无光敏剂光引发亲水性单体在嵌段聚醚氨酯膜上接枝聚合的研究

<正> 嵌段聚醚氨酯(SPEU)是一类应用广泛的医用高分子材料。用亲水性单体进行表面接枝改性,已有不少研究,接枝聚合方法有铈盐引发、辐射引发以及光敏引发等。 本文研究一种新的接枝方法,不加光敏剂,用紫外光照射,直接引发亲水性单体接枝于SPEU膜上、接枝的单体有丙烯酰胺(AAM)与N,N-二甲基丙烯酰胺(DMAA),从接枝前后膜的性能变化可以证实接枝反应的发生。文中研究了反应条件与单体结构对接枝率的影响,并通过模型化合物,对接枝部位进行了研究。     

Supramolecular framework adducts constructed of hexamethylenetetramine,aquated alkali metal cationic clusters,and hexacyanoferrates(II/III)

The reaction of alkali metal hexacyanoferrate(II/III) with (CH₂)₆N₄ (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK₂[Fe¹¹¹(CN)₆]·2HMT·4H₂O, H₂K₂[Fe¹¹(CN)₆]·2HMT·4H₂O, and HNa₂[Fe¹¹¹(CN)₆]· 2HMT·5H₂O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)₆]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate.     

HCl-NaCl-C3H8O3-H2O体系溶液热力学性质

在恒定丙三醇质量分数x=0．1的条件下，测定了无液接电池（A）和电池（B）的电动势根据电池（A）电动势确定了丙三醇和水混合溶剂中的Ag－AgCl电极的标准电极电势，讨论了HCl的迁移性质；由电池（B）测得的电动势计算了HCl在该体系中的活度系数γA，计算的结果表明，对于所讨论的体系，在溶液中总离子强度保持恒定，HCl的活度系数服从Harned规则．在溶液组成恒定时，IgγA是温度倒数1／T的线性函数，讨论了混合物中HCl的相对偏摩尔焓及介质效应．     

Determination of Tiopronin in Human Plasma by SPE then Reversed-Phase HPLC–UV

An accurate, simple and sensitive method based on reversed-phase high-performance liquid chromatography with UV detection has been developed for determination of tiopronin (TP) in human plasma. TP in plasma was reacted with p-bromophenacyl bromide (p-BPB) to give the TP-p-BPB adduct and this derivative was then extracted from the plasma on a silica gel cartridge. Potential interfering compounds were removed by washing with water, and the TP-p-BPB adduct was then eluted with acetonitrile. The organic phase obtained was evaporated to complete dryness under a stream of nitrogen. The residue was dissolved in acetonitrile and this solution was injected on to a reversed-phase ODS HPLC column. The mobile phase was usually the ternary mixture acetonitrile–water–trifluoroacetic acid, 40:59.88:0.12 (v/v). The retention times of TP-p-BPB and the internal standard adduct were 14.4 and 17.9 min, respectively. No interfering peaks were encountered in several blank plasma samples examined. The limit of detection for TP was 12 ng mL^?1. Extraction recovery exceeded 70%. The calibration plot for the TP derivative was linear in the range 40?4000 ng mL^?1, regression coefficient 0.9989, and the coefficient of the variation of the points of the calibration plot was below 10%. The method was validated appropriately and successfully applied to the determination of TP in human plasma.     

Syntheses, structures, and magnetic properties of unusual nonlinear polynuclear copper(II) complexes containing derivatives of 1,2,4-triazole and pivalate ligands

Novel polynuclear Cu(II) complexes containing derivatives of 1,2,4-trizaole and pivalate ligands, [Cu(3)(mu(3)-OH)(mu-adetrz)(2)(piv)(5)(H(2)O)].6.5H(2)O (1) (adetrz = 4-amino-3,5-diethyl-1,2,4-triazole, piv = pivalate), [Cu(4)(mu(3)-OH)(2)(mu-atrz)(2)(mu-piv)(4)(piv)(2)].2MeOH.H(2)O (2) (atrz = 4-amino-1,2,4-triazole), [Cu(4)(mu(3)-OH)(2)(mu-tbtrz)(2)(mu-piv)(2)(piv)(4)].4H(2)O (3) (tbtrz = 4-tert-butyl-1,2,4-trizaole), and [Cu(4)(mu(3)-O)(2)(mu-admtrz)(4)(admtrz)(2)(mu-piv)(2)(piv)(2)].2[Cu(2)(mu-H(2)O)(mu-admtrz)(piv)(4)].13H(2)O [4 = 4a.2(4b).13H(2)O; admtrz = 4-amino-3,5-dimethyl-1,2,4-triazole], have been prepared and structurally characterized. 1 is an asymmetrical triangular complex containing a [Cu(3)(mu(3)-OH)] core with two Cu---Cu edges spanned by bridging adetrz ligands. 2, 3, and 4a are novel tetranuclear compounds containing a [Cu(4)(mu(3)-O)(2)] or [Cu(4)(mu(3)-OH)(2)] core with Cu---Cu edges spanned by bridging 1,2,4-triazole or pivalate ligands. 4b is a dinuclear compound with one admtrz and one water bridge, and it is the first dinuclear Cu(II) triazole complex with one bridging water molecule. 1 is one of few reported triangular Cu(II) complexes with derivatives of 1,2,4-triazole, while 2, 3, and 4a are the first group of the nonlinear tetranuclear Cu(II) compounds with derivatives of 1,2,4-triazole. Variable-temperature magnetic susceptibility studies on the powder samples of 1-3 reveal the overall antiferromagnetic coupling between Cu(II) ions with J values of -55.6 to -12.8 cm(-1) (1), -216.4 to 0 cm(-1) (2), and -259.8 to 4.8 cm(-1) (3).     

Determination of phosphoamino acids by micellar electrokinetic capillary chromatography with laser-induced fluorescence detection

A micellar electrokinetic capillary chromatography (MEKC) method with laser-induced fluorescence detection (LIF) was developed for analyzing three phosphoamino acids including phosphotyrosine (P-Tyr), phosphoserine (P-Ser), and phosphothreonine (P-Thr). 3-(2-Furoyl)quinoline-2-carboxaldehyde (FQ), a fluorogenic dye, was employed for derivatization of these phosphoamino acids. Results indicated that the complete baseline resolution of each phosphoamino acid was obtained within 10 min, using 20 mmol l⁻¹ sodium borate buffer (pH 9.35) containing 20 mmol l⁻¹sodium deoxycholate (SDC) and 10 mmol l⁻¹ Brij35. Other common amino acids, especially Glu and Asp, did not disturb the assay of these phosphoamino acids. There was a linear relationship between the peak area for analyte and its concentration, with correlation coefficients in the range of 0.9966-0.9996. The concentration detection limits (signal-to-noise = 3) for P-Tyr, P-Ser, and P-Thr were 10, 40, and 75 nmol l⁻¹, respectively. The developed method was successfully applied for determining phosphoamino acids in the hydrolysis sample of a phosphorylated protein kinase.     

Thermal analysis study of the effect of molecular weight on constrained amorphous phase in poly(phenylene sulfide)

We report a thermal analysis study of the effect of molecular weight on the amorphous phase structure of poly(phenylene sulfide), PPS, crystallized at temperatures just above the glass transition temperature. Thermal properties of Fortron PPS, having viscosity average molecular weights of 30000 to 91000, were characterized using temperature modulated differential scanning calorimetry (MDSC). We find that while crystallinity varies little with molecular weight, the heat capacity increment at the glass transition decreases as molecular weight decreases. This leads to a smaller liquid-like amorphous phase, and a larger rigid amorphous fraction, in the lower molecular weight PPS. For all molecular weights, constrained fraction decreases as the scan rate decreases.This research is supported by the U. S. Army Research Office through contract DAAH04-96-1-0009. The authors thank Hoechst Celanese for providing different molecular weight Fortron samples and Dr. George Collins for providing sample information. The authors acknowledge the assistance of Elizabeth Oyebode and Leonardo Grimaldi with sample preparation and MDSC work.     

Energy Landscape of Aptamer/Protein Complexes Studied by Single‐Molecule Force Spectroscopy

Aptamers are single‐stranded nucleic acid molecules selected in vitro to bind to a variety of target molecules. Aptamers bound to proteins are emerging as a new class of molecules that rival commonly used antibodies in both therapeutic and diagnostic applications. With the increasing application of aptamers as molecular probes for protein recognition, it is important to understand the molecular mechanism of aptamer–protein interaction. Recently, we developed a method of using atomic force microscopy (AFM) to study the single‐molecule rupture force of aptamer/protein complexes. In this work, we investigate further the unbinding dynamics of aptamer/protein complexes and their dissociation‐energy landscape by AFM. The dependence of single‐molecule force on the AFM loading rate was plotted for three aptamer/protein complexes and their dissociation rate constants, and other parameters characterizing their dissociation pathways were obtained. Furthermore, the single‐molecule force spectra of three aptamer/protein complexes were compared to those of the corresponding antibody/protein complexes in the same loading‐rate range. The results revealed two activation barriers and one intermediate state in the unbinding process of aptamer/protein complexes, which is different from the energy landscape of antibody/protein complexes. The results provide new information for the study of aptamer–protein interaction at the molecular level.     

In situ formation of a biomimetic lipid membrane triggered by an aggregation-enhanced photoligation chemistry

Nature or synthetic systems that can self-assemble into biomimetic membranes and form compartments in aqueous solution have received extensive attention. However, these systems often have the problems of requiring complex processes or lacking of control in simulating lipid synthesis and membrane formation of cells. This paper demonstrates a conceptually new strategy that uses a photoligation chemistry to convert nonmembrane molecules to yield liposomes. Lysosphingomyelin (Lyso) and 2-nitrobenzyl alcohol derivatives (NBs) are used as precursors and the amphiphilic character of Lyso promotes the formation of mixed aggregates with NBs, bringing the lipid precursors into close proximity. Light irradiation triggers the conversion of NBs into reactive aldehyde intermediates, and the preassembly facilitates the efficient and specific ligation between aldehyde and Lyso amine over other biomolecules, thereby accelerating the synthesis of phospholipids and forming membrane compartments similar to natural lipids. The light-controllable transformation represents the use of an external energy stimulus to form a biomimetic phospholipid membrane, which has a wide range of applications in medicinal chemistry, synthetic biological and abiogenesis.

A photoligation chemistry was used to drive the formation of biomimetic membranes in situ. The preassembly of precursors promotes the synthesis of lipid, which is an important feature as a candidate for simulating natural membrane functions.