ELECTROCHEMICAL SYNTHESIS AND PROPERTIES OF POLY(AZURE B)*

A blue poly(azure B) film has been synthesized using repeated potential cycling between -0.25 and 1. 10 V (versusSCE). The electrolytic solution consisted of 2.5 mmol dm~(-3) azure B, 0.5 mol dm~(-3) NaCl and 0.2 mol dm~(-3) NaH_2PO_4 at the pHrange of 2.0 to 11.0. The in situ visible spectrum during electrolysis of azure B shows that the intensity at 740 nm peakincreases with increasing numbers of potential cycles, which is attributable to the formation of poly(azure B). Thewavelength of its corresponding absorption peak is 98 nm longer than that of azure B. The polymerization rate is stronglyaffected by pH values. The anodic peak potential and cathodic peak potential of the poly(azure B) in a solution of pH 3.0 arenot affected by increasing the scan rate from 25 to 600 mV s~(-1). Poly(azure B) has good electrochemical reversibility and fastcharge transfer characteristic in the pH range of 2.0 and 11.0. The conductivity of poly(azure B) is 1.5×10~(-4) S cm~(-1).According to the differences between FTIR spectra of poly(azure B) and azure B, an electrochemical polymerizationmechanism of azure B is proposed in this paper.     

陶瓷先驱体含锆聚硅烷的电化学合成与表征

采用电化学合成法,以三氯甲基硅烷、氯丙烯、环戊二烯和四氯化锆为单体合成出含锆聚硅烷,通过FTIR,UV,NMR,XRD等表征了其结构.测定了产物的各元素含量和双键含量,以及分子量和分子量分布,并对产物进行了交联固化和高温裂解实验.结果表明,含锆聚硅烷双键保留率为10.8%,锆含量为4.11%.含锆聚硅烷能溶于常见的溶剂...     

聚合物自由基锂二次电池正极材料的合成与电化学性能

合成了一种聚合物自由基聚 4 甲基丙烯酸 2 ,2 ,6 ,6 四甲基哌啶 1 氮氧自由基酯 (PTMA) ,并用红外光谱 (IR)、紫外光谱 (UV)、电子顺磁共振 (ESR)等证实了PTMA的结构 .PTMA的循环伏安曲线 (扫描速度为 5mV·s- 1)显示通过阳极的氧化电量和阴极的还原电量相等且氧化峰电流等于还原峰电流 ,表明PTMA的氧化还原反应可逆性很好 .PTMA的氧化峰电位 (Ea ,p=3 6 6VversusLi Li+ )与还原峰电位 (Ec,p=3 58V)之差为 80mV ,比其它锂二次电池的有机正极材料 (如有机二硫化物 )小得多 ,因此PTMA的氧化还原反应速度比较快 .PTMA的最大放电比容量为 78 4mAh·g- 1(以 0 2C充放电 ) ,是它理论比容量 ( 111mAh·g- 1)的 70 6 % ,它的充放电曲线分别在 3 6 5V和 3 56V处有一个很平稳的平台 ,经过 10 0次充放电循环后电池的放电比容量相对于最大放电比容量只衰减了 2 % ,表明PTMA 锂扣式电池具有优良的循环稳定性 .这些研究结果显示PTMA是一种非常有发展前景的有机聚合物自由基锂二次电池正极材料     

四种硝基苯的电化学行为及其反应活性的理论计算

在滴汞电极上研究了硝基苯、对硝基甲苯、间二硝基苯及2，4-二硝基氯苯的电化学行为，并用量子理论对四种硝基苯化合物的反应活性进行了预测，理论与试验结果基本一致，据此提出了预测分子的电化学活性的方法。     

电化学合成吡咯与己内酰胺导电共聚物

采用恒电位方法实现了吡咯与己内酰胺在导电玻璃电极上的直接电化学共聚,聚合反应在含有0.1mol/L吡咯和1.5 mol/L己内酰胺的硝基甲烷电解质溶液中进行,外加电位控制在1.2 V以上.聚合产物中聚吡咯与聚己内酰胺链段的组成可通过调节合成电位加以控制.共聚物的形貌、结构与性质采用扫描电子显微镜、热重分析、红外光谱等手...     

氯取代硫三碳菁染料的合成及性能

本文合成了七个硫三碳菁.其中四个具有桥环的菁染料。测定了它们的电子吸收光谱,讨论了结构对光稳定性的影响。并发现镍络合物能有效地抑制菁染料的光退色。     

SYNTHESIS, SPECTRA AND ELECTROCHEMICAL PROPERTIES OF OXYGEN ADDUCTS OF TETRAKIS(2-ANILINOPYRIDINATO) DIRHODIUM COMPLEXES

Two oxygen adducts of different geometric isomers of the tetrakis(μ-2-anilinopyridinato) dirhodium unit, Rh_2(ap)_4~+, have been synthesized and characterized. Rh_2(ap)_4O_2(4,0) is the oxygen adduct 1 of 4, 0 isomer; and Rh_2(ap)_4O_2(2, 2) is the oxygen adduct 2 of 2, 2 isomer. The ESR spectra of both oxygen adducts show that there is a characteristic signal of a superoxide ion, g=2.03. The 4, 0 isomer with different axial ligands gives the order of A_Ⅱ values; O_2~-≈ClO_4~-相似文献   

可溶性聚苯并噻吩的电化学合成

聚噻吩及其衍生物具有良好的导电性 ,优越的电致变色及荧光特性 ,可望用于研制各种新型微电子器件[1,2 ] .因此 ,这类聚合物的合成与表征一直受到广泛关注[3] .噻吩类聚合物是一个庞大的家族 ,其中聚异苯并噻吩早就被合成出来[4 ,5] .三氟化硼乙醚溶液 (ＢＦＥＥ)是电聚合芳香族化合物 (如噻吩、苯等 )的一种优良电解质[6～ 10 ] .在这一介质中 ,单体的氧化聚合电位很低 ,得到的导电高分子膜具有优良的机械力学性能 .本文将报道苯并噻吩在纯ＢＦＥＥ或ＢＦＥＥ与浓硫酸形成的混合电解质中的电化学聚合反应 .用这一方法合成得到了能发出蓝色…     

2,3-环氧羧酸-对-溴苯甲酰甲基酯的合成及其抗菌活性

环氧化合物,尤其是2,3-环氧羧酸类化合物既是一类重要的有机合成中间体,又是一类很有前途的生物活性物质,并广泛存在于自然界中,与生物体内的生理生化过程紧密相连。文献报导环氧化合物具有杀虫、杀螨、杀菌和生长调节的活性。Hendlin等从链霉菌的发酵液中分离到一种抗菌素(膦霉素),证明其为广谱的杀菌剂,其结构为2,3-环氧丙膦     

新型聚合物双氮杂假冠醚PACE的合成研究与吸附特性

以 2 苯氧基乙醇为起始剂 ,用先聚合后功能基化和钠离子模板的方法 ,合成了一种新型酚醛型聚合物双氮杂假冠醚PACE .应用FTIR光谱跟踪监控的方法研究了一系列合成反应 .获得了以苯氧乙醇为单体的酚醛交联反应的最佳实验配方和在该酚醛母体聚合物上进行的一系列取代反应的较佳实验条件 ,同时给出了一系列聚合物的红外光谱资料 .测试了PACE对常见金属离子的静态吸附性能 ,结果表明 ,PACE对K+ ,Na+ ,Hg2 + ,Cd2 + ,Fe3 + ,Pb2 + 和Cu2 + 离子具有良好的吸附性能 .其吸附容量分别达 1 43,0 98,1 84,0 6 8,0 79,0 6 1和 0 5 7mmol g r.通过FTIR光谱对吸附机理做了初步探讨 .结果表明 ,在聚合物PACE的金属离子配合物中 ,不仅CH2 OCH2 ,PhOCH2 和CH2 NCH2 参与了配位 ,同时CH2 OH亦不同程度地参与了配位 .PACE对Hg2 + 的吸附过程中伴随着缓慢的氧化还原现象 ,在此过程中 ,PACE中的CH2 OH被氧化成为COOH ,而Hg2 + 被还原为Hg22 + .     

磺酰脲类除草剂的合成及其除草活性

磺酰脲类除草剂具有用量低,活性高、选择性好、毒性小的优点。为开发和应用此类除草剂,我们合成了在氮原子上连正丁基的8个新的衍生物,并进行了室内药效测定。     

ELECTROCHEMICAL POLYMERIZATION OF ANILINE IN PHOSPHORIC ACID AND THE PROPERTIES OF POLYANILINE

The behavior of the electrochemical polymerization of aniline in a weak acid, phosphoric acid, is very similar to that in strong acids, i.e. its polymerization rate increases quickly with the electrolysis time. The FTIR spectra of polyaniline samples synthesized in phosphoric acid indicate that the counter ion H2PO4^- is present in both the oxidized form and the reduced form of polyaniline. The counter ion plays an important role in adjusting the pH value at the electrode surface of polyaniline during the oxidation and reduction processes. As a result, a pair of redox peaks still appear in cyclic voltammograms of polyaniline in a solution of sodium sulfate of pH 5.5 and in a solution of NaH2PO4 of pH 7.0,respectively, at low potential scan rate; and the color of polyaniline film also changes with applied potential at pH 7.0. Thus,the pH region for the electrochemical activity and the electrochromism of polyaniline is extended to pH 5.5 for a solution of sodium sulfate and to pH 7.0 for a solution of NaH2PO4. The conductivity of polyaniline is 3.3 S cm^-1, depending on the concentration of phosphoric acid used in the stage of polymerization of aniline. The result of elemental analysis of polyaniline is presented here.     

THE ELECTROCHEMICAL PREPARATION OF POLYPHENOL WITH CONDUCTIBILITY

Polyphenol film deposited on platinum foil can continuously grow with time during the electrolysis of a phenolsolution consisting of 0. 1 mol L~(-1) phenol, 3 mol L~(-1) NaOH and 0.5 mol L~(-1) Na_2SO_4, as has been proved by the methods ofsweep potential, constant potential and constant current, and visible spectra during the electrolysis of phenol. A polyphenolfilm with thickness of 0.11 mm was obtained by the electrolysis of phenol at a constant potential of 0.70 V (versus Ag/AClwith saturated KCl solution). Polyphenol film is inactive and stable in 2 mol L~(-1) H_2SO_4 solution, neutral solution and3 mol L~(-1) NaOH solution and in the potential range between -0.95 and 1.35 V. The usable potential range is dependent onthe pH value. Polyphenol has an ESR signal with a g factor of 2.0049. The conductivity of polyphenol is 1.2×10~(-4) S cm~(-1). Inthe solution of polyphenol dissolved in DMSO, the mobility of polyphenol anions is 8×10~(-9) m~2 s~(-1) V~(-1) at 20℃.     

5-(4-丙氨酸丁氧苯基)-10,15,20-三苯基卟啉及其配合物的合成和性质

本文首次合成了一种新型的单取代的丙氨酸四苯基卟啉，５－（４－丙氨酸丁氧苯基）－１０，１５，２０－三苯基卟啉（Ｈ２Ｌ），及其Ｃｏ（Ⅱ）、Ｃｕ（Ⅱ）、Ｚｎ（Ⅱ）配合物（ＣｏＬ、ＣｕＬ、ＺｎＬ），用元素分析、电子光谱、红外光谱、荧光光谱和激光拉曼光谱进行表征。研究了ＭＬ存在下，用氧气氧化芳醛的过程，测定了反应体系的吸氧动力学曲线，研究了氧化过程金属卟啉可见光谱变化以及底物和金属卟啉浓度对反应的影响。结果表明，ＣｏＬ能加速芳醛氧化反应，最大吸氧速率随ＣｏＬ浓度的增加而增大，但反应诱导期随ＣｏＬ浓度增大而延长。     

水杨醛缩2-氨基-4-苯基噻唑及其配合物的合成与仿酶催化活性研究

The new containing Surfur Schiff base Salicylaldelye-2-amino-4-Phenylthiazole(SAPTZ) and its Cu(Ⅱ)、Zn(Ⅱ)、Ni(Ⅱ) and Co(Ⅱ) compelexes were synthesized. The structures of the complexes were characterized by elemental analysis, IR and UV-vis. The peroxidase-like activity of the complexes for the oxidation of Vc with H₂O₂ was determined.     

电化学合成己二腈与其阴极极化曲线的测定

恒电位电解法制备己二腊可能有许多反应发生:阳极 H₂O→1/2O₂+2H⁺+2e 2Br^-→Br₂+2e 阴极 2CH₂=CHCN+2H₂O+2e→2CN(CH₂)₄CN+2OH^- CH₂=CHCN+2H⁺+2e→CH₃CH₂CN 2H⁺+2e→H₂ nCH₂=CHCN+H₂O+2e→齐聚物要使己二腈的收率有效的提高,除严格控制溶液体系的半波电位外,反应溶液体系最好是中性偏酸,即应控制pH=6-7为宜。同时,为了抑制氢气的生成,阴极材料应采用氢超电势高的铅等。     

SYNTHESIS,PROPERTIES AND BIOLOGICAL ACTIVITY OF RARE EARTH COMPLEXES OF 5-FLUOROURACIL-1-PROPIONIC ACID

Abstract

Seven new solid complexes of 5-fluorouracil-1-propionic acid with rare earth metals have been synthesized. Elemental analyses, molar conductance, TG-DTA, IR, UV-Vis, fluorescence, XPS and ¹H NMR spectra have been used to characterize these complexes. The general formula of the complexes is RE(FPA)₃. nH₂O where RE = Y(III), La(III), Pr(III), Sm(III), Eu(III), Dy(III), Er(III); n=3 or 5. Prooxidative and antitumor activity of these complexes was tested. The results showed that these complexes augment free radical generation; especially the Pr³+ complex which obviously increased the O₂ ^? and OH^? radicals. It was also found that La³+ and Y³+ complexes possess antitumor effects on human colon bladder HCT-B and human leukemia HL-60 cells in vitro.     

高取代度魔芋葡甘聚糖醋酸酯的制备及其热塑性和流变性研究

以魔芋葡甘聚糖(KGM)为原料,浓硫酸为催化剂,乙酸酐为改性剂,制备了KGM醋酸酯.研究了反应条件对KGM醋酸酯取代度(DS)的影响,KGM醋酸酯制备的最佳反应条件是乙醇∶水量比5∶5,反应时间2h,反应温度75℃,催化剂浓硫酸的浓度0.1mol/L,KGM与乙酸酐的量比5∶40(g/mL),取代度高达2.93,其分子量与KGM相比,则明显降低.运用傅立叶红外光谱仪(FTIR)、X射线衍射仪(XRD)、扫描电镜(SEM)、热重分析仪(TGA)、示差扫描量热仪(DSC)和旋转流变仪对KGM和高取代度KGM醋酸酯进行了表征.结果表明,KGM醋酸酯的羰基(CO)特征吸收峰较KGM明显增强,其表观形貌大部分为疏松絮状,KGM及其醋酸酯均为非晶态结构.与KGM相比,KGM醋酸酯的热稳定性下降,分解温度(Td)由KGM的261.10℃降低至KGM醋酸酯的204.56℃,KGM醋酸酯出现了明显的玻璃化转变,其玻璃化转变温度(Tg)为128.49℃.KGM醋酸酯是典型的黏弹性材料,其弹性比率占21.27%,其剪切黏度η对温度变化非常敏感,可通过温度的改变来调节KGM醋酸酯的加工流动性.KGM醋酸酯具有较好的热塑性.