell cross-sections. Our results showed that the distribution of reduced S (i.e., SC and SH) corresponded to the annual lines, whereas the distribution of oxidized S (i.e., SO42−) corresponded to the disturbance lines. Overall, this study revealed that speciation analysis of S in shell cross-sections can be used to determine the origin of visual lines in chronological studies.

Circular Dichroism in Fluorescence Emission Following the C 1s→π* Excitation and Resonant Auger Decay of Carbon Monoxide.

Dichroism in angle-resolved spectra of circularly polarized fluorescence from freely-rotating CO molecules was studied experimentally and theoretically. For this purpose, carbon monoxide in the gas phase was exposed to circularly polarized soft X-ray synchrotron radiation. The photon energy was tuned across the C 1s→π* resonant excitation, which decayed via the participator Auger transition into the CO+ A 2Π state. The dichroic parameter β1 of the subsequent CO+ (A 2Π → X 2Σ+) visible fluorescence was measured by photon-induced fluorescence spectroscopy. Present experimental results are explained with the ab initio electronic structure and dynamics calculations performed by the single center method. Our results confirm the possibility to perform partial wave analysis of the emitted photoelectrons in closed-shell molecules.

Morphological and chemical information in fresh and vitrified ovarian tissues revealed by X-ray Microscopy and Fluorescence: observational study

Many clinical circumstances impose the necessity of collection and prolonged storage of gametes and/or ovarian tissue in order to preserve the reproduction potential of subjects. This is particularly appropriate in the case of young women and pre-pubertal girls undergoing chemotherapeutic treatments. The success of later assisted fertilization will depend on the suitable cooling protocols minimizing cryo-damages and preserving their biological function. The freeze-thaw processes of cryopreservation may induce, in fact, morphological and structural damages of oocytes and tissue mainly due to the formation of intracellular ice and to the toxicity of cryoprotectant. The most used cryo-protocol is the slow freezing procedure, but recently many authors have proposed vitrification as an alternative, because of its simplicity. The damage extent and the quality of follicles after cryopreservation are usually evaluated morphologically by conventional histological procedures, light and electron microscopy. Our laboratory, to further improve the evaluation and to better investigate damages, is adopting a combination of Synchrotron soft X-ray Microscopy (at TwinMic – Elettra) and XRF at different incident energies (at TwinMic – Elettra and ID21 – ESRF). X-ray techniques were performed on histological sections at micro and sub-micron resolution. Phase contrast and absorption images revealed changes in the compactness of the tissues, as well as cellular abnormalities revealed at sub-micrometric resolution. The distributions of the elements detected at 7.3 and 1.5 keV were compared and particularly Cl resulted to be indicative of follicle integrity. The results demonstrate the utility and the potential of X-ray microscopy and fluorescence in this research field.

Nano-imaging of environmental dust in human lung tissue by soft and hard X-ray fluorescence microscopy

It is well recognized that a large number of pulmonary diseases are induced by the effects of inhaled particulates. Anthracosis is defined as an asymptomatic, mild form of pneumoconiosis caused by the accumulation of “black carbon” in the lungs due to repeated exposure to air pollution or inhalation of smoke or coal dust particles. Since the human population is progressively exposed to an increasing number and doses of anthropogenic micro and nano particles/compounds, there is a pressing urgency to explore toxicological impact arising from these exposures and the molecular mechanisms driving the body defense or possible related diseases. The toxicity mechanisms are clearly related to chemical composition and physical and surface properties of materials. A combination of synchrotron radiation-based (SR-based) nano X-ray fluorescence (XRF) imaging and soft X-ray microscopy was used to chemically characterize environmental particulates (anthracosis) in lung tissues from urban subjects with the aim of better understanding the complex nature of related lungs' deposits. High-resolution XRF analyses performed at ESRF and Elettra synchrotrons allowed discriminating single particles in the heterogeneous aggregates found in the lung tissue. The small particles have variable composition resulting from the different combinations of Ti with O, K and Si, Al and Si, or Zn and Fe with O. Interestingly, simultaneous absorption and phase contrast images showed the particulate morphology and allowed to predict the presence of very dense nanoparticles or high concentration of heavy elements.

Bimetallic zeolite imidazolate framework for enhanced lithium storage boosted by the redox participation of nitrogen atoms

In this work, a bimetallic zeolitic imidazolate framework (ZIF) CoZn-ZIF was synthesized via a facile solvothermal approach and applied in lithium-ion batteries. The as-prepared CoZn-ZIF shows a high reversible capacity of 605.8 mA h g−1 at a current density of 100 mA g−1, far beyond the performance of the corresponding monometallic Co-ZIF-67 and Zn-ZIF-8. Ex-situ synchrotron soft X-ray absorption spectroscopy, X-ray diffraction, and electron paramagnetic resonance techniques were employed to explore the Li-storage mechanism. The superior performance of CoZn-ZIF over Co-ZIF-67 and Zn-ZIF-8 could be mainly attributed to lithiation and delithiation of nitrogen atoms, accompanied by the breakage and recoordination of metal nitrogen bond. Morever, a few metal nitrogen bonds without recoordination will lead to the amorphization of CoZn-ZIF and the formation of few nitrogen radicals.