酸酐—吩噻嗪电荷转移络合物的热力学测定

测定了７种酸酐与吩噻嗪在２８８１５、２９８１５、３０８１５和３１８１５Ｋ时形成电荷转移络合物的平衡常数Ｋ值，并计算出了它们对应的△Ｈ、△Ｓ值和酸酐的电子亲核能（ＥＡ）值，以此表征了这类电荷转移络合物，结果表明△Ｈ－ＥＡ和Ｋ－ＥＡ呈线性关系。     

苯乙烯—马来酸酐自由基共聚反应：（Ⅰ）苯乙烯—马来酸酐电荷转移络？…

电荷转移络合物反应机理是研究苯乙烯－马来酸酐自由基交替共聚反应机理的关键。本文简述了苯乙烯－马来酸酐电荷转移络合物的研究进展。     

羰基在电荷转移络合过程中的作用及络合组成比的确定

以丁二酸酐作为马来酸酐的模型化合物,用NMR法研究了羰基在电荷转移络合过程中的作用,建立起用NMR法确定络合组成比的方法.实验结果表明:丁二酸酐以1:1与苯乙烯或N-乙烯基咔哇彤成电荷转移络合物,马来酸酐中的羰基比碳碳双键更强地参与电荷转移络合作用.     

苯酚钾及对位取代苯酚钾的电离势

在我们以前的研究工作中发现,酚类钾盐是很好的电荷给体,可以和顺丁烯二酸酐、三硝基苯以及醌类等电荷受体生成电荷转移(CT)络合物。表示分子的给电子能力的参数是分子的第一电离势(简称为电离势I_p)。对于苯酚的I_p值,近年来已有文献记载,但苯酚钾     

醋酸乙烯酯-马来酸酐共聚物与水解聚丙烯酰胺高分子络合物的研究

<正> 某些高分子在溶液中可以通过次价力形成高分子络合物.根据次价力的不同,可分为四类:聚电解质络合物、氢键络合物、立体络合物和电荷转移络合物.部分水解聚丙烯酰胺(简称HPAM)是在水悬浮体中被广泛使用的絮凝剂,醋酸乙烯酯-马来酸酐共聚物(简称VAMA)是一种能力很强的泥浆稀释剂.研究二者在水溶液中的相互作用,在理论上和应用上都有重要意义.我们曾研究了粘土对它们的吸附作用、改变泥浆流变性以     

碘鎓盐/胺体系基态和激发态的光谱研究

研究了碘鎓盐与胺在基态和激发态的相互作用,观察到它们形成以鎓盐为电子受体和胺为电子给体的基态和激发态电荷转移络合物。测定了二苯基碘鎓盐和三乙胺形成的络合物组成为1:1分子比,其缔合常数和克分子吸收系数分别为2.2×10mol^-1和2.8×10³mol^-1·1·cm^-1。实验结果表明,随着胺的给电性增加,电荷转移络合物的吸收波长红移,胺的空间体积增大,由于空间障碍,电荷转移络合物的克分子吸收系数下降。     

PVK／C60电荷转移络合物的光谱研究

利用紫外光谱、荧光光谱研究了ＰＶＫ／Ｃ_（６０）~＊（Ｃ_（６０）~＊与Ｃ_（７０）混合物）体系的光谱行为，实验结果表明，ＰＶＫ与Ｃ_（６０）之间存在电荷转移络合作用。紫外光谱结果表明ＰＶＫ／Ｃ_（６０）~＊电荷转移络合物的特征吸收峰在４７４ｎｍ附近，这与理论计算结果相吻合．ＰＶＫ单元与Ｃ_（６０）之间的最佳匹配约为５：１．荧光光谱结果进一步证明了ＰＶＫ与Ｃ_（６０）~＊之间的电荷转移络合作用的存在。     

阳离子艳蓝的薄层光谱电化学研究

用薄层光谱电化学技术研究了阳离子艳蓝的电还原过程。薄层循环伏安图表明阳离子艳蓝有一对接近可逆的氧化还原峰。从光谱发现它有顺反异构体互变现象与变色效应。在氧存在时，循环伏安图和光谱图上均出现新峰，推测阳离艳蓝分子与氧分子能形成电荷转移络合物。测得阳离艳蓝电还原的式电极电势，电子转移数以及扩散系数等参数。并讨论了可能的电极过程。     

N-丙烯酰-2-氯吩噻嗪、N-丙烯酰-2-乙酰基吩噻嗪单体和聚合物的合成以及荧光行为的研究

含芳杂环的丙烯酰类功能性单体及其聚合物的合成一直吸引人们的兴趣,原因之一是由于这类单体可用一般的自由基引发剂引发聚合,这类聚合物所表现出的光化学、电化学性质甚被瞩目。如含吩噻嗪的丙烯酰类衍生物可以和缺电子的化合物形成电荷转移     

N-苯基吩噻嗪和N-(2-吡啶基)吩噻嗪光物理过程的研究

通过测定N-苯基吩噻嗪(PHZ),N-(α-吡啶基)吩噻嗪(PYZ)荧光发射光谱和荧光寿命的溶剂效应及温度效应,证明了在PYZ发射光谱中表现出很强的分子内扭曲引起的电荷转移态(TICT),还研究了PHZ,PYZ和对苯二甲酸二甲酯所形成的激基复合物,并通过闪光光解观察到了在极性溶剂中由激基复合物解离而形成的正、负离子的瞬态吸收光谱。     

Formation and Photoelectrochemical Properties of Charge Transfer Complexes between Fullerene and Metallophthalocyanine

Fullerelleshavegeneratedarapidlygrowingandactiveresearchareabecauseoftheirunusualstructureandphysico-chemicalproperties.Fullerenes(C,.,.C,,)havehigherelectrollaffinity(2.75ev),soitiswellkllownthattheyareexcellentelectronacceptorsandhavealargenumberofcolljugatedrsbondswhichmayleadtolargenon-linearpolarizabilities'.C,,.,isreportedtoformchargetranstbrcomplexes(CTC)withappropriateelectrondonors,forexample,polymolecularPVK,y-cyclodextrin,aromaticandaliphaticammes'-3.Thecharge-transferinteraction…     

纳米银修饰电极差分脉冲伏安法测定盐酸金霉素

建立了快速测定盐酸金霉素(CTC)的方法。通过NaBH4还原法制备纳米银(AgNPs)溶胶,并利用X射线衍射和紫外-可见光谱进行表征。将制备好的AgNPs滴涂到玻碳电极表面制备修饰电极(AgNPs/GCE),研究了CTC在AgNPs/GCE上的电化学行为及伏安法测定,优化了缓冲溶液和pH等检测条件。结果表明,CTC在pH 3.3的柠檬酸-NaOH-HCl缓冲溶液中检测效果最佳。CTC在AgNPs/GCE上发生2个电子和2个质子的不可逆电化学氧化反应,且反应受吸附控制。最佳条件下,CTC的氧化峰电流与其浓度呈现良好的线性关系,线性范围为0.5~100μmol/L,检出限为0.14μmol/L。该修饰电极可用于河水样品检测。     

Undulated 2D Covalent Organic Frameworks Based on Bowl‐Shaped Cyclotricatechylene

Two 2D wavy hexagonal hexahydroxyl cyclotricatechylene (CTC) based COFs, CTC‐COF‐2 and CTC‐COF‐3 were synthesized through solvothermal reaction. The bowl‐shaped conformation caused CTC skeletons packed in a columnar manner with the same oriented units, thus forming an undulated structure. The gas adsorption properties of CTC‐COFs were investigated, which show the potential application abilities in hydrogen storage of CTC‐COFs. The introduction of pyrene into CTC‐COF‐3 makes it a potential semiconducting π‐conjugated material.     

Quantitative determination of chlortetracycline content in animal plasma at controlled keto-enol tautomerism by liquid chromatography-electrospray ionization-tandem mass spectrometry

Chlortetracycline (CTC) is a member of the group of the tetracycline antibiotics used in human and veterinary medicine. Its reliable measurement in plasma - necessary to study its pharmacokinetics - is hampered by the fact that CTC is subjected to keto-enol tautomerism resulting in its keto- and enol-form. Also, it undergoes epimerization to form its 4-epimer. In this paper, we present an LC-ESI-MS/MS method to analyze the CTC content in animal plasma, with the originality that it apports a solution to overcome the possible interference of the keto-enol tautomerism equilibrium, which is influenced by several factors. Therefore, the plasma samples were incubated at 56 degrees C, forcing the equilibrium completely in favour of the CTC keto-form. The CTC keto-tautomer was stable after deproteinization of the samples with concentrated trifluoroacetic acid, and was quantified by LC-ESI-MS/MS, as a measure of the total CTC content. The method could be validated for pig and chicken plasma by a series of parameters - linearity, trueness, precision, limit of quantification, specificity, stability - in accordance with the European guidelines, and was used for pharmacokinetic studies on pigs and chickens medicated with CTC via the feed.     

9-对位取代苯甲叉芴与电子受体相互作用的研究

电子给体(D)和电子受体(A)在基态下所形成的电荷转移络合物(CTC),在有机反应、催化、高分子等的理论及应用研究方面具有重要意义,故受到广泛地注意^[1-2]。分子间形成CTC的过程伴有电荷分布的变化,故往往可观察到与该过程相应的电荷转移吸收光谱。     

Control of the keto-enol tautomerism of chlortetracycline for its straightforward quantitation in pig tissues by liquid chromatography-electrospray ionization tandem mass spectrometry

Chlortetracycline (CTC) is a member of the group of the tetracycline antibiotics used in human and veterinary medicine. Its reliable measurement in edible tissues is hampered by the fact that CTC is subjected to keto-enol tautomerism resulting in its keto- and enol-form. Also, it undergoes epimerization to form its 4-epimer. In this paper, we present an LC-electrospray ionization (ESI)-MS/MS method to analyze the CTC content in pig tissues, with the originality that it apports a solution to overcome the possible interference on the measurement of the keto-enol tautomerism equilibrium, which is influenced by several factors. Therefore, the minced tissue samples were incubated at 56 degrees C, forcing the equilibrium in favour of the CTC keto-form. The CTC keto-tautomer, as a measure of the total CTC content, was then quantified by LC-ESI-MS/MS, after further extraction of the tissue samples, consisting of a liquid extraction with sodium succinate solution (pH 4.0), followed by protein removal with trichloroacetic acid and paper filtration, and finally solid-phase clean-up on an hydrophilic-lipophilic balance (HLB) polymeric reversed-phase column. The method could be validated for pig muscle, liver and kidney tissues--for which maximum residue limits (MRLs) have been fixed by the European Union--with respect to linearity, trueness and precision, in accordance with the European guidelines.     

Spectrophotometric study of the interaction between chlorotetracycline and bovine serum albumin using Eosin Y as site marker with the aid of chemometrics

Interaction of chlorotetracycline (CTC) with bovine serum albumin (BSA) was investigated under simulated physiological conditions by spectroscopy with the aid of multivariate curve resolution-alternating least squares (MCR-ALS). Eosin Y was selected as an alternative site I marker on the BSA to study the above molecular interaction. The binding of Eosin Y and CTC to BSA showed that CTC was displaced from CTC-BSA complex by Eosin Y, and Eosin Y-BSA complex was formed. However, the recorded fluorescence spectra of Eosin Y and Eosin Y-BSA overlapped and MCR-ALS was applied to resolve the two-way fluorescence spectra. From the resolved equilibrium concentration profiles, it was observed that Eosin Y competed with CTC in the binding process with BSA; it was also shown that the binding site of CTC on BSA was site I, and this was further confirmed by the fluorescence polarization method. Compared with some common site I markers for BSA, the fluorescence and UV-vis spectral shapes of the Eosin Y-BSA complex were quite different from that of Eosin Y, and this feature facilitated the investigation of the small molecule-BSA interaction.     

二茂铁／过氧化苯甲酰引发体系光谱行为的研究

二茂铁／过氧化苯甲酰引发体系光谱行为的研究刘日新，周晓红，吴世康（中国科学院感光化学研究所，北京，１００１０１）关键词二茂铁过氧化苯甲酰引发体系，基态电荷转移复合物，甲基丙烯酸甲酯室温聚合Ｍ茂铁（Ｆ。）和过氧化物组成的体系，用以引发烯类单体聚合［‘ｌ...     

EQCM监测高氯酸溶液中金电极上苯二酚电荷转移配合物的沉积

用电化学石英晶体微天平(EQCM)研究了高氯酸溶液中电位环扫过程中邻(间、对)苯二酚/醌电荷转移配合物(CTC)的生成和电沉积。结果发现,邻(对)苯二酚可产生CTC并在电极上沉积,而间苯二酚仅发生电聚合反应。以邻苯二酚为例考察了高氯酸和邻苯二酚浓度及电位扫描速度的影响。红外光谱证实了邻苯二酚/醌CTC的生成。结果发现,添加肝素钠对邻苯二酚/醌CTC的沉积有显著影响,肝素钠质量浓度分别低/高于0.05 g/L时,能增强/减弱沉积现象。EQCM技术可作为一种快速、简便、灵敏的工具可望用于CTC制备过程中的实时监测和筛选。     

Reactivity Ratios for Microemulsion Copolymeriration of N-butyl Maleimide and Styrene

IntroductionReactivityratioscanofferthemessageofrelativereactivityofcomonomers.TWomonomerreactivityratioscanbeacquiredfromtheend-groupmodelproposedbyMayoandLewis,howevef,thereareonlyapparentreactivityratiosavailablefromthiskineticmodelwhencharge-transfercomplex(CTC)participatesinthecopolymerization.Therefore,thecopolymeriZationinwhichCTCexistsisworthyoffurtherresearch.Sofar,therearethreekineticmodelsofcopolymerizationwiththeparticipationofCTCinall,namely,SeinerandLittmodel',Shirotamodel…