Hard X-ray absorption spectroscopy is a valuable in situ probe for non-destructive diagnostics of metal sites. The low-energy interval of a spectrum (XANES) contains information about the metal oxidation state, ligand type, symmetry and distances in the first coordination shell but shows almost no dependency on the bridged metal-metal bond length. The higher-energy interval (EXAFS), on the contrary, is more sensitive to the coordination numbers and can decouple the contribution from distances in different coordination shells. Supervised machine-learning methods can combine information from different intervals of a spectrum; however, computational approaches for the near-edge region of the spectrum and higher energies are different. This work aims to keep all benefits of XANES and extend its sensitivity towards the interatomic distances in the first and second coordination shells. Using a binuclear bridged copper complex as a case study and cross-validation analysis as a quantitative tool it is shown that the first 170â eV above the edge are already sufficient to balance the contributions of Cu-O/N scattering and Cu-Cu scattering. As a more general outcome this work highlights the trivial but often overlooked importance of using `longer' energy intervals of XANES for structural refinement and machine-learning predictions. The first 200â eV above the absorption edge still do not require parametrization of Debye-Waller damping and can be calculated within full multiple scattering or finite difference approximations with only moderately increased computational costs.
The design of water-stable photo and electrocatalysts of metal-organic frameworks (MOFs) for its promising catalytic applications at long-term irradiations or persisted current loads is extremely necessary but still remains as challenging. A limited number of reports on Ti-MOF-based catalysts for water splitting are only available to explain and understand the correlation between the nature of materials and MOFs array. Herein, spherical Ti-MOFs and corresponding partially annealed hollow core-shell Ti-MOFs (Ti-MOF/D) are designed and the correlation with their photo(electro)catalytic water splitting performance is evaluated. The switchable valence state of Ti for the Ti-MOF as a function of molecular bonding is the possible reason behind the observed photocatalytic hydrogen generation and light-harvesting ability of the system. Besides, the defect state, solid core-shell mesoporous structure, and active sites of Ti-MOF help to trap the charge carriers and the reduction of the recombination process. This phenomenon is absent for hollow core-shells Ti-MOF/D spheres due to the rigid TiO2 outer surface although there is a contradiction in surface area with Ti-MOF. Considering the diversity of Ti-MOF and Ti-MOF/D, further novel research can be designed using this way to manipulate their properties as per the requirements.
The bimetallic alloys often outperform their single-component counterparts due to synergistic effects. Being widely known, the Au-Pd alloy is a promising candidate for the novel heterogeneous nanocatalysts. Rational design of such systems requires theoretical simulations under ambient conditions.Ab initioquantum-mechanical calculations employ the density functional theory (DFT) and are limited to the systems with few tens of atoms and short timescales. The alternative solution implies development of reliable atomistic potentials. Among different approaches ReaxFF combines chemical accuracy and low computational costs. However, the development of a new potential is a problem without unique solution and thus requires accurate validation criteria. In this work we construct ReaxFF potential for the Au-Pd system based onab initioDFT calculations for bulk structures, slabs and nanoparticles with different stoichiometry. The validation was performed with molecular dynamics and Monte-Carlo calculations. We present several optimal parametrizations that describe experimental bulk mechanical and thermal properties, atomic order-disorder phase transition temperatures and the resulting ordered crystal structures.
This work establishes structure-property relationships in Ru-based catalytic systems for selective hydrodeoxygenation of ketones to alkenes by combining extensive catalytic testing, in situ X-ray absorption spectroscopy (XAS) under high pressures and temperatures and ex situ XAS structural characterization supported by density functional theory (DFT) calculations. Catalytic tests revealed the difference in hydrogenation selectivity for ketones (exemplified by acetone) or alkenes (exemplified by propene) upon changing the reaction conditions, more specifically in the presence of CO during a pretreatment step. XAS data demonstrated the evolution of the local ruthenium structure with different amounts of Cl/Br and CO ligands. In addition, in the absence of CO, the catalyst was reduced to Ru0, and this was associated with a significant decrease of the selectivity for ketone hydrogenation. For the Ru-bromide carbonyl complex, selectivity towards acetone hydrogenation over propene hydrogenation was explained on the basis of different relative energies of the first intermediate states of each reaction. These results give a complete understanding of the evolution of the Ru species, used for the catalytic valorization of biobased polyols to olefins in ionic liquids, identifying the undesired deactivation routes as well as possibilities for reactivation.
A novel approach for the analysis of extended X-ray absorption fine structure (EXAFS) spectra is developed exploiting an inverse machine learning-based algorithm. Through this approach, it is possible to explore and account for, in a precise way, the nonlinear geometry dependence of the photoelectron backscattering phases and amplitudes of single and multiple scattering paths. In addition, the determined parameters are directly related to the 3D atomic structure, without the need to use complex parametrization as in the classical fitting approach. The applicability of the approach, its potential and the advantages over the classical fit were demonstrated by fitting the EXAFS data of two molecular systems, namely, the KAu (CN)2 and the [RuCl2(CO)3]2 complexes.
Modern synchrotron radiation sources and free electron laser made X-ray absorption spectroscopy (XAS) an analytical tool for the structural analysis of materials under in situ or operando conditions. Fourier approach applied to the extended region of the XAS spectrum (EXAFS) allows the estimation of the number of structural and non-structural parameters which can be refined through a fitting procedure. The near edge region of the XAS spectrum (XANES) is also sensitive to the coordinates of all the atoms in the local cluster around the absorbing atom. However, in contrast to EXAFS, the existing approaches of quantitative analysis provide no estimation for the number of structural parameters that can be evaluated for a given XANES spectrum. This problem exists both for the classical gradient descent approaches and for modern machine learning methods based on neural networks. We developed a new approach for rational fit based on principal component descriptors of the spectrum. In this work the principal component analysis (PCA) is applied to a dataset of theoretical spectra calculated a priori on a grid of variable structural parameters of a molecule or cluster. Each principal component of the dataset is related then to a combined variation of several structural parameters, similar to the vibrational normal mode. Orthogonal principal components determine orthogonal deformations that can be extracted independently upon the analysis of the XANES spectrum. Applying statistical criteria, the PCA-based fit of the XANES determines the accessible structural information in the spectrum for a given system.
Valence tautomer transition occurs mainly in 3d metalorganic complexes with redox-active ligands and makes them potential candidates for single-molecular switches. The transition occurs under temperature, pressure, or light-induced stimuli and is strongly affected by the intermolecular interactions. However single-crystal x-ray diffraction is not always applicable to such systems when crystal structure is destroyed upon transition or system is studied in the solution. Such an example is bis(o-semiquinonato) cobalt complex with TEMPO-functionalized iminopyridine ancillary ligand. In this work we apply two complementary techniques-ligand-sensitive Fourier transform infrared spectroscopy (FTIR) and metal sensitive Co K-edge x-ray absorption spectroscopy (XAS). In a solid state, a temperature hysteresis of magnetization larger than 40 K was observed upon cyclic cooling-heating. So, the temperature of phase transition upon cooling is about 40 K lower than that upon heating. In solution, the x-ray absorption spectra for high-temperature and low-temperature states were similar to that in the solid form, but the hysteresis was absent. Two methods are can probe valence tautomer transition, but XAS has an advantage for the liquid phase analysis and FTIR has larger sensitivity to the ligand related interactions in solid.
Molybdenum disulfide (MoS2) has recently been considered as an effective material for potential photocatalytic applications; however, its photocatalytic activity was limited due to the low density of active sites. In this work, MoS2 Quantum dots (QDs) were synthesized via the ultrasonication technique to construct heterostructure with SnS2 nanosheets (SnS2@MoS2 QDs) and the prepared materials were tested for photocatalytic applications for Methylene blue (MB). Pristine SnS2 and SnS2@MoS2 QDs nanocomposite were analyzed by XRD, TEM, PL, and Uv-Vis. Both SnS2 and SnS2@MoS2 QDs exhibited a single trigonal phase with the P-3m1 space group. The TEM analysis confirmed the coupling between the pristine SnS2 and SnS2@MoS2 QDs. The results of photocatalytic activity toward MB indicated that SnS2@MoS2 QDs material exhibits much superior photocatalytic performance compared to pristine SnS2. The excellent photodegradation performance of SnS2@MoS2 QDs is due in the main to the formation of heterojunction between SnS2 and MoS2 QDs with narrow bandgap formation, which results in a facile carriers transfer and thus high photocatalytic efficiency. A representative mechanism of the photodegradation for SnS2@MoS2 QDs photocatalyst was proposed. Such an ultrasonic technique is capable of producing small metallic particle size that can be used to construct new heterostructures for water remediation applications.
In this work a multi-technique characterization was performed for the first time to trace the influence of structural defects on the physical properties of PbTiO3 ferroelectrics. The structural defects were generated by the mechanical activation in the pressure range of 40-320 MPa, by combining a uniaxial strain with a shear deformation in the Bridgman anvils. The induced defectivity of PbTiO3 was assessed via calculation of unit cell parameters, estimation of the regions of coherent scattering and analysis of micro-deformations. The Debye characteristic temperature, the static mean-square displacement, the Debye-Waller isotropic factor, the vibrational spectra and dielectric properties of the activated PbTiO3 ceramics are presented. The high-quality PbTiO3 ceramics was prepared without modifiers, hence, changing the concentration of structural defects via mechanical activation constitutes a chemically clean method for fine tuning of the dielectric properties of PbTiO3.
Thermal and photoinduced processes accompanying complexation of photochromic spiropyrans (SPP) with Zn ions in acetone solution were characterized by means of UV-vis and X-ray absorption spectroscopies in operando regime. SPP ligands are usually transparent at λ > 350 nm, but after mixing with Zn ions, they produce a stable colored (ε = 32 000-38 000 M-1 cm-1) complex with maximum absorption at 525 nm, which makes them a powerful tool for monitoring metal-ion concentration in solution. The complex revealed fluorescence and photochromic behavior under static irradiation with visible light with constant photoreaction quantum yield across its characteristic absorption band. Zn K-edge X-ray absorption spectra show prominent changes in Zn local atomic structure between free Zn ions and Zn complex. The pump-flow-probe scheme was adapted to measure operando changes in Zn coordination upon light irradiation. Within experimental time resolution, we have determined that 20 µs after light irradiation, Zn ion is released out of the complex. This is the first example of the direct spectroscopic probe of the Zn photorelease from the spiropyran complex.
Correction for 'New ferrocene-based 2-thio-imidazol-4-ones and their copper complexes. Synthesis and cytotoxicity' by D. A. Guk et al., Dalton Trans., 2018, DOI: 10.1039/c8dt03164a.
Synthesis, characterization (HRMS, NMR, EPR, XANES, UV-Vis spectroscopy, and electrochemistry), DNA and BSA binding and in vitro biological screening of two new ferrocene-incorporated thiohydantoin derivatives (5 and 6) and their copper coordination compounds are reported. The ferrocene-based thiohydantoin derivatives were prepared by copper-catalyzed azide alkyne cycloaddition reactions between alkynyl ferrocenes and 5-(Z)-3-(2-azidoethyl)-2-(methylthio)-5-(pyridin-2-ylmethylene)-1H-imidazol-4H-one. Alkynyl ferrocenes necessary for these syntheses were prepared by new procedures. Intermolecular redox reactions between the ferrocene fragment and copper(+2) coordinated ions were studied by different methods to determine the mechanism and kinetic constants of redox processes. Ferrocene-containing imidazolones (5 and 6) and their copper complexes were also tested for their in vitro cytotoxic activity against MCF-7 and A-549 carcinoma cells, and also against the noncancerous cell line Hek-293. The results showed modest cytotoxicity against the subjected cancer cell line compared with cisplatin. The ability of the obtained compounds to cause DNA degradation and cell apoptosis was investigated, and the distribution of cytosol/pellets was studied by AAS.
Antineoplastic Agents/pharmacology , Coordination Complexes/pharmacology , Copper/pharmacology , Enzyme Inhibitors/pharmacology , Imidazoles/pharmacology , Metallocenes/pharmacology , Telomerase/antagonists & inhibitors , Animals , Antineoplastic Agents/chemical synthesis , Antineoplastic Agents/chemistry , Apoptosis/drug effects , Cattle , Cell Line , Cell Proliferation/drug effects , Coordination Complexes/chemical synthesis , Coordination Complexes/chemistry , Copper/chemistry , DNA Cleavage , Dose-Response Relationship, Drug , Drug Screening Assays, Antitumor , Enzyme Inhibitors/chemical synthesis , Enzyme Inhibitors/chemistry , HEK293 Cells , Humans , Imidazoles/chemical synthesis , Imidazoles/chemistry , Metallocenes/chemistry , Molecular Structure , Serum Albumin, Bovine/chemistry , Structure-Activity Relationship , Telomerase/metabolism
An X-ray absorption spectroscopy study of the UiO-67 Pt functionalized metal organic frameworks (MOFs) demonstrates that under appropriate conditions, at least two types of catalytically active sites can be formed in the cavities of the MOF: isolated Pt-complexes and Pt nanoparticles (Pt-NPs). Both pre-made linker synthesis (PMLS) and post-synthesis functionalization (PSF) methods were adopted. XAS was used to monitor the temperature-dependent behaviour of UiO-67-Pt while heating from RT to 623 K, in different gas feeds (pure He, 3% H2/He and 10% H2/He). We collected static in situ Pt LIII XANES and EXAFS spectra at room temperature (RT) before and after the thermal treatment, as well as spectra acquired under operando conditions upon heating. Under 10% H2/He thermal treatment, we unambiguously detected Pt-NP formation which has been followed by a parametric EXAFS analysis of the data collected during temperature programmed H2-reduction (TPR), using the Einstein model to predict the temperature dependence of the Debye-Waller factors. Conversely, in pure He flow, the only significant change observed during TPR is the progressive decrease of the Pt-Cl single scattering contribution, leading to the conclusion that the Pt grafted to the bpydc-linkers remains naked. Advanced EXAFS/TEM analysis allowed us to quantify the fraction of Pt in the form of Pt-NPs, values that have been quantitatively confirmed by linear combination analysis of the XANES spectra. In situ XANES/EXAFS study was supported by ex situ XRPD and BET analyses, confirming the framework stability and testifying a loss of the internal volume after TPR due to the formation of Pt-NPs insides the MOF pores, more relevant in the sample where smaller Pt-NPs were formed.
Magnetic iron oxide nanoparticles doped with samarium were prepared by solvothermal polyol method. An introduction of 2,2'-bipyridine during the synthesis reduces the particle diameter to about 9nm in average. The difference in physical and magnetic properties of the samples prepared with and without capping agent was outlined on the basis of complex characterization by a number of experimental techniques. The characteristics of resulted product make it suitable for biomedical applications, for instance, as a contrast agent for MRI.
Magnetite Nanoparticles , 2,2'-Dipyridyl , Contrast Media , Magnetic Resonance Imaging , Magnetics , Samarium
The exceptional thermal and chemical stability of the UiO-66, -67 and -68 classes of isostructural MOFs [J. Am. Chem. Soc., 2008, 130, 13850] makes them ideal materials for functionalization purposes aimed at introducing active centres for potential application in heterogeneous catalysis. We previously demonstrated that a small fraction (up to 10%) of the linkers in the UiO-67 MOF can be replaced by bipyridine-dicarboxylate (bpydc) moieties exhibiting metal-chelating ability and enabling the grafting of Pt(ii) and Pt(iv) ions in the MOF framework [Chem. Mater., 2015, 27, 1042] upon interaction with PtCl2 or PtCl4 precursors. Herein we extend this functionalization approach in two directions. First, we show that by controlling the activation of the UiO-67-Pt we can move from a material hosting isolated Pt(ii) sites anchored to the MOF framework with Pt(ii) exhibiting two coordination vacancies (potentially interesting for C-H bond activation) to the formation of very small Pt nanoparticles hosted inside the MOF cavities (potentially interesting for hydrogenation reactions). The second direction consists of the extension of the approach to the insertion of Cu(ii), obtained via interaction with CuCl2, and exhibiting interesting redox properties. All materials have been characterized by in situ X-ray absorption spectroscopy at the Pt L3- and Cu K-edges.
This paper briefly reviews the ways of activation of the antitumor resistance mechanisms developed on the basis of the concept of the periodic system of general nonspecific adaptational reactions of the body. The principles of the formation of effective influences by electromagnetic radiation using biologically active substances are described. A comparison of the criteria and conceptions of the theory of adaptational reactions to some concepts and categories of synergetics is made. The features of dynamics of the studied parameters upon effective influences are considered. Antistress nature of the systemic effects of ferromagnetic nanoparticles on tumor bearing animals is shown. The, possible mechanisms of regression of large tumor under the influence of two different factors--modulated electromagnetic radiation and magnetite nanoparticles--are discussed. The cases of a change of the order parameter in connection with the development of antistress areactivity and regression of experimental tumors under the influence of the combined electromagnetic impact are analyzed.
Electromagnetic Fields , Magnetite Nanoparticles/therapeutic use , Neoplasms/physiopathology , Adaptation, Physiological/radiation effects , Animals , Cell Transformation, Neoplastic/radiation effects , Humans , Neoplasms/radiotherapy , Rats
Cu-SSZ-13 is a highly active NH3-SCR catalyst for the abatement of harmful nitrogen oxides (NO x , x = 1, 2) from the exhausts of lean-burn engines. The study of Cu-speciation occurring upon thermal dehydration is a key step for the understanding of the enhanced catalytic properties of this material and for identifying the SCR active sites and their redox capability. Herein, we combined FTIR, X-ray absorption (XAS) and emission (XES) spectroscopies with DFT computational analysis to elucidate the nature and location of the most abundant Cu sites in the activated catalyst. Different Cu species have been found to be dominant as a function of the dehydration temperature and conditions. Data analysis revealed that the dehydration process of Cu cations is essentially completed at 250 °C, with the formation of dehydrated [CuOH]+ species hosted in close proximity to 1-Al sites in both d6r and 8r units of the SSZ-13 matrix. These species persist at higher temperatures only if a certain amount of O2 is present in the gas feed, while under inert conditions they undergo virtually total "self-reduction" as a consequence of an OH extra-ligand loss, resulting in bi-coordinated bare Cu+ cations. Synchrotron characterization supported by computational analysis allowed an unprecedented quantitative refinement of the local environment and structural parameters of these Cu(ii) and Cu(i) species.
Novel mechanism of antioxidant activity of buckminsterfullerene C60 based on protons absorbing and mild uncoupling of mitochondrial respiration and phosphorylation was postulated. In the present study we confirm this hypothesis using computer modeling based on Density Functional Theory. Fullerene's geroprotective activity is sufficiently higher than those of the most powerful reactive oxygen species scavengers. We propose here that C60 has an ability to acquire positive charge by absorbing inside several protons and this complex could penetrate into mitochondria. Such a process allows for mild uncoupling of respiration and phosphorylation. This, in turn, leads to the decrease in ROS production.
Antioxidants/therapeutic use , Fullerenes/therapeutic use , Mitochondria/metabolism , Antioxidants/metabolism , Fullerenes/metabolism , Humans , Mitochondria/drug effects , Mitochondria/physiology , Oxidation-Reduction , Phosphorylation/drug effects , Protons , Reactive Oxygen Species/metabolism , Respiration/drug effects
A method for the analysis of time-resolved x-ray absorption near edge structure (XANES) spectra is proposed. It combines principal component analysis of the series of experimental spectra, multidimensional interpolation of theoretical XANES as a function of structural parameters, and ab initio XANES calculations. It allows to determine the values of structural parameters for intermediates of chemical reactions and the concentrations of different states as a function of time. This approach is tested using numerically generated data and its possibilities and limitations are discussed. The application of this method to a reaction with methylrhenium trioxide catalyst in solution, for which experimental data were measured using stopped-flow energy-dispersive x-ray absorption spectroscopy technique, is demonstrated. Possibilities and limitations of this experimental technique are also discussed.
We have used synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to study the electronic structure of nitrogen-related defects in InN(0001). Several defect levels within the band gap or the conduction band of InN were clearly resolved in NEXAFS spectra around the nitrogen K-edge. We attribute the level observed at 0.3 eV below the conduction band minimum (CBM) to interstitial nitrogen, the level at 1.7 eV above the CBM to antisite nitrogen, and a sharp resonance at 3.2 eV above the CBM to molecular nitrogen, in full agreement with theoretical simulations.
