Tight intermolecular packing through supramolecular interactions in crystals of cyano substituted oligo(para-phenylene vinylene): a key factor for aggregation-induced emission

Strong supramolecular interactions, which induced tight packing and rigid molecules in crystals of cyano substituent oligo(para-phenylene vinylene) (CN-DPDSB), are the key factor for the high luminescence efficiency of its crystals; opposite to its isolated molecules in solution which have very low luminescence efficiency.

Potential energy landscape and robustness of a gene regulatory network: Toggle switch

Finding a multidimensional potential landscape is the key for addressing important global issues, such as the robustness of cellular networks. We have uncovered the underlying potential energy landscape of a simple gene regulatory network: a toggle switch. This was realized by explicitly constructing the steady state probability of the gene switch in the protein concentration space in the presence of the intrinsic statistical fluctuations due to the small number of proteins in the cell. We explored the global phase space for the system. We found that the protein synthesis rate and the unbinding rate of proteins to the gene were small relative to the protein degradation rate; the gene switch is monostable with only one stable basin of attraction. When both the protein synthesis rate and the unbinding rate of proteins to the gene are large compared with the protein degradation rate, two global basins of attraction emerge for a toggle switch. These basins correspond to the biologically stable functional states. The potential energy barrier between the two basins determines the time scale of conversion from one to the other. We found as the protein synthesis rate and protein unbinding rate to the gene relative to the protein degradation rate became larger, the potential energy barrier became larger. This also corresponded to systems with less noise or the fluctuations on the protein numbers.

高分子科学实验中异常数据的判别与剔除

简单介绍了对测量值中异常数据进行判别与剔除的三种统计判别方法——3σ准则、格鲁布斯准则和Q检验方法的基本原理,并以高分子科学实验中的两个实例为代表,应用Visual Basic for Applica-tions(VBA)编写的程序模块,对测量值中异常数据的判别与剔除进行了详细讨论。

稀土化合物在高分子科学中的应用研究进展

综述了稀土化合物在高分子科学中的广泛应用烯烃聚合/共聚合催化剂、聚氯乙烯的热稳定剂、填充改性聚合物和制备功能材料等,并涉及了笔者在稀土催化接枝改性领域的最新研究成果。

基于2,5-二(4-氨基苯)嘧啶聚酰亚胺的合成及性能表征

1,5-二氮杂戊二烯盐(vinamidium salts)与4-硝基苯甲脒盐在碱性物质的存在下发生成环反应得含嘧啶环的硝基化合物;硝基化合物用Pd/C和水合肼还原得到棒状含氮芳杂环二胺——2,5-二(4-氨基苯基)嘧啶.通过1H-NMR,13C-NMR,IR,MS及元素分析确证了含氮芳杂环二胺及其中间产物的结构.这种二胺或加一定量对苯二胺与均苯二酐(PMDA)或联苯二酐(BPDA)通过两步法聚合获得一系列聚酰亚胺,通过红外、动态力学、静态力学、热重分析、广角X射线衍射等实验测试了该类聚合物的结构、热性能、机械性能及结晶性能.

Hydrazine-based polyimides from isomeric bis(chlorophthalimide)s

3,3-Dichloro-N,N'-biphthalimide (3,3'-DCBPI), 3,4'-dichloro-N,N'-biphthalimide (3,4'-DCBPI), and 4,4'-dichloro-N,N'X-biphthalimide (4,4'-DCBPI) were synthesized from 3- or 4-chlorophthalic anhydrides and hydrazine in glacial acetic acid. The yield of 3,3'-DCBPI (90%) was much higher than that of 4,4'-DCBPI (33%) because of the better stability of the intermediate, 3-chloro-N-aminophthalimide, and 3,3'-DCBPI. A series of hydrazine-based polyimides were prepared from isomeric DCBPIs and 4,4-thiobisbenzenethiol (TBBT) in N,N-dimethylacetamide in the presence of tributylamine. Inherent viscosity of these polymers was in the range of 0.51-0.69 dL/g in 1-methyl-2-pyrrolidinone (NMP) at 30 degrees C. These polyimides were soluble in 1,1,2,2-terachloroethane, NMP, and phenols. The 5% weight-loss temperatures (T(g)s) of the polymers were near 450 degrees C in N-2. Their glass-transition temperatures (T(g)s) determined by dynamic mechanical thermal analysis and differential scanning calorimetry increased according to the order of polyimides based on 4,4'-DCBPI, 3,4'-DCBPI, and 3,3'-DCBPI. The hydrolytic stability of these polymers was measured under acid, basic, and neutral conditions and the results indicated that the order was 3,3'-DCBPI/TBBT > 3,4'-DCBPI/TBBT > 4,4'-DCBPI/TBBT.

Synthesis, structure and luminescence properties of zinc (II) complexes with terpyridine derivatives as ligands

Five zinc (II) complexes (1-5) with 4 '-phenyl-2,2 ':6 ',2 ''-terpyridine (ptpy) derivatives as ligands have been synthesized and fully characterized. The para-position of phenyl in ptpy is substituted by the group (R), i.e. tert-butyl (t-Bu), hexyloxy (OHex), carbazole-9-yl (Cz), naphthalen-1-yl-phenyl-amine-N-yl (NPA) and diphenyl amine-N-yl (DPA), with different electron-donating ability. With increasing donor ability of the R, the emission color of the complexes in film was modulated from violet (392 nm) to reddish orange (604 nm). The photoexcited luminescence exhibits significant solvatochromism because the emission of the complexes involves the intra-ligand charge transfer (ILCT) excited state. The electrochemical investigations show that the complexes with stronger electro-donating substituent have lower oxidation potential and then higher HOMO level. The electroluminescence (EL) properties of these zinc (II) complexes were studied with the device structure of ITO/PEDOT/Zn (II) complex: PBD:PMMA/BCP/AlQ/ LiF/Al. Complexes 3, 4 and 5 exhibit EL wavelength at 552, 600 and 609 nm with maximum current efficiency of 5.28, 2.83 and 2.00 cd/A, respectively.

Isothermal and nonisothermal melt-crystallization kinetics of syndiotactic polystyrene

Analyses of the isothermal and nonisothermal melt kinetics for syndiotactic polystyrene have been performed with differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The regime II-->III transition, at a crystallization temperature of 239degrees, is found. The values of the nucleation parameter K-g for regimes II and III are estimated. The lateral-surface free energy, sigma = 3.24 erg cm(-2), the fold-surface free energy, sigma(e) = 52.3 +/- 4.2 erg cm(-2), and the average work of chain folding, q = 4.49 +/- 0.38 kcal/mol, are determined with the (040) plane assumed to be the growth plane. The observed crystallization characteristics of syndiotactic polystyrene are compared with those of isotactic polystyrene. The activation energies of isothermal and nonisothermal melt crystallization are determined to be DeltaE = -830.7 kJ/mol and DeltaE = -315.9 kJ/mol, respectively.

Hydroxylation of phenol by iron(II)-phenanthroline(Phen)/MCM-41 zeolite

MCM-41 zeolite and Tron (II)-Phen/MCM-41 zeolite have been prepared and characterized by XRD, IR, NH3-TPD, HET and UV-Vis. The Iron( II)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of phenol.

Phycobilisomes linker family in cyanobacterial genomes: divergence and evolution

Cyanobacteria are the oldest life form making important contributions to global CO2 fixation on the Earth. Phycobilisomes (PBSs) are the major light harvesting systems of most cyanobacteria species. Recent availability of the whole genome database of cyanobacteria provides us a global and further view on the complex structural PBSs. A PBSs linker family is crucial in structure and function of major light-harvesting PBSs complexes. Linker polypeptides are considered to have the same ancestor with other phycobiliproteins (PBPs), and might have been diverged and evolved under particularly selective forces together. In this paper, a total of 192 putative linkers including 167 putative PBSs-associated linker genes and 25 Ferredoxin-NADP oxidoreductase (FNR) genes were detected through whole genome analysis of all 25 cyanobacterial genomes (20 finished and 5 in draft state). We compared the PBSs linker family of cyanobacteria in terms of gene structure, chromosome location, conservation domain, and polymorphic variants, and discussed the features and functions of the PBSs linker family. Most of PBSs-associated linkers in PBSs linker family are assembled into gene clusters with PBPs. A phylogenetic analysis based on protein data demonstrates a possibility of six classes of the linker family in cyanobacteria. Emergence, divergence, and disappearance of PBSs linkers among cyanobacterial species were due to speciation, gene duplication, gene transfer, or gene loss, and acclimation to various environmental selective pressures especially light.

黄海太平洋磷虾种群生态学研究

太平洋磷虾（Euphausia pacifica Hansen）作为目前已开发利用的6种主要磷虾资源之一，广泛分布于北太平洋北部及其临近近岸海域。在黄海，太平洋磷虾是黄海海洋生态系统中大型浮游动物的优势种和重要功能群的组成种类，它还是黄海生态系统中鱼类等上层营养级生物的重要饵料。太平洋磷虾的种群组成以及数量变化会直接影响到黄海经济鱼类的资源动态，从而影响到整个黄海海洋生态系统的变化。 本论文依托国家重点基础研究发展计划项目（973-II）——“我国近海生态系统食物产出的关键过程及其可持续机理”和国家自然科学基金40306021号——“黄、东海太平洋磷虾种群补充机制研究”，在2006年4月到2007年8月的八个黄海调查航次中，通过网采固定样品和现场培养实验相结合的方法，对黄海海域太平洋磷虾的种群生态分布和补充、繁殖和发育策略、以及成体的摄食、代谢进行了较为全面、细致的研究。 种群生态分布：本文根据2006年4月（春季）和10月（秋季）两次黄海大面调查和2006年9月－2007年8月六次黄海断面调查所获得的样品，研究了太平洋磷虾在南黄海的种群生态分布和补充机制，并探讨了其生态分布与环境因子的关系。 春季，南黄海太平洋磷虾种群主要分布在33 °N－36 °N、50 m-75 m等深线之间的海域，种群总丰度（不包括卵）为152.90 ind. m-3，卵丰度非常高，成体丰度较低，仅占种群总数量的8.72%。调查海域的平均成体丰度为0.35 ind. m-3。种群组成以幼体为主，占到种群的90.85%。春季是太平洋磷虾种群补充的高峰期。秋季，种群主要分布在黄海冷水团海域，种群总丰度（不包括卵）为335.38 ind. m-3，成体丰度显著高于春季，调查海区成体的平均丰度为7.73 ind. m-3。成体和未成体以99.5%的总比例在种群中占绝对数量优势，卵和幼体都非常少。秋季太平洋磷虾种群处于稳定期。春季成体的体长显著大于秋季，春季成体全长以13-18 mm为主，而秋季成体的全长主要是9-13 mm。 春季，太平洋磷虾成体具有昼夜垂直迁移行为，白天主要停留在底层水域，夜间少部分成体会上升到中上层水域，但是大部分成体仍然停留在深层。幼体从C3期开始就具有一定昼夜垂直迁移行为，F2—F5期幼体的昼夜垂直迁移行为已经非常明显。由于从表层到底层叶绿素a浓度逐渐降低，因此，太平洋磷虾的昼夜垂直迁移行为可能与摄食有关。 太平洋磷虾成体的分布是与海水温度紧密相关，南黄海太平洋磷虾成体比较适宜生活的水温是8-16 °C。春、冬季水温较低，成体分布范围较广。夏、秋季表层水温急剧升高到20 °C以上，太平洋磷虾成体主要分布在黄海冷水团海域，丰度也达到一年中的最高值。另外，秋季在近长江口的北部海域有大量成体分布。 繁殖和发育：自2006年9月到2007年8月的一年内，在黄海进行了七个航次的太平洋磷虾现场培养产卵实验，结果表明：在南黄海，太平洋磷虾在3月—6月份都具有产卵行为，4月份达到产卵高峰期。单个雌体的最大产卵量为617 egg female-1，出现在4月份。8月、9月和12月在南黄海均未发现太平洋磷虾的产卵行为。太平洋磷虾具有二次产卵行为，并且第一次产卵量要高于第二次。太平洋磷虾的产卵行为与其干湿重紧密相关。成体干重低于5.0 mg，湿重低于26.0 mg，均不具有产卵能力。在产卵高峰期，太平洋磷虾的干湿重达到一年中的最高值。 在南黄海，太平洋磷虾的幼体发育主要遵循下面的发育途径：卵 → 无节幼体 → 后期无节幼体 → 原溞状幼体 → 溞状幼体F1（0' 7, 1' 7） → 溞状幼体F2（1' 4'' 7, 3' 1'' 7） → 溞状幼体F3（5'' 7） → 溞状幼体F4（5'' 5） → 溞状幼体F5（5'' 3） → 溞状幼体F6（5'' 1）。太平洋磷虾在15 °C下的幼体发育速度明显快于4 °C。15 °C下幼体发育到C1期只需5.6 d，而4 °C下则需要16.1 d。 摄食和代谢：2006年9、10、12月和2007年3、8月，在南黄海的五个断面调查航次中，在S1-4站进行了太平洋磷虾成体摄食实验，结果表明：太平洋磷虾在8月和9月份对水体中浮游植物的摄食率比较低，主要摄食水体中的微型浮游动物，从而由于营养级级联作用，致使水体中叶绿素a浓度升高。12月和3月，太平洋磷虾对水体中浮游植物有着很强的摄食活动，使得水体的叶绿素a浓度大量降低，当然太平洋磷虾也可能会同时摄食水体中微型浮游动物。 2006年9、12月和2007年3月，在南黄海的三个断面调查航次中，在S1-4站进行了太平洋磷虾现场耗氧率和排氨率实验，结果表明：太平洋磷虾在3月份的耗氧率是172.92 μg ind.-1 d-1，是9月份和12月份的6倍还要多。太平洋磷虾在9月和12月的耗碳率和体碳日损耗量相近，且都较低。3月份太平洋磷虾的代谢非常旺盛，体碳日损耗量达到2.70 % d-1，每日的耗碳率为62.9 µg C ind-1 d-1。9月和12月份太平洋磷虾代谢的氧氮比都较低，分别是11.3和7.0，太平洋磷虾成体的主要代谢基质是蛋白质。3月份的氧氮比为35.1，太平洋磷虾成体代谢主要以脂肪及碳水化合物为主。

渤黄海沉积物中的多环芳烃和多氯联苯及其与生态环境的耦合解析

海洋沉积环境中多氯联苯（PCBs）和多环芳烃（PAHs）的研究对于揭示其污染历史、来源途径、迁移转化以及评价其对环境的潜在生态风险都有重要的科学意义和应用价值，本研究选择我国典型近海中比较开阔的南黄海和受人为影响严重的渤海湾沉积物中的PAHs和PCBs作为主要研究对象，结合对生态环境对应关系的剖析，系统研究了沉积物中PAHs和PCBs的地球化学分布特征、影响控制因素、演变趋势、潜在生态风险等，获得了以下系统的认识： 1.南黄海表层沉积物中多环芳烃和多氯联苯的分布与沉积类型及模式相一致，受控于“沉积类型-动力过程-来源途径”。PCBs含量（范围：518～5848 pg/g，平均值：1715 pg/g）低于受人为影响严重的长江口、珠江口和渤海，分布具有中部海区＞东部海区＞西部海区的特征；PCBs随着沉积物粒径的减小和粘土含量的增加而增加，且与总有机碳（r=0.61，p＜0.01）含量呈显著线性正相关，表明PCBs在沉积物中的分布受控于被水动力过程原动力控制的沉积类型与沉积模式。 2. 1914～2004年间，南黄海沉积物中PAHs和PCBs的变化比较显著，在时间序列上经历了三个明显的不同阶段。近90年来，PAHs和PCBs在柱状样中垂直分布随深度的增加而降低，即近年南黄海沉积物中PAHs和PCBs的残留水平比上世纪初明显增加。其中1914～1932年间，PAHs和PCBs保持在较低的水平；1932～1962年间，PAHs和PCBs的含量发生急剧的变化，在1932～1944和1956～1962年两个时间段，PAHs和PCBs的含量达到峰值；自1962年至今，PAHs和PCBs呈稍有增加趋势。PAHs的组成和特征组分比值分析显示，1920～1944年间PAHs主要来自石油产品泄漏，1944～1980年间，主要来自草/木材/煤燃烧，1980年至2004年则显示出石油和燃烧产物混合来源的特征。 3.渤海湾沉积物中的PAHs、PCBs、DDTs和HCHs的分布模式不同，反映了这四种污染物的地球化学行为存在着明显的差异性。PAHs、PCBs、DDTs和HCHs的含量范围为149.0～393.4 ng/g，360.8～1728.3 pg/g，462.2～2007.3 pg/g和4.31～33.8 ng/g。马颊河口、海河口和黄河口附近的海区的沉积物中PAHs和PCBs的含量显著高于渤海湾内其它站位，DDTs在湾外沉积物中的含量大于湾内，在海河口附近站位测得HCHs含量的最高值，在其它站位其浓度变化不大。PAHs特征成分的比值显示渤海湾沉积物中PAHs主要来源于草/木材/煤燃烧的产物经过大气的输运过程进入水体；DDTs和HCHs的组成显示，在DDTs和HCHs被禁用后仍有新的输入源。 4.南黄海沉积物POPs总体水平不高，其环境污染危害和潜在生态风险不大，从沉积物POPs的角度来说南黄海的环境质量较好。潜在生态危害指数评价表明，渤海湾沉积物中芴可能会产生潜在的生态风险，DDTs和HCHs的含量低于一类沉积物质量标准值，总体而言，其沉积物质量良好，潜在生态风险较低。 论文的创新性点在于：1）首次研究了近百年南黄海沉积物中多环芳烃和多氯联苯的演变趋势，判断了其来源并对近百年二者的潜在生态风险进行评价。2）系统剖析了南黄海及渤海湾的生态环境与PAHs和PCBs的耦合关系，对阐明POPs的毒理效应有重要的科学意义。3）系统解析了渤海湾沉积物中PAHs，DDTs和HCHs的污染现状，来源和迁移途径，可为科学开发和利用渤海海域提供重要的理论依据。