Study of blood collection and sample preparation for analysis of vitamin D and its metabolites by liquid chromatography–tandem mass spectrometry

The analysis of vitamin D status, with special emphasis on 25-hydroxyvitamin D and 1,25-dihydroxyvitamin D, is gaining interest in clinical studies due to the classical and non-classical effects attributed to this prohormone. In this research, the influence of the two steps preceding determination (viz. sample collection and preparation) on the quantitative analysis of vitamin D and its more important metabolites has been studied. Two preparation approaches, deproteination and solid-phase extraction (SPE), have been evaluated in terms of sensitivity to delimit their application, thus establishing that detection of 1,25-dihydroxyvitamin D cannot be addressed by protein precipitation. Concerning sample collection, serum and plasma reported high accuracy (above 83.3%) for vitamin D and metabolites, while precision, expressed as relative standard deviation, was below 12.9% for all analytes in both samples. Statistical analysis revealed that serum and plasma provided similar physiological levels for vitamin D₃, 24,25-dihydroxyvitamin D₃ and 25-hydroxyvitamin D₃, while significantly different levels were obtained for 1,25-dihydroxyvitamin D₃, always higher in plasma than in serum. Sample collection and treatment have proved to be significant in the analysis of vitamin D and its relevant metabolites.     

Development of natural sorbent based micro-solid-phase extraction for determination of phthalate esters in milk samples

In the present study, a natural sorbent based micro-solid phase extraction (μ-SPE) was developed for determination of phthalate esters in milk samples. For the first time, an efficient and cost effective natural material (seed powder of Moringa oleifera) was employed as sorbent in μ-SPE. The sorbent was found to be naturally enriched with variety of functional groups and having a network of interconnected fibers. This method of extraction integrates different steps such as removal of proteins and fatty stuff, extraction and pre-concentration of target analytes into a single step. Thirteen phthalate esters were selected as target compounds for the development and evaluation of method. Some key parameters affecting the extraction efficiency were optimized, including selection of membrane, selection and amount of sorbent, extraction time, desorption solvent, volume of desorption solvent, desorption time and effect of salt addition. Under the optimum conditions, very good linearity was achieved for all the analytes with coefficient of determinations (R²) ranging between 0.9768 and 0.9977. The limits of detection ranged from 0.01 to 1.2 μg L⁻¹. Proposed method showed satisfactory reproducibility with relative standard deviations ranging from 3.6% to 10.2% (n = 7). Finally, the developed method was applied to tetra pack and bottled milk samples for the determination of phthalate esters. The performance of natural sorbent based μ-SPE was better or comparable to the methods reported in the literature.     

用于中温烟气脱硫的新型钙基脱硫剂

研究了高效钙基脱硫剂的制备原理,在石灰水合反应生成氢氧化钙和提高比表面积两个关键环节上,采用了一系列方法提高钙利用率,获得突破性进展。进一步研究了中温范围内脱硫温度对钙利用率的影响,得到700℃时超过95％的钙利用率,为发展中温干式烟气脱硫工艺开辟了新的道路。     

无筛板型固相萃取柱的制备及其在食品中苯甲酸的测定研究

结合固相萃取(SPE)盘与含支撑物的SPE柱技术,制备了一种新型的无筛板型固相萃取柱.以C18填料为例,以话梅样品为介质对其中的苯甲酸进行分析,并用传统固相萃取小柱平行比较;将SPE与HPLC-UV结合,考察了填料对简单介质中苯甲酸的最大吸附量及洗脱曲线,研究了新型SPE柱在实际应用中的分离纯化效果.结果表明,新型SPE柱对样品的吸附效果更好,规格为200 mg/3 mL的SPE柱对苯甲酸的吸附量达到0.951 mg,超过了传统柱的吸附量0.908 mg;其洗脱曲线与传统柱几乎重合;苯甲酸在1～100 mg/L浓度范围内线性关系良好, r=0.9999,用此SPE柱纯化后的样品加标回收率和相对误差分别在88.4%～102.3%和1.4%～2.9%之间.     

Hg(II)-imprinted thiol-functionalized mesoporous sorbent micro-column preconcentration of trace mercury and determination by inductively coupled plasma optical emission spectrometry

Hg(II)-imprinting thiol-functionalized mesoporous sorbent was prepared by a sol–gel method and characterized by X-ray diffraction (XRD), FT-IR spectroscopy and nitrogen gas adsorption–desorption. The static adsorption capacity of the Hg(II)-imprinted and non-imprinted sorbent was 78.5 and 26.6 mg g⁻¹, respectively. The breakthrough capacity was 4.46 mg g⁻¹, and the relative selectivity coefficient for Hg(II) in the presence of Cd and Pb was 3.3 and 3.9, respectively. A new method using a micro-column packed with Hg(II)-imprinting thiol-functionalized mesoporous sorbent has been developed for preconcentration of trace mercury prior to its determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The effects of pH, sample flow rate and volume, elution solution and interfering ions on the recovery of the analyte have been investigated. The limit of detection was 0.39 ng ml⁻¹ with a concentration factor of 150 times. The developed method has been applied to the determination of trace mercury in some biological and environmental samples with satisfactory results. The accuracy was assessed through recovery experiments and analysis of certified reference material.     

固体吸附管捕集冷原子吸收光谱法测定工作场所空气中汞的研究

建立了工作场所空气中汞及其化合物的高锰酸钾-二氧化锰混合固体吸附管捕集、冷原子吸收测定方法。用高锰酸钾与二氧化锰按质量比1∶1混合后填装玻璃管制成固体吸附管捕集工作场所空气中汞,并以0.90 mol·L-1的硫酸溶液解吸后冷原子吸收光谱法测定,与高锰酸钾-硫酸吸收液法的采样效率、样品稳定性、穿透容量进行了比对。在0.000 2~0.015 0 mg·L-1的浓度范围内线性关系良好,相关系数为0.999 1,空气中汞在0.001~2.820 mg·m-3范围内,平均采样效率为99.9%~100.0%,300 mg吸附剂对汞的穿透容量大于505.4 μg,吸附管对汞的平均加标回收率为96.4%~103.8%,日内、日间精密度分别为3.0%~3.3%,3.5%~5.2%,最低检出浓度为0.001 3 mg·m-3(以采集7.5 L空气样品计)、0.000 6(以96 L空气样品计)。采集后的吸附管在室温下保存30 d,下降率小于0.1%。固体吸附管采样方法简单,适用于工作场所空气中汞及其化合物的短时间、时间加权平均浓度及个体暴露浓度的采样检测。     

Impact of impregnation pressure on desulfurization performance of Zn-based sorbents supported on semi-coke

High-pressure impregnation, a new preparation method for sorbents to remove H2S from hot coal gas, is introduced in this paper. Semi-coke (SC) and ZnO is selected as the support and active component of sorbent, respectively. The sorbent preparation process includes high-pressure impregnation, filtration, ovendry and calcination. The aim of this research is to primarily study the effects of the impregnation pressure on physical properties and desulfurization ability of the sorbent. The desulfurization experiment was carried out in a fixed-bed reactor at 500°C and a simulated coal gas used in this work was composed of CO (33 vol%), H2 (39 vol%), H2S (300 ppm in volume), and N2 (balance). Experimental results show that the pore structure of the SC support can be improved effectively and ZnO active component can be uniformly dispersed on the support, with the small particle size of 10-500 nm. Sorbents prepared using high-pressure impregnation have better desulfurization capacity and their active components have higher utilization rate. P20-ZnSC sorbent, obtained by high-pressure impregnation at 20 atm, has the best desulfurization ability with a sulfur capacity of 7.54 g S/100g sorbent and a breakthrough time of 44 h. Its desulfurization precision and efficiency of removing H2S from the middle temperature gases can reach <1 ppm and >99.7%, respectively, before sorbent breakthrough.     

钙基载氧体煤化学链燃烧脱硫试验研究

在钙基载氧体燃煤化学链燃烧技术过程中由于煤气化产物与载氧体之间的副反应导致反应过程中产生大量的SO₂气体。本文选择MAC铁矿石,CaO和石灰石作为脱硫剂,在小型加压固定床上研究不同温度、压力、Ca/S比条件下SO₂气体的脱除问题。结果表明,单独采用CaSO₄载氧体时,随温度升高SO₂气体浓度逐渐增加。添加铁矿石后,SO₂排放浓度降低,主要与Fe₂O₃能够催化抑制CaSO₄分解有关。添加CaO和石灰石脱硫剂后,随温度、压力以及Ca/S比增加,两种脱硫剂的脱硫效率均增加,且在相同的实验条件下得到的CaO的脱硫效果更佳。     

Polyethyleneimine Methylenephosphonic Acid for the Solid-Phase Sorption of Lead(II)

Abstract

In the first part of this work, polyethyleneimine methylenephosphonic acid (PEIMPA) was used as an effective sorbent for solid-phase extraction of Pb(II) ions from an aqueous solution. Conditions for effective sorption are optimized with respect to different experimental parameters in a batch process. The results showed that the amount of extraction decreases with solution pH in the range between 3.5 and 5.8. The sorption capacity is 609 mg·g^?1. The second part of the study focuses on the recovery of Pb(II) from a synthesized binary solution of Pb(II)–Zn(II) and from real Zn(II)-electrolyzed wastewaters. The presence of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), and Zn(II) in large concentrations has a significantly negative effect on extraction properties.     

中温烟气脱硫过程中CO2对脱硫剂钙利用率的影响

本文在300～600℃的中温区段,实验研究了CO2在烟气脱硫过程中与钙基脱硫剂发生碳酸盐还原反应,削弱脱硫效果的规律,发现石灰钙利用率随温度升高呈跳跃式变化,并因碳酸盐反应程度的迅速增加而在500℃附近出现低谷.由此明确了减小碳酸盐反应效应,提高脱硫剂钙利用率的途径,为进一步发展中温烟气脱硫工艺提供了重要依据.