光电化学传感器的研究进展

光电化学传感器以光作为激发源,以光电流或光电压作为检测信号,具有响应快速、灵敏度高、设备简单等特点,目前已在环境、食品、医学等多个领域的分析测试中得到广泛应用。该文阐述了光电转换材料与光电化学传感器的制备方法,介绍了光电化学传感器的原理和分类。光电化学传感器包含光寻址电位型传感器和电流型光电化学传感器,其中,电流型光电化学传感器由于优良的光电性能、检出限低、所需材料低廉且易加工等优势而被广泛应用。文中着重介绍了电流型光电化学传感器在金属离子、有机污染物、核酸、蛋白质、细胞等方面的应用,并对光电化学传感器的发展前景进行了展望。     

溶胶-凝胶非标记免疫传感器检测乙肝表面抗原

采用溶胶 凝胶 (sol gel)技术包埋乙肝表面抗体 (HBsAb) ,涂布于金盘电极表面 ,构成sol gel HBsAb/Au非标记免疫传感器 ,用于检测人血清中乙肝表面抗原 (HBsAg)。该传感器对HBsAg的电位响应遵循Nernst方程 ,在 1～ 330 μg/L浓度范围内 ,传感器的电位响应值ΔE与HBsAg浓度C的对数呈线性关系 ,线性回归方程为ΔE =1 8.1 7+79.84lgC。响应时间为 3min。癌胚抗原、甲胎蛋白等对测定无明显影响。对于HBsAg阴性血清 ,电位响应值ΔE <30mV ,而对于阳性血清则ΔE >30mV ,据此 ,作为临床判别的依据。对1 0 0例临床血清分别用传感器和酶联免疫法 (ELISA)进行双盲检验 ,两法的符合率为 86 %。     

溶胶-凝胶非标记 CA15-3免疫传感器的研制与应用

采用溶胶-凝胶技术将乳腺癌抗体固定于电极表面,研制成用于检测乳腺癌抗原的非标记型溶胶-凝胶-抗体膜免疫传感器;用循环伏安法对电极的修饰过程进行表征,同时对乳腺癌抗原定量检测的可行性进行了探讨;随着抗体与抗原特异性反应的进行,形成的抗体-抗原免疫复合物使膜电位发生变化(△V),该变化的大小与溶胶-凝胶-抗体膜表面免疫反应进行的程度相关;本文以此为依据对CA15-3进行检测,在5～240U／mL范围内．△V／与lgCCA15-3呈良好的线性关系,线性相关系数r=O.998;该传感器响应迅速,灵敏度高,稳定性好,于4℃干态保存30d,其响应信号基本不变。     

基于水溶性共轭聚合物的蛋白质检测*

近年来,以共轭聚合物作为生物传感元件,在生物大分子（如核酸、蛋白质）特异性识别、检测方面的研究越来越受到人们的关注。共轭聚合物具有强的光捕获能力,具有倍增光学响应性,可用来放大荧光传感信号,大大提高检测的灵敏度,为生物传感器的发展提供了新的传感模式。基于共轭聚合物的新型生物传感器在医疗诊断、环境检测以及国家安全防御等方面具有广泛的应用前景。本文简要介绍了共轭聚合物的荧光信号放大机制以及在蛋白质、酶、抗原－抗体检测方面的应用。最后对共轭聚合物在蛋白质检测方面的未来发展趋势进行了展望。     

基于蛋白A/纳米金/壳聚糖分散的多壁碳纳米管修饰的电位型甲胎蛋白免疫传感器的研究

将壳聚糖分散的多壁碳纳米管(MWNT-CS)滴涂于金电极(Au)表面,利用壳聚糖大量的氨基将纳米金(nano-Au)固定到金电极表面,再利用蛋白A(PA)的定向固定效应将甲胎蛋白抗体(anti-AFP)固定到纳米金修饰的金电极表面,从而制得高灵敏、高稳定电位型甲胎蛋白免疫传感器。蛋白A为抗原和抗体的反应提供了合理的基础,纳米金的存在提高了抗体在电极表面的固定量,多壁碳纳米管(MWNT)促进了电子的传递,从而缩短电极的响应时间。在优化的实验条件下,该传感器响应的电极电位与甲胎蛋白浓度的对数在7.0~190.0μg/L的范围内保持良好的线性关系,检出限(S/N=3)为3.9μg/L。     

新型压电肿瘤标志物微阵列免疫传感器的研究

采用螺旋固定夹具构建一种新型插拔式压电石英晶体传感器,巯基化自组装技术固定抗人甲胎蛋白(AFP)、癌胚抗原(CEA)和前列腺特异抗原(PSA)的单克隆抗体,并组装成2×5型压电肿瘤标志物微阵列免疫传感器.研究了压电肿瘤标志物微阵列免疫传感器的响应特性及其影响因素.该微阵列传感器在AFP、CEA和PSA浓度分别为20～640 μg/L、1.56～50 μg/L和1.25～50 μg/L,压电石英晶体振荡频率偏移值对肿瘤标志物浓度呈现良好的响应特性.微阵列传感器用于68例临床血清标本的测定,结果与免疫化学发光法一致;相关系数分别为0.92、0.90和0.91.     

一种新型汞离子选择薄膜传感器

采用脉冲激光沉积技术,在光寻址电位传感器表面上沉积了对二价汞离子敏感的薄膜,制备了一种新型汞离子选择薄膜传感器,靶材成分为HgAgIS,基底为p型单晶硅片,金属接触层为Cr/Au。该薄膜传感器在3星期内显示了良好的重复性和稳定性;检出限为3×10-6mol/L;响应时间小于2min,适用pH范围小于2。对干扰离子和迟滞效应等也进行了研究。该传感器具有测量快速灵活、所需样品少、动态范围宽等特点,因为把电位信号转化为对光激发的交流电流信号进行测量,所以提高了灵敏度。同时也证明了脉冲激光沉积是适合制备薄膜传感器的一种新技术。     

用于氨氮检测的薄层氨气微传感芯片及其系统研究

设计并制备了一种具有微池薄液层结构的氨气微传感芯片,并构建了以此微传感芯片为敏感单元的氨氮检测系统,探索了使用安培型氨气微传感器检测氨氮的方法。此微传感芯片采用MEMS工艺制备,通过电化学方法在微电极表面修饰了对氨具有良好电催化氧化性能的纳米铂,提高了传感器的灵敏度。在芯片的SU-8微池中滴入微量碳酸丙烯酯(PC),形成可使氨气迅速扩散到电极表面的薄层电解液,使传感器具有较快的响应速度。使用自行设计的氨氮检测系统对氨氮进行检测,考察了氨氮检测的浓度响应特性、时间响应特性、重复性及选择性。氨氮检测系统的线性范围为0.1～5.0 mg/L;检测下限为0.1 mg/L;响应时间小于1 min;重复性偏差为4.0%。     

基于中性红电聚合膜的伏安型甲胎蛋白免疫传感器

用循环伏安法在玻碳电极上电聚合一层稳定的中性红聚合物膜,再通过共价键合作用将戊二醛和甲胎蛋白抗体自组装到电极表面,最后用辣根过氧化物酶封闭电极上的非特异性吸附位点,并同时起到放大响应电流信号的作用,制得高灵敏伏安型甲胎蛋白抗原免疫传感器。实验结果表明,该传感器对甲胎蛋白抗原具有良好的电流响应,该传感器的线性范围为1.00～10.0ng/mL和10.0～200ng/mL,检出限(3σ)为0.40ng/mL。     

微型电化学免疫传感器的研制及初步应用

利用微电子技术和电化学原理设计制作了一种微型电化学免疫传感器,应用恒电位法建立了该传感器的实验条件。在设定的实验条件下测试,阳性血清的电流响应曲线与阴性血清的电流响应曲线具有明显的离散度,并能检测不同类型的抗原抗体反应,不同抗原抗体之间没有交叉反应;测定一个样品用时不到1h,仅用血清10μL;传感器操作简便,微型小巧,便于携带,通过进一步的设计和条件优化,有望应用于临床和现场抗原抗体反应的快速检测分析和诊断。     

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.     

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.     

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^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

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。