石英粉/磷酸盐缓冲溶液体系中羟自由基荧光分光光度法定量检测研究

为了定量检测石英粉/磷酸盐缓冲溶液体系中极低浓度的羟自由基(·OH),依据对苯二甲酸(TA)在pH中性的缓冲溶液中与羟自由基反应生成唯一稳定且具有很强荧光特性的产物即2-羟基对苯二甲酸(HOTP),本文建立了滤液最大激发/发射波长EX_max/EM_max=316 nm/422 nm处的荧光强度与HOTP浓度关系的标准曲线,通过检测石英粉与缓冲溶液作用之后滤液的荧光强度,从而间接测定了体系产生的·OH累积浓度。通过重复试验并分析五个不同实验条件下体系产生的·OH累积浓度,最小检出限达到1.59×10-10 mol·L-1,相对偏差为1.20%~7.89%,标准偏差为1.09×10-9~2.17×10-9 mol·L-1,相对标准偏差为3.5%~5.8%,说明该方法具有较高的精确度和较好的重复性。该方法可用于定量检测pH中性溶液中极低浓度的·OH,与其他方法相比,具有明显的检测限低、成本低、灵敏度高、稳定性和重现性好等优势。     

石英矿物表面反应性的EPR谱学研究

采用顺磁共振谱（ＥＰＲ）方法对不同ｐＨ值条件下石英表面与Ｃｕ＾２＋离子反应的机理进行研究。当溶液的ｐＨ值在２至１１之间地,石英表面Ｃｕ＾２＋离子的吸附覆盖率相应地由０至１０．３２％变化;同时,其ＥＰＲ谱的线形、线宽及ｇ因子值也发生了特征的变化。研究表明,随着石英表面Ｃｕ＾２＋离子的吸附覆盖率的不断升高,表面反应产物的结合形态相应地出现单核化合物、多核化合物直至表面沉淀。     

金属螯合物印迹聚邻苯二胺膜的电化学合成及表征

以邻苯二胺(o-PD)为功能单体, 乙二胺四乙酸铜离子螯合物(Cu(II)-EDTA)为模板分子, 利用循环伏安法(CV)合成了Cu(II)-EDTA分子印迹聚合物(MIPs). 通过紫外-可见(UV-Vis)光谱、X射线光电子能谱(XPS)、差分脉冲伏安法(DPV)、石英晶体微天平(QCM)等手段对合成的聚合物进行了表征. UV-Vis光谱分析表明当溶液的pH≥5.0时有利于邻苯二胺电聚合形成聚合度较高的聚合物; XPS结果证明Cu(II)-EDTA螯合物被成功地包覆在聚合物膜中, 且推断出模板分子和聚合物之间可能主要靠氢键相互作用; DPV实验结果证明模板分子能够被有效洗脱; QCM的测试结果表明此方法合成的Cu(II)-EDTA印迹聚合物膜对Cu(II)-EDTA具有良好的响应度.     

Laser processing of micro-optical components in quartz

Laser induced backside wet etching combined with the diffractive gray tone phase mask has been used for the fabrication of a micro-lens array with a single lens diameter of 1 mm and a micro-prism in quartz. The micro-lens array was tested as beam homogenizer for high power XeCl excimer laser yielding a clear improvement in the quality of the laser beam.The optimum fluence range for fabrication of micro-lenses by laser induced backside wet etching using 1.4 M pyrene in THF solution and 308 nm irradiation wavelength is 1-1.6 J/cm². The etching mechanisms of LIBWE are based on a combination of pressure and temperature jumps at quartz-liquid interface.     

Synthesis and characterization of silver-polypyrrole film composite

In this work, we report the chemical polymerization of pyrrole to obtain thin film of polypyrrole (PPy) hydrochloride deposited onto the electrode of the quartz crystal microbalance (QCM). The film in the base form was exposed to a solution of AgNO₃. Electroless reduction for silver ions by the PPy film took place and silver particles were adsorbed onto the film surface. The silver particles content at the PPy films were analyzed by QCM and the results showed that the concentrations of silver uptakes increase as the original AgNO₃ solution increases. The morphology of the surface of the PPy film and the silver-PPy film composite were studied by the scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectrometry (EDX). They showed that the obtained silver particles have spherical, cubic and tetrahedral structures. X-ray diffraction (XRD) and Fourier transformed infra-red spectroscopy (FTIR) were used to characterize the structure of the powder composite. This work reveals the capability of PPy film coating on QCM in sensing and removing silver from several environmental samples.     

Methods for research on immune complement activation on modified sensor surfaces

We have developed a methodological system consisting of a new surface sensitive quartz crystal microbalance with dissipation monitoring (QCM-D) sensor surfaces together with different surface modification methods for the investigation of surface associated complement activation in human sera. The QCM-D surface, 10 mm in diameter, was modified by spin-coating of poly(urethane urea) (PUUR) and polystyrene (PS). Some sensor surfaces were also sputtered with titanium (Ti) or modified by hydrophobic self-assembled monolayer (SAM) of an 18-carbon alkane thiol with a ---CH₃ end group. The amount of surface deposited complement protein was investigated by incubation of the modified sensor surfaces in human sera, followed by incubation with antibodies directed against complement factor 3c (C3c). The amounts of bound anti-C3c were then used as an arbitrary measure of surface induced complement activation. The order of complement activation of the different surfaces, as judged by three separate measurements per surface modification, was PUUR>PS=SAM>Ti. The Ti surface had a similar low degree of anti-C3c binding as the negative controls (heat inactivated sera). The novel QCM-D methodology was found to be very simple, accurate, sensitive and well suited as a screening method for complement activation and protein adsorption on different materials. We also compared the sensitivity of QCM-D method with surface plasmon resonance (SPR) for the quantification of protein adsorption and complement activation on gold sensor surfaces. The QCM-D method was equally sensitive as the SPR for the detection of protein adsorption from a solution independently if low flow rate (5 μl/min) was used. A slight increase in sensitivity was found at higher flow rate (30 μl/min). However, we found it difficult to use the SPR method on the Ti, PS and PUUR surfaces due to decreased light penetration of the modified SPR sensor chip.     

GC/MS法分析油松节挥发油化学成分

用气相色谱-质谱法对山东昆嵛山产油松节挥发油进行化学成分的分析。采用水蒸气蒸馏法从油松节中提取挥发油。采用不同类型的毛细管柱进行分析，找出最佳分析条件，用归一化法测定其含量，并用气相色谱-质谱法对化学成分进行鉴定。共鉴定了48个成分，占挥发油总成分的84％以上。结果表明，此方法稳定可靠，重现性好，适用于中药挥发油的化学成分分析。     

Influence of the variable wall thickness of the sample tubes and a quartz Dewar on the EPR signal intensity in a single TE102 and double TE104 rectangular cavity

The response of a single TE₁₀₂ and double TE₁₀₄ rectangular cavity to the insertion of samples contained in tubes with variable wall thickness and a quartz Dewar into the cavity has been analyzed. A direct, indirect, and concurrent (positive or negative) “lens effect” inside the double TE₁₀₄ rectangular cavity is discussed. The experimental dependence of the EPR signal intensity on the wall thickness of the sample tube, δ, for the line-like samples with identical length of the sample material column, L=30 mm, recorded in the microwave cavity showed a directly proportional increase of the relative “lens effect” with the increase of the wall thickness of the tube in the interval, δ∈<0.1 mm, >0.5 mm. The insertion of the variable-temperature double-wall quartz Dewar (home-built, resonant frequency shift, ca. −300 MHz) into the single TE₁₀₂ rectangular cavity showed the same relative “lens effect”, with ca. 1.5-time increase of the EPR signal intensity, for a point-like sample and the line-like samples with material columns of diameter of 1 and 1.3 mm, and wall thickness of the sample tubes, δ∈<0.1 mm, >0.5 mm. The increased effect of the Dewar arises because the active volume of the quartz Dewar tube walls is always much more larger than the active volume of the sample tube wall. In the case of the double TE₁₀₄ rectangular cavity, the insertion of the quartz Dewar: (i) into the same cavity, in which the sample is present, caused a direct “lens effect”, with ca. 1.8-fold increase of the EPR signal intensity; however, (ii) into the complementary cavity, in which the sample is absent, caused an indirect “lens effect”, with ca. 0.6-fold decrease of the EPR signal intensity. With the Dewar and sample in one cavity and a large empty sample tube in the complementary cavity, a concurrent (positive or negative) “lens effect” can be observed. Thus, the possible increase/decrease of the EPR signal intensity depends on the volume ratio of the quartz Dewar tube walls and large sample tube wall inserted into the double TE₁₀₄ rectangular cavity. Each of the above phenomena may be a significant source error in quantitative EPR spectrometry unless the samples to be compared in the quantitative EPR analysis are contained in sample tubes having the same wall thickness and each EPR spectra should be recorded inside an identical quartz Dewar.     

聚甲基丙烯酸甲酯-牛血清白蛋白核壳纳米粒子在金表面的吸附过程及在传感器中的应用

利用铜离子引发体系, 制备出核层为聚甲基丙烯酸甲酯(PMMA)壳层为牛血清白蛋白(BSA)的PMMA-BSA核壳纳米粒子. 通过透射电子显微镜(TEM)表征, 直接观察到PMMA-BSA纳米粒子的核壳结构.结合X射线光电子能谱(XPS)测试, 分析PMMA-BSA纳米粒子的表面成分, 证明PMMA-BSA纳米粒子的壳层是BSA. 利用带耗散的石英晶体微天平(QCM-D)研究了PMMA-BSA纳米粒子在金片表面的吸附行为. 频率的迅速下降, 耗散因子的快速上升, 说明PMMA-BSA粒子快速地吸附到金片表面. 利用磷酸盐缓冲液反复冲洗时, 频率和耗散没有变化, 表明PMMA-BSA 纳米粒子在金片上吸附较牢固. 以金电极为基底电极, 吸附PMMA-BSA纳米粒子后, 利用戊二醛修饰粒子壳层, 再通过氨基与醛基的反应来固定葡萄糖氧化酶, 制备出电流型葡萄糖传感器. 电化学测试表明该传感器对葡萄糖具有良好的电流响应, 在0.3 V的工作电位下, 响应电流与葡萄糖浓度在0.20-5.85 mmol·L^-1范围内呈现出较好的线性关系, 相关系数为0.989. 传感器的灵敏度高达28.6 μA·L·mmol^-1·cm^-2, 响应时间仅为11 s. 传感器还具有良好的稳定性, 在25℃下储存30 d, 响应电流仅下降了16%.     

基于纳米β分子筛的石英晶体微天平沙林传感器研究

以纳米β(Cuβ)分子筛为敏感膜,结合石英晶体微天平(QCM)制备了对神经毒剂沙林(GB)敏感的传感器。结果表明,纳米β(Cuβ)分子筛对GB响应较纳米ZSM-5更灵敏,在热空气吹扫下可连续多次检测,其灵敏度为23.6Hz/(mg.m-3)(26.8Hz/(mg.m-3)),检出限(S/N=3)为0.96mg.m-3(0.90mg.m-3);线性范围1.50～18.24mg.m-3,线性相关系数为0.9910(0.9888)。该法在毒剂检测中具有一定的应用前景。