双核磺化酞菁铜(Ⅱ)催化氧化α-萘酚

本文研究了以乙醇为溶剂,CaCl_2为助催化剂,双核磺化酞菁铜(Ⅱ)催化氧化α-萘酚制备α-萘醌的各种因素。提出了可能的反应机理。     

Investigation on relation between TL and OSL of Li2B4O7:Cu, In

Polycrystal Li₂B₄O₇ (LBO) doped with Cu and In was prepared and then sintered at different temperatures. X-ray diffraction (XRD) was applied to get the parameters of the LBO structure, thermoluminescence (TL) and optically stimulated luminescence (OSL) were measured, and a second-order exponential decay model was fitted to the OSL decay curves. The results indicate that the original number of OSL traps that have captured electroncs is linearly related with the sum of TL decay during the OSL process. Mean decay constant of OSL is related to the sintered temperature. The possible reason is that the sintered temperature affects the crystal sizes of the polycrystal, and consequently affects the stimulating lights’s intensity and the photoionization cross-section of the electrons, which have been captured by the traps. __________ Translated from Acta Scientiarum Naturalium Universitatis Sunyatseni, 2005, 44(4) (in Chinese)     

Separation and determination of protocatechuic aldehyde and protocatechuic acid in Salivia miltorrhrza by capillary electrophoresis with amperometric detection

Capillary electrophoresis with amperometric detection was applied to separate and determine protocatechuic aldehyde and protocatechuic acid in Salivia miltorrhrza preparations. The electrode used was a 0.3 mm diameter carbon disk electrode fixed in a wall-jet with amperometric detection. Under the optimum conditions, the two analytes were separated completely within 8 min. Excellent linearity was obtained in the concentration ranges of 0.25-100.0 microg ml(-1) and 0.50-100.0 microg ml(-1) for protocatechuic aldehyde and protocatechuic acid, respectively. The detection limits were 0.10 microg ml(-1) of protocatechuic aldehyde and 0.25 microg ml(-1) of protocatechuic acid, which were found to be lower than those of other methods that determine protocatechuic aldehyde (3,4-dihydroxybenzaldehyde) and protocatechuic acid (3,4-dihydrobenzoic acid) simultaneously. The mean recoveries of protocatechuic aldehyde and protocatechuic acid were 97.4% and 103.3%. This method has been successfully applied to monitor these two components in real samples such as Salivia miltorrhrza and its two traditional Chinese medicinal preparations.     

Aqueous two-phase extraction as an effective tool for isolation of geniposide from gardenia fruit

Natural products are normally obtained by organic solvent extraction and many subsequent chromatographic separations. Compounds of interest are often isolated with very low yield and limited purity. An aqueous two-phase extraction process combined with a simple ethanol treatment, for removing excess inorganic salt, has been developed for preparation of geniposide from gardenia. The system was comprised of PE62, a random copolymer composed of 20% ethylene oxide and 80% propylene oxide, KH2PO4 and ethanol. To find optimal conditions, the partition behavior of geniposide under an aqueous two-phase system was investigated. Various factors were considered, including the concentration of salt, the concentration of polymer, the sample loading, and the addition of ethanol. The experimental results demonstrated that increasing salt concentration or decreasing PE62 concentration results in enhancement of the geniposide partition in the salt-rich phase. The addition of ethanol and higher sample loading also promoted the partition efficiency of geniposide. Based on this study, an optimized system containing 5% PE62, 7.5% KH2PO4, and 10% ethanol was tested on a large-scale extraction. A 39.0-g aliquot of final product (in powder form) with 77% purity of geniposide can be effectively extracted from 500 g of gardenia fruit. This process is proved to be useful for industrial application of geniposide preparation.     

A copper- and amine-free sonogashira reaction employing aminophosphines as ligands

An efficient Pd-catalyzed Sonogashira coupling reaction was achieved in the absence of a copper salt or amine with an inorganic base and easily prepared, air-stable aminophosphine ligands in commonly used organic solvents; good to excellent yields were obtained. Under optimized reaction conditions, the Sonogashira coupling reaction occurred selectively when an enyne substrate was employed and no Heck reaction product was detected; acetone-masked acetylene and trimethylsilylacetylene can also be efficiently coupled, providing a method to make terminal alkynes.     

Over 18% binary organic solar cells enabled by isomerization of non-fullerene acceptors with alkylthiophene side chains

Side-chain engineering has been demonstrated as an effective method for fine-tuning the optical, electrical, and morphological properties of organic semiconductors toward efficient organic solar cells (OSCs). In this work, three isomeric non-fullerene small molecule acceptors (SMAs), named BTP-4F-T2C8, BTP-4F-T2EH and BTP-4F-T3EH, with linear and branched alkyl chains substituted on the α or β positions of thiophene as the side chains, were synthesized and systematically investigated. The results demonstrate that the size and substitution position of alkyl side chains can greatly affect the electronic properties, molecular packing as well as crystallinity of the SMAs. After blending with donor polymer D18-Cl, the prominent device performance of 18.25% was achieved by the BTP-4F-T3EH-based solar cells, which is higher than those of the BTP-4F-T2EH-based (17.41%) and BTP-4F-T2C8-based (15.92%) ones. The enhanced performance of the BTP-4F-T3EH-based devices is attributed to its stronger crystallinity, higher electron mobility, suppressed biomolecular recombination, and the appropriate intermolecular interaction with the donor polymer. This work reveals that the side chain isomerization strategy can be a practical way in tuning the molecular packing and blend morphology for improving the performance of organic solar cells.

     

人γ晶体蛋白的一级结构测定 1.γ晶体蛋白的分离提纯及其顺序测定方法(GC/MS法)的研究

成功地从人眼晶体中分离出单纯组分的γ晶体蛋白,对γ晶体蛋白的纯度、相对分子质量、氨基酸组成、N末端氨基酸组成等进行了测定,利用酸水解法和酶解法对γ晶体蛋白进行了水解和酶解条件的摸索、找出了使γ晶体蛋白断裂成适合于GC/MS联用仪进行结构测定的肽段的裂解条件。对进行氨基酸顺序测定的GC/MS法化学衍生化条件作了一系列的摸索,找出了化学衍生化的合适条件。对衍生化过程中的一些影响因素也进行了探讨。     

丙烯腈水相沉淀聚合研究进展

结合近几年的研究成果,笔者对丙烯腈水相沉淀聚合机理、聚合动力学、动力学数学模型诸方面问题进行了系统的综述,反映了该领域的研究概况和最新研究成果.     

RNA Methylation m6A: A New Code and Drug Target?

The m⁶A‐RNA modification is a dynamic and reversible process, which has emerged as a new RNA code for the regulation of gene expression. The functional network of methyltransferases (writers), demethylases (erasers), and binding proteins (readers) modulate the level of m⁶A modification. Dysfunction of RNA methylation has been associated with various fundamental biological processes and human diseases. Herein, we briefly introduce an understanding‐enabled manipulation on m⁶A‐RNA modification with an emphasis on the use of small‐molecule intervention.      

Solid-state synthesis of a conducting polythiophene via an unprecedented heterocyclic coupling reaction

Prolonged storage ( approximately 2 years) or gentle heating (50-80 degrees C) of crystalline 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) affords a highly conducting, bromine-doped poly(3,4-ethylenedioxythiophene) (PEDOT), as confirmed by solid-state NMR, FTIR, CV, and vis-NIR spectroscopies. The novel solid-state polymerization (SSP) does not occur for 2,5-dichloro-3,4-ethylenedioxythiophene (DCEDOT), and requires a much higher temperature (>130 degrees C) for 2,5-diiodo-3,4-ethylenedioxythiophene (DIEDOT). X-ray structural analysis of the above dihalothiophenes reveals short Hal.Hal distances between adjacent molecules in DBEDOT and DIEDOT, but not in DCEDOT. The polymerization may also occur in the melt but is significantly slower and leads to poorly conductive material. Detailed studies of the reaction were performed using ESR, DSC, microscopy, and gravimetric analyses. SSP starts on crystal defect sites; it is exothermic by 14 kcal/mol and requires activation energy of approximately 26 kcal/mol (for DBEDOT). The temperature dependence of the conductivity of SSP-PEDOT (sigma(rt) = 20-80 S/cm) reveals a slight thermal activation. It can be further increased by a factor of 2 by doping with iodine. Using this approach, thin films of PEDOT with conductivity as high as 20 S/cm were fabricated on insulating flexible plastic surfaces.