RESUMEN
Septicemia caused by gram-negative bacteria is characterized by high death rate due to the endotoxin release. Since the septicemia depends not only on biochemical aspects of interactions in the system bloodstream, the study of mechanical interactions is also important. Using a model of experimental septicemia caused by E. coli, a hyperproduction of integrins CD11a and CD11b by neutrophils was shown, but this did not lead to the establishment of strong adhesion contacts between endothelial cells and neutrophils. On the contrary, adhesion force and work, as assessed by FS spectroscopy, were statistically significantly reduced in the presence of bacteria. It has also been shown that exposure to the pathogenic strain E. coli 321 increases the stiffness of the membrane-cytoskeleton complex of endothelial cells and bacteria significantly change their morphology on long-term observation. At the same time, we observed the death of neutrophils by apoptosis. Thus, it was shown that besides lipopolysaccharide release there are other pathogenic factors of E. coli: decrease in the interaction between neutrophil and endothelial cell caused by an increase of the endothelial cell rigidity and apoptotic death of neutrophils probably as a result of adhesins and exotoxin effects. Obtained results should be taken in mind during the therapy of septicemia.
RESUMEN
Gaining insights into the kinetics and the thermodynamic limits of nanostructures in high-temperature reactions is crucial for controlling their unique morphology, phase, and structure. Nanotubes from lanthanide-based misfit-layered compounds (MLCs) have been known for more than a decade and were successfully produced mostly via a chemical vapor transport protocol. The MLC nanotubes show diverse structural arrangements and lattice disorders, which could have a salient impact on their properties. Though their structure and charge transfer properties are reasonably well understood, a lack of information on their thermodynamic and kinetic stability limits their scalable synthesis and their applicability in modern technologies. In this study, the growth, thermodynamic stability, and decomposition kinetics of lanthanide-based misfit nanotubes of two model compounds, i.e., (LaS)1.14TaS2 and (SmS)1.19TaS2 are elucidated in detail. The nanotubes were carefully analyzed via atomic resolution electron microscopy imaging and synchrotron-based X-ray and electron diffraction techniques, and the information on their morphology, phase, and structures was deduced. The key insights gained would help to establish the parameters to explore their physio-chemical properties further. Furthermore, this study sheds light on the complex issue of the high-temperature stability of nanotubes and nanostructures in general.
RESUMEN
We report on the fabrication of a novel design of GaAs/(In,Ga)As/GaAs radial nanowire heterostructures on a Si 111 substrate, where, for the first time, the growth of inhomogeneous shells on a lattice mismatched core results in straight nanowires instead of bent. Nanowire bending caused by axial tensile strain induced by the (In,Ga)As shell on the GaAs core is reversed by axial compressive strain caused by the GaAs outer shell on the (In,Ga)As shell. Progressive nanowire bending and reverse bending in addition to the axial strain evolution during the two processes are accessed byin situby x-ray diffraction. The diameter of the core, thicknesses of the shells, as well as the indium concentration and distribution within the (In,Ga)As quantum well are revealed by 2D energy dispersive x-ray spectroscopy using a transmission electron microscope. Shell(s) growth on one side of the core without substrate rotation results in planar-like radial heterostructures in the form of free standing straight nanowires.
RESUMEN
During X-ray diffraction experiments on single crystals, the diffracted beam intensities may be affected by multiple-beam X-ray diffraction (MBD). This effect is particularly frequent at higher X-ray energies and for larger unit cells. The appearance of this so-called Renninger effect often impairs the interpretation of diffracted intensities. This applies in particular to energy spectra analysed in resonant experiments, since during scans of the incident photon energy these conditions are necessarily met for specific X-ray energies. This effect can be addressed by carefully avoiding multiple-beam reflection conditions at a given X-ray energy and a given position in reciprocal space. However, areas which are (nearly) free of MBD are not always available. This article presents a universal concept of data acquisition and post-processing for resonant X-ray diffraction experiments. Our concept facilitates the reliable determination of kinematic (MBD-free) resonant diffraction intensities even at relatively high energies which, in turn, enables the study of higher absorption edges. This way, the applicability of resonant diffraction, e.g. to reveal the local atomic and electronic structure or chemical environment, is extended for a vast majority of crystalline materials. The potential of this approach compared with conventional data reduction is demonstrated by the measurements of the Ta L3 edge of well studied lithium tantalate LiTaO3.
RESUMEN
The ordering structures of non-polar carbon tetrachloride liquid compressed to nano-scales between parallel substrates is studied in this work. The theoretical considerations show that the potential well formed by the confined parallel substrates induces orientational ordering of non-polar molecules. Through molecular dynamic (MD) simulations, the relations between various ordered structures of a non-polar liquid (carbon tetrachloride) and the confined gap size are demonstrated. The density distribution shows that the confinement does affect the ordering modes and induces an orientational ordering of molecules at the solid-liquid interface under extreme confinement conditions. This molecular orientation suggested from the theoretical model and MD simulation is directly supported by the experimental studies for the first time. The X-ray reflectivity data reveal a strong layering effect with splitting of the density profile in C and Cl-rich sublayers. The investigation shows that the liquid structure factor in confinement has a characteristic length similar to the short-range ordering in bulk, but the confined structure is strongly influenced by the surface potential and the interface properties. This introduces preferred molecular orientation and ordering which are not favorable in the bulk phase. As the orientational ordering is closely related to crystallization, our results provide a new perspective to control the crystallization in nano-confined space by compression.
RESUMEN
Here we report on the non-uniform shell growth of InxGa1-xAs on the GaAs nanowire (NW) core by molecular beam epitaxy (MBE). The growth was realized on pre-patterned silicon substrates with the pitch size (p) ranging from 0.1 µm to 10 µm. Considering the preferable bending direction with respect to the MBE cells as well as the layout of the substrate pattern, we were able to modify the strain distribution along the NW growth axis and the subsequent bending profile. For NW arrays with a high number density, the obtained bending profile of the NWs is composed of straight (barely-strained) and bent (strained) segments with different lengths which depend on the pitch size. A precise control of the bent and straight NW segment length provides a method to design NW based devices with length selective strain distribution.
RESUMEN
Switchable metal-organic frameworks (MOFs) change their structure in time and selectively open their pores adsorbing guest molecules, leading to highly selective separation, pressure amplification, sensing, and actuation applications. The 3D engineering of MOFs has reached a high level of maturity, but spatiotemporal evolution opens a new perspective toward engineering materials in the 4th dimension (time) by t-axis design, in essence exploiting the deliberate tuning of activation barriers. This work demonstrates the first example in which an explicit temporal engineering of a switchable MOF (DUT-8, [M1 M2 (2,6-ndc)2 dabco]n , 2,6-ndc = 2,6-naphthalene dicarboxylate, dabco = 1,4diazabicyclo[2.2.2]octane, M1 = Ni, M2 = Co) is presented. The temporal response is deliberately tuned by variations in cobalt content. A spectrum of advanced analytical methods is presented for analyzing the switching kinetics stimulated by vapor adsorption using in situ time-resolved techniques ranging from ensemble adsorption and advanced synchrotron X-ray diffraction experiments to individual crystal analysis. A novel analysis technique based on microscopic observation of individual crystals in a microfluidic channel reveals the lowest limit for adsorption switching reported so far. Differences in the spatiotemporal response of crystal ensembles originate from an induction time that varies statistically and widens characteristically with increasing cobalt content reflecting increasing activation barriers.
RESUMEN
Crystalline coordination polymers with high electrical conductivities and charge carrier mobilities might open new opportunities for electronic devices. However, current solvent-based synthesis methods hinder compatibility with microfabrication standards. Here, we describe a solvent-free chemical vapor deposition method to prepare high-quality films of the two-dimensional conjugated coordination polymer Cu-BHT (BHT = benzenehexanothiolate). This approach involves the conversion of a metal oxide precursor into Cu-BHT nanofilms with a controllable thickness (20-85 nm) and low roughness (<10 nm) through exposure to the vaporized organic linker. Moreover, the restricted metal ion mobility during the vapor-solid reaction enables high-resolution patterning via both bottom-up lithography, including the fabrication of micron-sized Hall bar and electrode patterns to accurately evaluate the conductivity and mobility values of the Cu-BHT films.
RESUMEN
Herein we analyze the switching kinetics of a breathing framework MIL-53(Al) with respect to different crystallite size regimes. Synchrotron time-resolved powder X-ray diffraction (PXRD) and adsorption rate analysis of n-butane physisorption at 298 K demonstrate the decisive role of crystal size affecting the time domain of breathing transitions in MIL-53(Al).
RESUMEN
Misfit layered compounds (MLCs) MX-TX2, where M, T = metal atoms and X = S, Se, or Te, and their nanotubes are of significant interest due to their rich chemistry and unique quasi-1D structure. In particular, LnX-TX2 (Ln = rare-earth atom) constitute a relatively large family of MLCs, from which nanotubes have been synthesized. The properties of MLCs can be tuned by the chemical and structural interplay between LnX and TX2 sublayers and alloying of each of the Ln, T, and X elements. In order to engineer them to gain desirable performance, a detailed understanding of their complex structure is indispensable. MLC nanotubes are a relative newcomer and offer new opportunities. In particular, like WS2 nanotubes before, the confinement of the free carriers in these quasi-1D nanostructures and their chiral nature offer intriguing physical behavior. High-resolution transmission electron microscopy in conjunction with a focused ion beam are engaged to study SmS-TaS2 nanotubes and their cross-sections at the atomic scale. The atomic resolution images distinctly reveal that Ta is in trigonal prismatic coordination with S atoms in a hexagonal structure. Furthermore, the position of the sulfur atoms in both the SmS and the TaS2 sublattices is revealed. X-ray photoelectron spectroscopy, electron energy loss spectroscopy, and X-ray absorption spectroscopy are carried out. These analyses conclude that charge transfer from the Sm to the Ta atoms leads to filling of the Ta 5d z 2 level, which is confirmed by density functional theory (DFT) calculations. Transport measurements show that the nanotubes are semimetallic with resistivities in the range of 10-4 Ω·cm at room temperature, and magnetic susceptibility measurements show a superconducting transition at 4 K.
RESUMEN
Protein adsorption to surfaces is at the heart of numerous technological and bioanalytical applications, but sometimes, it is also associated with medical risks. To deepen our insights into processes involving layers of surface-adsorbed proteins, high-resolution structural information is essential. Here, we use standing-wave X-ray fluorescence (SWXF) in combination with an optimized liquid-cell setup to investigate the underwater conformation of the random-coiled phosphoprotein ß-casein adsorbed to hydrophilic and hydrophobized solid surfaces. The orientation of the protein, as determined through the distributions of sulfur and phosphorus, is found to be sensitive to the chemical nature of the substrate. While no preferred orientations are observed on hydrophobized surfaces, on hydrophilic Al oxide, ß-casein is adsorbed as a diblock copolymer with the phosphorylated domain I attached to the surface. Our results demonstrate that targeting biologically relevant chemical elements with SWXF enables a detailed investigation of biomolecular layers under near-physiological conditions.
Asunto(s)
Proteínas de la Membrana , Adsorción , Fluorescencia , Conformación Proteica , Propiedades de Superficie , Rayos XRESUMEN
Misfit strain in core-shell nanowires can be elastically released by nanowire bending in case of asymmetric shell growth around the nanowire core. In this work, we investigate the bending of GaAs nanowires during the asymmetric overgrowth by an InxGa1-xAs shell caused by avoiding substrate rotation. We observe that the nanowire bending direction depends on the nature of the substrate's oxide layer, demonstrated by Si substrates covered by native and thermal oxide layers. Further, we follow the bending evolution by time-resolvedin situx-ray diffraction measurements during the deposition of the asymmetric shell. The XRD measurements give insight into the temporal development of the strain as well as the bending evolution in the core-shell nanowire.
RESUMEN
The role of metal-support epitaxy on shape and size heterogeneity of nanoparticles and their response to gas atmospheres is not very well explored. Here we show that an ensemble of Pd nanoparticles, grown on MgO(001) by deposition under ultrahigh vacuum, mostly consists of two distinctly epitaxially oriented particles, each having a different structural response to redox cycles. X-ray reciprocal space patterns were acquired in situ under oxidizing and reducing environments. Each type of nanoparticle has a truncated octahedral shape, whereby the majority grows with a cube-on-cube epitaxy on the substrate. Less frequently occurring and larger particles have their principal crystal axes rotated ±3.7° with respect to the substrate's. Upon oxidation, the top (001) facets of both types of particles shrink. The relative change of the rotated particles' top facets is much more pronounced. This finding indicates that a larger mass transfer is involved for the rotated particles and that a larger portion of high-index facets forms. On the main facets of the cube-on-cube particles, the oxidation process results in a considerable strain, as concluded from the evolution to largely asymmetric facet scattering signals. The shape and strain responses are reversible upon reduction, either by annealing to 973 K in vacuum or by reducing with hydrogen. The presented results are important for unraveling different elements of heterogeneity and their effect on the performance of real polycrystalline catalysts. It is shown that a correlation can exist between the particle-support epitaxy and redox-cycling-induced shape changes.
RESUMEN
We report on the results of an inâ situ synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated CeIV -based metal-organic frameworks (MOFs), analogues of the already well investigated ZrIV -based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as reagents, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds, varying parameters such as temperature, amount of the protonation modulator nitric acid and amount of the coordination modulator acetic acid. When only HNO3 is present in the reaction environment, only F4_MIL-140A(Ce) is obtained. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C. Upon addition of AcOH to the system, alongside HNO3 , mixed-phased products are obtained. F4_UiO-66(Ce) is always formed faster, and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate-determining step. A higher amount of HNO3 favours the formation of F4_MIL-140A(Ce), whereas increasing the amount of AcOH favours the formation of F4_UiO-66(Ce). Based on the inâ situ results, a new optimised route to achieving a pure, high-quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1â h) is also identified.
RESUMEN
Many scientific questions require X-ray experiments conducted at varying temperatures, sometimes combined with the application of electric fields. Here, a customized sample chamber developed for beamlines P23 and P24 of PETRA III at DESY to suit these demands is presented. The chamber body consists mainly of standard vacuum parts housing the heater/cooler assembly supplying a temperature range of 100â K to 1250â K and an xyz manipulator holding an electric contact needle for electric measurements at both high voltage and low current. The chamber is closed by an exchangeable hemispherical dome offering all degrees of freedom for single-crystal experiments within one hemisphere of solid angle. The currently available dome materials (PC, PS, PEEK polymers) differ in their absorption and scattering characteristics, with PEEK providing the best overall performance. The article further describes heating and cooling capabilities, electric characteristics, and plans for future upgrades of the chamber. Examples of applications are discussed.
RESUMEN
Core-shell nanowires (NWs) with asymmetric shells allow for strain engineering of NW properties because of the bending resulting from the lattice mismatch between core and shell material. The bending of NWs can be readily observed by electron microscopy. Using X-ray diffraction analysis with a micro- and nano-focused beam, the bending radii found by the microscopic investigations are confirmed and the strain in the NW core is analyzed. For that purpose, a kinematical diffraction theory for highly bent crystals is developed. The homogeneity of the bending and strain is studied along the growth axis of the NWs, and it is found that the lower parts, i.e. close to the substrate/wire interface, are bent less than the parts further up. Extreme bending radii down to â¼3â µm resulting in strain variation of â¼2.5% in the NW core are found.
RESUMEN
A new scandium metal-organic framework (Sc-MOF) with the composition of [Sc(OH)(OBA)], denoted as Sc-CAU-21, was prepared under solvothermal reaction conditions using 4,4'-oxidibenzoic acid (H2OBA) as the ligand. Single-crystal structure determination revealed the presence of the new inorganic building unit (IBU) {Sc8(µ-OH)8(O2C)16}. It is composed of cis-connected ScO6 polyhedra forming an eight-membered ring through bridging µ-OH groups. The connection of the IBUs leads to a 3D framework, containing 1D pores with a diameter between 4.2 and 5.6 Å. Pore access is limited by the size of the IBU, and in contrast to the isoreticular aluminum compound Al-CAU-21 [Al(OH)(OBA)], which is nonporous toward nitrogen at 77 K, Sc-CAU-21 exhibits a specific surface area of 610 m2 g-1. The title compound is thermally stable in air up to 350 °C and can be employed as a host for photoluminescent ions. Sc-CAU-21 exhibits a ligand-based blue emission, and (co)substituting Sc3+ ions with Ln3+ ions (Eu3+, Tb3+, and Dy3+) allows the tuning of the emitting color of the phosphor from red to green. Single-phase white-light emission with CIE color coordinates close to the ideal for white-light emission was also achieved. The luminescence property was utilized in combination with powder X-ray diffraction to study in situ the crystallization process of Sc-CAU-21:Tb and Sc-CAU-21:Eu. Both studies indicate a two-step crystallization process, with a crystalline intermediate, prior to the formation of Sc-CAU-21:Ln.
RESUMEN
Redox isomerism, that is, the change of a metal cation valence state in organic complexes, can find promising applications in multistable molecular switches for various molecular electronic devices. However, despite a large number of studies devoted to such processes in organic complexes of multivalent lanthanides, redox-isomeric transformations were never observed for europium. In the present work, we demonstrate the unique case of redox isomerization of Eu(III)/Eu(II) complexes on the example of Eu double-decker octa-n-butoxyphthalocyaninate (Eu[(BuO)8Pc]2) under ambient conditions (air and room temperature). It is shown that assumption of the face-on orientation on the aqueous subphase surface, in which two of each phthalocyanine decks in Eu[(BuO)8Pc]2 are located in different media (air and water), leads to the intramolecular electron transfer that results in the formation of a divalent Eu(II) cation in the complex. Lateral compression of the thus-formed monolayer results in the reorientation of bisphthalocyaninate to the edge-on state, in which the ligands can be considered identical, and occurrence of the reverse redox-isomeric transformation into the complex with a trivalent Eu cation. Both redox-isomeric states were directly observed by X-ray absorption near-edge structure spectroscopy in ultrathin films formed under different conditions.
RESUMEN
Physical properties of crystalline materials often manifest themselves as atomic displacements either away from symmetry positions or driven by external fields. Especially the origin of multiferroic or magnetoelectric effects may be hard to ascertain as the related displacements can reach the detection limit. Here we present a resonant X-ray crystal structure analysis technique that shows enhanced sensitivity to minute atomic displacements. It is applied to a recently found crystalline modification of strontium titanate that forms in single crystals under electric field due to oxygen vacancy migration. The phase has demonstrated unexpected properties, including piezoelectricity and pyroelectricity, which can only exist in non-centrosymmetric crystals. Apart from that, the atomic structure has remained elusive and could not be obtained by standard methods. Using resonant X-ray diffraction, we determine atomic displacements with sub-picometer precision and show that the modified structure of strontium titanate corresponds to that of well-known ferroelectrics such as lead titanate.
RESUMEN
Ion-surface interactions are of high practical importance in a wide range of technological, environmental and biological problems. In particular, they ultimately control the electric double layer structure, hence the interaction between particles in aqueous solutions. Despite numerous achievements, progress in their understanding is still limited by the lack of experimental determination of the surface composition with appropriate resolution. Tackling this challenge, we have developed a method based on X-ray standing waves coupled to nano-confinement which allows the determination of ion concentrations at a solid-solution interface with a sub-nm resolution. We have investigated mixtures of KCl/CsCl and KCl/KI in 0.1 mM to 10 mM concentrations on silica surfaces and obtained quantitative information on the partition of ions between bulk and Stern layer as well as their distribution in the Stern layer. Regarding partition of potassium ions, our results are in agreement with a recent AFM study. We show that in a mixture of KCl and KI, chloride ions exhibit a higher surface propensity than iodide ions, having a higher concentration within the Stern layer and being on average closer to the surface by ≈1-2 Å, in contrast to the solution water interface. Confronting such data with molecular simulations will lead to a precise understanding of ionic distributions at aqueous interfaces.