水溶性光聚合引发剂研究进展

近几年发展起来的水溶性光聚合引发剂（ＷＳＰ）属自由基引发剂，按结构可分为芳酮类，稠环类烃类，聚硅烷类，酰基膦酸盐等，偶氮类及金属有机配合物类，本文综述了这些光引发剂的结构特性，光化学行为，光引发效率及光反应机理等。     

Development of a capillary electrophoresis method for the characterization of collagens in cartilage tissue

The use of capillary electrophoresis (CE) for the separation of peptides specific to type I and type II collagen is evaluated. The aim of this work is to develop a method to characterize cartilage, cartilage repair tissue, and tissue engineered cartilage. The analysis is dependent on the cleavage of collagen into constituent peptides by cyanogen bromide. A number of these peptides are specific to the collagen type. CE is evaluated for the separation of these specific peptides using uncoated and coated capillaries over a wide range of pH and buffer concentrations. Separation of peptides specific to type I and type II collagen is achieved using a Supelco CElect N capillary and a 100mM phosphate buffer at pH 6. Meniscal cartilage is characterized using this method. The proportion of type I collagen to type II collagen corresponds well with that reported by others and indicates the potential of this method for the characterization of cartilage.     

Analytical laser ionization spectrometry in flame: Choice of the analytical form for the determination of rare earth elements

Based on the ionization potentials and dissociation energies of rare earth monoxides, these molecules are classified into two groups. For the molecules of the first type, the ionization potential is lower than the dissociation energy. Laser excitation of these molecules leads to their predominant ionization. For the molecules of the second type, the ionization potential is higher than the dissociation energy. Depending on the absolute values of the latter, atomic lines can be observed in the ionization spectrum. The elements that form molecules of the first type in flame should be determined as monoxide molecules. For the elements forming molecules of the second type, determination in the atomic form gives better results.     

PHTHALOCYANINE AND NAPHTHALOCYANINE PHOTOSENSITIZED OXIDATION OF 2'-DEOXYGUANOSINE: DISTINCT TYPE I AND TYPE II PRODUCTS

Abstract
The photodynamic properties of the di-and tetrasulfonated zinc and aluminium phthalocyanines and a tetrasulfonated aluminium napththalocyanine were studied using 2'-deoxyguanosine as a DNA model compound. The major photooxidation products of this nucleoside were identified and classified according to their formation through a radical mechanism (type I) or a singlet oxygen mediated mechanism (type II). The major type I product was obtained and identified as 2,2-diamino [(2-deoxy-β- d - erythro pentofuranosyl)-4-amino]-5( 2H )-oxazolone. Two major type II products were characterized as the 4R* and 4S* diastereomers of 9-(2-deoxy-β- d - erythro pentofuranosyl)-7,8-dihydro-4-hydroxy-8-oxoguanine. In addition a third product, also resulting from a type II photooxidation, was identified as 8-oxo-7,8-dihydro-2'-deoxyguanosine. Quantification of these products provided a means to estimate the contribution of type I and type II pathways during the phthalocyanine and naphthalocyanine mediated photooxidation of 2'-deoxyguanosine, confirming the major role of singlet oxygen in these processes.     

Three types of reactions with intramolecular five-membered ring compounds in organic synthesis

There are three types of reactions with intramolecular five-membered ring compounds in organic syntheses: The first type is reactions involving intramolecular five-membered ring compounds which are utilized for the ease of synthesis of these compounds and the stability of the products. The second is reactions performed via intramolecular five-membered ring intermediates, because such intermediates are very reactive and labile compounds. The third is the metal-catalyzed reactions with the intramolecular five-membered ring compounds because these metal compounds have catalytic activities. The third type reactions involving intramolecular five-membered ring pincer compounds are also provided.The first type reactions include carbonylations, alkenylations, alkynylations, acylations, isocyanations, Diels-Alder reactions, etc. The second type reactions include carbonylations, cross-coupling reactions, hydroacylations, ring expansion reactions, carbocyclizations, etc. The third type reactions include cross-coupling reactions, rearrangements, metatheses, reductions, Michael reactions, dehydrogenations, Diels-Alder reactions, etc.     

PHTHALOCYANINE AND NAPHTHALOCYANINE PHOTOSENSITIZED OXIDATION OF 2'-DEOXYGUANOSINE

Abstract— The photodynamic properties of the di-and tetrasulfonated zinc and aluminium phthalocyanines and a tetrasulfonated aluminium napththalocyanine were studied using 2'-deoxyguanosine as a DNA model compound. The major photooxidation products of this nucleoside were identified and classified according to their formation through a radical mechanism (type I) or a singlet oxygen mediated mechanism (type II). The major type I product was obtained and identified as 2,2-diamino [(2-deoxy-β- d - erythro pentofuranosyl)-4-amino]-5( 2H )-oxazolone. Two major type II products were characterized as the 4R* and 4S* diastereomers of 9-(2-deoxy-β- d - erythro pentofuranosyl)-7,8-dihydro-4-hydroxy-8-oxoguanine. In addition a third product, also resulting from a type II photooxidation, was identified as 8-oxo-7,8-dihydro-2'-deoxyguanosine. Quantification of these products provided a means to estimate the contribution of type I and type II pathways during the phthalocyanine and naphthalocyanine mediated photooxidation of 2'-deoxyguanosine, confirming the major role of singlet oxygen in these processes.     

主链型液晶聚硅氧烷聚氨酯的合成及性质

合成了主链型联苯类及氧化偶氯苯类液晶聚硅氧烷聚氨酯弹性体，采用红外光谱，示差扫描量热，动态粘弹谱及带热台偏光显微镜等方法对聚合物进行了表征，讨论了它们的结构与性能．研究结果表明，这一系列多嵌段聚氨酯多数是向列型的液晶高分子聚合物，液晶相的形成同嵌段聚氨酯样品的软硬段相互作用有着密切的联系     

Infrared spectra of some polybasic acid triphenyltin IV derivatives

Triphenyltin IV polybasic acid derivatives have been synthesized, and structures suggested on the basis of their IR spectra. Tetrahedral oxoanions behave as polydentate ligands giving infinite type structures. The cleavage of these infinite type structures occurs when the derivatives react with strong Lewis bases giving discrete structure adducts. A particular type of coordination of the selenite (tetradentate) has been established.     

POLYIONIC COMPLEXES DERIVED FROM POLYVINYL ALCOHOL Ⅰ. PREPARATION AND THEIR SOLVATION BEHAVIOR*

Polycations and polyanions of polyvinyl alcohol (PVA) with various substitution degrees were pre-pared by acetalization of PVA with aldehyde derivatives such as p-formylbenzoic acid, glyoxalic acid, p-formyl-benzenesulfonic acid, p-formylpyridine, and p-dimethylaminobenzaldehyde and then neutral-ized or quaternarized with methyl iodide. The corresponding PVA type polyionic complexes wereobtained by mixing the aqueous solutions of these polycations and polyanions. The solvation behaviourof these polyionic complexes were investigated. It was found that the H_2O-DMF-NaSCN solventsystem is superior to the H_2O-DMF-NaBr system for these PVA type polyionic complexes.     

Chromatographic separation of four Ser/Thr-protein phosphatases from solubilized ciliary membranes of Paramecium tetraurelia by heparin-sepharose

Chromatography of deoxycholate-solubilized proteins from Paramecium ciliary membranes on heparin-Sepharose resolved three peaks of protein phosphatase activities: one type 2A-like and a type 2C phosphatase in the flow-through fractions, another type 2A-like enzyme in the 0.1 M NaCl eluate and type 1 protein phosphatase in the 0.5 M NaCl eluate. The differential sensitivity of the two type 2A-like phosphatases to heparin and protamine further substantiated the existence of distinct isozymes. Once solubilized, none of these ciliary phosphatases required detergent to remain soluble. The molecular mass as determined by chromatography on Superose 6 was in the range 30,000-45,000 dalton for all four protein phosphatases.     

[2+3] Cyclopentene annulation and other trimethylsilyl iodide-mediated rearrangement pathways of vinylcyclopropanes

Vinylcyclopropanes of type 2 were converted to either annulated cyclopentenes of type 3 or bicyclo [3.2.1] octenes of type 4 through carefully controlled rearrangement pathways. Factors affecting these rearrangements and their utility in synthesis are described.     

New access to fluorinated ketoglycolic acid derivatives from trifluoropyruvamides

Hydrates of trifluoropyruvamides are readily obtained from isocyanides and trifluoroacetic anhydride. Under catalysis with secondary amines, these hydrates were successfully reacted with various methylketones to form fluorinated aldol type compounds. The effect of the amine is discussed as well as Henry type additions with nitromethane.     

Novel Emission Color‐Tuning Strategies in Heteroleptic Phosphorescent Ir(III) and Pt(II) Complexes

Color‐tuning for phosphorescent emitters in organic light‐emitting diodes (OLEDs) across the entire visible spectrum is prerequisite to fulfil flexible full‐color displays and white solid‐state lighting. Heteroleptic 2‐phenylpyridine‐type (ppy‐type) Ir(III) and Pt(II) complexes as phosphorescent emitters have been well exploited in the electroluminescence (EL) field due to their outstanding EL performance. Furthermore, the photophysical characters of these heteroleptic Ir(III) and Pt(II) complexes are generally dominated by the nature of cyclometalating ppy‐type ligands. Accordingly, either sophisticated modification or judicious combination of different cyclometalating ppy‐type ligands will provide a wonderful platform to tune their emission color. In this personal account, we put a special emphasis on our contributions to the novel color‐tuning strategies in these heteroleptic ppy‐type Ir(III) and Pt(II) complexes. In addition, afforded by our novel color‐tuning strategies, ambipolar character or enhanced electron injection/transport (EI/ET) features can be furnished to bring high EL performances.     

Design and synthesis of readily degradable acyloxysilane dendrimers

Two types of dendrimers with AB₂ branching, one with acyloxysilanes at the branching position (V type) and the other at the non-branching position (Y type), were synthesized using hydrosilylation with chlorosilanes followed by heterofunctional condensation with olefin-functional carboxylic acids, and examined as readily degradable template materials. The V type dendrimer was much more susceptible to ligand redistribution with chlorosilanes during preparation, whereas the Y type was less. The acyloxysilane linkages in these dendrimers could be cleaved readily by alcoholysis or hydrolysis on demand, making for suitable templates.     

羟基喹啉偶氮类化合物的互变异构与顺反异构的研究

本工作合成了数种带不同取代苯基的羟基喹啉偶氮类化合物。对它们在不同溶剂。不同酸碱度溶液中的偶氮式及腙式间互变异构平衡进行了研究。苯环上不同取代基的引入可引起平衡发生变化。拉电子基的引入有利于腙式结构的形成,而推电子基的引入则对偶氮的生成影响不大。此外,工作中还发现:羟基喹啉偶氮化合物在光照下存在着以偶氮顺-反异构化反应为主的变化过程。     

氮杂冠醚研究Ⅺ．叔胺型氮杂冠醚的合成

１１种酰胺型氮杂冠醚用ＬｉＡｌＨ４－ＴＨＦ体系还原，高收率地合成了新的叔胺型氮杂冠醚；通过２，３－苯并－１０－氮杂－１，４，７，１３－四氧杂环十五－２－烯与丙烯腈进行氰乙基化反应，同样制得了一种新的叔胺型氮杂冠醚。１２种新化合物的结构均经元素分析、ＩＲ、１ＨＮＭＲ和ＭＳ所证实。讨论了这类氮杂冠醚的质谱裂解过程     

基于分子间侧向氢键作用的电光材料制备及性能

通过重氮耦合和酯化等反应制备了一系列侧向含有酰胺基团的偶氮苯类非线性光学生色团, 并将其与聚合物进行掺杂或通过分子间的侧向氢键作用制备了主客体型及超分子型的电光薄膜材料. 生色团的结构通过核磁共振谱(¹H NMR, NMR)、 红外光谱(IR)、 质谱(MS)和元素分析(EA)等进行了表征, 结果表明, 生色团形成了分子间的氢键作用. 通过紫外-可见(UV-Vis) 光谱研究了材料的极化性能. 相比主客体型电光薄膜材料, 由分子间侧向氢键作用形成的超分子型电光薄膜材料无需与聚合物基体材料复合, 更有利于提高材料的生色团含量、 极化取向度及稳定性. 通过Teng-Man简单反射法研究了主客体型和超分子型电光材料的二阶非线性光学性质, 结果表明, 基于分子间侧向氢键作用形成的超分子体系具有更大的电光系数.     

Functionalized phosphorus derivatives of Salpen-like compounds: Synthesis and preliminary complexation studies

A new class of Salpen analogues based on phosphorus derivatives where the classical alkylene backbone has been replaced by a N-P-N linkage is described. Such linkage both affords a very good stability in water and an additional (fifth) potentially complexing site. The classical ortho-OH groups have been also replaced by various ortho-substituents, including diphenylphosphino groups. The synthesis of these compounds is easy and their structure can be varied at will at several levels. Several ways of synthesis can be used to combine the various fragments constituting these Salpen analogues. The structure of one of these fragments, an azide, was determined by X-ray crystallography. A preliminary study of the complexation ability of some of these new ligands was carried out with groups 10 (Ni) and 11 (Au) elements. Depending on the type of substituents and the type of metals used, these compounds can act as mono-, or tetra-dentate ligands.     

Interaction of poly(styrene sulfonate) with polycations carrying charges in the chain backbone

The interaction between sodium poly(styrene sulfonate) (NaSS) and side-chain charged polycation polymer (pendent type) or main-chain charged polycation polymer (integral type) has been studied. It was found that the polyion complex (the reaction product of these polyelectrolytes) of pendent–pendent type has an equimolar composition at any mixing ratio of two component polymers. However, a polyion complex of integral–pendent type can form a water-soluble complex with a ratio of [polycation]/[polyanion] = 1/3, in addition to a complex with a equimolar composition. The mechanism of formation of this specific complex is discussed.     

Organic nanodielectrics for low voltage carbon nanotube thin film transistors and complementary logic gates

We report the implementation of three dimensionally cross-linked, organic nanodielectric multilayers as ultrathin gate dielectrics for a type of thin film transistor device that uses networks of single-walled carbon nanotubes as effective semiconductor thin films. Unipolar n- and p-channel devices are demonstrated by use of polymer coatings to control the behavior of the networks. Monolithically integrating these devices yields complementary logic gates. The organic multilayers provide exceptionally good gate dielectrics for these systems and allow for low voltage, low hysteresis operation. The excellent performance characteristics suggest that organic dielectrics of this general type could provide a promising path to SWNT-based thin film electronics.