纳米碳管修饰铂结合溶胶-凝胶固定酶制备高性能胆碱生物传感器

为了提高胆碱传感器的灵敏度和抗干扰性,以纳米碳管修饰铂电极为基础电极,采用溶胶-凝胶法固定胆碱氧化酶(ChOx),构建了电流型胆碱检测生物传感器,对纳米碳管修饰电极的电化学特征进行分析,得知纳米碳管的引入不仅使电极对H2O2的催化电流增大,同时降低了电催化所需的恒定电位。讨论了缓冲液介质、pH值、酶负载量对传感器响应的影响。研究表明,所制备的传感器在pH 7.2、电位为0.15V条件下对氯化胆碱的线性响应范围为5.0×10-6~1.0×10-4mol/L;检出限为5.0×10-7mol/L;灵敏度为9.48μA/mmol/L。传感器的稳定性好,经过1个月,仍可保持初始电流的85%。抗干扰能力有很大提高。用于人体血清中的胆碱浓度测定,结果令人满意。     

层层自组装制备基于多壁碳纳米管的胆碱生物传感器

以经混酸处理的多壁碳纳米管(MWCNTs)修饰铂(Pt)电极,在此基础上固定(PAA/PVS)3复合膜,采用层层自组装技术将高分子聚电解质PDDA与胆碱氧化酶交替组装在已修饰的电极上,构建了电流型胆碱生物传感器。实验结果表明,MWCNTs的引入使电极对H2O2的催化电流明显增大,制成的酶电极可以有效控制酶量的使用,酶膜组装层数为8时最优,对胆碱的线性响应范围为5×10-7～1×10-4mol/L;灵敏度为12.53μA/mmol;响应时间为7.60s;检出限为2×10-7mol/L(S/N=3)。传感器的抗干扰能力强,稳定性好,30d时的响应电流值仍保持最初的89.5%。3次平行实验的RSD为3.64%。     

基于硫堇/碳纳米管修饰金电极的过氧化氢生物传感器

制备了以硫堇(TH)、纳米金(Nano-Au)及多壁碳纳米管(MWNT)修饰的H2O2生物传感器.探讨了工作电位、温度、pH对电极响应的影响,考察了电极的重现性、抗干扰能力及使用寿命.该传感器具有线性范围宽、检出限低、灵敏度高、稳定性好和抗干扰能力强等特点.其线性范围为7.0×10-7～4.0×10-3 mol/L;检出限为2.3×10-7 mol/L;灵敏度为0.13 A/(mol L-1 cm2);达到稳定电流所用时间《9 s.米氏常数为0.62 mmol/L,表明所固定的酶具有较高的生物活性.     

层层自组装技术制备PDDA-多壁碳纳米管-胆碱生物传感器

以PDDA分散多壁碳纳米管(MWCNTs),制得PDDA-MWCNTs悬浮液,采用层层自组装技术将PDDA-MWCNTs与胆碱氧化酶(ChOx)交替组装在铂(Pt)电极上,最后滴加Nafion制备抗干扰膜,构建了电流型胆碱生物传感器。实验结果表明,构建的复合酶膜(PDDA-MWCNTs/ChOx)n对底物胆碱的催化电流随着组装层数增多而明显增大,酶膜组装6层时最优。此传感器在5×10-6～2.5×10-4mol/L浓度范围内对胆碱有良好线性范围,响应时间为6.6s;灵敏度为21.97μA/mmol;检出限为2×10-6mol/L(S/N=3),RSD<5%,且传感器抗干扰能力强、稳定性好。     

多壁纳米碳管/二氧化硅复合膜中的联吡啶钌电化学发光法测定氧氟沙星的研究与应用

基于氧氟沙星对联吡啶钌(Ru(bpy)_3~(2+))电化学发光的增敏作用,建立了一种以多壁纳米碳管(MWCNTs)/二氧化硅-联吡啶钌复合物修饰的玻碳电极电化学发光检测氧氟沙星的新方法.利用溶胶-凝胶(sol-gel)固定化稳定的优点和纳米碳管的电催化作用,提高了传感器的电流响应.在最佳实验条件下,氧氟沙星浓度在4.0×10~(-6) ～1.0×10~(-4) mol/L范围内与相对发光强度呈线性关系(r~2=0.994 8),检出限(S/N=3)为2.0×10~(-6) mol/L.连续平行测定2.4×10~(-5) mol/L的氧氟沙星溶液 5次,发光强度的RSD为1.8%.     

RuO_2/MWNTs纳米复合材料用于无酶型葡萄糖传感器的研究

采用水热合成法在多壁碳纳米管(MWNTs)上负载了Ru O2纳米颗粒,并以Nafion为固定剂将复合材料修饰于玻碳电极的表面,制备了一种新型无酶型葡萄糖传感器。利用扫描电镜(SEM)、X射线衍射(XRD)、电化学方法对复合材料进行表征,发现碳纳米管上的Ru O2为纳米级,分散均匀。该复合材料修饰的电极对葡萄糖响应电流明显,并且受抗坏血酸(AA)、多巴胺(DA)和尿酸(UA)的干扰小。采用安培法测定葡萄糖,其线性范围为1.0×10-5~1.2×10-2 mol/L(R2=0.998),灵敏度41.826μA cm-2(mmol/L)-1,检测限2.2×10-5 mol/L(信噪比为3),响应时间5.2 s,具有较好的稳定性。     

基于纳米铁氰化镍修饰二氧化钛纳米管阵列电极的非酶葡萄糖传感器

以二氧化钛纳米管阵列(TNTs)为基底,利用脉冲电沉积的方法将Ni纳米粒子沉积在TNTs管内,通过循环伏安法将Ni转化为铁氰化镍(NiHCF),构造了新型的非酶型葡萄糖生物传感器(NiHCF/TNTs修饰电极)。在优化的实验条件下,传感电极的灵敏度为663μA/(mmol cm2);响应电流与葡萄糖浓度在1～23mmol/L范围内呈现良好的线性关系。在低浓度检测下,线性范围为2×10-3～1.0 mmol/L;检出限为0.5μmol/L。本传感电极具有灵敏度高、稳定性好和抗干扰能力强等特点。     

基于多壁碳纳米管和聚丙烯胺层层自组装的葡萄糖生物传感器

经混酸处理后的多壁碳纳米管(MWCNTs)末端及侧壁带有含氧基团,能与阳离子聚电解质通过静电作用结合,也能与酶蛋白非特异性结合。利用层层自组装法在铂(Pt)电极表面构建了聚丙烯胺(PAA)-MWC-NTs-葡萄糖氧化酶(GOx)膜,研究了自组装薄膜的表面微观形貌和电化学性质。组装层数为6层时最优,对葡萄糖响应线性范围为5.0×10-4~2.10×10-2mol/L;检出限为1.0×10-4mol/L(S/N=3);灵敏度为4.95μA/(mmolcm2),响应时间3.80s;GOx表观米氏常数为17.79mmol。对抗坏血酸等具有较强的抗干扰能力,10天后电极响应电流保持最初的91.79%。3次平行实验的RSD为4.85%。     

碳纳米管负载铂-二氧化钌纳米颗粒用于葡萄糖传感器的研究

建立了多壁碳纳米管(MWNTs)负载铂二二氧化钌纳米颗粒的液相化学还原法.以Nafion为固定剂,将Pt-RuO2/MWNTs复合材料修饰于玻碳电极的表面,制备了一种无酶型葡萄糖传感器.实验表明:复合材料修饰的电极对葡萄糖响应电流明显,并且受抗坏血酸(AA)、多巴胺(DA)和尿酸(UA)的干扰小.本实验采用安培法测定葡萄糖,线性范围为2 0×10 3～1.0×10-2 mol/L(R～0.9965);灵敏度为119.26 μA cm-2(mmol/L)-1;检出限为1.25×10 -5 mol/L(信噪比为3);响应时间为4.8 s.PtRuO2/MWNTs修饰电极可作为性能良好的无酶型葡萄糖传感器.     

血红蛋白-氮掺杂碳纳米管电化学生物传感器检测水中溴酸盐

以高导电性的氮掺杂碳纳米管为固载基底，以血红蛋白为识别元件，构建了一种新型溴酸盐(BrO₃^-)电化学生物传感器。该传感器对BrO₃^-表现出较高的灵敏度(0.02519μA/(μmol/L))、较低的检出限(75.43 nmol/L)和较宽的线性范围(1×10^-7～4.66×10-5 mol/L)，已成功应用于实际水样中BrO₃^-的高灵敏快速定量检测。     

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.