羧基膦－钯－酸体系催化烯烃氢酯基化反应

以钯－膦－酸体系催化烯烃氢酯基化的反应日显重要，而膦配体是决定此反应的重要因素，用二苯基膦乙酸（ＤＰＡ）为配体的钯催化剂体系，对烯烃的氢酯基化反应作了研究。对影响反应的各种因素如反应温度、反应压力、不同的溶剂、膦配体及酸助剂的量等作了考察，发现此配体对烯烃的区域选择性有改善。并用此催化体系对不同结构的烯烃进行了研究，发现有如下的活性顺序：环烯烃＞直链端烯＞直链内烯。     

Triterpenoid Saponins from Schefflera arboricola

Four new triterpenoid saponins, named scheffarboside A – D ( 1 – 4 ), along with five known saponins were isolated from the stems of Schefflera arboricola. The structures of the four new saponins were determined as 3‐O‐(O‐β‐glucuronopyranosyl‐(1 → 3)‐O‐α‐rhamnopyranosyl‐(1 → 2)‐α‐arabinopyranosyl)oleanolic acid ( 1 ), 3‐O‐(O‐α‐arabinopyranosyl‐(1 → 4)‐O‐α‐arabinopyranosyl‐(1 → 3)‐O‐α‐rhamnopyranosyl‐(1 → 2)‐α‐arabinopyranosyl)oleanolic acid ( 2 ), 3‐O‐(O‐α‐arabinopyranosyl‐(1 → 4)‐O‐α‐arabinopyranosyl‐(1 → 3)‐O‐α‐rhamnopyranosyl‐(1 → 2)‐α‐arabinopyranosyl)hederagenin ( 3 ), 3‐O‐(O‐α‐arabinopyranosyl‐(1 → 4)‐O‐α‐arabinopyranosyl‐(1 → 3)‐O‐α‐rhamnopyranosyl‐(1 → 2)‐α‐arabinopyranosyl)oleanolic acid O‐α‐rhamnopyranosyl‐(1 → 4)‐O‐β‐glucopyranosyl‐(1 → 6)‐β‐glucopyranosylester ( 4 ), respectively, on the basis of spectroscopic and chemical degradation methods.     

树脂吸附法处理3,6-二氯水杨酸生产废水

研究了树脂吸附法处理3,6-二氯水杨酸生产废水的工艺过程。结果表明,NDA-77吸附树脂对该废水具有良好的吸附-脱附效果。经树脂吸附处理,废水中主要有机污染物2,5-二氯苯酚和3,6-二氯水杨酸均得到去除,总有机碳(TOC)由210mg/L降为20mg/L以下,吸附饱和的树脂可采用稀碱液实现完全再生。经吸附处理去除有机物后,废水中含有20%的KCl,可进入工厂现有的KCl隔膜电解装置,用于KOH的生产。     

Novel CaCO3/g-C3N4 composites with enhanced charge separation and photocatalytic activity

A novel CaCO₃/graphitic carbon nitride (g-C₃N₄) photocatalyst was synthesized for the first time via a facile calcination method using CaCO₃ and melamine as precursors. The as-prepared samples were characterized using various techniques, such as scanning and transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller analysis, as well as Fourier-transform infrared, X-ray photoelectron, photoluminescence, and UV–vis diffuse reflectance spectroscopy. The results of the experiments confirm the successful coupling of CaCO₃ to g-C₃N₄. The photocatalytic activity of the synthesized CaCO₃/g-C₃N₄ composites was evaluated by assessing their performance in the photocatalytic degradation of crystal violet (CV) in water under visible light irradiation. The analysis shows that CaCO₃/g-C₃N₄ exhibits higher photocatalytic activity towards CV degradation (76.0%) than pristine g-C₃N₄ (21.6%) and CaCO₃ (23.2%). Radical trapping and electron spin resonance experiments show that hydroxyl radicals (OH) and holes (h⁺) are the key reactive species in the photocatalytic process. The enhanced photocatalytic activity of the composite is mainly attributed to the efficient separation rate of electron-hole pairs achieved through the incorporation of CaCO₃.     

Immobilization of a Monolayer of Bovine Serum Albumin on Gold Nanoparticles for Stereo‐specified Recognition of Dansyl‐norvaline

The assembly strategy to prepare a monolayer of bovine serum albumin on the surface of silica gel supported gold nanoparticles is described. The stereo‐specific recognition ability of this material was evaluated by enantioresolution of Dansyl‐norvaline. For enantiomeric separation, the influences of buffer concentration and the concentration of organic modifier on the separation performance were investigated. A better separation in terms of enantioresolution and peak shape was found with the phosphate concentration at 30 mM. Moreover, the peak shape and resolution can be improved by the addition of methanol solution. Enantioresolution of Dansyl‐norvaline was obtained from this material at optimized conditions. It appears that the immobilization of a monolayer of bovine serum albumin on gold nanoparticles as the chiral selector of Dansyl‐derivative amino acid is promising.     

Single-molecule nanopore sensing of actin dynamics and drug binding

Actin is a key protein in the dynamic processes within the eukaryotic cell. To date, methods exploring the molecular state of actin are limited to insights gained from structural approaches, providing a snapshot of protein folding, or methods that require chemical modifications compromising actin monomer thermostability. Nanopore sensing permits label-free investigation of native proteins and is ideally suited to study proteins such as actin that require specialised buffers and cofactors. Using nanopores, we determined the state of actin at the macromolecular level (filamentous or globular) and in its monomeric form bound to inhibitors. We revealed urea-dependent and voltage-dependent transitional states and observed the unfolding process within which sub-populations of transient actin oligomers are visible. We detected, in real-time, filament-growth, and drug-binding at the single-molecule level demonstrating the promise of nanopore sensing for in-depth understanding of protein folding landscapes and for drug discovery.

Nanopipettes were used for real-time investigation into actin dynamics and drug binding at single-molecule resolution, showing promise for a better understanding of the mechanism of protein–protein interactions and drug discovery.     

四元交互体系Li+, Mg2+/SO42-, B4O72-—H2O25℃溶解度和溶液物化性质的研究

研究了Li⁺,Mg²+/SO₄^2-,B₄O₇^2-—H₂O四元交互体系25℃时的溶解度和溶液的密度及折光率.四种原始组份未发生脱水作用,体系中也没有复盐或固溶体形成.体系25℃溶解度等温线由五段组成,有四个结晶区,分别对应于四种原始组份,其中以MgB₄O₇·9H₂O的结晶区最大.溶解度等温线上有两个零变量点,其一为MgB₄O₇·9H₂O,MgSO₄·7H₂O,Li₂SO₄·H₂O三盐共饱点,另一为MgB₄O₇·9H₂O,Li₂B₄O₇·3H₂O,Li₂SO₄·H₂O三盐不相称共饱点.     

Electronic structure and intrinsic redox properties of [2Fe-2S]+ clusters with tri- and tetracoordinate iron sites

Using potentially bidentate ligands (-SC2H4NH2), we produced [2Fe-2S]+ species of different coordination geometries by fission of [4Fe-4S]2+ complexes. Even though the ligands are monodentate in the cubane complexes, both mono- and bidentate complexes were observed in the [2Fe] fission products through self-assembly because of the high reactivity of the tricoordinate iron sites. The electronic structure of the [2Fe] species was probed using photoelectron spectroscopy and density functional calculations. It was found that tetracoordination significantly decreases the electron binding energies of the [2Fe] complexes, thus increasing the reducing capability of the [2Fe-2S]+ clusters.     

Comparative analysis of blue‐shifted hydrogen bond versus conventional hydrogen bond in methyl radical complexes

Methyl radical complexes H₃C…HCN and H₃C…HNC have been investigated at the UMP2(full)/aug‐cc‐pVTZ level to elucidate the nature of hydrogen bonds. To better understand the intermolecular H‐bond interactions, topological analysis of electron density at bond critical points (BCP) is executed using Bader's atoms‐in‐molecules (AIM) theory. Natural bond orbital (NBO) analysis has also been performed to study the orbital interactions and change of hybridization. Theoretical calculations show that there is no essential difference between the blue‐shift H‐bond and the conventional one. In H₃C…HNC complex, rehybridization is responsible for shortening of the N? H bond. The hyperconjugative interaction between the single electron of the methyl radical and N? H antibonding orbital is up to 7.0 kcal/mol, exceeding 3.0 kcal/mol, the upper limit of hyperconjugative n(Y)→σ*(X–H) interaction to form the blue‐shifted H‐bond according to Alabugin's theory. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Direct evidence of oxidized gold on supported gold catalysts

Supported gold catalysts have drawn worldwide interest due to the novel properties and potential applications in industries. However, the origin of the catalytic activity in gold nanoparticles is still not well understood. In this study, time-of-flight secondary ion mass spectroscopy (TOF-SIMS) has been applied to investigate the nature of gold in Au (1.3 wt %)/gamma-Al2O3 and Au (2.8 wt %)/TiO2 catalysts prepared by the deposition-precipitation method. The SIMS spectrum of the supported gold catalysts presented AuO-, AuO2-, and AuOH- ion clusters. These measurements show direct evidence for oxidized gold on supported gold catalysts and may be helpful to gaining better understanding of the origin of the catalytic activity.