外偶极电场作用下H_2O,D_2O和T_2O的可逆分解电压

采用密度泛函B3P86方法和6-311++G(3df,3pf)基组,计算了在-0.05～0.05a.u.外偶极电场作用下,H2O,D2O,T2O,H2,D2,T2,O2的电子能量、核运动能量和熵值,在此基础上通过计算H2O(g)→H2(g)+O2(g)、D2O(g)→D2(g)+O2(g)、T2O(g)→T2(g)+O2(g)的焓变ΔH、熵变ΔS、Gibbs函数变化ΔG,最后得到了H2O,D2O,T2O的可逆分解电压Er.计算结果表明,外偶极电场存在时,H2O,D2O,T2O的Gibbs自由能变ΔG和可逆分解电压Er都有明显的变化,当外偶极电场正方向增加时,其Gibbs自由能变ΔG和可逆分解电压Er均趋于线性增加;当外偶极电场负方向增加时,其Gibbs自由能变ΔG和可逆分解电压Er均趋于线性减小;在相同外偶极电场作用下,Gibbs自由能变ΔG和可逆分解电压Er随H2O,D2O,T2O依次增加.     

吗啡啉功能化酸性离子液体的合成、表征及其催化酯化性能

制备和表征了三种新型质子酸离子液体: 吗啡啉硫酸氢盐([Hnhm]HSO4)、4-甲基吗啡啉硫酸氢盐 ([Hnmm]HSO4)和SO3H-功能化的4-(3-磺丙基)吗啡啉硫酸氢盐([C3SO3Hnhm]HSO4). 以氯乙酸(CAA)和乙醇合成氯乙酸乙酯的酯化反应考察了它们的酸性和催化活性, 并与1-(3-磺酸基)丙基-3-甲基咪唑硫酸氢盐、1-(3-磺丙基)吡啶硫酸氢盐、1-(3-磺丙基)-2-吡咯烷酮硫酸氢盐等三种具有不同氮杂环的SO3H-功能化酸性离子液体以及浓硫酸相对照. 结果表明, 上述SO3H-功能化离子液体对酯化反应的催化性能比非SO3H-功能化的[Hnhm]HSO4和[Hnmm]HSO4都高, 等同甚至优于浓硫酸. 当反应条件为: n(EtOH)∶n(CAA)∶n([C3SO3Hnhm]HSO4)＝1.3∶1∶0.2, 反应温度80 ℃, 反应时间3 h, 酯收率可达93.4%. 而且离子液体经真空干燥重复使用9次, 催化活性仍无明显下降. 以[C3SO3Hnhm]HSO4催化乙酸和不同醇的酯化反应获得较高的酯收率和选择性, 离子液体跟酯产物均能自动分相. 还考察了SO3H-功能化酸性离子液体对奥氏体316不锈钢的腐蚀性. 尽管SO3H-功能化离子液体与硫酸的酸性相近, 但对钢试样的腐蚀率不到硫酸的1/3.     

环境内分泌干扰物毒理学研究

传统上,环境内分泌干扰物的研究对象主要是对动物生殖器官的作用.但是脊椎动物体内存在复杂的内分泌系统,来调节其生长发育及繁殖.本文从环境内分泌干扰物对生物完整内分泌系统的影响总结了最近的研究进展.内分泌干扰物可通过作用于下丘脑.脑垂体.性腺轴的内分泌系统途径,影响重要激素或者受体,并最终影响动物的繁殖;也可作用于下丘脑一脑垂体.甲状腺轴途径,影响甲状腺激素的合成、转运、结合等过程,破坏甲状腺激素内环境的稳定而对生长发育造成危害.环境污染物也可通过影响类固醇激素的合成途径,即通过非受体途径而发挥内分泌干扰物作用.水体缺氧也可干扰鱼类的内分泌系统,因此也是内分泌干扰物.分子生物学技术,如组学、转基因技术等不仅可为环境污染物的内分泌干扰作用的危险评价提供可靠的手段而且也可揭示污染物作用的模式.     

A novel 3D mammalian cell perfusion-culture system in microfluidic channels

Mammalian cells cultured on 2D surfaces in microfluidic channels are increasingly used in drug development and biological research applications. These systems would have more biological or clinical relevance if the cells exhibit 3D phenotypes similar to the cells in vivo. We have developed a microfluidic channel based system that allows cells to be perfusion-cultured in 3D by supporting them with adequate 3D cell-cell and cell-matrix interactions. The maximal cell-cell interaction was achieved by perfusion-seeding cells through an array of micropillars; and 3D cell-matrix interactions were achieved by a polyelectrolyte complex coacervation process to form a thin layer of matrix conforming to the 3D cell shapes. Carcinoma cell lines (HepG2, MCF7), primary differentiated (hepatocytes) and primary progenitor cells (bone marrow mesenchymal stem cells) were perfusion-cultured for 72 hours to 1 week in the microfluidic channel, which preserved their 3D cyto-architecture and cell-specific functions or differentiation competence. This transparent 3D microfluidic channel-based cell culture system also allows direct optical monitoring of cellular events for a wide range of applications.     

Pd催化的配体导向C—H键乙酰化反应的理论研究

Pd催化的配体导向C-H键官能化反应已经成为有机化学中一种重要的合成手段. 我们用B3PW91密度泛函方法研究了Pd催化的配体导向C-H键乙酰化反应中催化剂和底物配合步骤以及C-H键活化步骤中的热力学性质. 研究发现, 具有不同导向基团的反应物之间竞争反应的选择性取决于导向基团与Pd(OAc)₂的配合步骤, 配合反应稳定常数大的较容易生成乙酰化的产物. 另一方面, 反应的选择性与C-H键的活化步骤无关, 并且与导向基团的配位原子的气相碱性、原子上的电荷密度以及最高占据轨道能量都没有相关性.     

5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌配合物的合成表征

设计合成了5种未见文献报道的5,10,15,20-四{对[3,5-二-(烷氧基)苯甲酰胺基]苯基}卟啉及其锌金属配合物,并用IR,UV-Vis,1H NMR,元素分析以及XPS对其组成和结构进行了表征,研究了这10种酰胺基系列卟啉化合物的拉曼光谱和荧光光谱的变化.结果显示链长对荧光和拉曼光谱没有明显影响,其取代基效应基本相同,配体的荧光强度强于锌配合物的荧光强度.在拉曼光谱中,由于卟啉分子平面的对称性由D2h变为D4h群及其锌离子d轨道的电子效应,卟啉配体和锌配合物之间的拉曼光谱有很大差别.     

熊果酸-3’-取代丙醇酯衍生物的合成及抗肿瘤活性研究

熊果酸与1,3-二溴丙烷反应制得中间体熊果酸-3’-溴代丙醇酯(1),含溴醇酯1与含氮化合物反应,合成了系列熊果酸含氮衍生物2a～2j,均未见文献报道,其结构经1H NMR,13C NMR,IR,MS确认.初步的抗肿瘤生物活性研究表明,部分化合物的抗肿瘤活性与熊果酸相比均有提高,其中化合物2e具有更强的抑制活性.     

多环麝香(PCMs)的环境行为及毒性效应

多环麝香(PCMs)作为重要的人工合成麝香广泛应用于日用品中,目前在各种环境介质中都能检测到PCMs的存在。由于其持续不断地进入环境并能够在生物体内积累,其效应类似于持久性污染物。作为一类新型污染物,PCMs所引起的环境问题受到了广泛重视。本文介绍了PCMs的物理化学性质、来源以及在不同环境介质中的分析方法和污染现状,概述了其在环境中的降解转化、生物富集行为,并总结了其能产生的急性毒性效应、亚慢性毒性效应、内分泌干扰效应和其他潜在的毒性效应,最后讨论了目前研究中存在的问题,并对未来研究进行了展望。今后,应该建立有效的、可比对的标准分析方法,更加系统地进行环境污染现状、迁移转化规律和生物降解代谢途径的研究;重视暴露途径和生物有效性的研究,并与风险评价结合;结合环境中PCMs的污染现状,探讨低剂量长期暴露和复合暴露对生物的影响。     

Assessing the dynamics of chromophoric dissolved organic matter (CDOM) in the Yellow Sea and the East China Sea in autumn by EEMs-PARAFAC

In this study we have successfully characterized the fluorescent components of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn using excitation-emission matrix fluorescence spectroscopy(EEMs) combined with parallel factor analysis(PARAFAC).PARAFAC aids the characterization of fluorescence CDOM by decomposing the fluorescence matrices into individual components.Four humic-like components(C1,C2,C3,and C4),one marine biological production component(C6),and two protein-like components(C5 and C7) were identified by PARAFAC.We researched the distributional patterns of fluorescence intensity,regression analyses between salinity,chlorophyll a concentration and fluorescence intensities of individual fluorophore,and regression analysis between salinity and fluorescence intensities percent of individual fluorophore.The results revealed that C2 and C4 showed conservative mixing behavior,while C1 and C3 possessed conservative mixing behavior in high salinity region and additional behavior in low and middle salinity region,which were considered to be derived from riverine and degradation of organic matter from resuspended and/or sinking particles and show non-conservative mixing behavior.In addition to riverine sources,the tryptophan-like C5 may receive widespread addition(likely from photo-degradation or biodegradation),while the most likely sources for the one marine humic-like C6 and tyrosine-like C7 were biological activity and microbial processing of plankton-derived CDOM,which were suggested to be of autochthonous origin and biologically labile.The application of EEM-PARAFAC modeling presents a unique opportunity to observe compositional changes,different mixing behavior and temporal variability in CDOM in the Yellow Sea and the East China Sea.     

Morphine-induced conditioned place preference in mice: Metabolomic profiling of brain tissue to find “molecular switch” of drug abuse by gas chromatography/mass spectrometry

Conditioned place preference (CPP) is a widely used model to explore the mechanism of context-dependent learning. In this work, we developed a GC–MS method to investigate the metabolites in mice brain which was used to study the mechanism of context-dependent learning associated with rewarding effect of morphine. Metabolites were extracted from brain tissues and derivatized followed by analysis by gas chromatography/mass spectrometry (GC–MS). In total, 69 peaks were identified as known compounds. By a Wilcoxon ran sum test with p value ≤0.05, 21 metabolites were selected and considered as the potential biomarkers of morphine in mice brain. Using principal component analysis (PCA) and receiver-operator characteristic (ROC) curves, a model was constructed with a combination of these 21 metabolic markers. Multivariate statistics of the model yielded separation between the two groups with an area under the curve value of 0.947. Some metabolites were further discussed in detail about their pathway. Results showed that our technique can be successfully applied to profile for biomarkers and in understanding molecular mechanisms of drug abuse.