对乙酰氨基酚在多壁碳纳米管修饰电极上的电化学行为

制备了多壁碳纳米管修饰玻碳电极,研究了对乙酰氨基酚在多壁碳纳米管修饰电极上的循环伏安行为,并建立了测定对乙酰氨基酚含量的电化学分析方法。在pH为6.89的磷酸盐缓冲液中,多壁碳纳米管修饰电极对对乙酰氨基酚有明显的电催化作用,其氧化峰电流与对乙酰氨基酚浓度在1.0×10-6～1.0×10-4mol·L-1范围内呈良好的线性关系,检测限为2.0×10-7mol·L-1。     

毛细管电泳电化学法检测过氧化氢

以金微盘电极和离子液体修饰单壁碳纳米管糊微盘电极分别作为毛细管电泳电化学检测器,试验了两种电极对过氧化氢的响应情况,将金微盘电极与毛细管电泳联用,对过氧化氢进行了定性和定量检测.探讨了分离电压、缓冲溶液pH值和工作电位等条件对H2O2检测的影响.实验结果表明,峰电流与H2O2浓度在1.0×10-6～1.0×10-5mo...     

预阳极化碳糊电极同时测定对乙酰氨基酚和多巴胺

采用循环伏安法制备了预阳极化碳糊电极,研究了对乙酰氨基酚和多巴胺在该修饰电极上的电化学行为。结果表明,预阳极化碳糊电极对对乙酰氨基酚和多巴胺的电化学行为具有良好的电催化作用。对乙酰氨基酚和多巴胺的氧化峰电流与其浓度在2.0×10-6～5.0×10-4mol/L的范围内呈良好的线性关系,检出限分别为6.3×10-7mol/L,2.5×10-7mol/L。方法已用于药物样品中对乙酰氨基酚和多巴胺的测定。     

肾上腺素在碳纳米管-离子液体糊修饰电极上的伏安行为

研究了肾上腺素(EP)在多壁碳纳米管与离子液体糊修饰玻碳电极上的电化学行为,发现该修饰电极对肾上腺素的氧化具有良好的催化促进作用。在pH=7.0的磷酸盐缓冲溶液中,肾上腺素在0.13 V产生的阳极峰比相应的多壁碳纳米管修饰电极上的峰负移约40 mV,峰电流则显著增大。优化了实验条件,在选定的条件下,EP的浓度在5.0×10-7~2.0×10-5mol.L-1范围内与阳极峰电流呈线性关系,相关系数为0.998,方法检出限为1.0×10-7mol.L-1。利用该方法对注射液中肾上腺素的含量进行了测定,其回收率达98.1%~100.5%。此外,还对有关物质的干扰及电极反应参数等进行了测试。     

二茂铁-离子液体修饰碳糊电极的研制

以室温离子液体N-辛基吡啶六氟磷酸盐为粘合剂与二茂铁和石墨粉相混合制备了一种新型二茂铁-离子液体修饰碳糊电极。以该电极为工作电极,采用循环伏安法、计时安培法研究了多巴胺(DA)在该糊电极上的电化学行为。实验结果表明:该电极在pH 5.0的乙酸-乙酸钠缓冲溶液中,外加电压0.8 V条件下,灵敏度最高。电流增量与DA浓度在1.0×10-5～1.0×10-3 mol/L范围内呈良好的线性关系,检出限为5.0×10-6 mol/L(S/N=3)。     

黄嘌呤在离子液体-纳米金-碳纳米管复合物修饰电极上的电化学行为

研究了黄嘌呤在离子液体-纳米金-碳纳米管修饰玻碳电极上的电化学行为。结果表明,在0.1mol/L磷酸盐(pH=4.4)介质中,修饰电极对黄嘌呤氧化具有强的电催化作用,黄嘌呤在0.9V(vs.SCE)左右产生一灵敏的氧化峰。在优化的实验条件下,用此峰测定黄嘌呤的线性范围为1.5×10-7～1.0×10-5mol/L,检出限为3.5×10-8mol/L。该修饰电极具有良好的重现性和稳定性。     

谷胱甘肽在多壁碳纳米管-离子液体修饰碳糊电极上的间接电化学测定

制备了多壁碳纳米管-离子液体修饰碳糊电极(MWCNTs-ILs/CPE),并以对乙酰氨基酚(PA)为电催化媒介,研究了谷胱甘肽(GSH)在该修饰电极上的电化学行为。结果表明,GSH能明显增强PA在MWCNTs-ILs/CPE上的电化学响应,且示差脉冲伏安法(DPV)的氧化峰电流与其浓度在7.50×10-7~1.00×10-4 mol/L范围内呈良好线性关系,检测限(S/N=3)为1.65×10-7 mol/L。该方法简单、快速、灵敏,用于含GSH药物的测定,加标回收率为99.5%~101.8%。     

多壁碳纳米管-离子液体凝胶修饰电极对放线菌素D的高灵敏检测

以多壁碳纳米管和离子液体1-正丁基-3-甲基咪唑六氟磷酸盐(BMIMPF6)为修饰剂,研制了多壁碳纳米管-离子液体凝胶修饰玻碳电极(MWNTs-BMIMPF6/GCE),并研究了放线菌素D在该电极上的电化学行为。实验结果表明,放线菌素D于-0.09 V处有一明显的氧化峰,在pH=4.8的HAc-NaAc缓冲溶液中,放线菌素D在该修饰电极上产生的氧化峰电流比在多壁碳纳米管修饰玻碳电极上显著增大。在选定实验条件下,放线菌素D的氧化峰电流与其浓度在2.0×10-8~8.0×10-7mol/L的范围内呈良好的线性关系,检出限为7.5×10-9mol/L。该方法可用于注射液中放线菌素D的测定。     

氧化石墨烯修饰碳离子液体电极同时测定鸟嘌呤和腺嘌呤

以离子液体1-丁基-3-甲基咪唑六氟磷酸盐为粘合剂制备了碳糊电极,然后将氧化石墨烯滴涂到碳糊电极表面制成了一种新型的氧化石墨烯修饰碳离子液体电极。研究了鸟嘌呤和腺嘌呤在修饰电极上的电化学行为。实验结果表明,在0.1 mol/L醋酸盐缓冲溶液中(pH4.5),鸟嘌呤和腺嘌呤在该修饰电极上具有良好的电化学行为,在2.0×10-7～1.5×10-5mol/L浓度范围内鸟嘌呤和腺嘌呤的浓度在该电极上与电化学响应信号呈良好的线性关系,相关系数分别为为0.992和0.996。信噪比为3时,检出限为1.0×10-8mol/L。     

多壁碳纳米管修饰玻碳电极测定铜离子

以多壁碳纳米管(MWCNTs)修饰玻碳电极为工作电极,采用阳极溶出线性扫描法研究了铜离子的电化学测定方法。探讨了MWCNTs修饰层数、富集电位、富集时间、溶液pH、支持电解质对峰电流的影响。实验表明,铜离子浓度在1.0×10-8~1.0×10-5mol·L-1范围内与峰电流呈良好的线性关系,检测限为2.0×10-9mol·L-1,且该电极具有良好的稳定性和抗干扰能力。     

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.