Fluctuation X-ray scattering (FXS) offers a complementary approach for nano- and bioparticle imaging with an X-ray free-electron laser (XFEL), by extracting structural information from correlations in scattered XFEL pulses. Here a workflow is presented for single-particle structure determination using FXS. The workflow includes procedures for extracting the rotational invariants from FXS patterns, performing structure reconstructions via iterative phasing of the invariants, and aligning and averaging multiple reconstructions.
View Article and Find Full Text PDFThe design of new composite materials using extreme biomimetics is of crucial importance for bioinspired materials science. Further progress in research and application of these new materials is impossible without understanding the mechanisms of formation, as well as structural features at the molecular and nano-level. It presents a challenge to obtain a holistic understanding of the mechanisms underlying the interaction of organic and inorganic phases under conditions of harsh chemical reactions for biopolymers.
View Article and Find Full Text PDFWe present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner.
View Article and Find Full Text PDFX-ray absorption spectroscopy (XAS) was used to elucidate changes in the electronic structure caused by the pressure-induced structural collapse in EuCo P . The spectral changes observed at the L -edge of Eu and K-edges of Co and P suggest electron density redistribution, which contradicts the formal charges calculated from the commonly used Zintl-Klemm concept. Quantum-chemical calculations show that, despite the increase in the oxidation state of Eu and the formation of a weak P-P bond in the high-pressure phase, the electron transfer from the Eu 4f orbitals to the hybridized 5d and 6s states causes strengthening of the Eu-P and P-P bonds.
View Article and Find Full Text PDFJ Phys Condens Matter
August 2016
We report a time-resolved study of the ultrafast dynamics of the magnetic moments formed by the [Formula: see text] states in Sr2IrO4 by directly probing the localized iridium 5d magnetic state through resonant x-ray diffraction. Using optical pump-hard x-ray probe measurements, two relaxation time scales were determined: a fast fluence-independent relaxation is found to take place on a time scale of 1.5 ps, followed by a slower relaxation on a time scale of 500 ps-1.
View Article and Find Full Text PDFThe spin transition in LaCoO_{3} has been investigated using density-functional theory in combination with dynamical mean-field theory employing continuous time quantum Monte Carlo and exact diagonalization impurity solvers. Calculations on the experimental rhombohedral atomic structure with two Co sites per unit cell show that an independent treatment of the Co atoms results in a ground state with strong charge fluctuations induced by electronic correlations. Each atom shows a contribution from either a d^{5} or a d^{7} state in addition to the main d^{6} state.
View Article and Find Full Text PDFChitinous scaffolds isolated from the skeleton of marine sponge Aplysina cauliformis were used as a template for the deposition of polyhedral oligomeric silsesquioxanes (POSS). These chitin-POSS based composites with hydrophobic properties were prepared for the first time using solvothermal synthesis (pH 3, temp 80 °C), and were thoroughly characterized. The resulting material was studied using scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and thermogravimetry.
View Article and Find Full Text PDFThe mechanisms of interaction between inorganic matter and biomolecules, as well as properties of resulting hybrids, are receiving growing interest due to the rapidly developing field of bionanotechnology. The majority of potential applications for metal-biohybrid structures require stability of these systems under vacuum conditions, where their chemistry is elusive, and may differ dramatically from the interaction between biomolecules and metal ions in vivo. Here we report for the first time a photoemission and X-ray absorption study of the formation of a hybrid metal-protein system, tracing step-by-step the chemical interactions between the protein and metals (Cu and Fe) in vacuo.
View Article and Find Full Text PDFSponges are probably the earliest branching animals, and their fossil record dates back to the Precambrian. Identifying their skeletal structure and composition is thus a crucial step in improving our understanding of the early evolution of metazoans. Here, we present the discovery of 505-million-year-old chitin, found in exceptionally well preserved Vauxia gracilenta sponges from the Middle Cambrian Burgess Shale.
View Article and Find Full Text PDFβ-Chitinous scaffolds isolated from the skeleton of marine cephalopod Sepia officinalis were used as a template for the in vitro formation of ZnO under conditions (70 °C) which are extreme for biological materials. Novel β-chitin/ZnO film-like composites were prepared for the first time by hydrothermal synthesis, and were thoroughly characterized using numerous analytical methods including Raman spectroscopy, HR-TEM and XRD. We demonstrate the growth of hexagonal ZnO nanocrystals on the β-chitin substrate.
View Article and Find Full Text PDFMany-body interactions in crystalline solids can be conveniently described in terms of quasiparticles with strongly renormalized masses as compared with those of non-interacting particles. Examples of extreme mass renormalization are on the one hand graphene, where the charge carriers obey the linear dispersion relation of massless Dirac fermions, and on the other hand heavy-fermion materials where the effective electron mass approaches the mass of a proton. Here we show that both extremes, Dirac fermions, like they are found in graphene and extremely heavy quasiparticles characteristic for Kondo materials, may not only coexist in a solid but can also undergo strong mutual interactions.
View Article and Find Full Text PDFThe recent development of x-ray free electron lasers providing coherent, femtosecond-long pulses of high brilliance and variable energy opens new areas of scientific research in a variety of disciplines such as physics, chemistry, and biology. Pump-probe experimental techniques which observe the temporal evolution of systems after optical or x-ray pulse excitation are one of the main experimental schemes currently in use for ultrafast studies. The key challenge in these experiments is to reliably achieve temporal and spatial overlap of the x-ray and optical pulses.
View Article and Find Full Text PDFUntil now, there is a lack of knowledge about the presence of chitin in numerous representatives of corals (Cnidaria). However, investigations concerning the chitin-based skeletal organization in different coral taxa are significant from biochemical, structural, developmental, ecological and evolutionary points of view. In this paper, we present a thorough screening for the presence of chitin within the skeletal formations of a poorly investigated Mediterranean black coral, Parantipathes larix (Esper, 1792), as a typical representative of the Schizopathidae family.
View Article and Find Full Text PDFAngle-resolved photoelectron spectroscopy (ARPES) was used to study the Fermi surface of the heavy-fermion system YbRh(2)Si(2) at a temperature of about 10 K, i.e., a factor of 2 below the Kondo energy scale.
View Article and Find Full Text PDFStrong chemical interaction between bacterial surface protein layers and calcium atoms deposited in situ on top was revealed by means of photoemission spectroscopy. The interaction appears to mainly happen at the oxygen site of the peptide bonds and involves a large charge transfer from Ca 4s states into the peptide backbone. Chemical kinetics of this reaction was characterized using time-dependent valence band photoemission, and the reaction rate constant was determined.
View Article and Find Full Text PDFThe occupation, energy separation, and order of the crystal-field-split 4f states are crucial for the understanding of the magnetic properties of rare-earth systems. We provide the experimental evidence that crystal-field-split 4f states exhibit energy dispersion in momentum space leading to variations of energy spacings between them and even of their energy sequence across the Brillouin zone. These observations were made by performing angle-resolved photoemission experiments on YbRh(2)Si(2) and properly simulated within a simple model based on results obtained by inelastic neutron scattering experiments and band structure calculations.
View Article and Find Full Text PDFThe minerals involved in the formation of metazoan skeletons principally comprise glassy silica, calcium phosphate or carbonate. Because of their ancient heritage, glass sponges (Hexactinellida) may shed light on fundamental questions such as molecular evolution, the unique chemistry and formation of the first skeletal silica-based structures, and the origin of multicellular animals. We have studied anchoring spicules from the metre-long stalk of the glass rope sponge (Hyalonema sieboldi; Porifera, Class Hexactinellida), which are remarkable for their size, durability, flexibility and optical properties.
View Article and Find Full Text PDFBacterial surface layer protein sheets (S layer) coated with an ultrathin cobalt or silver film were studied by means of laterally resolved near-edge X-ray absorption fine structure spectroscopy performed by photoemission electron microscopy. Comparison with results obtained on pristine S layers allowed us to characterize both chemical interaction and X-ray damage in these protein-metal hybrid systems. In particular, we found that besides direct damage upon exposure to X-ray radiation the biomolecules experience additional contribution of the deposited metals, by low-energy electron generation in the metal particles.
View Article and Find Full Text PDFIn order to evaluate the biomedical potential of three-dimensional chitinous scaffolds of poriferan origin, chondrocyte culturing experiments were performed. It was shown for the first time that freshly isolated chondrocytes attached well to the chitin scaffold and synthesized an extracellular matrix similar to that found in other cartilage tissue engineering constructs. Chitin scaffolds also supported deposition of a proteoglycan-rich extracellular matrix of chondrocytes seeded bioconstructs in an in vivo environment.
View Article and Find Full Text PDFMarine invertebrate organisms including sponges (Porifera) not only provide an abundant source of biologically active secondary metabolites but also inspire investigations to develop biomimetic composites, scaffolds and templates for practical use in materials science, biomedicine and tissue engineering. Here, we presented a detailed study of the structural and physico-chemical properties of three-dimensional skeletal scaffolds of the marine sponges Aiolochroia crassa, Aplysina aerophoba, A. cauliformis, A.
View Article and Find Full Text PDFAs a homologue to the new, Fe-based type of high-temperature superconductors, the electronic structure of the heavy-fermion compound CeFePO was studied by means of angle-resolved resonant photoemission. It was experimentally found-and later on confirmed by local-density approximation (LDA) as well as dynamical mean-field theory (DMFT) calculations-that the Ce 4f states hybridize to the Fe 3d states of d{3z{2}-r{2}} symmetry near the Fermi level that discloses their participation in the occurring electron-correlation phenomena and provides insight into mechanism of superconductivity in oxopnictides.
View Article and Find Full Text PDFElectron-hybridization phenomena in YbRh_{2}Si_{2} were probed by angle-resolved photoemission. It was shown that the Yb 4f-Rh 4d hybridization strength in the surface region of this heavy-fermion material can be varied by deposition of Ag. Site-specific charge transfer from adatoms leads to change of the energy overlap of the interacting states close to the Fermi energy.
View Article and Find Full Text PDFThe degrees of charge localization in the highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO) of the bacterial surface layer protein of Bacillus sphaericus NCTC 9602 were studied by resonant photoemission. In agreement with a charge transport hopping mechanism that involves torsional motions of the peptide backbone, the lifetime of electrons excited into the LUMO was found to be approximately 100 fs.
View Article and Find Full Text PDFThe mixed-valent compound EuNi2P2 was studied by photoemission. Observed splittings and dispersions of the Eu 4f;{6} final state close to energy crossings of the Eu 4f and Ni 3d states are explained in terms of hybridization by a momentum and energy dependence of the electron hopping matrix element. These data obtained for a system with more than one 4f electron (hole) show that dispersions and hybridization gaps related to Kondo and heavy-fermion behavior can be found in other rare-earth-metal compounds apart from Ce and Yb-based ones.
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