(CH_3C_5H_4)_3Ln·THF(Ln=Sm,Ho,Tb,Yb)与环戊二烯生成(C_5H_5)_3Ln·THF的新反应

研究了(CH_3C_5H_4)_3Ln·THF (Ln = Sm,Ho,Tb,Yb)与环戊二烯高产率生成 (C_5H_5)_3Ln·THF的新反应。反应产物经过了元素分析、质谱和X射线的表征。产 物(C_5H_5)_3Ln·THF的特征结构参数,如五元碳环的碳原子与中心金属的平均距 离,五元碳环质心与中心金属距离,配位的四氢呋喃氧原子与中心金属距离,由于 “镧系收缩现象”,随着中心原子序数的增加而减小。     

Morphology control of soap-free seeded P(St-EA-AA) latex particles

Soap-free poly(styrene-ethyl acrylate-acrylic acid) latex particles with narrow size distribution and with surface carboxyl groups were synthesized by semicontinuous emulsion polymerization, and the particles with homogeneous multihollow structure were obtained after alkali posttreatment. Effects of treatment conditions and crosslinking agents on particle morphology were investigated. Results showed that the multihollow structure can be formed inside the uncrosslinked particles only when the treatment temperature exceeded 50 °C, the pH was higher than 10.0, the amount of 2-butanone was more than 3.0 ml and the treatment time was longer than 30 min. Furthermore, the volume expansion of the particles increased with the temperature increased to 90 °C, the pH to 12.5 or the amount of 2-butanone to 7.0 ml, and this value increased first and then decreased with the treatment time prolonged. Fine pores can be generated in the shell of particles crosslinked by 0.2 g of ethyl glycol dimethylacrylate (EGDMA), while no hollow structure formed inside particles when 0.4 g of EGDMA or 0.2 g of divinyl benzene was used.     

First Synthesis of 2a-Thiol Ether Analog of Docetaxel

The chemistry of anticancer drug paclitaxel (=Taxol, 1a) has been extensively explored in recent years. A variety of its analogs with modified taxane frame work or substitutions to its core structure, as well as C-13 substituted isoserine side chains have been synthesized and biologically evaluated1. The marketing of docetaxel (=Taxotere, 1b) is one of the fruitful results from these research efforts. The beginning of clinical trial for analog 2 developed by Indena is the new example. Ba…     

Intriguing self-assembly of large granules of F-actin facilitated by gelsolin and alpha-actinin

We report microscopic observations and a structural determination of actin granules self-assembled in concentrated solutions of actin filaments (F-actin). Optical microscopy shows reproducible formation of numerous and stable granules of densely packed F-actin of variable sizes on the order of 10 microm. These granules coexist with a uniform network of F-actin of a lower concentration. The microscopic segregation of F-actin into two distinct states is assisted by an actin cross-linking protein, alpha-actinin. The rapid on and off rates and temperature sensitivity of the alpha-actinin/F-actin interaction facilitate the formation of multi-micrometer-sized granules of well-defined shapes. Additional physical factors such as the excluded volume effect and the minimization of surface energy act in concert with the specific molecular interactions to define the intriguing granular formation. Both the biochemical specificity of alpha-actinin and the thermodynamics of phase transitions are required for understanding such large scale self-assembly.     

The synthesis of dicationic extended bis-benzimidazoles

The synthesis of extended dicationic bis-benzimidazoles starting from trans-1,2-bis(4-cyanophenyl)ethene and trans-1,2-bis(4-cyanophenyl)cyclopropane is reported. The target diamidines show significant in vitro activity against B. subtilis.     

PU大分子单体水溶液性质

双亲聚合物一般由亲水和亲油 2种链段构成 ,有嵌段型[1,2 ] 和接枝型[3 ] 2种 ,其中通过大分子单体法合成双亲接枝聚合物备受关注[4] 。如以亲水性大分子单体和亲油性小分子单体共聚 ,大分子单体构成共聚物主链上支链 ,具有较大活动性 ,亲水效能高。采用对氯甲基苯乙烯[5] 或甲基丙烯酰氯[6] 与聚氧化乙烯大分子的一端相反应 ,可得到亲水性大分子单体 ,但其分子量及结构变化有限。本文采用常规条件 ,合成了嵌段式水溶性聚氨酯大分子单体 ,其分子量较大 ,共聚接枝的支链较长。利用该大分子单体具有非离子高分子表面活性剂的性质 ,采用无皂乳…     

Distance dependence of electron transfer in rigid,cofacially compressed,pi-stacked porphyrin-bridge-quinone systems

The electron-transfer (ET) dynamics of a series of unusually rigid pi-stacked porphyrin-quinone (P-Q) systems, in which sub-van der Waals interplanar distances separate juxtaposed porphyryl, aromatic bridge, and quinonyl components of these assemblies, are reported. The photoinduced charge separation (CS) and thermal charge recombination (CR) ET reactions of [5-[8'-(2',5'-benzoquinonyl)-1'-naphthyl]-10,20-diphenylporphinato]zinc(II) (1a-Zn), [5-[8'-(4'-[8'"-(2'"',5'"'-benzoquinonyl)-1'"-naphthyl]-1'-phenyl)-1'-naphthyl]-10,20-diphenylporphinato]zinc(II) (2a-Zn), and [5-(8'-[4'-(8'"-[4'"'-(8'"-[2'"',5'"'-benzoquinonyl]-1'"-naphthyl)-1'"'-phenyl]-1'"-naphthyl)-1'-phenyl]-1'-naphthyl)-10,20-diphenylporphinato]zinc(II) (3a-Zn) in CH(2)Cl(2) were investigated by pump-probe transient absorption spectroscopy. Analyses of these data show that the phenomenological ET distance dependence (beta) for both the CS and CR reactions in these systems is soft (beta(CS) = 0.43 A(-1); beta(CR) = 0.35 +/- 0.16 A(-1)). This work demonstrates that simple aromatic building blocks such as benzene, which are characterized by highly stabilized filled molecular orbitals and large HOMO-LUMO gaps, can provide substantial D-A electronic coupling when organized within a pi-stacked structural motif that features a modest degree of arene-arene interplanar compression.     

超高效液相色谱-串联质谱法快速同时测定生姜中10种营养成分

建立了超高效液相色谱-串联质谱（UHPLC-MS/MS）快速同时测定生姜中姜辣素类和姜黄素类营养成分的分析方法，具体包括6-姜酚、8-姜酚、10-姜酚、6-姜烯酚、8-姜烯酚、10-姜烯酚、四氢姜黄素、姜黄素、去甲氧基姜黄素、双去甲氧基姜黄素10种目标物。采用ZORBAX RRHD Eclipse Plus C18色谱柱（100 mm×2.1 mm，1.8 μm）分离，以0.1%（v/v）甲酸水溶液和0.1%（v/v）甲酸甲醇溶液为流动相进行梯度洗脱，采用电喷雾电离（ESI）源、正离子和多反应监测（MRM）模式对目标物进行定性确证和定量分析。10种营养成分的线性相关系数（r）均≥ 0.9995，方法的定量限为0.10~7.71 μg/L，样品基质在3个水平下的平均加标回收率为82.8%~115.3%，相对标准偏差（RSD）为0.58%~11.49%。分析结果显示，生姜中10种营养成分均有检出，其中6-姜酚的含量最高且集中分布于373.35~702.48 mg/kg。该法简便快速，准确可靠，适用于生姜中姜辣素类和姜黄素类营养成分的分析，可为生姜质量鉴定和控制提供技术手段。     

Thermally produced biodegradable scaffolds for cartilage tissue engineering

A novel process was developed to fabricate biodegradable polymer scaffolds for tissue engineering applications, without using organic solvents. Solvent residues in scaffolds fabricated by processes involving organic solvents may damage cells transplanted onto the scaffolds or tissue near the transplantation site. Poly(L-lactic acid) (PLLA) powder and NaCl particles in a mold were compressed and subsequently heated at 180 degrees C (near the PLLA melting temperature) for 3 min. The heat treatment caused the polymer particles to fuse and form a continuous matrix containing entrapped NaCl particles. After dissolving the NaCl salts, which served as a porogen, porous biodegradable PLLA scaffolds were formed. The scaffold porosity and pore size were controlled by adjusting the NaCl/PLLA weight ratio and the NaCl particle size. The characteristics of the scaffolds were compared to those of scaffolds fabricated using a conventional solvent casting/particulate leaching (SC/PL) process, in terms of pore structure, pore-size distribution, and mechanical properties. A scanning electron microscopic examination showed highly interconnected and open pore structures in the scaffolds fabricated using the thermal process, whereas the SC/PL process yielded scaffolds with less interconnected and closed pore structures. Mercury intrusion porosimetry revealed that the thermally produced scaffolds had a much more uniform distribution of pore sizes than the SC/PL process. The utility of the thermally produced scaffolds was demonstrated by engineering cartilaginous tissues in vivo. In summary, the thermal process developed in this study yields tissue-engineering scaffolds with more favorable characteristics, with respect to, freedom from organic solvents, pore structure, and size distribution than the SC/PL process. Moreover, the thermal process could also be used to fabricate scaffolds from polymers that are insoluble in organic solvents, such as poly(glycolic acid). Cartilage tissue regenerated from thermally produced PLLA scaffold.     

Two—dimensional Network Crown Ether Complex.Synthesis and Crystal Structure of 18—Crown—6 Complex：[K（18—C—6）]2[Cd—（nmt）2]

The novel complex [K(18-C-6)]2[Cd(mnt)2][18-C-6-18-crown-6,nmt=1,2-dicyanoethene-1,2-dithiolate,C2S2-(CN)2^2-] was synthesized and characterized by elemental analysis,IR spectrum and X-ray diffraction analysis.The complex displays two-dimensional network structure of [K(18-C-6)] complex segments and [Cd(nmt)2] complex segment bridged by S-K-S,S-K-N and N-K-N interactions between adjacent[K(18-C-6)] and [Cd(mnt)2]units.