Sulfur: not a "silent" element any more

To understand the many important functions of sulfur, a ubiquitous element in biological systems, in the environment and for industrial applications, detailed analyses are needed. Characterization of the variety of sulfur functional groups in a natural sample, often occurring in a wide range of oxidation states, became possible when the development of dedicated X-ray absorption near-edge structure (XANES) spectroscopy started in the mid-1980s. This tutorial review provides an overview of sulfur XANES spectroscopic investigations into the role of sulfur in all kinds of natural samples, from sediment and oil to marine-archaeological wood and plants.     

Nonlinear finite element analysis and modeling of a precast hybrid beam–column connection subjected to cyclic loads

In this work, a detailed three-dimensional (3D) nonlinear finite element model is developed to study the response and predict the behavior of precast hybrid beam–column connection subjected to cyclic loads that was tested at the National Institute of Standards and Technology (NIST) laboratory. The precast joint is modeled using 3D solid elements and surface-to-surface contact elements between the beam/column faces and interface grout in the vicinity of the connection. The model takes into account the pre-tension effect in the post-tensioning strand and the nonlinear material behavior of concrete. The model response is compared with experimental test results and yielded good agreement at all stages of loading. Fracture of the mild-steel bars resulted in the failure of the connection. In order to predict this failure mode, stress and strain fields in the mild-steel bars at the beam–column interface were generated from the analyzed model. Such fields of stresses and strains are hard to measure in experimental testing. In addition, the magnitude of the force developed in the post-tensioning steel tendon was also monitored and it was observed that it did not yield during the entire loading history. Successful finite element modeling will provide a practical and economical tool to investigate the behavior of such connections.     

Novel One‐Pot Synthesis of Functionalized Quinolines from Isocyanides,Aniline, and Acetylene Dicarboxylate via Cu‐Catalyzed Intramolecular C─H Activation Reactions

The one‐pot synthesis of a novel class of substituted quinoline derivatives with good yields is achieved via the Cu‐catalyzed intramolecular C─H activation reaction between isocyanides, aniline, and acetylene dicarboxylate in MeCN at room temperature. The existence of one‐pot conditions, availability of a starting material‐catalyst, the absence of column chromatography, and a high yield of products are among the advantages of this method. The structures are confirmed spectroscopically (¹H NMR and ¹³C NMR, IR, and EI‐MS) and through elemental analyses.     

Structural characterization of molybdenum(V) species in aqueous HCl solutions

Mo(V) aqua-chloro complexes in hydrochloric acid solutions have been studied by means of Mo K- and L2,3-edge X-ray absorption and Raman spectroscopic methods. The solid compounds (HPPh3)2[MoOCl5] (1), 6[MoOCl4(H2O)]-.10(pyH)+.4Cl- (2), and (pyH)2[Mo2O4Cl4(trans-OH2)2] (3) were used for structural comparisons. The compound 2 crystallizes in the orthorhombic space group Pmma (no. 51) with a=21.398(3), b=8.057(4), c=13.330(4) A, and Z=4. In 0.2 M solutions of MoCl5 in 7.4-9.4 M HCl the mononuclear [MoOCl4(OH2)]- complex dominates with the bond distances Mo=O 1.66(2) A, Mo-Cl 2.38(2) A, and Mo-OH2 2.30(2) A. Its Raman band at 994 cm-1 for the Mo=O symmetric stretching vibration is closer to that of 2 (988 cm-1) than of 1 (969 cm-1). The Mo K-edge EXAFS spectrum for 0.2 M MoCl5 in 1.7 M HCl solution reveals a dinuclear [Mo2O4Cl6-n(OH2)n]n-4 (n=2, 3) complex with a double oxygen bridge and the average distances Mo=O 1.67(2) A, Mo-(mu-O) 1.93(2) A, Mo-Cl 2.47(3) A, Mo-Mo 2.56(2) A, and a short Mo-OH2 distance of 2.15(2) A, which implies that at least one of the aqua ligands is in equatorial position relative to the two axial Mo=O bonds. This position differs from the Mo-OH2 configuration exclusively trans to the M=O groups of the isomeric (with n=2) dinuclear complex in 3. The difference in the ligand field is also reflected in their L2,3-edge XANES spectra. For 0.2 M MoCl5 solutions in intermediate HCl concentrations (3.7-6.3 M) the Raman bands at 802 cm-1 (Mo-O-Mo) and 738 cm-1 (Mo-(mu-O)2-Mo) verify three coexisting classes of Mo(V) complexes: mononuclear complexes together with dinuclear mono-oxo (e.g., [Mo2O3Cl6(H2O)2]2-) and dioxo bridged species, even though principal component analysis (PCA) of the corresponding series of EXAFS spectra only could distinguish two major components. By fitting linear combinations of the appropriate EXAFS oscillation components, dioxo-bridged dinuclear complexes were found to dominate at HCl concentrations相似文献   

Investigation of the π–π stacking interactions without direct electrostatic effects of substituents: the aromatic∥aromatic and aromatic∥anti-aromatic complexes

Stability of the π–π stacking interactions in the ben∥substituted-ben and ben∥substituted-COT complexes was studied using the computational quantum chemistry methods (where ben and COT are benzene and cyclooctatetraene, ∥ denotes π–π stacking interaction, substituted-ben and substituted-COT are benzene and cyclooctatetraene which substituted with four ethynyl-X groups, respectively, and X = OH, CH₃, H, F, CF₃, CN and NO₂). In these complexes electron-withdrawing substituents lead to larger binding energies and electron-donating ones lead to weaker interactions compared to X = H. There are meaningful correlations between the Hammett constants and binding energies. The atoms in molecules (AIM) analysis shows that formation of these complexes is accompanied by increase in the electron charge densities at the ring critical points of the substituted-ben and substituted-COT rings which leads to increase/decrease of the π–π stacking interactions in the ben∥substituted-ben/ben∥substituted-COT complexes. The charge transfer occurs from benzene to substituted-ben in the ben∥substituted-ben complexes and from substituted-COT to benzene (with the exception of X = CN) in the ben∥substituted-COT ones. Nuclear magnetic resonance calculations demonstrate that interactions of the more aromatic substituted-ben/less anti-aromatic substituted-COT rings with benzene in the ben∥substituted-ben/ben∥substituted-COT complexes can be helpful to enhance strength of the π–π stacking interactions. Thus, regardless of ring size, the π–π stacking interaction is an aromatic–aromatic interaction and π electron cloud properties of interacting rings affect on the strength of this interaction.     

Hyperbolastic modeling of wound healing

A new mathematical model for wound healing is introduced and applied to three sets of experimental data. The model is easy to implement but can accommodate a wide range of factors affecting the wound healing process. The data sets represent the areas of trace elements, diabetic wounds, growth factors, and nutrition within the field of wound healing. The model produces an explicit function accurately representing the time course of healing wounds from a given data set. Such a function is used to study variations in the healing velocity among different types of wounds and at different stages in the healing process. A new multivariable model of wound healing capable of analyzing the effects of several variables on accelerating the wound healing process is also introduced. Such a model can help to formulate appropriate strategies to treat wounds. It also would enable us to evaluate the efficacy of different treatment modalities during the inflammatory, proliferative, and tissue remodeling phases.     

ChemInform Abstract: Structure Studies of Dimeric [Pt2(CN)10]4‐ Pentacyanoplatinum(III) and Monomeric Pentacyanoplatinum(IV) Complexes by EXAFS,Vibrational Spectroscopy,and X‐Ray Crystallography.

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