聚苯基膦酸双酚A酯的合成与表征

聚苯基膦酸双酚Ａ酯的合成与表征唐旭东陈晓婷王玉忠杨科珂王波（四川联合大学化学系成都６１００６４）吴大诚（四川联合大学轻纺学院成都６１００６５）关键词聚膦酸酯，阻燃剂，熔融缩聚，热性能聚膦酸酯类化合物是一类重要的磷系阻燃剂［１～３］，与传统的非聚...     

Raman spectroscopic analysis of supersaturated aqueous solution of MgO.B2O3-32%MgCl2-H2O during acidification and dilution

Raman spectra of supersaturated aqueous solution of MgO.B2O3-32%MgCl2-H2O during acidification/alkalization and dilution have been studied. The assignments of the recorded Raman shift are given. The main existing forms of polyborate anions and their interaction in borate aqueous solution have been proposed through spectroscopic analysis. The experimental results indicate that the higher concentration of cation are beneficial not only to the dissolution of boric acid but also to the polymerization of polyborate anions. The existing forms and interaction among them also depend on the concentration of boron and the pH value in solution.     

Theoretical and Experimental Studies on a Metallorganic Complex of (Isopropylxanthato)(Phenyl)Mercury(I) [Hg(I)(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)(C<Subscript>4</Subscript>H<Subscript>7</Subscript>OS<Subscript>2</Subscript>)]

The title compound, (isopropylxanthato)(phenyl)mercury(I), was synthesized and characterized by elemental analysis, IR and thermogravimetric analysis. Density functional theory (DFT) method calculations were performed at B3LYP/CEP-121G and B3LYP/CEP-31G levels of theory, respectively. Vibrational frequencies were predicted, assigned, compared with the experimental values, and they are supported each other. The calculated results show that the strength of bond Hg—C is stronger than that of Hg—S, which is good agreement with the experimental data. The calculations of the second order optical nonlinearity and electronic absorption spectra are also performed.     

苎麻叶中绿原酸的分光光度法测定

探讨了采用分光光度法测定苎麻叶中绿原酸的含量的方法。12.5%的醋酸用量为0.1mL,7%尿素2.0mL,0.5%亚硝酸钠0.25mL,3min后加入5%氢氧化钠0.5mL,绿原酸与试剂形成鲜红色络合物,通过在510nm处测定溶液的吸光度确定绿原酸的含量。绿原酸浓度在0.01~0.12g/L范围内与吸光度值有良好的线性关系,回收率为95%~107%,相对标准偏差(RSD)为2.4%。该方法简便、快速。     

‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.      

Zeb1 for RCP-induced oral cancer cell invasion and its suppression by resveratrol

Rab coupling protein (RCP) is upregulated in head and neck squamous cell carcinoma (HNSCC) and is correlated with the progression and survival of patients. However, the role of RCP in one of the aggressive types of HNSCC, oral squamous cell carcinoma (OSCC), remains elusive. In the present study, we identified the important role of Zeb1 in RCP-induced OSCC epithelial-to-mesenchymal transition (EMT) and invasion. RCP induces Zeb1 expression, and silencing Zeb1 expression significantly inhibits RCP-induced OSCC invasion. In addition, Zeb1 upregulates MT1-MMP expression to promote OSCC EMT and invasion. Furthermore, we observed that the β1 integrin/EGFR/β-catenin signaling cascade mediates RCP-induced Zeb1 expression to promote OSCC invasion. Notably, we provide evidence that resveratrol (REV) strongly inhibits RCP-induced Zeb1 expression through blocking β1 integrin endosome recycling and EGFR activation, leading to suppression of RCP-induced OSCC invasion, demonstrating the important role of RCP in OSCC invasion and its reversion by REV. Collectively, the present study provides evidence for the first time that RCP aggravates OSCC invasion through increasing Zeb1 expression and subsequently upregulating MT1-MMP expression and that this process is reversed by REV, providing novel biomarkers and indicating the therapeutic potential of REV in OSCC.Subject terms: Oral cancer, Cell invasion     

蒂巴茵衍生物的合成研究

The reaction of 7α-acetyl-6,14-endoethano-6,7,8,14-tetrahydrothebaine with 2-（thien-2-yl）ethylmagnesium bromide was investigated. The tertiary alcohol derivative 7α-[R-l-hydroxyl-l-methyl-3-（thien-2-yl）propyl]）-6,14- endoethano-6,7,8,14-tetrahydrothebaine （3） and a by-product 4 were isolated. The structure of 4 was elucidated by X-ray analysis. The Grignard reaction shows high degree of stereoselectivity according with Cram rule. The crystal structure of 4 indicates that dihydrofuran ring was opened to form a phenolic hydroxyl group and a three-membered ring structure. It maintains the main rigid structure of morphine and contains a C（6）-C（14） enthano bridge. The 1-hydroxyl-1-methyl-3-（thien-2-yl）propyl group at C（7） position adopted S-configuration.     

模糊正交法用于石墨炉探针原子化测定铋条件的研究

模糊正交法是通过把正交试验结果模糊化,然后用模糊数学的理论和方法来处理实验数据。与常规正交设计相比,能在同样实验工作量的情况下获得更多的信息。本文采用模糊正交法对元素Bi的测定条件进行优化,并将其同常规正交设计方差分析的结果进行了比较,并提出一个综合评价参数,对建立的分析方法进行了综合评价。     

Methodological modifications on quantification of phosphatidylethanol in blood from humans abusing alcohol,using high-performance liquid chromatography and evaporative light scattering detection

Background  

Phosphatidylethanol (PEth) is an abnormal phospholipid formed slowly in cell membranes by a transphosphatidylation reaction from phosphatidylcholine in the presence of ethanol and catalyzed by the enzyme phospholipase D. PEth in blood is a promising new marker of ethanol abuse depending on the high specificity and sensitivity of this marker. None of the biological markers used in clinical routine at the present time are sensitive and specific enough for the diagnosis of alcohol abuse.