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.     

CexTi1-xO2复合氧化物表面结构和体相结构的演变

利用X射线衍射、N₂吸附等温线、X射线光电子能谱、X射线吸收谱、H₂-程序升温还原、甲基橙选择化学吸附和等电点测定等方法研究了共沉淀方法制备的一系列Ce_xTi_1-xO₂复合氧化物的结构. 成功发展了甲基橙选择化学吸附和等电点方法研究Ce_xTi_1-xO₂复合氧化物的最外层表面结构, 并定义了“等价CeO₂表面覆盖度”来描述Ce_xTi_1-xO₂复合氧化物的最外层表面结构. Ce_xTi_1-xO₂复合氧化物 (x ≥ 0.7)形成立方萤石相固溶体, Ce_0.3Ti_0.7O₂表现出纯的单斜相, 而其它复合氧化物表现出混合相. Ce_xTi_1-xO₂复合氧化物最外层表面结构的演变行为不同于其体相结构.Ce_0.7Ti_0.3O₂立方萤石相固溶体最外层表面已经部分形成了单斜相Ce_0.3Ti_0.7O₂, 随Ce含量的降低, 单斜相Ce_0.3Ti_0.7O₂从最外层表面向体相生长. Ce_xTi_1-xO₂复合氧化物立方萤石相固溶体和单斜相Ce_0.3Ti_0.7O₂分别在相对较低和较高的温度表现出好的还原性能. 上述结果提供了全面和深层次的Ce_xTi_1-xO₂复合氧化物结构信息.     

原油乳状液稳定性和破乳研究进展

本文从控制乳状液稳定性的一些因素－界面膜、界面张力、双电层、空间位阻、固体粒子、液晶、油相溶解度、连续相粘度等方面综述了有关乳状液稳定性的一些研究进展。对国内外有关原油乳状液的破乳研究也做了综述。同时，介绍了应用于乳状液稳定性研究的新的实验技术和仪器。     

新型纳米复合杂多酸催化剂H3PW12O40/SiO2催化合成水杨酸异丙酯的研究

水杨酸异丙酯是合成水胺硫磷、甲基异柳磷等农药的重要中间体[1], 还可用作香料和有机合成的中间体. 工业上一般通过水杨酸与异丙醇的酯化反应来合成, 常用的方法有硫酸法、水杨酰氯法和混酸法等, 然而这些方法都不同程度地存在着设备腐蚀严重, 能耗较高, 环境污染大等缺点. 杂多酸是一类具有笼形结构的多核配合物, 具有强酸性、强氧化性、"假液相"等特性, 在催化领域有广泛的应用[2]. 但杂多酸存在比表面小、易失活、难回收和使用寿命短等缺点.     

SO42-促进的中孔含锆分子筛催化合成乙酸松油酯的研究

合成了中孔含锆分子筛Zr-MCM-41，用H2SO4对Zr-MCM-41进行修饰，得到SO4^2-促进的中孔含锆分子筛SO4^2-／Zr-MCM-41．通过XRD、FT—IR表征了其结构．结果表明：Zr—MCM-41和SO4^2-／Zr—MCM-41具有中孔分子筛的特征结构、良好的长程有序性和结晶度；SO4^2-已进入Zr—MCM-41骨架内部，并与骨架原子形成了化学键，从而产生强酸中心，将SO4^2-／Zr—MCM-41用于催化合成乙酸松油酯，考察了催化剂的种类、反应温度、反应时间及反应物配比对松油醇酯化反应结果的影响．     

激光Raman光谱研究2,4己二炔-1,6二醇的双苯异氰酸酯的聚合——晶型对固相聚合活性的影响

用激光Raman光谱研究了三种不同晶型的2,4-已二炔-1,6二醇的双苯异氰酸酯(HDPU)的聚合,发现不同晶型的HDPU的聚合活性与其C=C伸缩振动频率的频移之间存在内在联系。这说明单体晶格与聚合物晶格的匹配是HDPU具有高的聚合活性的必要条件。