5—羟色胺敏感膜电极的研究：Ⅱ.中性载体5—羟色胺膜电极的研制和应用

通过比较６种冠醚组成的２种不同配比的１１个配方，研制出了对５－羟色胺有较好的灵敏性和较高的选择性的涂碳膜电极。电极敏感膜的活性成分是１８－冠－６，增塑剂为磷酸三（２－乙基乙基）酯。电极的线性是１．００×１０＾－２～１．７８×１０＾－５ｍｏｌ／Ｌ，斜率为５８．４ｍＶ／Ｐ＾５－ＨＴ，检测下限为５．０１×１０＾－６ｍｏｌ／Ｌ，电极寿命超过９５天。用该电极测定了１９５名健康人血小板中的５－羟色胺浓度，算术     

以双核有机锡化合物为载体的PVC膜磷酸根离子敏感电极

以双（三苄基锡）氧化物为载体制备了一种对磷酸氢根离子具有良好电位响应性能的溶剂聚合膜离子敏感电极。在ｐＨ为７．２０±０．０２的测试液中，电极的线性响应范围为５ ×１０＾－６￣１０＾－１ｍｏｌ／Ｌ，斜率为－３０．１ｍＶ／ｄｅｃ．．用分别溶液法测得其对于各种阴离子的选择性次序：ＨＰＯ４＾２－￣Ｉ＾－〉Ｂｒ＾－〉Ｃｌ＾－〉Ａｃ〉ＳＯ４＾２－。膜相中荷电离子添加实验的结果表明，电极响应系中性载体作用机制。     

洛美沙星离子选择电极的研制及应用

用正交设计法研究了离子缔合物的种类,膜相中活性物浓度和增塑剂３个因素对电极性能的影响,以四苯硼－洛美沙星形成的缔合物为电活性物质研制了涂碳ＰＶＣ膜洛美沙星电极。其能斯特响应范围为２．０×１０＾－３－１．０×１０＾－５ｍｏｌ／Ｌ;检测限为４．０×１０＾－６ｍｏｌ／Ｌ,级差为２８．９ｍＶ／ｐＣ。     

阿霉素在钴离子注入修饰电极上的电化学行为及其应用

阿霉素在０．１ｍｏｌ／Ｌ ＨＡｃ－ＮａＡｃ（ｐＨ４．６２）缓冲溶液中用注入钴的修饰玻碳电极为工作电极进行伏安测定,得到一良好的还原峰;Ｅｐ＝－０．５２２Ｖ（ｖｓ．ＳＣＥ）。峰电流与阿霉素浓度在１．４×１０＾－６－１．４×１０＾－６ｍｏｌ／Ｌ和１．４×１０＾－６－５．６×１０＾－５ｍｏｌ／Ｌ范围内呈线性关系,。     

秋兰姆衍生物作中性载体的铜离子敏感电极

合成了二硫化二（Ｎ，Ｎ－１，４－亚丁基）秋兰姆，以此为载体，制备了ＰＶＣ膜铜离子敏感电极。结果表明，电极对铜离子具有好的选择性和灵敏度。线性范围为８．０×１０＾－＾７－１．０×１０＾－＾２ｍｏｌ／Ｌ。实验发现有选定的底液条件下此电极对蛋白质蛮具有较好的响应，线性范围为１２．５－２００ｍｇ／Ｌ。讨论了电极有关性能。     

铜（Ⅱ）锌（Ⅱ）—氟哌酸体系电化学行为及示波极谱法研究

铜（Ⅱ）和锌（Ⅱ）分别在０．１ｍｏｌ／ＬＫＨ２ＰＯ４－Ｎａ２ＨＰＯ４缓冲溶液（ｐＨ６．５）和０．２５ｍｏｌ／ＬＮＨ４Ｃｌ溶液中，与氟哌酸形成良好的络合吸附波，峰电位分别为－０．２６Ｖ和－１．２８Ｖ（ｖｓ．ＳＣＥ），络合比分别为１：３和１：２，峰电流与铜（Ⅱ）和锌（Ⅱ）的浓度均在４．０×１０＾－７～５．０×１０＾－６ｎｏｌ／Ｌ范围内呈线性关系，检测限分别为７．０×１０＾－８和５．０×１０＾－８ｍｏｌ     

哌仑西平的单扫描示波极谱法测定

本报道一种测定哌仑西平的单扫描示波极谱法，在０．１ｍｏｌ／ＬＮＨ４Ｃｌ－ＮＨ３．Ｈ２Ｏ（ｐＨ８．０±０．１）缓冲液中，哌仑西平有一极谱还原波，其峰电位为－１．５１Ｖ（ｖｓ．ＳＣＥ），其一阶导数峰高与哌仑西闰浓度在６．６×１０＾－７－４．６×１０＾－６ｍｏｌ／Ｌ（ｒ＝０．９９８１）和６．６×１０＾－６－１．６×１０＾－５ｍｏｌ／Ｌ（ｒ＝０．９９９１）范围内有线性关系，检测限为３．４×１０－７ｍｏｌ     

用流动注射法研究巯基化合物—铈（IV）—氢化可的松的化学发光反应

采用流动注射法研究了巯基化合物－铈（Ⅳ）－氢化可的松（ＨＣＲｓ）体系的化学发光行为，对影响化学发光强度的诸因素进行试验和探讨，建立了流动注射化学发光法检测谷胱甘肽（ＧＳＨ），半胱氨酸（Ｃｙｓ）等含巯基化合物的新方法。检测ＧＳＨ和Ｃｙｓ和线性范围分别为２．０×１０＾－６￣１０．０×１０＾－５ｍｏｌ／Ｌ和１．０×１０＾－６ｍｏｌ／Ｌ￣１０．０×１０＾－５ｍｏｌ／Ｌ；检测限分别为２．０×１０＾－７ｍｏｌ     

磷钼杂多酸-L-半胱氨酸自组装超分子膜电极对亚硝酸根电催化还原的研究

制备了磷钼杂多酸－Ｌ－半胱氨酸自组装超分子膜电极（Ｐ２Ｍｏ１８－Ｌ－Ｃｙｓ／Ａｕ）。采用水平衰减全反射（ＡＴＲ－ＦＴＩＲ）光谱表征了膜的组成。研究了该膜电极的电化学性质，发现它在１．０ ｍｏｌ／Ｌ　Ｈ２ＳＯ４溶液中，于０．０～０．７Ｖ（ｖｓ．ＳＣＥ）间ＣＶ扫描出现两对稳定、可逆的氧化还原峰，其中峰电位分别为Ｅｍ１＝０．３３４ Ｖ，Ｅｍ２＝０．１８８Ｖ，对应着Ｐ２Ｍｏ１８Ｏ_(６２)~(６－)的两步２电子－２质子反应；计时库仑法计算了薄膜内的电子传递系数Ｄ为５．０１ × １０~（－８）ｃｍ２·ｓ～（－１）。该膜电极对酸性溶液中的ＮＯ_２~－有明显的电催化还原作用，初步探讨了电催化机理。用差分脉冲伏安法（ＤＰＶ）测定其还原峰电流与ＮＯ_２~－的浓度在２．０ ×１０~（－６）～２．０ × １０~（－４）ｍｏｌ／Ｌ范围内呈良好的线性关系，相关系数为０．９９５３，检测限５．０×１０~（－７）ｍｏｌ／Ｌ。该电极用于模拟水样中ＮＯ_２~－的测定，结果满意。     

盐酸氟桂嗪离子选择性电极的制备及应用

研制了盐酸氟桂嗪离子选择性电极。利用正交设计法综合研究了活性的类型、含量以及增塑剂等因素对ＰＶＣ膜电极响应性能的影响，结果表明，以盐酸氟桂嗪－四苯硼钠离子缔合物为活性物质，ＤＢＰ或ＤＯＰ为增塑剂制成的ＰＶＣ膜电极的性能最佳。其响应范围为１．０×１０＾－４－５．０×１０＾－３ｍｏｌ／Ｌ，检测下限为３．５×１０＾５ｍｏｌ／Ｌ，响应斜率为５８ｍＶ（２５℃）。应用该电极对合成样品及胶囊样品中盐酸氟桂嗪含量     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.