I_2-KIO_3-AcOH-H_2O体系氧化3,5-环-24S-乙基-胆甾-22烯-6-酮反应的研究

油莱甾醇内酯(Brassinolide)(1)是一种高效的植物生长激素,其生理活性与侧链中C_(22)、C_(23)的构型密切相关。当C_(22)、C_(23)为S、S构型时,其活性仅为1的十分之一。在1的     

一类新的4-取代胂酸型变色酸偶氮多卤显色剂的合成及其与稀土元素显色反应的研究

本文研究了五个结构新颖的显色剂与稀土元素的显色反应。其中的二溴羧基偶氮氯肿(CAsA-DBK)与稀土元素反应具有对比度大、灵敏度高、选择性好等优点。在0.6mol/LHClO_4介质中,不加任何掩蔽剂条件下,只与铈组稀土显色,与钇组稀土几乎不显色,是一个较有特色的铈组稀土试剂。     

Synthesis and characterization of organophosphoryl polyoxotungstates [RP(O)]2X n+W11O39 (8−n)− (X n+ = P5+, Si4+, Ge4+, Ga3+)

In the presence of n-Bu₄NBr acting as phase-transfer reagent, n-Bu₄N⁺ salts of organophosphoryl polyoxotungstate derivatives [RP(O)]₂X ⁿ⁺W₁₁O₃₉ ^(8–n)– [R = PhCH₂CH₂P(O), X = P, Si; R = C₆H₁₁P(O); X = Ge, Ga] have been prepared and characterized by elemental analysis, i.r., ³¹P- and ¹⁸³W-n.m.r. spectroscopy. According to the elemental analysis and spectroscopic data, the hybrid anions consist of an -[XW₁₁O₃₉] framework on which are grafted two equivalent organophosphoryl groups through P—O—W bridges; these new species still retain the Keggin structure. The six-line ¹⁸³W spectrum indicates that hybrid anions possess C _s symmetry in MeCN.     

Synthesis,characterization, and theoretical studies of group 4 amido hydrotris(pyrazolyl)borate complexes

Titanium and zirconium amido complexes containing a hydrotris(pyrazolyl)borate (Tp) or hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) ligand TpM(NMe(2))(3) (M = Ti, 1; M = Zr, 2) and Tp*M(NMe(2))(3) (M = Ti, 3; M = Zr, 4) were prepared by the reactions of M(NMe(2))(3)Cl (M = Ti, Zr) with sodium hydridotris(pyrazol-1-yl)borate and potassium hydridotris(3,5-dimethylpyrazol-1-yl)borate, respectively. The structures of 1, 2, and 4.CH(2)Cl(2) were determined by X-ray diffraction and show octahedral coordination geometry around the metal centers. Density functional theory calculations at the B3PW91 level were performed to understand the orientations and the rotational behavior of amido ligands in these metal complexes.     

Study on the new fluorescence enhancement system of Tb-1,10-bis(2′-carboxylphenyl)-1,4,7,10-tetraoxadecane in silver chloride collosol and its analytical application

A new salicylic-based open-chain crown ether ligand, 1,10-bis(2′-carboxylphenyl)-1,4,7,10-tetraoxadecane (BCPTD) was synthesized. Solutions of its complex with Tb³⁺ can emit the intrinsic fluorescence of Tb³⁺. The fluorescence intensity of the complex in KCl solution was enhanced by the addition of silver(I), leading to a new fluorescence enhancement phenomenon. The spectrofluorimetric determination of traces of silver(I) based on the above phenomenon was carried out. The excitation and emission wavelengths are 298 and 545 nm, respectively. Under optimal conditions, the differential value of fluorescence intensity in the absence and presence of Ag⁺ was proportional to the concentration of silver(I) in the range 0.5-20 μg ml⁻¹. The method was applied to the determination of silver(I) in a standard ore sample. The analytical performance is investigated in detail by using common aromatic carboxylic acids or synthetic analogues of BCPTD as ligands to replace BCPTD. It was found that Tb-aromatic acid complexes did not result in fluorescence enhancement of Tb³⁺ in AgCl collosol. The phenomenon was only observed in Tb(III) with BCPTD or its open-chain crown ether analogues solutions.In addition, the enhancement of the fluorescence intensity of terbium(III) in these complexes depends on the extent of formation of the AgCl collosol.     

Direct dynamics trajectory study of the reaction of formaldehyde cation with D2: vibrational and zero-point energy effects on quasiclassical trajectories

Quasiclassical, direct dynamics trajectories have been used to study the reaction of formaldehyde cation with molecular hydrogen, simulating the conditions in an experimental study of H2CO+ vibrational effects on this reaction. Effects of five different H2CO+ modes were probed, and we also examined different approaches to treating zero-point energy in quasiclassical trajectories. The calculated absolute cross-sections are in excellent agreement with experiments, and the results provide insight into the reaction mechanism, product scattering behavior, and energy disposal, and how they vary with impact parameter and reactant state. The reaction is sharply orientation-dependent, even at high collision energies, and both trajectories and experiment find that H2CO+ vibration inhibits reaction. On the other hand, the trajectories do not reproduce the anomalously strong effect of nu2(+) (the CO stretch). The origin of the discrepancy and approaches for minimizing such problems in quasiclassical trajectories are discussed.     

Concise Synthesis and Antimicrobial Activities of New Substituted 5‐Isoxazolpenicillins

The synthesis of a series of new 5‐isoxazolpenicillins is described, which were obtained by coupling substituted isoxazoles with 6‐APA. Concise large‐scale synthesis of 3,5‐disubstituted isoxazoles by 1,3‐dipolar cycloaddition using copper(I) as catalyst was also investigated. Representative compounds were assayed for antimicrobial activities, showing satisfactory antimicrobial activities against Gram‐negative bacteria.     

Fluorometric investigation of the interaction of bovine serum albumin with surfactants and 6-mercaptopurine

Fluorescence quenching in solutions of bovine serum albumin has been investigated in the presence of 6-mercaptopurine and ionic surfactants. Spectroscopic analysis of the emission quenching at different temperatures revealed that the quenching mechanism of bovine serum albumin by 6-mercaptopurine was dynamic quenching mechanism. The Stern–Volmer quenching model has been successfully applied, and the activation energy of the interaction between 6-mercaptopurine and bovine serum albumin as much as 4.26 kJ mol⁻¹ was calculated. The distance r between donor (bovine serum albumin) and acceptor (6-mercaptopurine) was obtained according to fluorescence resonance energy transfer (FRET). The result of synchronous fluorescence spectra shows that the conformation of bovine serum albumin has been changed at the present of 6-mercaptopurine.     

Synthesis of silk-like FeS2/NiS2 hybrid nanocrystals with improved reversible oxygen catalytic performance in a Zn-air battery

The development of highly active and stable reversible oxygen electrocatalysts is crucial for improving the efficiency of metal-air battery devices. Herein, an efficient liquid exfoliation strategy was designed for producing silk-like FeS₂/NiS₂ hybrid nanocrystals with enhanced reversible oxygen catalytic performance that displayed excellent properties for Zn-air batteries. Because of the unique silk-like morphology and interface nanocrystal structure, they can catalyze the oxygen evolution reaction (OER) efficiently with a low overpotential of 233 mV at j = 10 mA cm^?2. This is an improvement from the recently reported catalysts in 1.0 M KOH. Meanwhile, the oxygen reduction reaction (ORR) activity of the silk-like FeS₂/NiS₂ hybrid nanocrystals showed an onset potential of 911 mV and a half-wave potential of 640 mV. In addition, the reversible oxygen electrode activity of the silk-like FeS₂/NiS₂ hybrid nanocrystals was calculated to be 0.823 V, based on the potential of the OER and ORR. Further, the homemade rechargeable Zn-air batteries using FeS₂/NiS₂ hybrid nanocrystals as the air-cathode displayed a high open-circuit voltage of 1.25 V for more than 17 h and an excellent rechargeable performance for 25 h. The solid Zn-air batteries exhibited an excellent rechargeable performance for 15 h. This study provided a new method for designing interface nanocrystals with a unique morphology for efficient multifunctional electrocatalysts in electrochemical reactions and renewable energy devices.     

Structural mining: self-consistent design on flexible protein-peptide docking and transferable binding affinity potential

A flexible protein-peptide docking method has been designed to consider not only ligand flexibility but also the flexibility of the protein. The method is based on a Monte Carlo annealing process. Simulations with a distance root-mean-square (dRMS) virtual energy function revealed that the flexibility of protein side chains was as important as ligand flexibility for successful protein-peptide docking. On the basis of mean field theory, a transferable potential was designed to evaluate distance-dependent protein-ligand interactions and atomic solvation energies. The potential parameters were developed using a self-consistent process based on only 10 known complex structures. The effectiveness of each intermediate potential was judged on the basis of a Z score, approximating the gap between the energy of the native complex and the average energy of a decoy set. The Z score was determined using experimentally determined native structures and decoys generated by docking with the intermediate potentials. Using 6600 generated decoys and the Z score optimization criterion proposed in this work, the developed potential yielded an acceptable correlation of R(2) = 0.77, with binding free energies determined for known MHC I complexes (Class I Major Histocompatibility protein HLA-A(*)0201) which were not present in the training set. Test docking on 25 complexes further revealed a significant correlation between energy and dRMS, important for identifying native-like conformations. The near-native structures always belonged to one of the conformational classes with lower predicted binding energy. The lowest energy docked conformations are generally associated with near-native conformations, less than 3.0 Angstrom dRMS (and in many cases less than 1.0 Angstrom) from the experimentally determined structures.