木犀草素在玻碳电极上的直接电化学行为及其测定

应用循环伏安法研究木犀草素于玻碳电极的电化学行为.在磷酸盐缓冲液中(pH 4.0),-0.2~+0.8V电位区间内,木犀草素于玻碳电极表面发生的电极反应是吸附控制的准可逆2电子转移过程,电子转移系数α=0.66;建立了检测木犀草素含量的差示脉冲伏安法(DPV).在富集电位+0.4 V下,经富集240 s后,测得木犀草素氧化峰电流Ip与其浓度在1.0×10-8~1.0×10-6mol.L-1范围内呈良好的线性关系,最低检出限为5.0×10-9mol.L-1.本法操作简单、快速、灵敏、准确,可为木犀草素药物质量的控制和检测提供一种简便的新方法.     

木犀草素在离子液体修饰电极上的电催化氧化及其测定

用1-丁基-3-甲基咪唑六氟磷酸盐([BMIM]PF₆)疏水性离子液体修饰玻碳电极,在0.2 mol/L磷酸盐缓冲溶液(pH为4.0～8.0)中,运用循环伏安法（CV）和差示脉冲溶出伏安法(DPSV)研究了木犀草素在修饰电极上的电化学行为,建立了测定木犀草素含量的新方法。 实验结果表明,该修饰电极上木犀草素氧化、还原峰电位均负移,峰电流增大。 在-0.2～0.7 V电位区间,pH=7.0的磷酸盐缓冲溶液体系中,木犀草素在修饰电极表面发生的是受吸附控制的准可逆等电子等质子电极反应,电子转移系数α=0.5,吸附量为4.6×10-10 mol/cm²;木犀草素氧化峰电流与其浓度在1.0×10^-10～1.6×10^-8 mol/L范围内呈良好的线性关系,检出限达到3.2×10^-11 mol/L,回收率为98.7%～102.0%;该法操作简单、快速、灵敏、准确;可用于野菊花中类黄酮的测定。     

木犀草素在多壁碳纳米管修饰碳糊电极上的电化学行为及其与DNA相互作用

采用循环伏安法、差分脉冲法研究了木犀草素在多壁碳纳米管修饰碳糊电极上的电化学行为。在p H 3.29的B-R缓冲体系中,木犀草素在0.502 V和0.452 V处产生一对明显的氧化还原峰,其峰电流与木犀草素浓度在5.0×10~(-8)~1.0×10~(-5)mol/L范围内呈良好的线性关系,木犀草素在电极上是受吸附控制的2质子、2电子电极反应过程;在此基础上研究了木犀草素与DNA的相互作用,随着DNA的浓度增加木犀草素的电化学信号逐渐降低,表明木犀草素能与DNA发生明显的相互作用,进一步研究表明木犀草素与DNA的相互作用是以嵌入方式为主。     

2,3-二巯基丁二酸修饰金电极伏安法同时测定肾上腺素及多巴胺

研究结果表明:肾上腺素(EP)及多巴胺(DA)在2,3-二巯基丁二酸修饰金电极上的电化学响应,由于该修饰电极的催化作用而明显增强。在pH6.7的磷酸盐缓冲溶液中,肾上腺素及多巴胺的氧化峰电流(ipc)值依次为0.793,1.059μA,多巴胺的还原峰电流(ipa)为1.249μA,肾上腺素在此条件下无还原峰。在肾上腺素及多巴胺共存的溶液中,还原峰电流只与多巴胺的存在有关,而氧化峰电流值恰为两者氧化峰电流值之和。多巴胺浓度在4.0×10-6～1.0×10-4mol.L-1范围内与相应的ipa值之间呈线性关系,而肾上腺素浓度在1.0×10-5～1.0×10-4mol.L-1之间与相应的ipc值之间呈线性关系。据此提出了同时测定肾上腺素及多巴胺的伏安法。此方法对肾上腺素及多巴胺的测定结果分别在0.98～1.03 g.L-1和0.97～1.02 g.L-1之间。     

花旗松素在碳纳米管-离子液体修饰碳糊电极上的电催化氧化及其测定

制备了碳纳米管(MWCNTs)和疏水性离子液体N-丁基吡啶六氟磷酸盐([Bu Py]PF6)复合修饰碳糊电极(MWCNTs-[Bu Py]PF6/CPE),利用循环伏安法研究了花旗松素在MWCNTs-[Bu Py]PF6/CPE上的电化学氧化行为。结果表明,花旗松素在修饰电极上出现一对灵敏、准可逆的氧化还原峰,氧化峰电位Epa=0.60 V,还原峰电位Epc=0.24 V,△Ep=0.46 V,氧化峰电流ipa=3.96μA,还原峰电流ipc=5.03μA,ipa/ipc=0.79,表明MWCNTs-[Bu Py]PF6/CPE对花旗松素具有良好的电催化氧化作用。用差分脉冲伏安法(DPV)测得花旗松素的氧化峰电流ipa与浓度c在1.2×10-5~4.0×10-2g·L-1范围内呈良好线性,检出限为2.2×10-6g·L-1。该法用于水红花子中花旗松素含量的测定,RSD为1.1%~1.5%,加标回收率为97.3%~101.3%。     

芦荟苷的循环伏安测定及其在玻碳电极上的电化学行为

用循环伏安法在pH 1.7的氯化钾-盐酸的底液中,得到了芦荟苷良好的氧化峰和还原峰,氧化峰电位(Epc)为-0.386 V,还原峰电位(Epa)为-0.441 V。峰电流(ipa)与芦荟苷浓度在1.195×10-6~2.152×10-4mol.L-1范围内呈线性关系。检出限(3S/N)为4.78×10-7mol.L-1。据此提出了循环伏安法测定芦荟中芦荟苷的含量。还研究了芦荟苷在玻碳电极上的电化学行为,结果表明芦荟苷的电极过程具有吸附性和不可逆性。     

纳米二氧化铈修饰碳糊电极线性扫描伏安法测定苯酚

在0.01mol.L-1硼砂溶液(pH 9.18)中,用纳米二氧化铈修饰碳糊电极作为工作电极,线性扫描伏安法测定苯酚。伏安图上出现一灵敏的氧化峰,其峰电位为+0.56V(vs.SCE),峰电流与苯酚的浓度在1.0×10-7～2.0×10-4 mol.L-1范围内呈线性关系,检出限(3s/k)为5.0×10-8 mol.L-1。富集时间为30s,同时采用线性扫描伏安法研究苯酚在纳米二氧化铈修饰碳糊电极上的氧化还原反应,结果表明此电极反应为一不可逆的吸附过程。     

灯盏花素在多壁碳纳米管丝网印刷电极上的电化学行为及测定

采用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了黄酮化合物灯盏花素在多壁碳纳米管丝网印刷电极(MWCNT/SPE)上的电化学行为及其测定方法.实验表明,在pH=5.0的HAc-NaAc缓冲溶液中,浓度为5.0×10-4 g/L的灯盏花素在MWC-NT/SPE电极上出现了一对准可逆氧化还原峰,峰电位Epa=0.21 V,Epc=-0.05 V,△E=0.26 V,峰电流ipa=1.18 μA,ipc＝0.205 μA,ipa/ipc=5.76.灯盏花素的DPV氧化峰电流值与其浓度在1.2×10-4～2.8×10-3 g/L范围内呈线性关系(R=0.9990),检出限为1.2×10-4g/L.结果表明,该法测定灯盏花素便捷、可靠、较灵敏.     

银掺杂聚L-天冬氨酸修饰电极的制备及对肾上腺素的测定

利用循环伏安法,研究了银和L-天冬氨酸在玻碳电极表面电化学聚合的条件,制备了银掺杂聚L-天冬氨酸修饰电极。研究了肾上腺素在修饰电极上的电化学行为,建立了循环伏安法测定肾上腺素的新方法。在pH=3.5的磷酸盐缓冲溶液中,扫描速率为50mV/s时,肾上腺素在修饰电极上产生一对明显的氧化还原峰,峰电位分别为Epa=0.447V,Epc=0.387V。用循环伏安法测定时,氧化峰电流与肾上腺素浓度分别在8.00×10-8～1.00×10-5mol/L和1.00×10-5～1.00×10-4mol/L范围内呈良好的线性关系,检出限为8.0×10-9mol/L。     

对乙酰氨基酚在活化玻碳电极上的电化学行为及测定

应用循环伏安法,研究了对乙酰氨基酚(PCT)在活化玻碳电极上的电化学行为.在pH=4.00的HAc-NaAc缓冲溶液中,PCT的CV扫描于0.54 V左右出现一对明显的氧化-还原峰.电极反应为2电子、2质子的受吸附控制的准可逆过程.其氧化峰电流与PCT浓度在8.00×10-6~2.00×10-4mol.L-1范围内呈良好的线性关系,相关系数r=-0.99918;检出限为6.34×10-6mol.L-1.用于药物样品PCT的含量测定,结果满意.     

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.     

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.     

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.