反相离子对高效液相色谱法分离和测定铝、镓和铟

以芪－４,４‘－双（１－偶氮）－３,４－二羟基苯－２,２’－二磺酸铵（芪唑）为柱前衍生试剂,采用反相离子对高效液相色谱法分离和测定铝,镓和铟。在ｓｐｈｅｒｅｘ Ｃ１８柱上,用浓度为１２ｍｍｏｌ／Ｌ的ＳＤＳ,浓度为２０ｍｍｏｌ／ｌ ｐＨ３．５的ＡＨｃ－ＮａＡｃ的甲醇－水溶液作流动相,检测波长为５０６ｎｍ。     

双吖啶衍生物与核酸作用的光谱分析

用荧光光谱、紫外可见吸收光谱等方法研究合成的核酸探针与核酸的作用方式,发现DNA对这些物质的荧光具有较强的猝灭效应,其中又以10,10’二乙基-3,3’-二磺酸基-双吖啶（DESAC）、10,10’-二烯丙基-3,3’-二磺酸基-9,9＇-双吖啶（DASAC）、10,10’-二烯丙基-3,3’-二氨基-9,9＇-双吖啶（DAAAC）和10,10’-二乙基-3,3＇-二氨基-双吖啶（DEAAC）这4种物质效果最好,因此有望从这类物质中筛选出良好的核酸探针。     

由A_2, B_2和BB’_2型单体合成超支化共聚物──Ⅳ.N-乙基乙二胺、4,4’-三亚甲基二哌啶与二乙烯基砜的共聚反应

将二官能度单体（Ａ_２）和三官能度单体（ＢＢ’２）反应合成超支化聚合物的方法推广应用于共聚反应．用Ａ２——二乙烯基砜（ＤＶ）,Ｂ２——４,４’－三亚甲基二哌啶（ＴＭ ＤＰ）和ＢＢ’２——Ｎ－乙基乙二胺（ＮＤＡ）单体直接反应合成了超支化共聚物．聚合反应时,ＴＭＤＰ和ＮＤＡ的仲胺基与ＤＶ的双键迅速加成,生成一种带有双键和伯胺基的ＡＢ’２型中间体,该中间体进一步聚合得到超支化聚砜胺．用Ｆｏｕｒｉｅｒ变换红外光谱（ＦＴＩＲ）,色－质联用谱（ＬＣ／ＭＳＤ）等测试手段验证了这一反应机理．产物的支化度随着ＴＭＤＰ与ＮＤＡ的加料比增大而减小,因而可通过这种共聚合方法来控制超支化聚合物的支化度．当ＴＭＤＰ与ＮＤＡ的加料比大于或等于４时,产物是半结晶的．     

含手性膦配体的钯（Ⅱ）配合物的二维核磁共振研究

利用一维和二维ＮＭＲ技术，对含有手性膦配体甲基－３脱氧－３（二苯膦基）－４，６－氧－苄叉基－α－Ｄ一吡喃阿卓糖苷（３－ＭＢＰＡ）和甲基－２－脱氧－２－（二苯膦基）－４，６－氧－苄叉基－α－Ｄ－吡喃阿卓糖苷（２－ＭＢＰＡ）的钯配合物ｔｒａｎｓ—［Ｐｄ（３－ＭＢＰＡＨ）２ＣＩ２」（１），ｔｒａｎｓ－［Ｐｄ（２－ＭＢＰＡＨ）２ＣＩ２］（２）和ｃｉｓ－［Ｐｄ（３－ＭＢＰＡ）２］（３），ｃｉｓ－［Ｐｄ（２－ＭＢＰＡ）２］（４）进行~１Ｈ和~（１３）Ｃ ＮＭＲ谱分析，归属了全部的~１Ｈ和~（１３）Ｃ ＮＭＲ谱线，并根据磷的化学位移及Ｒａｍａｎ谱确定化合物（３）和（４）是顺式构型，对实验中的一些现象也做了简单讨论。     

新显色剂3,3'-二甲基联苯重氮氨基偶氮苯与钯显色反应的研究及其应用

研究了在表面活性剂Ｎ－氯代十六烷基吡啶（ＣＰＣ）存在下,新显色剂３,３’－二甲基联苯重氮氮基偶氮苯（ＤＭＤＰＤＡＡ）与钯（Ⅱ）显色反应的适宜条件。结果表明,在ｐＨ８．０￣９．０范围内,钯（Ⅱ）与ＤＭＤＰＤＡＡ形成２：２紫红色配合物,其最大吸收波长位于６００ｎｍ,配合物的表观摩尔吸光系数为８．４１×１０＾４Ｌ·ｍｏｌ＾－１·ｃｍ＾－１,钯浓度在０￣１２μｇ／２５ｍＬ范围内遵守比尔定律,该方法灵敏度较     

10,10’-二甲基-3,3’-二磺酸基-9,9’-双吖啶的电致化学发光行为

研究了新试剂10,10'-二甲基-3,3'-二磺酸基-9,9'-双吖啶(简称DMDSBA)的电致化学发光(ECL)行为. 考察了电化学参数、反应介质以及pH等条件对DMDSBA电致化学发光信号的影响. 结果表明, 在玻碳电极上施加适当电压时, DMDSBA在KNO₃溶液介质中产生很强的电化学发光信号, 于优化的实验条件下, 发光强度的自然对数与DMDSBA浓度的自然对数在1.0×10^-5-1.0×10^-8 mol·L^-1范围内呈良好的线性关系,检出限可达2.3×10^-9 mol·L^-1. 并用循环伏安法、电致化学发光光谱以及荧光光谱, 研究了DMDSBA的电致化学发光机理.     

二羟丙酮的气相色谱分析

用衍生气相色谱法测定了二羟丙酮的酶制法体系中二羟丙酮的含量,选用六甲基二硅胺烷（ＨＭＤＳ）、六甲基二硅胺烷加三甲基氯硅烷（ＴＭＣＳ）、Ｎ,Ｏ－双（三甲基硅烷基）乙酰胺（ＢＳＡ）为衍生试剂,并对其衍生条件进行了研究。该法的回收率为９８．３１％～１０１．３１％,ＲＳＤ为２．０２％～３．５８％。     

一种新的含杂原子电子受体的双重荧光N, N-二甲基苯胺衍生物4-(N, N-二甲基氨基)苯磺酸钠的光诱导分子内电荷转移

报道了一种新的双重荧光Ｎ,Ｎ－二甲基苯胺（ＤＭＡ）衍生物,４－Ｎ,Ｎ－二甲基氨基 苯磺酸钠（ＳＤＭＡＳ）,其电子受体经硫杂原子联接于电子给体的对位．ＳＤＭＡＳ在强极性 的水中发射双重荧光,在有机溶剂如甲酰胺,甲醇和乙腈中则只发射位于短波长侧的 单重荧光．纯水中 ＳＤＭＡＳ的荧光峰分别位于 ３６５ ｎｍ和 ４７５ ｎｍ处,引入有机溶剂如乙 醇,乙腈和１,４－二氧六环,长波长荧光被猝灭且峰位置蓝移,稳态及皮秒时间分辨荧光 测量表明,ＳＤＭＡＳ的长波长荧光为光诱导的分子内电荷转移（ＣＴ）态所发射,短波长的 荧光为局域激发（ＬＥ）态所发射,并且ＣＴ态产生自ＬＥ态．只能在高极性的水中观察到 ＳＤＭＡＳ的ＣＴ双重荧光发射的实验事实意味着ＣＴ过程具有高的活化能,激发态超快 反应动力学研究证实该活化能（Ｅ_a）高达 １５．３５ ｋＪ· ｍｏｌ~-1, ＳＤＭＡＳ分子中硫原子的 ｄ－轨道 参与磺酸基和苯环的共轭以及二甲基氨基所在平面相对于苯环的强烈扭转和弯折可能 是导致高活化能的原因,ＣＴ过程的热力学参数分析表明伴随着电荷转移ＳＤＭＡＳ的分 子构型发生了变化报道的ＳＤＭＡＳ是具有双重荧光的氨基取代芳香磺酸衍生物。     

N-乙酰-1,6-二氨基己烷的固定化及其诱导肿瘤细胞分化机理的研究

合成了Ｎ－乙酰－１,６－二氨基己烷（Ｎ－ａｃｅｔｙｌ－１,６－ｄｉａｍｉｎｏｈｅｘａｎｅ,ＮＡＤＡＨ）并偶联到甘油氧丙基硅胶上用以制备高效液相色谱柱,用液相色谱法研究了ＮＡＤＡＨ及六亚甲基二乙酰胺（ｈｅｘａｍｅｔｈｙｌｅｎｅｂｉｓａｃｅｔａｍｉｅｄ,ＨＭＢＡ）诱导肿瘤细胞分化的机理。结果表明ＮＡＤＡＨ对肿瘤细胞的成分无离子交换及亲和效应,而对一些膜蛋白提取物和ＤＮＡ有强的疏水作用。因此,ＮＡＤＡＨ和ＨＭＢＡ对肿瘤细胞的诱导分化与它们对蛋白质和ＤＮＡ的疏水作用有关。     

苊酮对二氰蒽的电子转移荧光猝灭研究——激基络合物的形成…

研究了苊酮（ＡＮＯ）对９，１０－二氰蒽（ＤＣＡ）的荧光猝灭与激基络合物形成的动力学与机理，基于瞬态荧光双指数衰减，测定了激基络合物的光化学动力学和有关速度常数，论证荧光猝灭作用主要由ＡＮＯ／ＤＣＡ激基络合物的生成以及快速正向电子转移所致。     

A Study of the Electrochemistry of Two Biacridine Derivatives and Their Application

The electrochemlcal behavior of two new synthesized biacridine derivatives,3,3’－disulfonyl－9,9’－biacridine dinitrate（DSBADN）and 10,10’－dimethyl－3,3’－disulfonyl－9,9’－biacridine（DMDSBA）was investigated by means of cyclic voltammetry and linear sweep polarography．Ina HCl solution,the reduction peak current was proportional to the concentrations of DSBADNand DMDSBA．The electrochemical study demonstrated that the reduction peak currents ofDSBADN and DMDSBA exhibited adsorptive and diffusion－controlled characteristics,and the     

Flow-injection determination of trace amounts of dopamine by chemiluminescence detection

A flow-injection analysis (FIA) for the determination of dopamine has been developed. The method is based on the inhibition effect of dopamine on the iron(II)-induced chemiluminescence (CL) of 10,10'-dimethyl-9,9'-biacridinium dinitrate (lucigenin). The presence of a non-ionic surfactant, polyoxyethylene (23) lauryl ether (Brij 35), caused an increase in the inhibition effect. The present method allows the determination of dopamine over the range 1x10(-8)-2x10(-7) mol dm(-3). The relative standard deviation was 0.7% for eight determinations of 6x10(-8) mol dm(-3) dopamine. The detection limit (S/N=3) was 2x10(-9) mol dm(-3) with the sampling rate of 40 samples h(-1). The effect of other catecholamines and compounds of similar structure on the lucigenin CL reaction was studied: quinone, hydroquinone, norepinephrine, pyrocatechol and l-dopa suppressed the CL intensity.     

Electron transfer reduction of a highly electron-deficient fullerene,C60F18

Electron transfer reduction of a highly electron-deficient fullerene, C60F18, to the defluorinated anion, C60F17- occurs efficiently by a relatively weak one-electron reductant, p-chloranil radical anion; the one-electron reduction potential of C60F18 is evaluated as 0.04 V (vs. SCE) by comparison of the rate constant for electron-transfer from 10,10'-dimethyl-9,9',10,10'-tetrahydro-9,9'-biacridine to C60F18 with those of other one-electron reductants.     

Comparison between electron transfer and nucleophilic reactivities of ketene silyl acetals with cationic electrophiles

The products and kinetics for the reactions of ketone silyl acetals with a series of p-methoxy-substituted trityl cations have been examined, and they are compared with those of outer-sphere electron transfer reactions from 10,10'-dimethyl-9,9', 10, 10'- tetrahydro-9,9'-biacridine [(AcrH)2] to the same series of trityl cations as well as other electron acceptors. The C-C bond formation in the reaction of beta,beta-dimethyl-substituted ketene silyl acetal (1: (Me2C=C(OMe)OSiMe3) with trityl cation salt (Ph3C+ClO4-) takes place between 1 and the carbon of para-positon of phenyl group of Ph3C+, whereas a much less sterically hindered ketene silyl acetal (3: H2C=C(OEt)OSiEt3) reacts with Ph3C+ at the central carbon of Ph3C+. The kinetic comparison indicates that the nucleophilic reactivities of ketene silyl acetals are well correlated with the electron transfer reactivities provided that the steric demand at the reaction center for the C-C bond formation remains constant.     

10,10’-二烃基-9,9’-联二吖啶烯的电荷转移光谱和氧化反应研究

研究了10,10'-二烃基-9,9'-联二吖啶烯的DDQ的电荷转移光谱,用两种方法计算出了它们的电离热(I_p)值,并研究了该系列化合物与DDQ、TCNE和CA的氧化反应,其氧化结果和用HNO₃氧化所得到的10,10'-烃基-9,9'-联二吖啶硝酸盐结果一致。在DDQ、TCNE和CA中,只有DDQ可以和该系列化合物形成CTC,其原因是DDQ有弱的氧化能力而有强的络合能力。     

Study on the Electrochemical Behavior of 10,10'-Dimethyl-3,3'-disulfonyl -biacridinium Dinitrate and Its Application

10,10'-dimethyl-3,3'-disulfonyl-biacridinium dinitrate(DMDSBA) synthesized in our laboratory is a derivative of lucigenin with two sulfonic group Althpugh the electrochemical reduction of lucigenin at various types of electrodes has been studied^[1-4], the electrochemical behavior of its derivatives Has not been reportedl In this essays the electrochemistry of DMDSBA is investigated and its application is also discussed.     

对位取代酚钾与10′10′-二烃基-9,9′-联二吖啶盐电荷转移光谱的研究

10,10′-二烃基-9, 9′-联二吖啶盐有很强的荧光, 在光学材料^[1]和重金属离子的分析^[2]中有重要的应用价值。     

化学发光物质9-[2',6'-二甲基-4'-(琥珀酰亚胺氧羰基)苯氧羰基]-10-甲基吖啶-单甲基-磺酸盐的合成

报道了一种化学发光物质吖啶酯衍生物9-[2',6'-二甲基-4'-(琥珀酰亚胺氧羰基)苯氧羰基]-10-甲基吖啶-单甲基-磺酸盐(DMAE•NHS)的合成, 合成共经历7个步骤, 每步合成的产物经IR, ¹H NMR, MS和元素分析表征, 结果表明合成产物为所期望的化合物. 该合成产物显示为一种非常理想的化学发光物质.     

Driving force dependence of intermolecular electron-transfer reactions of fullerenes

Pulse-radiolytic studies were performed to determine the rate constants of intermolecular electron transfer (k(et)) from fullerenes (C(60), C(76), and C(78)) to a series of arene radical cations in dichloromethane. The one-electron oxidation potentials of the employed arenes-corresponding to the one-electron reduction potentials of arene pi-radical cations-were determined in dichloromethane to evaluate the driving forces of electron-transfer oxidation of fullerenes with arene pi-radical cations. The driving force dependence of log k(et) shows a pronounced decrease towards the highly exothermic region, representing the first definitive confirmation of the existence of the Marcus inverted region in a truly intermolecular electron transfer. Electron-transfer reduction of fullerenes with anthracene radical anion was also examined by laser flash photolysis in benzonitrile. The anthracene radical anion was produced by photoinduced electron transfer from 10,10'-dimethyl-9,9',10,10'-tetrahydro-9,9'-biacridine [(AcrH)(2)] to the singlet excited state of anthracene in benzonitrile. The rate constants of electron transfer (k(et)) from anthracene radical anion to C(60), C(70), and a C(60) derivative were determined from the decay of anthracene radical anion in the presence of various concentrations of the fullerene. Importantly, a significant decrease in the k(et) value was observed at large driving forces (1.50 eV) as compared to the diffusion-limited value seen at smaller driving forces (0.96 eV). In conclusion, our study presents clear evidence for the Marcus inverted region in both the electron-transfer reduction and oxidation of fullerenes.