_f-A_aD_d氢键体系的统计特征

基于氢键的形成和缩聚反应机理在统计意义下的相似性,利用高分子反应统计理论和反应动力学理论对氢键溶液的一个模型体系进行了相关讨论.给出了体系的溶胶分数和发生溶胶-凝胶相变的条件,指出质子受体基团间的竞争作用对溶胶凝胶相变点的影响,进而讨论了体系的数量分布函数和相关问题.     

Marcus theory of outer-sphere heterogeneous electron transfer reactions: dependence of the standard electrochemical rate constant on the hydrodynamic radius from high precision measurements of the oxidation of anthracene and its derivatives in nonaqueous solvents using the high-speed channel electrode

The validity of Marcus theory for outer-sphere heterogeneous electron transfer for the electro-oxidation of a range of anthracene derivatives in alkyl cyanide solvents is investigated. The precision measurement of these fast electron transfers (k(0) >or= 1 cm s(-1)) is achieved by use of the high-speed channel electrode and, where necessary, fast-scan cyclic voltammetry. First, the solvent effect on the rate of electron transfer is studied by considering the first oxidation wave of 9,10-diphenylanthracene in the alkyl cyanide solvents: acetonitrile, propionitrile, butyronitrile, and valeronitrile. Second, the variation of k(0) for a series of substituted anthracenes is investigated by analyzing the voltammetric response of the one-electron oxidations of 9-phenylanthracene, 9,10-dichloroanthracene, 9-chloroanthracene, 9,10-dicyanoanthracene, 9-cyanoanthracene, 9-nitroanthracene, 9,10-diphenylanthracene, and anthracene in acetonitrile. It is shown that the rate of electron transfer of a single compound in different alkyl cyanides is determined by the longitudinal dielectric relaxation properties of the solvent, while differences in rate between the substituted anthracenes in acetonitrile can be quantitatively rationalized by considering their relative hydrodynamic radii. This makes possible the accurate prediction of electron-transfer rates for a molecule by interpolation of rate constants known for related molecules.     

AB_3型超支化聚(酰胺-酯)的合成及缩聚动力学研究

采用丁二酸酐、三羟甲基氨基甲烷为主要原料 ,在冰水浴条件下 ,合成AB3型单体 ,然后进行熔融缩聚制得超支化聚 (酰胺 酯 ) ,没有出现凝胶现象 .采用Fourier变换红外谱仪 (FTIR)、粘度测试、端基分析等方法对其结构、特性粘数进行了表征 .同时对AB3型超支化聚 (酰胺 酯 )的缩聚反应动力学进行了研究 ,得出了130℃、14 0℃和 15 0℃时的缩聚反应速率常数 ,并进一步得出了缩聚反应活化能 .实验结果证明缩聚过程为自催化过程 ,且为三级反应     

A novel ditopic receptor and reversal of anion binding selectivity in the presence and absence of bound cation

A calix[4]arene-derived ditopic receptor 1 has been synthesized. In the absence of Na+, the receptor binds acetate in preference to diphenyl phosphate (as the tetrabutylammonium salts), but in the presence of Na+, the selectivity is reversed and the receptor, instead, binds diphenyl phosphate, and not acetate, which preferentially forms a salt ion-pair in free solution. [structure: see text]     

Dye guest-host effects in ferroelectric liquid crystals

Here we present the optic and electro-optic characteristics of ferroelectric dye guest-host devices incorporating different dye and S*_C host materials. We demonstrate fast response time (< 100 μs) single polarizer and zero-polarizer device configurations for high order parameter dichroic dyes and single polarizer fluorescent dye devices. The dynamic data include measurements of response times as functions of voltage, temperature and dye concentration, from which we conclude that the inclusion of certain dyes does not adversely affect the ferroelectric phase. The contrast ratios of these novel guest-host devices are also presented and are shown, as expected, to be functions of tilt angle (and therefore temperature). However, we demonstrate that the high tilt angle of 45° is not necessary for high contrast devices, and in fact for certain devices configurations θ = 22½° is optimum. These results are discussed.     

New synthetic routes to the kainoids: a synthesis of kainic acid and its analogues

New approaches to the synthesis of kainic acid and its analogues are presented. Two distinctly different approaches are described; the former utilised an intermolecular nitrile oxide addition to a homochiral substrate to furnish epikainate models and the second utilised amino acid chemistry to secure kainic acid.     

Developing expertise: how enactivism re-frames mathematics teacher development

In this article, we present a re-framing of teacher development that derives from our convictions regarding the enactive approach to cognition and the biological basis of being. We firstly set out our enactivist stance and then distinguish our approach to teacher development from others in the mathematics education literature. We show how a way of working that develops expertise runs through all mathematics education courses at the University of Bristol, and distil key principles for running collaborative groups of teachers. We exemplify these principles further through analysis of one group that met over 2 years as part of a research project focused on the work of Gattegno. We provide evidence for the effectiveness of the group in terms of teacher development. We conclude by arguing that the way of working in this group cannot be separated from the history of interaction of participants.     

Formation of spiro and ansa derivatives in the reaction of 2,2,3,3,4,4-hexafluoropentane-1,5-diol with cyclotriphosphazene: Comparison with 2,2,3,3-tetrafluorobutane-1,4-diol

Reaction of cyclophosphazene, N₃P₃Cl₆ (1), with the sodium derivative of the fluorinated diol, 2,2,3,3,4,4-hexafluoropentane-1,5-diol (2), in THF solution at room temperature afforded five isolated products, whose structures have been characterised by X-ray crystallography and ¹H, ¹⁹F and ³¹P NMR spectroscopy: the mono-spiro compound, N₃P₃Cl₄(OCH₂CF₂CF₂CF₂CH₂O) (3), its ansa isomer (4), a di-spiro derivative N₃P₃Cl₂(OCH₂CF₂CF₂CF₂CH₂O)₂ (5), its spiro-ansa (6) isomer and the tri-spiro compound N₃P₃(OCH₂CF₂CF₂CF₂CH₂O)₃ (7). Quantitative ³¹P NMR measurements of the soluble portion of the reaction mixture show that in the reaction of (1) with the sodium derivative of the fluorinated pentanediol (2) there is a small preference for spiro compounds compared to ansa compounds (ratio ca. 1.3:1), similar to the analogous reaction of (1) with the sodium derivative of the fluorinated butanediol where there is a slightly greater proportion of spiro compared to ansa compounds (ratio ca. 1.5:1). The relative proportions of spiro and ansa compounds is likely to depend on the fine balance in stabilities of the different medium-sized rings in the fluorinated pentanediol (spiro, 8- and ansa, 10-membered rings) compared to the fluorinated butanediol (spiro, 7- and ansa, nine-membered rings) derivatives of cyclophosphazene.     

2-amidopyrroles and 2,5-diamidopyrroles as simple anion binding agents.

Four new 2-amidopyrroles and 2,5-diamidopyrroles have been synthesized and their anion complexation properties investigated. The crystal structures of these receptors have been elucidated and reveal hydrogen bonding in the solid state leading to dimer and network formation. Selectivity for oxo-anions has been demonstrated by (1)H NMR titration techniques.     

The synthesis and characterization of lipophilic peptide-based carriers for gene delivery

Lipophilic carriers have shown great potential in improving the delivery of gene therapeutics. We have synthesized positively charged peptide-based carriers including lipoamino acids. The carriers were shown to interact with DNA by performing isothermal titration calorimetry and particle size and zeta potential experiments. An exothermic reaction resulted from the titration of carrier into DNA. The particle sizes of the carrier/DNA complexes varied over the different charge ratios from 200-800 nm. The zeta potential was negative at a low charge ratio but positive when the amount of carrier was increased. The utilisation of lipophilic carriers is a promising approach to improve the bioavailability of gene delivery.