On-line preconcentration using dual mini-columns for the speciation of chromium(III) and chromium(VI) and its application to water samples as studied by inductively coupled plasma-atomic emission spectrometry

On-line preconcentration system for the selective, sensitive and simultaneous determination of chromium species was investigated. Dual mini-columns containing chelating resin were utilized for the speciation and preconcentration of Cr(III) and Cr(VI) in water samples. In this system, Cr(III) was collected on first column packed with iminodiacetate resin. Cr(VI) in the effluent from the first column was reduced to Cr(III), which was collected on the second column packed with iminodiacetate resin. Hydroxyammonium chloride was examined as a potential reducing agent for Cr(VI) to Cr(III).The effects of pH, sample flow rate, column length, and interfering ions on the recoveries of Cr(III) were carefully studied. Five millilitres of a sample solution was introduced into the system. The collected species were then sequentially washed by 1 M ammonium acetate, eluted by 2 M nitric acid and measured by ICP-AES. The detection limit for Cr(III) and Cr(VI) was 0.08 and 0.15 μg l⁻¹, respectively. The total analysis time was about 9.4 min.The developed method was successfully applied to the speciation of chromium in river, tap water and wastewater samples with satisfied results.     

Automated high performance liquid chromatography with on-line reduction of disulfides and chemiluminescence detection for determination of thiols and disulfides in biological fluids

In general, the reduction of disulfide bonds with tris(2-carboxyethyl)phosphine (TCEP) is performed using off-line operation, which is not only time-consuming but also vulnerable to the spontaneous re-oxidation of thiols during sample preparation and subsequent analysis procedures. To the best of our knowledge, there has been not any case on the on-line reduction for biological disulfides coupled with high performance liquid chromatography (HPLC). In this study, these obstacles are overcome by packing Zn(II)-TCEP complexes into a home-made column. The as-synthesized Zn(II)-TCEP complexes enable efficient reduction of disulfide bonds at pH 3.0. This acidic pH value was compatible with that of the mobile phase for HPLC separation of thiols and disulfides. Therefore, using fluorosurfactant-prepared triangular gold nanoparticles as HPLC postcolumn specific chemiluminescence (CL) reagents for thiols, the feasibility of the established on-line reduction column has been confirmed for the direct identification of both thiols and disulfides by incorporating this reduction column into a single chromatographic separation. Detection limits for these analytes range from 8.3 to 25.4 nM and the linear range in a log–log plot can comprise three orders of magnitude. Finally, the utility of this automated on-line reduction of disulfides-HPLC-CL system has been demonstrated for the reliable determination of thiols and disulfides in human urine and plasma samples.     

Quantification of phytochelatins in plants by reversed-phase HPLC–ESI–MS–MS

An on-line HPLC–ESI–MS–MS method has been developed for determination of glutathione and phytochelatins (PC) in plant tissues. For sample pretreatment, dithiothreitol (DTT) must be added at the very beginning, as an anti-oxidant. Optimization of instrumental conditions i.e. composition of HPLC mobile phase, ionization efficiency of the electrospray interface, and MS–MS detection in the multiple ion-monitoring mode, are the central aspects of this work. A polystyrene-packed column was found to be superior to a standard silica-packed reversed-phase column. A concave quadratic gradient of ammonium formate buffer and acetonitrile was found to be optimum. The limits of quantitation were 0.2 mol kg^–1 plant tissue for glutathione and PC. The method has been applied to analysis of tissue samples from Vicia faba grown in Cd-containing nutrient solutions.Dedicated to the memory of Wilhelm Fresenius     

The effect of cooking and washing rice on the bio-accessibility of As,Cu, Fe,V and Zn using an on-line continuous leaching method

A previously developed method based on continuous on-line leaching with artificial gastro-intestinal fluids was used to determine the bio-accessible fraction of As, Cu, Fe, V and Zn in brown and white rice from California by inductively coupled mass spectrometry (ICP-MS). Saliva generally accounted for the largest percentage of total element leached in comparison to gastric and intestinal juices. Arsenic speciation analysis was performed on the saliva and gastric juice leachates using ion exchange chromatography coupled to ICP-MS. The four most toxic species of As (As(III), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) and As(V)), as well as Cl⁻ in the gastric juice leachate, were successfully separated within 5.5 min using a simple nitric acid gradient. While cooking rice had relatively little effect on total bio-accessibility, a change in species from As(V) and DMA to As(III) was observed for both types of rice. On the other hand, washing the rice with doubly deionized water prior to cooking removed a large percentage of the total bio-accessible fraction of As, Cu, Fe, V and Zn.     

Comparison by capillary SFC and SFC-MS of soxhlet and supercritical fluid extraction of hamster feces

Components of hamster feces ranging from low molecular weight fatty acids through the expected range of triglycerides have been eluted in a single SFC run with simultaneous pressure and temperature programming. Temperature programming from 140°C to 240°C was required to provide optimum conditions for separation of the fatty acids and to move the elution region of the sterol esters away from that of the triglycerides. Data from chemical ionization and electron impact mass spectrometry of compounds separated by SFC were used to confirm identities suggested by retention measurements and to provide tentative identities of unknown compounds. SFC with flame ionization detection was used to compare Soxhlet extraction, off-line supercritical fluid extraction (SFE), and on-line SFE of the feces. Although samples obtained by Soxhlet extraction and SFE produced very similar chromatograms, SFE required far less time and consumed much smaller quantities of organic solvent.     

“线上线下-虚实结合”在有机化学实验教学中的应用探索——以正溴丁烷的制备实验为例

In response to the impact of the Covid-19 epidemic on organic chemistry laboratory teaching, this article analyzes and discusses the current limitation of traditional organic chemistry laboratory teaching. Taking the "preparation of n-bromobutane" as an example, a new "online-offline and virtual-actual combination" teaching mode with the combination of "Tencent Meeting, MLabs, laboratory and WeChat group" is introduced. The practice of the new mode of teaching includes the following steps: pre-class online guiding by teacher, student preview and practice based on the virtual simulation platform, students and teacher discussion and operation in laboratory, and post-classcomprehensive assessment and Q&A", and good teaching effects have been received. It is significant in cultivating and improving the independent innovation and practical ability, and provides reference for the organic chemistry laboratory teaching reform and also lays a foundation for the construction of "outstanding course" of organic chemistry.     

高浓度二氧化氯气体的在线检测研究

在40℃下,高浓度ClO2气体在盘管中迅速溶解于水中达到平衡,使用分光光度法检测平衡溶液的浓度,从而间接测定出ClO2气体的浓度。该方法可检测体积分数大于0.14%的ClO2,响应时间为15~30s,相对标准偏差为0.3%,与连续碘量法相比测定结果没有显著性差异(P<0.01),全过程中未使用化学试剂,操作简便,干扰小,适用于的高浓度ClO2气体在线检测。     

在线螯合树脂富集火焰原子吸收光谱法测定天然水体中铜和锌

对螯合树脂富集——火焰原子吸收光谱法测定天然水体中痕量铜和锌的在线富集条件、干扰因素等进行研究,在线富集倍数达到两个数量级,在灵敏度与石墨炉原子吸收光谱法相当情况下,提高了测定准确度。     

SIAmate-a compact and modular sequential injection analysis controller

A number of sequential injection analysis (SIA) measurement methods have been developed during the last years. Almost all have been used in laboratory conditions with good results, but very few have been implemented as on-line methods, applied to non-stop measurements, producing immediate results for process control. The transfer of an SIA system from laboratory to an industrial facility [J. Ruzicka, Anal. Chim. Acta 261 (1992) 3] requires a whole new range of details to be taken into account. Some SIA platform related topics will be discussed. There are numerous ways of building an SIA system that meets the needs of the industry. One alternative, SIAmate, is presented.