无富集进样原子荧光光谱法测定地表水中的痕量汞

通过增大样品进样量的方式,样品进样量是标准进样量的10-100倍,降低了汞的检出限,从而达到了无富集直接进样测定地表水中痕量汞.其检出限为0.008μg/L;浓度为0.05μg/L和0.10μg/L左右的有证标准物质测定均值分别为0.0483μg/L和0.1016μg/L,加标回收率为92.3％和95.2％.灵敏度高,精密度好,能达到准确定量Ⅰ类和Ⅱ类地表水汞(0.05μg/L以下)的要求.对汉江湖北段水样进行测定,在较洁净的地表水分析中,氧化还原处理后与酸化水样测定结果差异不大,处理后水样结果略微增大.建议对较洁净的地表水样品将氧化还原预处理步骤省略掉,直接进样.     

维生素B2片中维生素B2的测定及稳定性

以pH=7.0的水作为溶液,激发、发射波长分别为443、523nm,运用荧光光谱法测定了维生素B₂的荧光强度,以荧光强度与浓度的关系作图,得到了回归曲线,本实验条件下,在5×10^-8—6×10^-7g/mL范围内呈良好的线性关系,回收率在98.53%—103.59%之间,该方法具有灵敏度高、重现性和稳定性好的特点,但维生素B₂不稳定。     

Trace-level analysis of organic contaminants in drinking waters and groundwaters

We expect drinking water and groundwater samples to be contaminated very little, so they are subject to trace-level analysis. Due to the very low levels of contamination, this sort of analysis requires not only powerful analytical technologies to reach limits around the ng/L level, but also quality-control parameters (e.g., blank and spike samples) to monitor potential contamination or losses during sample treatment. Based on a literature review and laboratory experience, we discuss the problems linked to the difficulties of calculating limits of detection, distinguishing instrumental from methodological limits and preventing false-positive results in cases of sample contamination, or false-negative results in cases of compound losses. When possible, we suggest solutions to compensate for, or to prevent, these problems.     

Limits of detection and decision. Part 2

Extensive Monte Carlo studies of instrumental limits of detection (LODs) were performed on a simple univariate chemical measurement system having homoscedastic, Gaussian measurement noise and using ordinary least squares (OLS) processing of tens of millions of independent calibration curve data sets. It was found that experimental decision and detection limits in the content domain were distributed as scaled reciprocals of noncentral t variates. In the response domain, the decision and detection limits were distributed as scaled χ variates. Rates of false negatives were found to be as expected statistically and no bias was found. However, use of detection limit expressions based on critical values of the noncentrality parameter of the noncentral t distribution were found to be significantly biased, resulting in substantial bias in rates of false negatives.     

Simultaneous derivatization and air-assisted liquid–liquid microextraction of some aliphatic amines in different aqueous samples followed by gas chromatography-flame ionization detection

The paper presents a new method based on simultaneous derivatization and air-assisted liquid–liquid microextraction (AALLME) for the extraction and preconcentration of some aliphatic amines prior to gas chromatography-flame ionization detection (GC-FID). Primary aliphatic amines are derivatized and extracted simultaneously by a fast reaction with butylchloroformate (derivatization agent/extraction solvent) under mild conditions. The mixture of butylchloroformate and aqueous sample solution is rapidly sucked into a 10-mL glass syringe and then is injected into a test tube with conical bottom and the procedure is repeated seven times. After centrifuging the resulted cloudy solution, the derivatized analytes in the sedimented phase are determined by GC-FID. The influence of main factors on the efficiency of derivatization/extraction procedure is studied. Under the optimal conditions, the enrichment factors (EFs) for aliphatic amines are obtained in the range of 248–360 and limits of detection (LODs) are between 0.30 and 2.6 μg L⁻¹. The obtained extraction recoveries ranged from 50 to 72% and the relative standard deviation (RSD) was less than 4.8% for intra-day (n = 6) and inter-days (n = 4) precision. The method is successfully applied to determine some aliphatic amines in environmental water samples.     

Extension and application of multivariate curve resolution-alternating least squares to four-way quadrilinear data-obtained in the investigation of pollution patterns on Yamuna River,India—A case study

This study focuses on the development and extension of Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) to the analysis of four-way datasets. The proposed extension of the MCR-ALS method with non-negativity and the newly developed quadrilinear constraints can be exploited to summarize and manage huge multidimensional datasets and resolve their four way component profiles. In this study, its application is demonstrated by analyzing a four-way data set obtained in a long term environmental monitoring study (15 sampling sites × 9 variables × 12 months × 7 years) belonging to the Yamuna River, one of the most polluted rivers of India and the largest tributary of the Ganges river. MCR-ALS resolved pollution profiles described appropriately the major observed changes on pH, organic pollution, bacteriological pollution and temperature, along with their spatial and temporal distribution patterns for the studied stretch of Yamuna River. Results obtained by MCR-ALS have also been compared with those obtained by another multi-way method, PARAFAC. The methodology used in this study is completely general and it can be applied to other multi-way datasets.     

两性霉素B与鞘磷脂单分子层的相互作用

选取哺乳动物生物膜中的重要脂质分子鞘磷脂(SM)作为单分子膜的基本组分, 采用Langmuir-Blodgett(LB)膜技术研究了不同比例的两性霉素B/鞘磷脂单层膜的表面压力-平均分子面积(π-A)曲线以及基于π-A曲线的混合性分析, 同时通过原子力显微镜(AFM)研究了其表面形态的变化. 结果表明, 组分间的摩尔比和表面压力对混合单层膜稳定性、混合性以及分子间相互作用具有重要影响.     

Chromatographic impulse response technique with curve fitting to measure binary diffusion coefficients and retention factors using polymer-coated capillary columns

The theoretical basis of a Gaussian-like approximate solution was applied to a chromatographic impulse response technique with curve fitting for measuring binary diffusion coefficients and retention factors using a polymer-coated capillary column. The formulae were derived for evaluating both the accuracy of the approximate solution and the sensitivity of the parameters. The validity of the solution also was confirmed experimentally for pulse injection of phenol in acetone into supercritical carbon dioxide flowing at 313.15 K and 11.6-28.6 MPa. Potential sources for experimental errors of the method are discussed.