磁性石墨烯修饰辛基酚印迹传感器制备及应用研究

以辛基酚(4-OP)为模板分子,多巴胺为功能单体,采用电聚合技术在磁性石墨烯修饰碳电极表面制备对辛基酚具有高选择性与灵敏性的印迹电化学传感器。采用循环伏安法(CV)和差分脉冲伏安法(DPV)对此印迹传感器的电化学性能进行详细表征;采用扫描电子显微技术对修饰电极的形貌进行表征。结果表明,此印迹电化学传感器对辛基酚具有良好的特异识别性能。采用 DPV 法考察了孵化时间和洗脱溶剂对印迹传感器性能影响,结果表明,最佳孵化时间为14 min。此印迹电化学传感器的响应电流(△IR )与辛基酚在5.0×10-6~5.0×10-9 mol/ L 范围内浓度的负对数(-lgC)呈良好的线性关系,线性方程为△IR ( mA)=-0.25lgC(mol/ L)+2.35,检出限为3.64×10-10 mol/ L (S/ N=3)。此印迹电化学传感器对辛基酚具有良好的选择性和灵敏性,成功用于实际水样中辛基酚的检测,回收率为96.0%~104.0%。     

盐酸阿霉素分子印迹传感器的制备及识别特性

采用自组装以及电聚合的方法,在磷酸盐缓冲液(PBS)中以3,4-乙烯二氧噻吩(EDOT)为功能单体,盐酸阿霉素(DOX)为模板,在金电极表面电聚合制备DOX印迹敏感膜(MIPs),构建了一种选择性检测DOX的分子印迹电化学传感器.采用循环伏安法(CV)及交流阻抗法(EIS)对其性能进行了表征.优化实验条件后,在含0.005 mol/L K3[Fe(CN)_6]及0.1 mol/L KCl的PBS中,应用差分脉冲伏安法(DPV)测试了该传感器的响应性能.实验结果表明,该传感器检测DOX的线性范围为4.0×10~(-7)~1.0×10~(-6)mol/L,相关系数为0.9967,检出限(S/N=3)达6.5×10~(-8)mol/L;采用电化学洗脱法可使传感器再生,对DOX的测定具有良好重现性及稳定性;该传感器对于干扰物长春碱、放线菌素D及5-氟尿嘧啶有微弱的电流响应,显示出良好的选择性.将该传感器用于人体血样中盐酸阿霉素的分析,回收率为96.0%~106.7%,表明其具有潜在的实用价值.     

基于石墨烯-纳米金修饰分子印迹传感器测定黑茶中芦丁

在金电极表面滴涂石墨烯(GR),通过电沉积技术沉积纳米金(Au)构成石墨烯-纳米金修饰电极(Au-GR/GE)。以芦丁为模板分子,邻氨基酚为功能单体,通过电聚合反应在Au-GR/GE表面合成一种对芦丁具有特异性识别能力的分子印迹传感器膜(MIP)。采用循环伏安法(CV)、差分脉冲伏安法(DPV)研究了印迹膜的性能、结构和分子印迹效应,并与槲皮素进行了选择性响应的比较,发现此传感器对芦丁具有良好的选择性。在最佳实验条件下,其对芦丁浓度的定量测定线性范围为6.30×10-7~1.70×10-4mol/L,线性方程为I(μA)=3.8136-8.6247 lg c(mol/L),R=0.9961,检出限为2.10×10-7mol/L。     

盐酸林可霉素分子印迹膜电化学传感器的制备及应用

本文以盐酸林可霉素为目标分子,邻苯二胺为功能单体,采用循环伏安(CV)法,在玻碳电极表面成功制备了盐酸林可霉素聚合膜传感器。应用差分脉冲伏安(DPV)法和CV法对所制传感器的性能进行了研究。实验结果表明,该传感器具有良好的稳定性、重现性、选择性及准确性。用DPV法测定,盐酸林可霉素浓度在6.604×10~(-8)~1.204×10~(-6) mol/L范围内与其峰电流呈线性关系,相关系数r=0.9959,检出限为5.0×10~(-9) mol/L。该方法可用于实际样品的测定。     

盐酸普萘洛尔分子印迹电化学传感器的制备与研究

以盐酸普萘洛尔为目标模板分子,通过电聚合多巴胺,在多壁碳纳米管修饰的玻碳电极表面制备了对目标分子有特异响应的分子印迹电化学传感器.利用扫描电子显微镜、循环伏安法和差示脉冲伏安法对此传感器的表面形貌及性能进行了表征,并且优化了检测条件,研究了印迹传感器对模板分子及其结构类似物的选择性响应.结果表明:此传感器具有较好的选择性响应,而且碳纳米管的存在显著提高了传感器的灵敏度.盐酸普萘洛尔的浓度在0.20～100 μmol/L范围内与峰电流呈良好的线性关系;检出限为2.53×10-8 mol/L(S/N=3).此传感器还具有良好的稳定性和重现性.     

基于电聚合的苯巴比妥分子印迹电化学传感器的制备及其应用研究

以马来松香丙烯酸乙二醇酯(EGMRA)为交联剂,甲基丙烯酸为功能单体,在玻碳电极表面电聚合了一种对苯巴比妥分子具有专一性识别的聚合膜。在最佳实验条件下,采用循环伏安法(CV)、差分脉冲伏安法(DPV)及电化学交流阻抗法(EIS)对印迹传感器的性能进行研究。实验结果表明:该印迹传感器对苯巴比妥具有快速响应、专一性识别和高灵敏度的特点,且苯巴比妥的浓度在8.0×10-7~1.0×10-4mol/L范围内与DPV电流信号呈良好的线性关系,相关系数(r)为0.998 3。检出限(S/N=3)为5.4×10-8mol/L。将此印迹传感器应用于实际样品中苯巴比妥的检测,加标回收率为95.7%~105.0%。     

电聚合分子印迹传感器测定黑茶中芦丁的含量

以芦丁作为模板分子,邻氨基酚为功能单体,在金电极表面循环伏安法电聚合具有选择性识别芦丁的分子印迹膜。以Fe(CN)3-/4-作为探针分子,采用循环伏安法(CV)、差分脉冲伏安法(DPV)、交流阻抗法(EIS)研究了印迹膜的性能、分子印迹效应。优化了测定芦丁含量的条件,芦丁浓度在5.56×10-6~2.22×10-4mol·L-1范围内,其对数与峰电流呈线性关系,线性方程为:I(μA)=9.83 lgc(mol·L-1)+14.63,检出限为1.85×10-6mol·L-1,并比较了传感器对其结构相似化合物的选择性响应,发现传感器对芦丁检测具有良好的选择性。该传感器成功应用于黑茶中芦丁含量的测定。     

基于分子印迹电聚合膜的褪黑素传感器的研究

在弱酸条件下,以邻苯二胺为功能单体,褪黑素为模板,以电化学聚合物法在铂电极表面合成了性能稳定的褪黑素分子印迹聚合物膜.采用循环伏安法(CV)和差分脉冲法(DPV)对分子印迹传感器的识别性能进行了研究.结果表明:此传感器对褪黑素具有快的响应、良好的选择性和高的灵敏度.以K3Fe(CN)6为电子传递媒介,建立了一种差分脉冲伏安法(DPV)间接检测褪黑素的分析方法.在1×10-10～1×10-8 moL/L范围内,褪黑素的浓度与K3Fe(CN)6的相对峰电流变化呈良好的线性关系;检出限为1×10-11 mol/L(S/N=3).将此传感器应用于复合褪黑素及尿样中褪黑素含量的测定,加标平均回收率大于94％.     

基于石墨烯修饰碳电极的铜离子印迹电化学传感器的制备与应用

以铜离子为模板,多巴胺为功能单体,采用电聚合法在石墨烯修饰碳电极表面成功制备对铜离子有高选择性和灵敏性的印迹电化学传感器。采用差分脉冲伏安法和循环伏安法对该印迹传感器的电化学行为进行详细研究。在优化检测条件下,该印迹电化学传感器的响应电流与铜离子浓度的负对数在5.0×10~(-6)~5.0×10~(-11)mol/L浓度范围内呈良好的线性关系,最低检测限为1.0×10~(-11)mol/L。该印迹电化学传感器成功用于实际水样中的微量铜离子分析。     

3D石墨烯修饰的猛杀威分子印迹电化学传感器的制备

以猛杀威为模板分子、丙烯酰胺( AM)为功能单体、马来松香丙烯酸乙二醇酯( EGMRA)为交联剂、自制的3D石墨烯(3D-rGO)为增敏材料,在玻碳电极表面合成分子印迹聚合物,制备检测猛杀威的分子印迹电化学传感器。运用扫描电镜(SEM)对自制3D石墨烯的形貌进行了表征,通过循环伏安法(CV)、差分脉冲伏安法(DPV)和交流阻抗法(EIS)对猛杀威传感器的性能进行了研究。结果表明,猛杀威的浓度在8.0×10-8~8.0×10-6 mol/L范围内与响应电流值呈良好的线性关系,线性相关系数R=0.9954,检出限为7.3×10-8 mol/L (S/N=3),猛杀威分子印迹敏感膜的印迹因子β=3.88,且相对于3种结构类似物的选择因子α垌1,说明此传感器具有良好的选择性。将此传感器应用于生菜样品检测,加标回收率在96.7%~98.7%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.     

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.     

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。     

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.     

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.

     

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。     

Investigation of Kinetics of Solid-Phase Synthesis of Lithium Orthosilicate

The kinetics of the interaction between lithium carbonate and silica with various degrees of dispersion was investigated by TG and DTA methods. It was found that the utilization of pyrogenic silica with a specific surface area of about 300 m²g^-1 instead of aerosil with one of 175 m²g^-1 leads to an increase of the reaction rate between lithium carbonate and silica, which depends on the formation and growth of lithium orthosilicate crystals in the first stage, and is conditioned by the diffusion of lithium and oxygen ions through the lithium orthosilicate layer formed at temperatures above 800 K. This supposition is supported by the kinetic analysis results obtained with the use of the different models. The optimal regime of heating is recommended. This revised version was published online in July 2006 with corrections to the Cover Date.     

小环化合物中饱和碳质子化学位移的计算

小环化合物由于其张力、构型、构象和各向异性效应等原因,环碳上质子化学位移缺乏规律性,难以预测,对此作者曾提出一种近似算法。本文根据303种小环化合物中饱和碳质子的化学位移实验数据,将适于计算这类质子化学位移的公式表述为:     

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。