氮杂冠醚合成中的双功能基试剂

综述了氮杂冠醚合成中的双功能基试剂的进展。着重讨论了典型的双功能基试剂,如取代多甘醇、二胺、氨基二醇、二卤代物、二醛和二酮以及3-烷氧丙烯醛等的制备方法。     

Synthesis and Evaluation of Blends Formed by Polymeric Crown Ethers and a Fullerene-Containing Primary Ammonium Salt in Organic Thin Films

The synthesis of a series of polymers and cyclopolymers bearing crown ethers of differing structure and affinities towards primary ammonium ions is discussed. These polymers have been tested in their efficiency to form structurally homogeneous thin films when blended with an amphiphilic C₆₀ compound containing a primary ammonium ion functional group. The X-ray reflectivity characterization of the films revealed that the polymer bearing the crown ether with the least affinity for primary ammonium ions, but having the highest degree of polymerization, is the most effective in forming structurally homogeneous thin films.     

Influence of post‐treatments on the properties of porous poly(vinyl alcohol) membranes

Porous poly(vinyl alcohol) (PVA) membranes were prepared by a phase‐inversion method. The influence of chemical crosslinking and heat treatments on the swelling degree, resistance to compaction, mechanical strength, and morphology of porous PVA membranes was extensively studied. The crosslinking degree and crystallinity of the membranes, calculated from IR spectra, increased with the treatment time. The porosity, calculated on the basis of swelling experiments, showed a decreasing trend for heat‐treated membranes but remained almost at a constant value for crosslinked membranes. Such a change was further proved with scanning electron microscopy pictures. The behavior was explained by the rearrangement of PVA chains during the heat‐treatment process, which led to morphological changes in the membranes. The mechanical properties of the porous membranes in dry and wet states were measured, and a great difference was observed between crosslinked and heat‐treated membranes in the dry and wet states. The crosslinked membranes showed good mechanical properties in the dry state but became fragile in the wet state. On the contrary, the heat‐treated membranes were more flexible in the wet state than in the dry state. This change was explained by the turnaround of inner stress in the systems during the swelling process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at     

岩石样品中铷的中子活化分析

研究了苦味酸溶液的ｐＨ变化对用１８－Ｃ－６（１８Ｃ６）的硝基苯溶液定量萃取Ｒｂ的影响及１８Ｃ６浓度变化对定量萃取Ｒｂ的影响，确定了定量反萃Ｒｂ的实验条件。作出了磷酸锆无机离子交换柱上的Ｒｂ－Ｃｓ分离曲线。测定了岩石样品的微量Ｒｂ和痕量＾８４Ｒｂ。     

Cuticular hydrocarbons ofReticulitermes virginicus (Banks) and their role as potential species- and caste-recognition cues

The cuticular hydrocarbon components of four castes ofReticulitermes virginicus (Banks) have been identified and quantitated. Components identified includen-alkanes; 2-, 3-, 11-, 13-, and 15-methyl-alkanes; 11,15-dimethylalkanes, (Z)-9-alkenes; (Z,Z)-7,9-dienes; and (E/Z)-6,9-dienes ranging in carbon number from C₂₁ to C₄₀. All caste forms ofR.virginicus contained the same components, but showed caste-specific proportions. Comparison of these hydrocarbons with those of the sympatric termiteR. flavipes (Kollar) suggest that cuticular hydrocarbons might serve as species- and caste-recognition cues. A bioassay was developed to test this species-recognition hypothesis, with the experimental results supporting the hypothesis.Isoptera: Rhinotermitidae.     

HEC influence on cement hydration measured by conductometry

Cellulose ethers are of universal use in factory-made mortars, though their influences on mortar properties at a molecular scale are poorly understood. Recent studies dealt with the influence of hydroxyethylmethyl cellulose (HEMC) and hydroxypropylmethyl cellulose (HPMC) molecular parameters on cement hydration. It was concluded that the degree of substitution is the most relevant factor on cement hydration kinetics, contrary to the molecular weight. Nevertheless, the major role played by the substitution degree has not been verified for other types of cellulose ethers such as hydroxyethyl cellulose (HEC), which generally possesses a higher hydration retarding capacity compared to HPMC and HEMC. In this frame, a study of the impact of HEC molecular parameters on cement hydration was performed. A negligible influence of the molecular weight was observed. Moreover, the results emphasize that the hydroxyethyl group content mainly determines the delay of cement hydration.     

纤维素醚的特点、制备及在工业中的应用

综述了纤维素醚的种类、制备方法、性能和特点,以及纤维素醚在石油、建筑、造纸、纺织、医药、食品、光电材料及日化工业中的应用,介绍了一些具有发展前景的纤维素醚类衍生物的新品种并展望其应用前景。     

取代基及分子量对非离子型纤维素醚表面特性的影响

根据Washburn的浸渍理论(Penetration Theory)和van Oss-Good- Chaudhury的组合理论(Combining Theory)及应用柱状灯芯技术(Column Wicking Technique),对几种非离子型纤维素醚,如甲基纤维素、羟丙基纤维素和羟丙基甲基纤维素的表面特性进行了测试。由于这些纤维素醚的取代基、取代度和分子量不同,所以它们的表面能及其组成部分有着明显的差异。数据说明,非离子型纤维素醚Lewis碱大于Lewis酸,表面自由能的主要成分是Lifshitz-van der Waals力。羟丙基的表面能及其成分都大于羟甲基。而在相同取代基和取代度的前提下,羟丙基纤维素的表面自由能正比于分子量;而羟丙基甲基纤维素的表面自由能则正比于取代度,反比于分子量。实验还发现非离子型纤维素醚中的取代基羟丙基和羟丙基甲基的表面能似乎都大于纤维素的表面能,而实验证明所测试得出的纤维素的表面能及其成分的数据是与文献所吻合的。     

乙羧氟草醚的合成

以间羟基苯甲酸和3,4-二氯三氟甲苯为原料,经过成盐、醚化、硝化、缩合4步反应得到乙羧氟草醚,所得产物化学结构经红外光谱、核磁共振谱及质谱等确证。反应总收率在75.0%以上,含量(HPLC)达89.0%。