Formation mechanisms and properties of semifluorinated molecular gradients on silica surfaces

The goal of this study is to elucidate the formation of molecular gradients made of semifluorinated organosilanes (SFOs) on flat substrates by using a methodology developed by Chaudhury and Whitesides (Science 1992, 256, 1539). We use surface-sensitive combinatorial near-edge X-ray absorption fine structure (combi-NEXAFS) spectroscopy to measure the position-dependent concentration and orientation of SFO molecules in SFO molecular gradients on flat silica surfaces. Using the combi-NEXAFS data, we establish the correlation between the fraction of the F(CF(2))(8)(CH(2))(2)- species on the substrate and the average tilt angle of the -(CF(2))(8)F group in the SFO as a function of the deposition gas medium (air vs nitrogen) and the end group around the silicon atom (monofunctional vs trifunctional). In addition, we utilize the gradient geometry to comprehend the mechanism of formation of SFO self-assembled monolayers (SAMs). Specifically, we provide evidence that depending on the nature of the end group in the SFO and the vapor phase the SFO molecules add themselves into the existing SAMs either as individual molecules or as multimolecular complexes.     

Nonempirical calculations of NMR indirect spin-spin coupling constants. Part 14: azomethines of the alpha, beta-unsaturated aldehydes

Configurational assignment of seven azomethines obtained from the alpha-functionally substituted and nonsubstituted alpha,beta-unsaturated aldehydes has been performed on the basis of experimental measurements and the high-level ab initio calculations of their 1J(C,C) and 1J(C,H), involving the alpha-imino carbon that demonstrated the marked stereochemical dependence of both coupling constants upon the orientation of the nitrogen lone pair in the diverse isomers of the title azomethines.     

电环形谐振腔表面几何参数对太赫兹超材料吸收体性能的影响

本文分析了电环形谐振腔的几何参数对超材料吸收体吸收率的影响。文中详细分析了电环形谐振腔参数、介电层（间隔物）厚度和电环形谐振腔厚度对超材料吸收体的影响,在此基础上,设置正交实验分析了几种参数的综合影响,最终获得超材料的理论吸收率。根据上述结果,制备了2个超材料吸收体的原理样机,经实验测得,原理样机的窄带吸收率高于98%。本文的研究成果为高性能吸收器的设计提供了指导。     

Evaluation of Activation Energies for Pairwise and Non-Pairwise Hydrogen Addition to Propyne Over Pd/Aluminosilicate Fiberglass Catalyst by Parahydrogen-Induced Polarization (PHIP)

Hydrogenation of propyne to propene over Pd/aluminosilicate fiberglass catalyst in the temperature range 175–350 °C was investigated with the use of parahydrogen-induced polarization (PHIP) technique. Activation energies for both pairwise and non-pairwise H₂ addition routes were estimated. It was found that at 175–275 °C the activation energies for hydrogen addition to the triple bond of propyne have similar values (about 60–70 kJ/mol) for both routes of hydrogen addition. At higher temperatures (275–350 °C), the rate constant for pairwise hydrogen addition reaches a maximum value while the rate constant for non-pairwise hydrogen addition continues to increase with increasing temperature.     

Psoromic acid is a selective and covalent Rab-prenylation inhibitor targeting autoinhibited RabGGTase

Post-translational attachment of geranylgeranyl isoprenoids to Rab GTPases, the key organizers of intracellular vesicular transport, is essential for their function. Rab geranylgeranyl transferase (RabGGTase) is responsible for prenylation of Rab proteins. Recently, RabGGTase inhibitors have been proposed to be potential therapeutics for treatment of cancer and osteoporosis. However, the development of RabGGTase selective inhibitors is complicated by its structural and functional similarity to other protein prenyltransferases. Herein we report identification of the natural product psoromic acid (PA) that potently and selectively inhibits RabGGTase with an IC(50) of 1.3 μM. Structure-activity relationship analysis suggested a minimal structure involving the depsidone core with a 3-hydroxyl and 4-aldehyde motif for binding to RabGGTase. Analysis of the crystal structure of the RabGGTase:PA complex revealed that PA forms largely hydrophobic interactions with the isoprenoid binding site of RabGGTase and that it attaches covalently to the N-terminus of the α subunit. We found that in contrast to other protein prenyltransferases, RabGGTase is autoinhibited through N-terminal (α)His2 coordination with the catalytic zinc ion. Mutation of (α)His dramatically enhances the reaction rate, indicating that the activity of RabGGTase is likely regulated in vivo. The covalent binding of PA to the N-terminus of the RabGGTase α subunit seems to potentiate its interaction with the active site and explains the selectivity of PA for RabGGTase. Therefore, psoromic acid provides a new starting point for the development of selective RabGGTase inhibitors.     

Heteroleptic FeII Complexes of 2,2′‐Biimidazole and Its Alkylated Derivatives: Spin‐Crossover and Photomagnetic Behavior

Three iron(II) complexes, [Fe(TPMA)(BIM)](ClO₄)₂?0.5H₂O ( 1 ), [Fe(TPMA)(XBIM)](ClO₄)₂ ( 2 ), and [Fe(TPMA)(XBBIM)](ClO₄)₂ ?0.75CH₃OH ( 3 ), were prepared by reactions of Fe^II perchlorate and the corresponding ligands (TPMA=tris(2‐pyridylmethyl)amine, BIM=2,2′‐biimidazole, XBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐biimidazole, XBBIM=1,1′‐(α,α′‐o‐xylyl)‐2,2′‐bibenzimidazole). The compounds were investigated by a combination of X‐ray crystallography, magnetic and photomagnetic measurements, and Mössbauer and optical absorption spectroscopy. Complex 1 exhibits a gradual spin crossover (SCO) with T_1/2=190 K, whereas 2 exhibits an abrupt SCO with approximately 7 K thermal hysteresis (T_1/2=196 K on cooling and 203 K on heating). Complex 3 is in the high‐spin state in the 2–300 K range. The difference in the magnetic behavior was traced to differences between the inter‐ and intramolecular interactions in 1 and 2 . The crystal packing of 2 features a hierarchy of intermolecular interactions that result in increased cooperativity and abruptness of the spin transition. In 3 , steric repulsion between H atoms of one of the pyridyl substituents of TPMA and one of the benzene rings of XBBIM results in a strong distortion of the Fe^II coordination environment, which stabilizes the high‐spin state of the complex. Both 1 and 2 exhibit a photoinduced low‐spin to high‐spin transition (LIESST effect) at 5 K. The difference in the character of intermolecular interactions of 1 and 2 also manifests in the kinetics of the decay of the photoinduced high‐spin state. For 1 , the decay rate constant follows the single‐exponential law, whereas for 2 it is a stretched exponential, reflecting the hierarchical nature of intermolecular contacts. The structural parameters of the photoinduced high‐spin state at 50 K are similar to those determined for the high‐spin state at 295 K. This study shows that N‐alkylation of BIM has a negligible effect on the ligand field strength. Therefore, the combination of TPMA and BIM offers a promising ligand platform for the design of functionalized SCO complexes.     

Synthesis of panchromatic Ru(II) thienyl-dipyrrin complexes and evaluation of their light-harvesting capacity

Ru(II) complexes with 5-(3-thienyl)-4,6-dipyrrin (3-TDP), containing 2,2'-bipyridine (bpy) or 4,4'-bis(methoxycarbonyl)-2,2'-bipyridine (dcmb) as coligands, have been prepared and extensively characterized. Crystal structure determination of [Ru(bpy)(2)(3-TDP)]PF(6) (1a) and [Ru(bpy)(3-TDP)(2)] (2) reveals that the 3-thienyl substituent is rotated with respect to the plane of the dipyrrinato moiety. These complexes, as well as [Ru(dcmb)(2)(3-TDP)]PF(6) (1b), act as panchromatic light absorbers in the visible range, with two strong absorption bands observable in each case. A comparison to known Ru(II) complexes and quantum-chemical calculations at the density functional theory (DFT) level indicate that the lower-energy band is due to metal-to-ligand charge transfer (MLCT) excitation, although the frontier occupied metal-based molecular orbitals (MOs) contain significant contributions from the 3-TDP moiety. The higher energy band is assigned to the π-π* transition of the 3-TDP ligand. Each complex exhibits an easily accessible one-electron oxidation. According to DFT calculations and spectroelectrochemical experiments, the first oxidation takes place at the Ru(II) center in 1a, but is shifted to the 3-TDP ligand in 1b. An analysis of MO energy diagrams suggests that complex 1b has potential to be used for light harvesting in the dye-sensitized (Gr?tzel) solar cell.     

Heptabismuthate [Bi7I24]3–: a main group element anderson-type structure and its relationships with the polyoxometalates

We describe the unique structural and electronic arrangement in the heptanuclear polyiodobismuthate [Bi(7)I(24)](3-) which displays striking similarities with the Anderson-type structures found in polyoxometalates. This main group element anion is part of the complex [Bi(OAc)(2)(thf)(4)](3)[Bi(7)I(24)] (1) which has been characterized by X-ray crystallography. We investigated the structure, stability, and bonding of [Bi(7)I(24)](3-) using relativistic dispersion-corrected density functional theory in combination with a quantitative energy decomposition and electron localization function analysis in order to better understand the main features of this isopolyanion. A comparative analysis of the properties of [Bi(7)I(24)](3-) and previously reported high-nuclearity [Bi(n)X(3n+m)](m-) anions, in the gas phase and in solution, has been performed, in the latter case to track the macroscopic solvent effects. [Bi(7)I(24)](3-) is the largest building block in the class of trianionic iodobismuthates and the sole heptanuclear framework in the family of iodobismuthates.     

Assessment of Subgrid-Scale Models for Decaying Compressible MHD Turbulence

Large eddy simulation method is formulated for study of compressible magnetohydrodynamic turbulence and assessment of different subgrid-scale models as applied for decaying case is performed. The filtered equations of compressible magnetopause using the mass-weighted filtering operation are obtained. Mass-weighted filtered equations for large-scale turbulent component comprise subgrid-scale terms and five models for closure of the subgrid-scale terms are suggested. In present paper the obtained results of numerical computations for large eddy simulation are compared with the results of direct numerical simulation of three-dimensional compressible magnetohydrodynamic turbulence. Assessment of five subgrid-scale models of large eddy simulation for MHD flows is fulfilled. The comparisons between large eddy simulation and direct numerical simulation are carried out regarding the temporal evolution of the global quantities kinetic and magnetic energy, cross helicity and the spectra of kinetic and magnetic energy.