乳过氧化物酶与伴刀豆球蛋白A共修饰电极的电化学活性研究

用乳过氧化物酶(LPO)和伴刀豆球蛋白A(Con A)共修饰金电极,首次得到了乳过氧化物酶的直接电化学响应,在此基础上研究了乳过氧化物酶对过氧化氢(H2O2)的电催化活性,并研究了一氧化氮(NO)对LPO电催化活性的影响.在Con A的作用下,乳过氧化物酶在循环伏安图中显示1对准可逆的氧化还原峰,表现出薄层电化学行为.在pH 7.4的磷酸缓冲溶液中的表观氧化还原电位为 -190 mV.该共修饰电极对H2O2表现出电催化还原活性,由此构建的传感器对H2O2的检测范围是2.0×10-5 ～4.0×10-3 mol/L.实验发现,微摩尔量级的NO会抑制乳过氧化物酶对H2O2的催化活性.     

UPLC-MS/MS对卷烟烟气中4种烟草特有亚硝胺的快速测定

建立了卷烟主流烟气中烟草特有亚硝胺的超高效液相色谱-电喷雾串联质谱(UPLC-MS/MS)测定方法。在标准吸烟条件下,采用剑桥滤片收集卷烟烟气粒相物,用醋酸铵缓冲液提取粒相物,经固相萃取净化后,以电喷雾正离子多反应监测方式,实现了烟气中N-亚硝基降烟碱、4-甲基亚硝基吡啶基丁酮、N-亚硝基新烟草碱和N-亚硝基假木贼碱的基线分离和快速测定。4种烟草特有亚硝胺在0~400μg/L范围内具有良好线性,相关系数大于0.998,定量下限为0.08~0.15μg/L,加标回收率为72%~104%,相对标准偏差为3.8%~9.7%。该方法灵敏、快速、准确,适用于卷烟烟气中烟草特有亚硝胺的测定。     

紫外分光光度法测定氯氟吡氧乙酸十二酯的研究

以甲醇作为溶剂,用紫外分光光度法测定氯氟吡氧乙酸十二酯的含量,测得氯氟吡氧乙酸十二酯对照品溶液浓度在12.0～20.0μg/mL范围之内线性关系良好,其线性方程为A=0.0815C+0.0318(R2=0.9832).平均回收率为90.86%,RSD为5.3%(n=6),结果说明方法简便、灵敏、准确,重现性好.     

补中益气汤对肝硬化患者机体微量元素的影响

为探讨补中益气汤对肝硬化患者机体微量元素水平的影响,采用全自动生化分析仪检测了30例服用补中益气汤肝硬化患者及30例肝硬化对照组患者血清中镁、铁、铜、锌的水平。结果表明,服用补中益气汤患者血清镁、铁、锌水平均显著高于对照组患者(P0.05),服用补中益气汤患者血清铜水平均显著低于对照组患者(P0.05)。提示了补中益气汤能显著提高肝硬化患者机体微量元素水平,对改善患者肝脏功能具有一定的作用。     

气相色谱-表面声波快速分析仪性能评价

本文评价了自行研制的气相色谱-表面声波(GC-SAW)联用快速分析仪的性能。实验结果表明:在6 s以内,GC-SAW快速分析仪能分离五种苯系物和C6~C14九种正构烷烃。该仪器对甲苯测定的相对标准偏差(RSD)为2.5%(n=6);最小检出浓度为2.05μg.L-3;线性范围为2.05~205μg.L-3;对标准样品连续6次分析,经双边t检验,分析结果均值与标样标准值无显著差异。     

纤维素基水处理剂研究进展

根据纤维素基水处理剂的结构特点对其进行了分类和划分,从载体形态、接枝链与载体接枝方法、功能吸附/脱附基团选取及功能化方法、吸附/脱附性能的影响因素和脱附方法等五个方面综述了国内外在该领域的研究现状;并对其发展前景进行了展望.     

Variable-weighted least-squares support vector machine for multivariate spectral analysis

Multivariate spectral analysis has been widely applied in chemistry and other fields. Spectral data consisting of measurements at hundreds and even thousands of analytical channels can now be obtained in a few seconds. It is widely accepted that before a multivariate regression model is built, a well-performed variable selection can be helpful to improve the predictive ability of the model. In this paper, the concept of traditional wavelength variable selection has been extended and the idea of variable weighting is incorporated into least-squares support vector machine (LS-SVM). A recently proposed global optimization method, particle swarm optimization (PSO) algorithm is used to search for the weights of variables and the hyper-parameters involved in LS-SVM optimizing the training of a calibration set and the prediction of an independent validation set. All the computation process of this method is automatic. Two real data sets are investigated and the results are compared those of PLS, uninformative variable elimination-PLS (UVE-PLS) and LS-SVM models to demonstrate the advantages of the proposed method.     

Quantitative analysis of levodopa, carbidopa and methyldopa in human plasma samples using HPLC-DAD combined with second-order calibration based on alternating trilinear decomposition algorithm

An HPLC method combined with second-order calibration based on alternating trilinear decomposition (ATLD) algorithm has been developed for the quantitative analysis of levodopa (LVD), carbidopa (CBD) and methyldopa (MTD) in human plasma samples. Prior to the analysis of the analytes by ATLD algorithm, three time regions of chromatograms were selected purposely for each analyte to avoid serious collinearity. Although the spectra of these analytes were similar and interferents coeluted with the analytes studied in biological samples, good recoveries of the analytes could be obtained with HPLC-DAD coupled with second-order calibration based on ATLD algorithm, additional benefits are decreasing times of analysis and less solvent consumption. The average recoveries achieved from ATLD with the factor number of 3 (N = 3) were 100.1 ± 2.1, 96.8 ± 1.7 and 104.2 ± 2.6% for LVD, CBD and MTD, respectively. In addition, elliptical joint confidence region (EJCR) tests as well as figures of merit (FOM) were employed to evaluate the accuracy of the method.     

Quantitative analysis of triazine herbicides in environmental samples by using high performance liquid chromatography and diode array detection combined with second-order calibration based on an alternating penalty trilinear decomposition algorithm

A novel application of second-order calibration method based on an alternating penalty trilinear decomposition (APTLD) algorithm is presented to treat the data from high performance liquid chromatography-diode array detection (HPLC-DAD). The method makes it possible to accurately and reliably analyze atrazine (ATR), ametryn (AME) and prometryne (PRO) contents in soil, river sediment and wastewater samples. Satisfactory results are obtained although the elution and spectral profiles of the analytes are heavily overlapped with the background in environmental samples. The obtained average recoveries for ATR, AME and PRO are 99.7 ± 1.5, 98.4 ± 4.7 and 97.0 ± 4.4% in soil samples, 100.1 ± 3.2, 100.7 ± 3.4 and 96.4 ± 3.8% in river sediment samples, and 100.1 ± 3.5, 101.8 ± 4.2 and 101.4 ± 3.6% in wastewater samples, respectively. Furthermore, the accuracy and precision of the proposed method are evaluated with the elliptical joint confidence region (EJCR) test. It lights a new avenue to determine quantitatively herbicides in environmental samples with a simple pretreatment procedure and provides the scientific basis for an improved environment management through a better understanding of the wastewater-soil-river sediment system as a whole.     

草酸根桥联手性双核铜的合成、表征、结构与磁性

分别以(8R,10R)-(-)-[4,5]-pineno-2,2′-bipyridine或(8S,10S)-(+)-[4,5]-pineno-2,2′-bipyridine(LRR和LSS)为手性配体合成双核铜络合物[Cu2(μ-ox)(LRR)2(H2O)2(ClO4)2](1)、[Cu2(μ-ox)(LRR)2(CH3COCH3)2(ClO4)2](1a)、[Cu2(μ-ox)(LSS)2(H2O)2(ClO4)2](2)和[Cu2(μ-ox)-(LRR)(LSS)(CH3COCH3)2(ClO4)2](3)(ox2-=草酸根),并探讨了其反应机理.由元素分析、电导率、紫外可见谱(UV-vis)、圆二色(CD)谱和晶体结构分析推测:该系列络合物具有草酸根桥联的双核结构,两个铜(II)离子与草酸根几乎成共平面;1a和3的晶体结构分析表明,每个Cu(II)的配位构型为拉长畸变八面体,双核分子中轴向的两个溶剂分子和两个高氯酸根互为反式配位.对映体络合物1和2的溶液CD光谱大致呈镜像对称,在可见区的极弱CD吸收峰可能源于LRR和LSS蒎烯基上的手性中心对Cu(II)d-d生色团的手性微扰产生的邻位效应.采用最小二乘法和Bleaney-Bowers方程对络合物1的变温磁化率测试数据进行拟合,求得交换积分J=-338.41(4)cm-1,表明铜(II)离子间有较强的反铁磁自旋交换作用.