中国专利摘要

具有双乙烯砜基和双发色团的活性染料及其合成方法公开号 CN 1182769申请人 华东理工大学（上海市梅陇路130号,200237）发明人 姚胜 公开了一种具有双乙烯砜基和双发色团的活性染料及真合成方法,该染料以均三嗪环为桥基连接了两个发色母体,其中一个发色母体含有乙烯砜活性基,另一个乙烯砜活性基连在均三嗪环上,另一个发色母体则可以是任一常见的含氨基的发色母体,该染料具有相当广的色谱,同时该染料具有较高的分     

喹喔啉类抗生素的定性构效关系研究进展

通过分析发色团、硫交联桥、核心环缩肽及其氨基酸组成与其抗菌活性的关系,对一组喹喔啉类抗生素进行了定性构效关系研究.结果显示,发色团对活性有一定影响,具喹喔啉发色团的化合物抗菌活性高于喹啉发色团,6位溴取代喹啉发色团可能有利于抗菌活性的提高;硫缩醛交联桥对活性的贡献优于甲基化的二硫桥,交联桥的烷基化程度对活性也有影响,核心环缩肽的存在是维持抗菌活性的必要条件.     

乙撑双二硫代氨基甲酸盐类农药残留研究进展

主要概述了乙撑双二硫代氨基甲酸盐类农药残留分析方法研究进展。内容包括国内外关于乙撑双二硫代氨基甲酸盐类农药在不同作物上的残留动态、在食品加工过程中残留量的变化、在样品储藏过程中残留量的变化以及在农产品中残留的变化。     

乙撑双二硫代氨基甲酸锰二水合物脱水热力学研究

本文确定了乙撑双二硫代氨基甲酸锰二水合物(Maneb·2H_2O)在80℃脱去结晶水的离解压力为12557.23Pa,应用差示扫描量热法(DSC)测定其脱水焓变为84.30KJ·m0l~(-1),根据范特霍夫方程得到了脱结晶水离解压与脱水温度的关系式,因而提供了制备高纯度乙撑双二硫代氯基甲酸锰的理论指导。     

亚胺基二甲撑膦酸的合成研究

以碳酸铵、三氯化磷、甲醛为原料合成亚胺二甲撑膦酸，并经过一步转化催化使亚胺基二甲撑膦酸上对于二甲撑和三甲撑的含量达９５％以上。     

白色阻燃剂N，N′-乙撑双四溴邻苯二甲酰亚胺合成新方法

以邻苯二甲酸酐和乙二胺为原料,水作介质,先制得N,N′-乙撑双邻苯二甲酰亚胺(EPB),然后经溴代及老化处理合成出白色阻燃剂N,N′-乙撑双四溴邻苯二甲酰亚胺。讨论了回流时间对EPB产率的影响及发烟硫酸中SO3对溴素的利用率、溴代产率的影响,并分析了老化前后EBT的热失重情况。此新方法不采用任何有机溶剂和有机助剂,成本低,污染小,产品纯度高,外观洁白,全程总收率大于80％。     

不同取代基的噻碳菁和吲哚碳菁染料对其在溴化银微晶上吸附能力及形成J-聚集体尺寸分布的影响

本文研究了５－位不同取代基的噻碳菁和吲哚碳菁染料对其在立方型颗粒和Ｔ－颗粒溴化银微晶上吸附能力的影响，并采用ＡＣＦＥＭ（ＡｎａｌｙｔｉｃａｌＣｏｌｏｒＦｌｕｏｒｅｓｃｅｎｃｅＥｌｅｃｔｒｏｎＭｉｃｒｏｓｃｏｐｙ）研究了上述结构染料对其吸附在溴化银微晶所形成的Ｊ－聚集体尺寸分布的影响．实验结果表明，对吲哚碳菁染料来说，立方体溴化银微晶表面的吸附能力较Ｔ－颗粒溴化银微晶表面的吸附能力强；但对噻碳菁染料来说则相反，它们在Ｔ－颗粒溴化银微晶表面的吸附能力较立方体溴化银微晶表面的吸附能力强．另外，对５－位不同取代基的噻碳菁染料而言，无论是在立方型颗粒或Ｔ－颗粒溴化银微晶上的吸附能力来说，含取代基（无论４－取代基是吸电子型还是推电子型）的噻碳菁染料较未取代的噻碳菁染料强；而５－位取代基是吸电子型的噻碳菁染料更有利于其吸附在Ｔ－颗粒溴化银微晶表面．此外，本文还进一步证明了溴化银微晶表面上染料Ｊ－聚集体的生长过程是符合奥斯瓦尔特成熟过程的．吲哚碳菁染料在Ｔ－颗粒溴化银微晶上形成的Ｊ－聚集体的平均尺寸明显大于在立方体溴化银微晶上形成的Ｊ－聚集体的平均尺寸．吸附在立方体溴化银微晶上的５－不同取代基的噻碳菁染料对其形成Ｊ－聚集体     

红藻条斑紫菜R—藻红蛋白中的能量传递过程

本文通过对条斑紫菜Ｒ－ＰＥ（藻红蛋白）及其α、β、２亚基的吸收光谱和荧光光谱进行计算机解叠，研究了Ｒ－ＰＥ内发色团之间的能量传递过程，并对Ｒ－ＰＥ及亚基门的各发色团进行了“Ｓ”和“ｆ”型的指认。发现在亚基中为“ｆ”型的发色团在Ｒ－ＰＥ中起着“ｓ”型发色团的作用，且将能量传递给量最后的“ｆ”型发色团。荣光激发偏振光谱进一步证明了Ｒ－ＰＥ内的能量转移过程与计算机解叠的结果一致。     

双-β-萘甲酸多缩乙二醇酯在甲醇溶液中分子的构象和分子内激基缔合物的形成

本文研究了双-β-萘甲酸多缩乙二醇酯(P_n)在不同溶剂中的稳态和时间分辨荧光光谱。在甲醇中与在四氢呋喃中不同,P_n显示很强的激基缔合物荧光。表明在甲醇中疏水的两个末端发色团彼此靠近,亲水的多缩乙二醇链段包于两个发色团外部。热力学和动力学研究求出了P_n分子内激基缔合物形成的焓变是—20kJ/mol,活化能为～8.5kJ/mol,激基缔合物形成和离解的速度常数分别为4.5×10~8s~(-1)和3.1×10~8s~(-1)。     

红藻条斑紫菜R－藻红蛋白中的能量传递过程

本文通过对条斑紫菜Ｒ－ＰＥ（藻红蛋白）及其α－β－γ亚基的吸收光谱和荧光光谱进行计算机解叠，研究了Ｒ－ＰＥ内发色团之间的能量传递过程，并对Ｒ－ＰＥ及亚基内的各发色团进行了“ｓ”和“ｆ”型的指认。发现在亚基中为“ｆ”型的发色团在Ｒ－ｐＥ（αβ）＿６γ中起着“ｓ”型发色团的作用，且将能量传递给最后的“ｆ”型发色团。荧光激发偏振光谱进一步证明了Ｒ－ＰＥ内的能量转移过程与计算机解叠的结果一致。     

Environmental Effects on the Fluorescence of Tryptophan and Other Indole Derivatives

The fluorescence quantum yields of tryptophan, 3-methylindole and 3-β-hydroxyethylindole were investigated as a function of temperature in a variety of polar and non polar solvents. Similar quantum yields and “activation energies” were found for the different systems. It was concluded that the same collisional solvent deactivation is responsible for the decrease in quantum yield with temperature irrespective of solvent system used. A notable exception is water where a different mechanism is indicated. The quenching of the indole chromophore fluorescence by a variety of specific agents both attached to the ring by an ethylene bridge and in homogeneous solution was also studied. It was found that potential proton donating groups were good quenching agents, the effect being much greater for groups carrying a positive charge. Polarization by a neighboring group also enhanced the quenching ability of any specific group. It was concluded that an excited state charge transfer complex is probably involved as a first step in the quenching process.     

Polymethine dyes derived from the boron difluoride complex of 3-acetyl-5,7-di(pyrrolidin-1-yl)-4-hydroxycoumarin

A boron difluoride complex of 3-acetyl-5,7-di(pyrrolidin-1-yl)-4-hydroxycoumarin was synthesized and converted into polymethine dyes which included an anionic, symmetric cyanine and several merocyanine compounds. The spectral luminescent behaviour of the dyes was studied. As the electron-withdrawing ability of the 2,2-difluoro-1,3,2-dioxaborine ring was significantly reduced by the two pyrrolidino groups on the latter nucleus, the newly synthesized dyes exhibited changes in spectral parameters and much increased resistance to hydrolysis.     

New second-order nonlinear optical polymers containing the same isolation groups: Optimized syntheses and nonlinear optical properties

Based on control experiments, a new series of second-order nonlinear optical polymers with fluorene moieties as isolation spacers were successfully prepared. In the polymers, the chromophore moieties were embedded into the polymer backbone with one position at the donor side, and another point in the π bridge. Different acceptors were used to construct the push-pull structure of chromophore moieties, including nitro groups, sulfonyl groups, 3-phenyl-5-isoxazolone, 1,3-diethylthiobarbituric acid and TCF groups. The tested NLO properties of the polymers demonstrated that the isolation groups with big size do not always benefit the resultant NLO effect. Also, for different acceptors, there should be different suitable isolation groups to balance the good and bad effects caused by the introduced isolation spacers.     

Cyanine dyes from polynitro- and poly(trifluoromethylsulphonyl)-benzenes

New monomethine and trimethine cyanine dyes with benzothiazole or indole and polynitro- or poly(trifluoromethylsulphonyl)-substituted benzene rings attached to the ends of the polymethine chain have been synthesised. Atoms of fluorine or methyl groups were introduced to the α-position of the polymethine chain. The influence of nitro and trifluoromethylsulphonyl groups on the colour of these dyes is compared. It is shown that the CF₃SO₂ group is a weaker auxochrome than the nitro group.     

Control of the J-Aggregation Phenomenon by variation of the N-alkyl-substituents

Cyanine dyes ( 1a–d ) with the 5,5′,6,6′-tetrachloro-1,1′-dialkyl-3,3′-di-(3-carboxypropyl)-benzimidocarbocyanine chromophore differing only in the chain length of their alkyl groups in 1,1′-position have been synthesized, spectroscopically characterized, and compared with 5,5′6,6′-tetrachloro-1,1′-diethyl-3,3′-di-(4-sulfobutyl)-benzimidocarbocyanine( TDBC ). In aqueous solution the dyes form J-aggregates which, depending on the alkyl group chain length, exhibit J-bands differing in spectral positions, bandwidth, and in the number of peaks.     

Preparation of multiphase block copolymers by redox polymerization process, 4. Polymerization of methyl methacrylate by the redox system Mn(III)-poly(ethylene glycol) containing azo groups

Redox polymerization of methyl methacrylate using Mn(III) with poly(ethylene glycol) having azo and hydroxy functions was carried out to yield ethylene glycolmethyl methacrylate block copolymers with labile azo linkages in the main chain. These prepolymers were used to initiate free-radical polymerization of styrene through thermal decomposition of the azo groups, resulting in the formation of multiblock copolymers. Successful blocking has been confirmed by fractional precipitation, a strong change in the molecular weight, and spectral measurements.     

茂金属催化剂用于乙烯聚合的研究和开发

在研究开发适合于浆液法聚乙烯生产工艺的茂金属催化剂的实验研究中，深入研究了桥链和非桥链，不同中心金属和茂环引入取代基等催化剂对乙烯聚合的影响。     

Mutagenic stabilization of the photocycle intermediate of green fluorescent protein (GFP)

The optical spectra of the Aequorea victoria green fluorescent protein (GFP) are governed by an equilibrium between three different chromophore states. Mutants that predominantly show either the protonated (A) or the deprotonated (B) form of the chromophore have previously been described. In contrast, the I form, which is formed by rapid excited-state deprotonation of the A form of the chromophore, has only been described as an obligatory photochemical intermediate. We report the design of a new GFP mutant with a stabilized I form. For this purpose, we introduced two isosteric point mutations, Thr203Val and Glu222Gln, that selectively raise the potential energy of both the A and the B form. Knowledge of the absorption spectrum of the I form at room temperature allows the detailed analysis of concentration dependent changes in bulk wild-type(wt)-GFP spectra, as well as the determination of the dimerization constant of GFP. This information expands the use of GFP to that of a spectral probe for protein concentration. We determined energy differences between the chromophore ground states in the monomer and the dimer and reconstructed part of the potential energy surface.     

Synthesis and Antimalarial Properties of Streptocyanine Dyes

Several streptocyanine dyes were synthesized that contain polymethine chains of varying length. Their in vitro antimalarial activities were evaluated against the virulent P. falciparum parasite. In addition to the influence of polymethine chain length, the effects of structural modifications at nitrogen end groups, para substitution of the phenyl groups, and counter‐anions were studied. The most potent antimalarial activities were found for heptacarbon chain streptocyanines, with an IC₅₀ value of 60 nM . Interestingly, most of the compounds were less cytotoxic toward the mammalian cells tested. The best selective toxicity profiles were found for pentacarbon chain streptocyanines, which have a good in vitro specificity index.     

Photoresponsive optically active polymers—a review

Photoresponsive macromolecules are of interest both as novel organic materials for applications in photodevices and as models for photomodulated biological processes. The presence in polymer chains of photosensitive groups and of chiral groups capable of inducing optical activity into the polymer is very useful for the analysis of photomodulated structural variations and allows storage of the light effect in the form of chiral information. Polypeptides bearing photochromic groups in the side chains are very convenient as the chiroptical properties of the peptide chromophore can be correlated to the backbone conformation. Thus polymers of L-aspartic acid, L-glutamic acid and L-lysine with azobenzene or stilbene groups attached covalently to the side chains are discussed in terms of photoinduced conformational changes and chiroptical information storage in the spectral region of the peptide and of the photoresponsive chromophore. Optically active photochromic macromolecules with hydrocarbon backbone, such as copolymers of (—)-menthyl acrylate with vinyl or acryloyl derivatives of azobenzene, stilbene and indolinospirobenzopyran, also show in some cases photodependence of chiroptical properties with evidence of at least local conformational changes as a consequence of light irradiation which can be used for chiral information.