新的不对称双Schiff碱镍配合物

乙二胺中2个氨基具有相同的反应活性,易同时反应形成对称的双Schiff碱,随着不对称配合物的设计和金属酶模型化合物的不断开发,业已发现严格控制反应条件和改变反应物摩尔比,可以有效地实现单个氨基的选择性反应,例如,在低温、稀的反应液中,乙酰丙     

链状[NH3CH2CH2NH3]AgAsS4的溶剂热合成及表征

利用溶剂热方法合成了链状[NH3CH2CH2NH3]AgAsS4,通过单晶X射线衍射技术对其进行了晶体结构分析,该化合物晶体属单斜晶系,空间群C2/c,晶胞参数a=1.35805(8)nm,b=0.65331(3)nm,c=2.27711(9)nm,β=106.42(3)°,Z=8.化合物具有有趣的梯子状双链结构,该阴离子链由AsS4与AgS3共用顶点交替连接而成,有机阳离子在阴离子链之间存在较强的N—H…S氢键.DSC和Tg分析结果表明化合物在200℃以下是稳定的.     

Vapor pressure measurement for water,methanol, ethanol,and their binary mixtures in the presence of an ionic liquid 1-ethyl-3-methylimidazolium dimethylphosphate

Vapor pressure data were measured for water, methanol and ethanol as well as their binary mixtures with an ionic liquid (IL) 1-ethyl-3-methylimidazolium dimethylphosphate ([EMIM][DMP]) at varying temperature and IL-content ranging from mass fraction of 0.10–0.70 by a quasi-static method. The vapor pressure data for the IL-containing binary systems were correlated using NRTL equation with average absolute relative deviation (ARD) within 0.0076, and the binary NRTL parameters was used for predicting the vapor pressure of the IL-containing ternary systems with reasonable accuracy. In addition, the infinite activity coefficients of solvents in [EMIM][DMP] and isobaric vapor–liquid equilibrium for IL-containing ternary systems at 101.325 kPa and mass fraction of IL being 0.5 were predicted with the regressed NRTL parameters. The results indicate that ionic liquid [EMIM][DMP] can depress the volatility of the solvents of water, methanol and ethanol but to a varying degree, leading to the variation of relative volatility of a solvent and even removal of azeotrope for water–ethanol mixture.     

手性配体的空间结构与产物对映选择性的关系

首次采用4－烷氧羰基噻唑烷、E唑烷作为手性配体，诱导烷基锌对醛类的亲核加成反应，获得产物是烷基化的醛，最高达90％ee，产率98％的（S）－二级醇。系统地考察了该类手性配体三维空间结构变化与产物对映选择性的关系，当配体4－位烷氧羰基上的R、2－位R′基和环体上原子X发生变化时都会引起产物（S）－二 级醇的对映选择性发生规律性变化。对五种不同结构的底物醛在同一手性配体催化下，诱导烷基锌对醛类的亲核加成反应，底物结构变化也会引起（S）－二级醇对映选择性变化。     

Light- and temperature-assisted spin state annealing: accessing the hidden multistability

Among responsive multistable materials, spin crossover (SCO) systems are of particular interest for stabilizing multiple spin states with various stimulus inputs and physical outputs. Here, in a 2D Hofmann-type coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂] (isoq = isoquinoline), a medium-temperature annealing process is introduced after light/temperature stimulation, which accesses the hidden multistability of the spin state. With the combined effort of magnetic, crystallographic and Mössbauer spectral investigation, these distinct spin states are identified and the light- and temperature-assisted transition pathways are clarified. Such excitation-relaxation and trapping-relaxation joint mechanisms, as ingenious interplays between the kinetic and thermodynamic effects, uncover hidden possibilities for the discovery of multistable materials and the development of multistate intelligent devices.

Two new two-stage manipulation protocols, namely light- and temperature-assisted spin state annealing (LASSA/TASSA), are applied to a spin crossover coordination polymer, [Fe(isoq)₂{Au(CN)₂}₂], revealing the hidden multistability of spin states.     

Two salts of 5‐sulfosalicylic acid and 3‐aminopyridine

5‐Sulfosalicylic acid (5‐SSA) and 3‐aminopyridine (3‐APy) crystallize in the same solvent system, resulting in two kinds of 1:1 proton‐transfer organic adduct, namely 3‐aminopyridinium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, C₅H₇N₂⁺·C₇H₅O₆S⁻·H₂O or 3‐APy·5‐SSA·H₂O, (I), and the anhydrous adduct, C₅H₇N₂⁺·C₇H₅O₆S⁻ or 3‐APy·5‐SSA, (II). Both compounds have extensively hydrogen‐bonded three‐dimensional layered polymer structures, with interlayer homo‐ and heterogeneous π–π interactions in (I) and (II), respectively.     

Antidepressant-like effect of triterpenoids extracts from Poria cocos on the CUMS rats by 16S rRNA gene sequencing and LC–MS metabolomics

Abstract

Poria cocos is an edible medicinal mushroom with the effects of inducing diuresis, excreting dampness, invigorating the spleen and tranquilizing the mind. The triterpenoids of Poria cocos as the main active ingredients have shown health benefits of the central nervous system of the human body. Accordingly, this study aimed at further understanding the antidepressant-like effect and a potential mechanism of the triterpenoids extracts from Poria cocos (TPC). As a result, the TPC significantly ameliorated depression-like behaviors on chronic unpredictable mild stress (CUMS) rats, and restored the levels of brain-derived neurotrophic factor and nerve growth factor in the hippocampus of rats. Gut microiota analysis revealed that TPC could increase the biodiversity and markedly regulate the relative abundance of [Prevotella], Allobaculum and Ochrobactrum of CUMS rats. The cecal contents metabolomics pointed to thirteen biomarkers associated with TPC antidepressant effect, which involved in primary bile acid biosynthesis, taurine and hypotaurine metabolism, arginine and proline metabolism. Correlation analysis further showed that there was a strong correlation relationship between the gut microbiota and the cecal contents metabolites, especially compounds involved in energy metabolism, inflammation and immunity. In conclusion, TPC showed a potential antidepressant effect, which was possibly mediated the gut microbiota and cecal contents metabolism.     

Ru-Catalyzed asymmetric hydrogenation of alpha-ketoesters with CeCl3.7H2O as additive

[reaction: see text] An efficient asymmetric hydrogenation of alpha-ketoesters is reported with use of a catalyst prepared from [Ru((S)-3)(benzene)Cl]Cl and CeCl(3).7H(2)O. Alpha-hydroxy esters are obtained in up to 96% ee. The addition of CeCl(3).7H(2)O not only improves the enantioselectivity, but also enhances the stability of the catalyst. As a result, the hydrogenation of methyl benzoylformate affords the product with 92% ee with a substrate/catalyst ratio of 10 000. Hydrolysis of 2 provides the final compound with 83% yield at 99% ee after a single recrystallization from 1,2-dichloroethylene.     

Synthesis and screening of a molecularly imprinted polymer library targeted for penicillin G

A library of molecularly imprinted polymers (MIPs) was synthesized by radical bulk polymerization using the beta-lactam antibiotic penicillin G as the template. Diversity of the library was obtained by combining various functionalized monomers and cross-linkers and by varying the stoichiometry and the concentration of the components in the prepolymerization mixtures. The library was screened for selectivity to penicillin G by a radioligand binding assay and was compared to a corresponding control library. The best MIP candidate, showing the highest selectivity for penicillin G, was prepared from methacrylic acid and trimethylolpropane trimethacrylate as the functionalized monomer and cross-linker, respectively. Cross-reactivity studies with other beta-lactam antibiotics showed a low cross-reactivity of penicillin V (15%), ampicillin (16%), and amoxicillin (19%). Nafcillin and oxacillin showed less cross-reactivity (<1%). Cross-reaction with a cephalosporin antibiotic (cephapirin) and structurally nonrelated antibiotics (chloramphenicol, tetracycline, dapsone, and erythromycin) was less than 0.01%.