C NMR spectra of cyclomercurated ferrocenylimines: Substituent effects and conformations in the ferrocenes

Three series of cyclomercurated ferrocenylimines (2-chloromercurio-ferrocenylimines) have been studied using ¹³C NMR spectroscopy. Good to excellent linear relationships have been found to exist between the chemical shifts of the carbon atoms in the ferrocenyl moiety and normal Hammett substituent constants σ_m and σ_p. The δ values of the iminyl carbon atoms show excellent linear correlations with the σ values. In three series of the ferrocenes, the sensitivity of the carbon atoms to the substituent effect is different, which is discussed in terms of the twist angle between the N-phenyl ring and the C---C=N---C plane. The relative sensitivity of the chemical shifts on different positions in ferrocenyl moiety to the substituent effect has also been presented.     

环糊精-六次甲基四胺超分子络合物电化学研究及应用

在0.05 mol/L KCl底液中,β-环糊精(β-CD)-六次甲基四胺超分子络合物在2.5次微分极谱仪上于-0.78V(vs.SCE)处产生吸附还原波,峰形对称且稳定,其峰电流与六次甲基四胺浓度在4.0×10-4-1.0×10～mol/L之间呈良好线性关系;检出限为1.5×10-4mol/L。应用该法测定了有机工业产品六次甲基四胺,并与传统方法进行了比较,结果令人满意。对超分子络合物电化学性质及分子识别机理进行了探讨。     

Preparation and Characterization of Al8.31Si1.91Mg3.78O20/Al4.8Si1.2O9.6/Mg2.0Al4.02Si4.98O18 Multiphase Material

A two-step sintering method was used to prepare Al8.31Si1.91Mg3.78O20 (corundum solid solution)/Al4.8Si1.2O9.6 (mullite solid solution)/Mg2.0Al4.02Si4.98O18 (cordierite solid solution) multiphase material, for the purposes of making these three crystal structures have point defects which could help the particles diffuse and transfer at high temperature, accelerate the sintering efficiently and enhance the material strength as well as the bulk density. The impacts of different formulas on the structure and properties of the multiphase material were investigated. With XRD and SEM analyses, for each sample, the crystal structure and microstructure were characterized, the crystalline phase content and cell parameters were determined with Rietveld Quantification software, and the properties were tested. The comparative optimal formula determined was calcinated chamotte of 80wt% and calcinated sludge of 20wt%; and its corresponding bending strength and retention rate of bending strength after a thermal shock were 29.74 MPa and 80.15%, respectively.     

复方维生素B片中主要成分的高效毛细管电泳电化学法检测

采用高效毛细管电泳－电化学检测法同时测定复方维生素B片中的主要成分维生素B1，B12，B6和C的含量；研究了电极电位，运行缓冲溶液的浓度和酸度，电泳电压和进样时间等对电泳的影响，以微铂电极为工作电极，检测电位＋0．5V（vs SCE)，在pH9.0的15mmol/L Tris-1mmol/L H3BO3缓冲溶液中，上述4组分在5min内获得基线分离；维生素B1，B12，B6和C的线性范围分别为2．1mg/L-1.0g/L,6.0mg/L-0.80g/L,1.4mg/L-0.72g/L和0．97mg/L-0.44g/L检出限分别为0．50mg/L,1.0mg/L,,0.65mg/L和0．40mg/L；5次测定峰高的相对标准偏差分别为2．4％，3．0％，3．1％，和2．5％，5次测定的平均回收率分别为99％，102％，98％和100％。     

一类2(1H)-喹喔啉衍生物的电子轰击质谱分析

以邻苯二胺为原料合成表征了一类喹喔啉衍生物；1-烷基-3-甲基-2（1H）-喹喔啉-2-酮（1-alkyl-3-methly-2(1H)-quinoxalin-2-one，简称AMQ，其中alky=H、CH3、Et、n-C3H5、n-C5H11、n-C16H33)。用电子轰击电离质谱（EI-MS）和核磁共振谱图（^1H-NMR)鉴定了AMQ，研究了不同取代基对这类化合物EI-MS谱图的影响，分析得到一些裂解规律。结果表明：所有样品谱图中均有芳香化合物的特征CnHn^ 系列峰m/z78，65，52，39和（或）m/z77、76、64、63、51、50、38、37。对于末取代的样品及低级烷烃取代的样品，谱图中的基峰为分子离子峰，对于取代基中碳数大于等于3的样品。谱图中的基峰不是分子离子峰，分子离子峰强度随着碳数的增加而降低。这些样品一般容易发生骨架重排，丢失一分子CO，生成1-烷基-2-甲基苯并哒唑正离子。此外，还讨论了谱图中其它的一些碎片离子峰。这对于研究和指导喹喔啉衍生物 的合成，探讨它们在药效及结构特征与生理活性的关系等方面具有重要的应用价值和理论意义。     

高效离子交换色谱法分离皖南尖吻蝮蛇毒活性组分

采用高效离子交换色谱法对经初步分离的皖南尖吻蝮蛇毒活性成分进行进一步的分离纯化。采用线性梯度洗脱,得到蝮蛇毒活性组分纯品,并用峰面积归一化法计算其含量为４５．４１％左右,纯度在９０％以上。     

Synthesis of thermal‐stable and photo‐crosslinkable polyfluorenes for the applications of polymer light‐emitting diodes

Three polyfluorene derivatives which have oxetane‐containing phenyl group at C‐9 position were synthesized via the palladium‐catalyzed Suzuki‐coupling reaction. The synthesized polymers PFB, PFG, and PFR emit blue, green, and red light, respectively. A double‐layer device with the configuration of ITO/PEDOT/polymer/Ca/Al using PFB as the active layer showed a threshold voltage of 5 V, a maximum brightness of 2030 cd/m², and a maximum current efficiency of 0.35 cd/A. Using PFG as the active layer, the device exhibited a threshold voltage of 6 V, a maximum brightness of 6447 cd/m², and a maximum current efficiency of 1.27 cd/A. Using PFR as the active layer, the device showed a threshold voltage of 4 V, a maximum brightness of 2135 cd/m², and a maximum current efficiency of 0.16 cd/A. Better electroluminescent performance was also found based on different design of device structures. Due to photo‐crosslinking property of oxetane groups, the UV‐exposed thin films are insoluble in common organic solvents. A device comprised of blue, green, and red‐emissive pixels was successfully fabricated by spin‐coating and photo‐lithographic processes. In addition, a white light‐emitting device with CIE coordinate of (0.34, 0.33) was achieved by blending PFR into a host material PFB as the active layer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 516–524, 2010     

Synthesis of seco-chlorinated derivatives of phenanthroindolizidine precursors via Friedel-Crafts reaction

In the course of synthesizing 3-demethyltylophorine (1) by Lewis acid catalyzed intramolecular Friedel-Crafts reaction starting from N-(3-hydroxy-2,6,7-trimethoxy-phenanthr-9-ylmethyl)-2-chloromethylpyrrolidine, two chlorinated phenanthrene derivatives N-(4,10-dichloro-3-hydroxy-2,6,7-trimethoxyphenanthr-9-ylmethyl)-2-chloromethylpyrrolidine (4) and N-(4-chloro-3-hydroxy-2,6,7-trimethoxyphenanthr-9-ylmethyl)-2-chloromethylpyrrolidine (5) were obtained. The structures of these compounds were determined by spectroscopic analysis.     

Self‐Assembled Micelles Based on PEG‐Polypeptide Hybrid Copolymers for Drug Delivery

A series of amphiphilic poly(L ‐leucine)‐block‐poly(ethylene glycol)‐block‐poly(L ‐leucine) (PLL‐PEG‐PLL) hybrid triblock copolymers have been synthesized. All the blocks in this system have good biocompatibility and low toxicity. The PLL‐PEG‐PLL copolymers could self‐assemble into micelles with PLL blocks as the hydrophobic core and PEG blocks as the hydrophilic shell, which were characterized by FT‐IR, ¹H NMR, and transmission electron microscopy analysis. The critical micellar concentration of the copolymer was 95.0 mg · L⁻¹. The circular dichroism spectrum shows that the PLL segments adopt a unique α‐helical conformation, which is found to play an important role in controlling the drug release rate. The drug release could be effectively sustained by encapsulation in the micelles. The copolymers may have potential applications in drug delivery.

     

A novel soluble polyamide containing xanthene structure and trifluoromethylphenoxy pendent

<正>A novel polyamide containing xanthene structure and trifluoromethylphenoxy pendent was prepared from 9,9-bis[4-(4- aminophenoxy)phenyl]xanthene,a novel diamine with 2-(4-trifluoromethylphenoxy)terephthaloyl chloride,by the low temperature polycondensation.This new polyamide with the inherent viscosity of 0.95 dL/g was amorphous and readily soluble in polar solvents such as DMAc,m-cresol,etc.This polyamide showed the glass transition temperature(T_g) of 236℃,decomposition temperature (Td) at 5%weight loss of 455℃and char yield of 56%at 800℃in N_2.Transparent,flexible,and tough film of the polymer cast from DMAc solution exhibited tensile strength of 93 MPa,elongation at break of 14%,initial moduli of 2.2 GPa.The electric properties such as the dielectric constant of 3.03(1 MHz) and surface resistance(2.78×10~(14)Ω),and the moisture uptake of 1.36% were also described.