几种烟煤及其热处理后的溶胀性能研究

研究了四种不同变质程度烟煤及其二硫化碳/N-甲基-2-吡咯烷酮（CS2/NMP）混合溶剂(1∶1,vol)的抽提物在不同溶剂中的溶胀性能,同时考察了四种煤样不同温度热处理后其溶胀性能的变化。结果表明,煤的溶胀率随煤化度增加而有所降低;变质程度较低的烟煤在极性溶剂中的溶胀率大于非极性溶剂,随着煤化度的增加,两者溶胀度差距减小;四种烟煤经混合溶剂抽提后,其抽余煤的交联密度降低,溶胀率增加。四种煤样150℃热处理后在CS2中的溶胀率均有所增加,表明热处理可以降低煤的交联密度。随着热处理温度提高至240℃,除气煤外,其余三种煤样在NMP和CS2中溶胀率均进一步增大,说明其交联密度进一步降低。这一结果与热处理煤样在混合溶剂中抽提率的变化趋势一致,如240℃热处理后瘦煤的抽提率由原煤的6.9%提高到17.3%。红外光谱研究表明,经过适当温度的热处理,可以脱除煤分子中的羰基和羟基等含氧官能团,破坏煤结构中的氢键,从而降低煤的交联密度,提高煤的溶胀率及其在混合溶剂中的抽提率。     

对氨基苯亚甲基硫代若丹宁固相萃取分离光度法测定环境水和食品样品中的铅

合成了新试剂对氨基苯亚甲基硫代若丹宁(ABTR),并用红外光谱、核磁共振氢谱和元素分析鉴定其结构。研究了ABTR与铅的显色反应,在pH3.8的HAc NaAc缓冲介质中,吐温80存在下,ABTR与铅反应生成2∶1稳定络合物,该络合物可被WatersSep PakC18小柱固相萃取,小柱上富集的络合物用乙醇洗脱后富集倍数可达50倍,在乙醇介质中,λmax=545nm,体系摩尔吸光系数ε=1.09×105L·mol-1·cm-1。铅量在0.05～4.0μg/mL内符合比尔定律,本法可用于环境水和食品样品中铅的测定。     

Preparation of highly selective solid-phase extractants for Cibacron reactive dyes using molecularly imprinted polymers

Selective polymeric extractants were prepared for preconcentration of Cibacron reactive red dye, a dye that is often applied with Cibacron reactive blue and Cibacron reactive yellow for dyeing of fabrics. The best extractant was fabricated (in chloroform) using methacrylic acid (as monomer), ethylene glycol dimethacrylate (as crosslinker), AIBN (as initiator for polymerization), and red dye as template molecule, with a molar stoichiometric ratio of 8.0:40.0:2.5:0.63, respectively. The structure of the molecularly imprinted polymer (MIP) was robust, and resisted dissolution up to 260 °C. Compared with the un-imprinted polymer, the imprinted product has a large specific surface area which improved its adsorption capacity. The effect of imprinting was obvious from the adsorption capacity measured at pH 4 for red dye (the imprinted molecule), which was increased from 24.0 to 79.3 mg g⁻¹ after imprinting. Equilibrium adsorption studies revealed that the dye-imprinted-polymer enables efficient extraction of red dye even in the presence of blue and yellow dyes which have similar chemical natures to the red dye. The selectivity coefficients S _{red dye/dye}, were 13.9 and 17.1 relative to the yellow and blue dyes, respectively. The MIP was found to be effective for red dye preconcentration, with a preconcentration factor of 100, from tap water and treated textile wastewater. The factors affecting extraction of red dye by the MIP were studied and optimized. Under the optimized extraction conditions, red dye was selectively quantified in the presence of other competing dyes at a concentration of 20 μg L⁻¹ from different water systems with satisfactory recoveries (91–95%) and RSD values (∼5.0%).     

Identification and quantification of 13 components in Angelica sinensis (Danggui) by gas chromatography-mass spectrometry coupled with pressurized liquid extraction

Angelica sinensis (Danggui in Chinese), a well-known traditional Chinese medicine, is also used as a health food product for women's care in Europe and America. Therefore, the demand for Danggui is enormous throughout the world. Due to the shortage of Angelica sinensis, Angelica acutiloba and Angelica gigas are commonly used as the substitutes of Danggui in the market of southeast Asia. However, the three common Angelica roots showed variation in their genetic and chemical composition. Up to date, it is thought that ferulic acid, ligustilide and other phthalides such as butylidenephthalide are the biologically active components of Danggui. In this paper, the contents of 13 compounds including ferulic acid, Z-ligustilide, E-ligustilide, Z-butylidenephthalide, E-butylidenephthalide, 3-butylphthalide, 3-butylidene-4-hydroxyphthalide, senkyunolide A, 6,7-epoxyligustilide, senkyunolide F, senkyunolide H, senkyunolide I, and 6,7-dihydroxyligustilide were determined or estimated by using gas chromatography-mass spectrometry (GC-MS) coupled with pressurized liquid extraction (PLE). The results showed that GC-MS coupled with PLE offered a simple, rapid and high sensitive method to analysis of components in Angelica root. And the contents of investigated compounds in Angelica sinensis, Angelica acutiloba and Angelica gigas, which are used as Danggui in China, Japan and Korea, respectively, were highly variant. It is thought that interaction of multiple chemical compounds contributes to the therapeutic effects of Chinese medicines. However, the overall clinical efficacy of these different Danggui has not been determined. Therefore, comparison of chemical components and pharmacological activities of different Angelica root is helpful to elucidate the mechanism of therapeutic effects of Danggui.     

超声波提取-气相色谱法测定土壤中21种酚类化合物

建立了超声波提取-气相色谱法同时测定土壤中21种酚类化合物的分析方法。用二氯甲烷和正己烷混合溶剂提取土壤中的酚类化合物,提取液经碱性水溶液分配净化,去除非酸性有机杂质,再酸化萃取酚类化合物,浓缩后采用气相色谱-氢火焰离子化检测器进行检测,外标法定量。以10 g土壤样品计,酚类化合物的检出限为0.01~0.06 mg/kg。实际样品添加回收试验的回收率为62.9%~111.4%,相对标准偏差为4.3%~24.0%(n=6),准确度和精密度均较好。结果表明:该法操作方便,净化效果好,可用于土壤中多种酚类化合物的测定。     

A novel application of immobilization on membranes for the separation and spectrofluorimetric quantification of amiloride and furosemide in pharmaceutical samples

A new, simple and highly sensitive method for spectrofluorimetric determination of amiloride (AMI) and furosemide (FUR) in pharmaceuticals is presented. The proposed method is based on the separation of AMI from FUR by solid-phase extraction using a nylon membrane, followed by spectrofluorimetric determination of both drugs, on the solid surface and the filtered aqueous solution, respectively. AMI shows low native fluorescence, but its separation-preconcentration by immobilization (solid-phase extraction) on nylon membrane surface provides a considerable enhancement in fluorescence intensity. The fluorescence determination is carried out at λ_ex = 237, λ_em = 415 nm for FUR; and λ_ex = 365, λ_em = 406 nm for AMI. The calibration graphs are linear in the range 3.20 × 10⁻⁴ to 0.8 μg mL⁻¹and 1.33 × 10⁻³ to 4.0 μg mL⁻¹, for AMI and FUR, respectively, with a detection limit of 9.62 × 10⁻⁵ and 4.01 × 10⁻⁴ μg mL⁻¹ (S/N = 3). The commonly found excipients in commercial pharmaceutical formulations do not interfere. The developed method is successfully applied to the determination of both drugs in pharmaceutical formulations.     

Hollow fiber supported liquid membrane extraction for ultrasensitive determination of trace lead by portable tungsten coil electrothermal atomic absorption spectrometry

Hollow fiber supported liquid membrane extraction (HF-SLME) was used to separate and enrich trace lead from a large volume of 250 mL water sample to a final tiny volume of 30 μL of 1-octanol, 5 μL of which was inject into a tungsten coil electrothermal atomic absorption spectrometer (W-coil ET-AAS) for determination of lead. Some important parameters that influenced the extraction and determination were investigated in detail, such as the concentration of ammonium pyrrolidine dithiocarbamate (APDC), pH of sample solution, stirring rate, extraction time, pyrolysis current, atomization current, carrier gas flow rate, as well as interferences. Under the optimized conditions, a practical enrichment factor of 499 and a limit of detection (3σ) of 0.2 ng mL^{− 1} were obtained. The calibration curve was linear in the range of 0.5–10 ng mL^{− 1}. The relative standard deviation (RSD) was 5.6% for five measurements of a 4 ng mL^{− 1} lead standard solution. The accuracy of this method was examined by the analysis of certified reference water samples (GBW(E)080398 and GSBZ(E) 50009-88) for lead. Finally, the proposed method was applied to the determination of lead in local tap water, pond water and river water, with recoveries in the range of 96–109% for spiked samples.     

preconcentration and determination of amoxicillin and ceftriaxone in hospital sewage using vortex-assisted liquid-phase microextraction based on the solidification of the deep eutectic solvent followed by HPLC–UV

In the present study, a new method for extraction and preconcentration of amoxicillin and ceftriaxone was used in hospitalised sewage samples, called vortex-assisted liquid-phase microextraction based on the solidification of deep eutectic solvent. Samples were analysed by high-performance liquid chromatography–ultraviolet detection after preparation and extraction. In this method, the new deep eutectic solvent is used as the extraction solvent, which is obtained from the combination of 1-decyl-3-methylimidazolium chloride and n-butanoic acid. The important advantages of this novel extraction solvent include material stability, low density and good freezing point near room temperature. Under the optimum conditions, enrichment factors are in the range of 164–172. Repeatability and reproducibility of the method based on seven replicate measurements of 50.0 µg L^?1 of the target analytes in analysed samples were in the range of 2.1–3.5% and 3.8–5.2%, respectively. The limit of detections and linearity are in the range of 0.005–0.10 and 3–600 µg L^?1, respectively. The method was successfully applied for the determination of amoxicillin and ceftriaxone in the real sewage samples. The relative recoveries of sewage samples spiked with amoxicillin and ceftriaxone are 91–107%.     

Design of selective molecularly imprinted sorbent for the optimized solid‐phase extraction of S‐pramipexole from the model multicomponent sample of human urine

The objective of this article was to design the selective molecularly imprinted sorbent dedicated to the solid‐phase extraction of S‐pramipexole from the complex matrix such as human urine. For that purpose, S‐2,6‐diamino‐4,5,6,7‐tetrahydrobenzothiazole was used as the template acting as the structural analog of S‐pramipexole and five various monomers were employed in the presence of ethylene glycol dimethacrylate to produce molecularly imprinted polymers. The binding capabilities of resulted polymers revealed that the highest imprinting effect was noted for polymer prepared from the itaconic acid. The comprehensive analysis of morphology and the characterization of binding sites showed not only negligible differences in the extension of surfaces of imprinted and nonimprinted polymers but also higher heterogeneity of binding sites in the imprinted material. Comprehensive optimization of the molecularly imprinted solid‐phase extraction allowed to select the most appropriate solvents for loading, washing, and elution steps. Subsequent optimization of mass of sorbent and volumes of solvents allowed to achieve satisfactory total recoveries of S‐pramipexole from the model multicomponent real sample of human urine that equals to 91.8 ± 3.2% for imprinted sorbent with comparison to only 37.1 ± 1.1% for Oasis MCX.     

A robust LC–MS/MS assay with online cleanup for measurement of serum testosterone

Accurate measurement of low levels of testosterone is critical for diagnosis and treatment of androgen disorders. The very low concentrations of testosterone in children, females, and males with androgen suppression therapies necessitate the use of mass spectrometry‐based methods. We aimed to develop a liquid chromatography with tandem mass spectrometry method with simplified sample preparation and online solid‐phase extraction cleanup to achieve enhanced precision, accuracy, robustness, and cost‐effectiveness. The assay was linear from 10 to 20 000 pg/mL with an analytical recovery of 93–104%. The total coefficient of variation was 2.5, 1.9, and 1.7% at concentration levels of 348, 5432, and 10 848 pg/mL, respectively. No significant carryover was observed from samples with concentrations up to 20 000 pg/mL. No significant interference was observed from androstenedione, dehydroepiandrosterone, epi‐testosterone, and estriol. Comparison with CDC Hormone Standardization program (HoSt) reference samples with defined values (n = 40) showed a Deming regression slope of 0.963, intercept of 28.06 pg/mL, standard error of estimate was 66.9, a correlation coefficient of 0.9996, and a mean bias of ?0.6%. The method met the accuracy criteria by the CDC HoSt program. In addition, we achieved >12 000 injections on a single analytical column without significant performance deterioration due to the specific online solid‐phase extraction settings.