烟酸-卟啉二元化合物的合成、表征及其电化学性质

通过亲核取代反应合成了3个新的烟酸-卟啉二元化合物, 并用红外光谱、紫外-可见光谱、核磁共振氢谱、元素分析和质谱对化合物的结构进行确认, 通过循环伏安法研究了其电化学性质.     

Electrochemical studies of biologically active indolizines

The electrochemical behavior of indolizine ethers, esters, tosylates, sulfonates and other indolizine and azaindolizine derivatives has been investigated by cyclic voltammetry and preparative electrolysis. The cyclic voltammetric data show that the E° values, taken as the midpoints between the anodic and cathodic peak potentials, are sensitive to the identities of the substituents at C-1, C-2 and C-7 positions. The E° values have been correlated with the Hammett substituent parameters. As expected, low E° values are seen for electron donating substituents and higher E° values are seen for electron withdrawing substituents. The cyclic voltammograms of indolizine derivatives with an oxygen atom connected to the C-1 position exhibit a one-electron reversible oxidation and a further, less well-defined, one-electron irreversible oxidation at higher E° values. The cyclic voltammograms of indolizines with hydrogen atom or thienyl substituents connected to the C-1 position exhibit only a one-electron irreversible oxidation. Electrochemical bulk oxidations of indolizines with an oxygen atom at the C-1 position afforded oxoindolizinium salts in decent yields, whereas indolizines with a hydrogen atom at C-1 afforded 1,1′ dimers of indolizines as products in good yields. Bulk oxidation of 1-(α-hydroxybenzyl)-2,3-diphenylindolizine-7-carbonitrile afforded an unexpected ketone product in which the carbonyl group of the indolizine is connected at C-8 instead of at the C-1 position of the starting material. The findings described herein support our hypothesis that certain indolizine derivatives may inhibit lipid peroxidation by an electron transfer mechanism.     

含磷C_(60)衍生物的电化学性能研究

利用循环伏安法测试了 3种新合成的C60 膦酸酯衍生物的电化学性能 .通过比较不同取代基的C60 衍生物的电化学性能 ,研究引入基团的结构特性与其得电子能力之间的关系     

对甲苯磺酸铜的电化学表征

合成了对甲苯磺酸铜,用X光单晶衍射确定了其结构.实验结果表明,该盐容易脱除全部结晶水,在空气中不潮解.分别测定了对甲苯磺酸铜(Cu(p-OTs)2)在H2O、CH3OH和DMF中的电化学参数.实验结果表明Cu(p-OTs)2在不同溶剂中的反应机理各异. Cu(II)的电化学还原在H2O中是分两步进行,而在CH3OH和DMF中的电化学还原是一步两电子过程.对实验结果进行了分析讨论.     

硒芳香杂环化合物的光谱和电化学性质

用紫外光谱，荧光光谱和循环伏安法研究了含硒芳香杂环化合物（苤硒脑）在不同溶剂中的谱学和电化学性质，对不同分子结构或取代基的苤硒脑化合物的性质进行了比较，并初步探讨了溶剂对苤硒脑化合物谱学性质的影响规律。     

四烃硫基四硫富瓦烯的电化学性质及三维定量结构性能关系研究

以四烃硫基四硫富瓦烯(TTF)为研究对象,合成了6个新的π电子给体化合物,并用循环伏安法考察了其电化学性质,同时用比较分子力场(CoMFA)研究了TTF衍生物的结构与其电化学性质的三维定量结构性能关系,提出了对TTF结构改造的方法,对新型TTF类化合物的合成有重要的指导意义.     

二茂铁氨基化合物的合成

二茂铁与邻甲氧基苯甲酰氯反应生成邻甲氧基苯甲酰基二茂铁,再与一系列芳胺反应合成亚胺,最终还原为二茂铁氨基化合物,其结构均经元素分析、^1H NMR确证。     

芦丁与DNA相互作用的电化学研究

研究了芦丁与 DNA在 p H 5.72条件下相互作用的电化学行为。 DNA的存在能导致芦丁氧化还原峰电流降低 ,峰电位基本不变。通过测定 DNA引入前后的一些电化学参数 ,推测芦丁与 DNA在该条件下结合生成了一种非电活性的超分子化合物。针对该类型体系 ,推导出了一系列的方程 ,求得该超分子化合物的组成为 1∶ 1 ,结合常数 β=2 .49× 1 0 5mol- 1·L。     

第四周期过渡金属钼磷三元杂多化合物的氧化还原性质研究

研究了Keggin结构钼磷杂多化合物Na₅[PM(H₂O)Mo₁₁O₃₉]·nH₂O(M=Mn²⁺,Co²⁺,Ni²⁺,Cu²⁺,Zn²⁺在溶液中的氧化还原性质,发现环境的改变可对杂多阴离子的极谱半波电位产生影响,其影响程度的大小决定于过渡金属离子本身的性质。取代后的钼磷杂多阴离子的半波电位顺序为Ni²⁺>Co²⁺>Zn²⁺>Cu²⁺>Mn²⁺,pH值的变化影响氧化还原性质,并阐述了变价金属Cu²⁺对杂多阴离子氧化还原性质的影响.     

具有长侧碳链的苯醌类化合物在LB膜上的电化学行为

用LB膜技术将含有长侧碳链的泛醌或质体醌类似物转移到导电玻璃上，用循环伏安法研究了它们的电化学行为．发现醌环上的取代基对其电化学行为有明显影响，提出了泛醌类似物和质体醌类似物在LB膜上的具体电化学过程．     

Electrochemical Synthesis and Research of Two Polymers Composed of Alternate Carbazole and Thiophene Units

Two organic conjugated molecules composed of central carbazole and bithiophene groups were prepared via the Stille coupling reaction, conductive polymers were prepared by elec-trochemical method. Structure and photoelectric research of polymers were investigated. ¹H NMR and ¹³C NMR of molecules were consistent with the theorical results, FT-IR showed electrochemical polymeric site were α-position of thiophene units. The smooth morphology and distributed holes were beneficial to improve the electrical conductivity by SEM. When applied voltage was from -0.1 V to 1.2 V, both of the polymer films P1 and P2 showed good electrochromic performances. Compared with P1, P2 had better electrochemical stability and thermal stability due to the better coplanarity by repeated cyclic voltammograms and TGA. The P2 was a promising material in the electrochemical field, meanwhile, it showed that the monomer structure had greatly impact on the performance of polymer.     

循环伏安法研究天青A与dsDNA的相互作用

用循环伏安法研究了染料天青A(AA)与鲱鱼精DNA(dsDNA)在0.20 mol/L pH4.5的HAc-NaAc缓冲溶液中的相互作用。AA在玻碳电极上分别于-0.134 V和-0.082 V(vs.SCE)有一个还原峰和相应的氧化峰。加入dsDNA后,AA的还原峰和氧化峰电流均明显减小,但电子转移系数和电极反应标准速率常数基本不变。AA与dsDNA相互作用生成了一种非电活性的超分子复合物。求得AA与dsDNA复合物的结合比为n(AA)∶n(DNA)=3∶1,结合常数β=2.51×1015。紫外-可见吸收光谱法结果与循环伏安法结果一致。     

Carbon Nanotube‐Adsorbed Electrospun Nanofibrous Membranes as Coating for Electrochemical Sensors for Sulfhydryl Compounds

A new method to modify electrodes with carbon nanotubes (CNT) was developed. Multiwalled carbon nanotubes (MWNT) were adsorbed on the electrospun nylon‐6 nanofibrous membranes (Ny‐6‐NFM) and used as a coating to modify conventional glassy carbon electrodes. The modified electrode was designed for the amperometric detection of sulfhydryl compounds with the potential held at +0.3 V vs. Ag/AgCl. The modified electrode showed a linear response for cysteine up to 0.4 mM (R²=0.997), with a sensitivity of 5.1 µA/mM and a detection limit of 15 µM. Other sulfhydryl compounds showed similar results. After use, the Ny‐6‐NFM was easily peeled off, leaving the bare electrode surface back to its original electrochemical behaviour. This is the first attempt to use a disposable membrane functionalized with MWNT for electroanalytical purposes.     

两亲性丙烯酸酯共聚物的聚合研究

利用过氧化苯甲酰为引发剂探讨了甲基丙烯酸β－羟乙酯和丙烯酸长链烷基酯的自由基共聚合。重点讨论了合成条件如溶剂、沉淀剂、引发剂用量、单体配比、反应时间等对共聚反应的影响以及各种聚合条件对该共聚物的组成、结构和性能的影响。并用ＩＲ，ＧＰＣ，＾１３ＣＮＭＲ等手段对共聚物进行了表征。     

Electrochemical Formation of Al-Li Alloys by Codeposition of Al and Li from LiCl-KCl-AlF3 Melts at 853 K

The electrochemical behavior of Al(III) ions was studied in molten LiCl-KCl melts on a molybdenum electrode. Cyclic voltammetry, chronopotentiometry and chronoamperometry were used to explore the deposition mechanism of Al and Li. Cyclic voltammetry expriment indicates that under potential deposition(UPD) of lithium on pre-deposited aluminium led to the formation of liquid Al-Li alloys at 853 K. The diffusion coefficient of Al(III) ions at 853 K in LiCl-KCl-AlF₃(1%, mass fraction) melts was determined to be (2.79±0.05)×10^?5 cm²/s. Chronopotentiograms and chronoamperograms demonstrate that the codeposition of Al(III) and Li(I) ions formed Al-Li alloys at cathodic current densities higher than ?0.28 A/cm² or cathodic potentials more negative than ?2.20 V. X-Ray diffraction(XRD) pattern indicates that Al-Li alloys with different phases formed via galvanostatic electrolysis. Inductively coupled plasma(ICP) analyses of the samples obtained by electrolysis show that lithium and aluminium contents of Al-Li alloys could be controlled by AlF₃ concentration and current intensity.     

吖啶酮类衍生物的光电性质研究

测定了8个吖啶酮类衍生物的紫外吸收光谱、荧光光谱和荧光量子产率,以研究它们的结构与光学性质之间的关系,用循环伏安法测出它们各自的电子势．发现吖啶酮类衍生物都具有较高的电子亲和势,表现出比常用的电子传输材料2-(4-联苯基)-5-(叔丁苯基1—1,3,4-二唑(PBD)更容易被还原的优良电化学性能。     

C60系列螺亚甲基衍生物的电化学性质

考虑到在生物、新型材料等方面的应用，采用循环伏安(CV)的方法，系统研究了11个C60螺亚甲基衍生物的电化学性质. 分析比较了螺碳原子上所连不同基团的性质及链的长度等因素对C60得电子能力的影响.结果发现，引入推电子基团，如烷基，会使C60得电子能力降低，第一个还原电位有较大的负移；引入具有拉电子性质的基团，如羧酸酯基，则会部分抵消由于C60共轭结构被破坏而引起的电位负移，结果使得电位负移值减少.增加引入基团链的长度对C60的得电子的能力影响较小.同时，对于因电化学反应所引起的异构化而使还原峰发生分裂的现象作了解释.     

大黄酸与牛血清白蛋白相互作用的电化学研究

在pH3.5的Britton -Robinson缓冲液中 ,研究了大黄酸与牛血清白蛋白 (BSA)相互作用的电化学行为 ,二者结合生成了一种非电活性的超分子化合物。用循环伏安法和示差脉冲伏安法对该体系进行了研究 ,并对结合反应的机理进行了探讨。BSA的存在导致大黄酸氧化还原峰电流降低 ,峰电位基本不变 ,峰电流的下降值同所加入的BSA浓度在一定范围内呈线性关系。线性范围3.0×10 -8～8.0×10 -7mol/L ,检出限1.21×10 -8mol/L。     

Regioselective Synthesis of trans-1 Fullerene Bis-Adducts Directed by a Crown Ether Tether: Alkali Metal Cation Modulated Redox Properties of Fullerene–Crown Ether Conjugates

Regioselective Bingel macrocyclization of C₆₀ with a bis-malonate containing a novel dibenzo[18] crown-6 tether provides a versatile access to trans-1 fullerene bis-adducts such as (±)- 1 . Complexation of a potassium ion by (±)- 1 has a pronounced effect on the redox properties of the carbon sphere as a result of the close proximity of the fullerene surface to the crown ether bound cation, which is enforced by the double bridging.     

哌啶氮氧自由基与环糊精作用的电化学研究

采用循环伏安法测量水溶液中β-环糊精(β-CD)/哌啶氮氧自由基(以2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)为例)体系氧化还原电位及峰值电流,并基于此探讨TEMPO与β-CD之间的包结反应。电化学测量表明,在pH=7.4的磷酸盐缓冲溶液中,以玻碳电极为工作电极,随β-CD浓度增大,β-CD/TEMPO体系的峰电位不断增大,峰电流不断减小。通过电位法测得TEMPO与β-CD的包络比为1∶1,包络常数KS为154L/mol,与电流法测得的包络常数基本吻合。