Hb/Fe3O4/CILE修饰电极的制备及应用

以类离子液体碳糊电极(CILE)为基体电极,采用滴涂法和利用静电吸附作用,制备了Hb/Fe3O4/CILE修饰电极,研究了Hb的直接电化学及其电催化行为,建立了H2O2的计时安培测定新方法。结果表明:Hb在该修饰电极上,Hb呈现了一对准可逆的氧化还原峰,且其在该修饰电极表面表观覆盖度为2.65×10-9moL/cm2;电子转移速率常数为1.35/s;表观米氏常数为1.59×10-5mol/L。在1.0×10-6~4.0×10-5mol/L范围内,催化电流与H2O2浓度呈线性关系(r=0.9976),检出限为3.0×10-7mol/L(S/N=3)。     

血红蛋白在二维纳米金Langmuir—Blodgett单层膜修饰电极上的直接电化学

利用Langmuir-Blodgett(LB)技术在氧化铟锡(ITO)电极上制备了分散均匀的二维纳米金单层膜,并将血红蛋白(Hb)直接固定于该修饰电极表面,研究了Hb在电极上的直接电化学行为.实验结果表明:纳米金可以改善Hb和电极间的直接电子传递,提高电子传递效率.Hb/Nano-Au修饰电极在pH 5.0～9.0范围内的式电位与溶液pH呈线性关系,斜率为-57 mV/pH,说明Hb的电子传递过程伴随质子转移;该修饰电极对H2O2具有良好的催化作用,在0.1 mol/L pH 7.0 的磷酸盐缓冲溶液(PBS)中,H2O2在2.5×10-6～4.1×10-4 mol/L浓度范围内与响应电流呈良好的线性关系,检出限为6.2×10-7 mol/L;其异相电子转移速率常数为0.66 s-1,米氏常数为0.20 mmol/L.     

基于Nafion-氧化石墨烯复合物/硫堇/纳米金构建过氧化氢传感器的研究

利用Nafion(全氟聚苯乙烯磺酸溶液)-氧化石墨烯复合物、硫堇和纳米金构建了H2O2酶传感器。首先将氧化石墨烯分散在体积分数0.2%Nafion溶液中制得Nafion-氧化石墨烯的复合物,并将其固定在玻碳电极表面,通过静电吸附将带正电荷的硫堇吸附到Nafion-氧化石墨烯复合膜修饰的玻碳电极表面,再利用静电吸附将纳米金修饰于电极上,通过纳米金来固定辣根过氧化物酶从而制得H2O2传感器。用循环伏安法和计时电流法考察该修饰电极的电化学特性。H2O2浓度为5.5×10-6~1.0×10-3mol/L时,酶电极的响应电流值与H2O2的浓度呈良好的线性关系,检出限为1.80×10-6mol/L。     

还原石墨烯-碳纳米管-金纳米复合物的电化学发光过氧化氢传感器

以聚乙烯亚胺(PEI)为还原剂,采用一步还原法制备纳米金修饰的还原石墨烯-碳纳米管(AuNPs-rGO-CNTs)复合纳米材料。PEI同时作为交联试剂,使得AuNPs-rGO-CNTs复合物具有良好的成膜性质,能均匀的修饰到玻碳电极表面,制得AuNPs-rGO-CNTs修饰电极。基于过氧化氢(H2O2)作为鲁米诺-电化学发光(鲁米诺-ECL)体系的共反应试剂能显著增强鲁米诺的电化学发光信号,构建了AuNPs-rGO-CNTs复合物修饰的玻碳电极用于电化学发光测定H2O2的新方法。实验采用循环伏安法对传感器的修饰过程进行了表征。对测试底液中鲁米诺的浓度、pH等条件进行了优化,在最优实验条件下,该传感器的电化学发光信号强度与H2O2浓度在3.4×10-2~1.4×102μmol/L范围内呈良好的线性关系,检出限为1.1×10-2μmol/L。传感器适用于H2O2的测定。     

电聚合茜素黄R构建辣根过氧化物酶传感器的研究

利用电聚合茜素黄R(AYR)的方法,将辣根过氧化物酶(HRP)和细胞色素c(Cyt c)固载于通过一步法电沉积的碳纳米管-金纳米粒子(MWCNTsAu NPs)复合纳米材料修饰电极表面,构筑PAYR-HRP-Cyt c/M WCNTs-Au NPs修饰电极,并利用HRP对H2O2的直接电化学催化行为对H2O2进行检测。采用扫描电镜对MWCNTs-Au NPs和PAYR-HRP-Cyt c的表面形貌进行表征。利用电化学阻抗对修饰电极的构筑过程进行了监测。采用循环伏安法和计时电流法对修饰电极的电化学行为进行了研究。探讨了p H和电位对该修饰电极测定H2O2的性能的影响。该传感器对H2O2在5.0×10-7~3.14×10-3mol/L范围内呈良好的线性响应,相关系数为0.9997,灵敏度为0.50 A·L/mol,检出限(S/N=3)为9.6×10-8mol/L。     

HA-[CePy][PF6]-Mb/GCE修饰电极的制备与应用

将肌红蛋白(Mb)包埋在十六烷基吡啶六氟磷酸盐([CePy][PF6])与透明质酸(HA)混合得到的复合膜内,采用滴涂法将其修饰在玻碳电极(GCE)表面,制备了HA-[CePy][PF6]-Mb/GCE修饰电极,研究了Mb的直接电化学及电催化行为,建立了H2O2的计时安培测定新方法。结果表明,在0.1 mol/LPBS(pH 7.0)中,该修饰电极上产生了一对准可逆的氧化还原峰,电子转移速率常数(ks)为3.9/s,电极表面表观覆盖度(Γ*)为4.36×10-9mol/cm2,表观米氏常数(Km)为2.6×10-5mol/L;该修饰电极上的Mb对H2O2的还原表现出良好的电催化作用,催化电流与H2O2浓度在2.5×10-6～5.0×10-5mol/L范围内呈线性关系,检出限为8.0×10-7mol/L(S/N=3)。     

二氧化铅修饰玻碳电极的镀膜/循环伏安法制备及电催化性能

采用镀膜/循环伏安法制备了PbO2修饰玻碳电极.在Pb(NO3)2溶液中,在-0.7 V 将Pb膜沉积在玻碳电极表面,然后在5 mol/L NaOH溶液中以100 mV/s速度在-1.0～1.0 V循环伏安扫描20次,PbO2膜均匀沉积在玻碳电极表面.采用交流阻抗法监控电极修饰每一过程,环境扫描电镜表征电极表面形貌.探讨了PbO2膜的沉积机理及其电化学行为,表面活性位点覆盖量为7.5×10-10 mol/cm2.PbO2修饰电极对H2O2电氧化表现出较高催化活性,起始氧化电位低至0.1 V,考察了影响催化活性的因素.计时电流法测定H2O2 (工作电位0.40 V),响应时间小于2 s; 线性范围为5.0 ×10-6 ～ 5.5×10-4 mol/L;检出限1.1×10-6 mol/L (信噪比为3).在实际水样中H2O2测定结果满意.电极在室温环境下储存30 d,其催化活性基本不变.该修饰电极制备工艺简单、重现性良好、稳定性高.     

电沉积普鲁士蓝/壳聚糖修饰金电极的电化学研究

应用控制电位电解法在金电极上进行了普鲁士蓝(PB)/壳聚糖(CS)修饰膜的电沉积。在pH2、溶液组成为2.5 mmol/L FeCl3 2.5 mmol/L K3[Fe(CN)6] 0.01%CS 0.01 mol/L HCl和0.1 mol/L KCl的溶液中,于0.4 V(vs.SCE)电沉积300 s,获得性能理想的沉积膜。对修饰膜进行了红外和显微表征,结果表明,PB和CS同时沉积在电极上,且膜结构较纯PB沉积膜粗糙,修饰量大,具有更强的空间结构性。研究了PB/CS/金修饰电极(PB/CS/Au/CME)的电化学行为,该电极在中性(pH7.0~8.0)条件下性能比纯PB修饰膜更稳定,具有良好的电化学活性和对H2O2的电催化性能。氧化峰电流与H2O2浓度在1×10-6~5×10-3mol/L范围内呈良好线性关系,为研制基于酶催化反应的电化学生物传感器奠定了良好基础。     

电沉积纳米ZnO修饰玻碳电极交流阻抗法测定硫离子

以Zn(NO3)2和KCl为支持解液,在裸玻碳电极(GCE)上电化学沉积一层纳米Zn O薄膜,制备出一种基于纳米Zn O修饰电极(Zn O/GCE)用于检测S2-的电化学传感器。电化学循环伏安法(CV)表明该修饰电极具有大的比表面积及良好导电性能。将Zn O/GCE置于微酸性的Na2S(p H 6.5)溶液中进行富集反应12 min后,可得到恒定的电化学交流阻抗值(Ret)。在最优实验条件下,该制备电极可成功应用于检测不同浓度的Na2S溶液,其ΔRet值与Na2S浓度范围(1.0×10-7~1.0×10-3mol/L)的对数呈良好的线性关系,检出限为6.37×10-8mol/L。制备电极(Zn O/GCE)可应用于实际水样中硫化物的检测。     

基于聚酰胺-胺功能化碳纳米管负载钯纳米粒子的过氧化氢传感器

采用电化学法将钯纳米粒子(PdNPs)沉积在第四代聚酰胺-胺树状大分子(G4.0 PAMAM)功能化碳纳米管(MWCNTs)复合材料(G4.0-MWCNTs)修饰的玻碳电极表面,构建了一种新型过氧化氢(H2O2)传感器。采用场发射扫描电镜、循环伏安法和电化学阻抗谱对修饰电极进行表征,结果表明,大量高分散的PdNPs沉积在G4.0-MWCNTs修饰的电极上,修饰电极对H2 O2还原具有优异的电催化性能。在优化条件下,H2 O2浓度在1.0×10-9~1.0×10-3 mol/L范围内与电流响应呈线性关系,检出限为3×10-10 mol/L (S/N=3),测定血清实样加标回收率在96.7％~103.1％之间。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

解决能源问题的新途径--光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。