Research progress of rapid detection of typical environmental pollutants based on chromatographic technologiesEI北大核心CSCD

对复杂环境介质中的典型污染物进行快速、精准甚至远程连续自动的检测,是控制环境污染、确保环境和生态安全的重要前提。近年来,基于色谱技术的典型环境污染物快速检测方法发展迅猛,主要包括样品快速制备和目标物快速检测两方面。辅助萃取、快速液相萃取、QuEChERS等样品前处理方法具有萃取效率高、溶剂消耗少、操作简便快速等优点。快速检测技术可在几秒到半小时内提供检测结果,主要包括实验室和现场检测。本文综述了2019年以来基于色谱技术的典型环境污染物快速检测研究新进展。介绍了萃取技术和基于试验设计的样品快速制备,实验室快速检测、便携仪器现场检测及遥感技术远程检测,提出了色谱技术快速检测环境污染物的挑战和展望。     

Research progress in mass spectrometry analysis for samples containing non-volatile saltsEI北大核心CSCD

It’s still a challenge for mass spectrometers （MS） to analyze samples in non-volatile salts systems. On the one hand, non-volatile salts are easy to crystallize, which will seriously contaminate and clog the transmission system of mass spectrometry, such as capillaries, ion transfer tubes, sampling cones, etc., thus the analysis results can be affected and the MS can be damaged. On the other hand, non-volatile salts always bring ion suppression, which significantly reduces the signal intensity of the analytes. At the same time, the mass spectrum will be dominated by a large number of salt cluster peaks, interfering with the discrimination of charge state. Recently, different methods have been developed to solve above two problems. This article reviewed the present research progress of mass spectrometry analysis for salt-containing samples, focusing on the role of conventional ion source modification and ambientionization mass spectrometry in the analysis of salt-containing samples. Pretreatment methods were also summarized briefly. Finally, the development tendency of mass spectrometry analysis for salt containing samples is predicted and prospected. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Advances in the thin layer chromatographic analysis of counterfeit pharmaceutical products: 2008–2019

Publications reporting thin layer chromatography (TLC) screening and high performance TLC (HPTLC)-densitometry quantification analyses of counterfeit pharmaceutical products are reviewed for the 2008–2019 period. Screening using TLC methods published in the Global Pharma Health Fund (GPHF) Minilab Manual and U.S. Food and Drug Administration (FDA) Compendium, as well as in other sources, are covered. Also included are publications on TLC analysis hyphenated with Raman and mass spectrometry; analyses of counterfeit traditional herbal medicines; earlier published reviews; transfer of screening methods for counterfeit pharmaceutical products in the Minilab Manual and FDA Compendium to HPTLC-densitometry using a model process; development of HPTLC-densitometry methods for pharmaceutical products not included in the Minilab Manual or FDA Compendium using the model process followed by development of corresponding Supplemental FDA Compendium TLC screening methods; and modified Minilab methods with simplified detection based on heating of silica gel F layers to produce fluorescence quenching zones (thermochemical activation) rather than detection using spray, dip, or vapor phase derivatization reagents. Some thoughts on future prospects for the field are also offered.     

引言北大核心CSCD

灵敏、可靠地检测复杂样品中痕量、超痕量目标物对分析测量学提出了巨大挑战,目前市场上虽已有诸多智能化的现代分析检测仪器,但考虑到复杂的样品基底及目标组分的低含量,在进行仪器分析检测前,需进行有效的样品制备,以降低复杂样品基底的干扰,提高检测准确性,同时对目标组分进行富集,从而改善检测灵敏度。可以说,样品制备过程是整个分析过程中最为重要和耗时的步骤,影响着分析结果的准确性和可靠性。     

Rapid analysis of impurities in deuterium by micro gas chromatographyEI北大核心CSCD

A quantitative analysis method was established for detecting Ar, N2, CH4, CO and CO2 in fuel gas deuterium of fusion reactor by the INFICON 3000 micro gas chromatography. We studied the effects of column temperature, pressure and injection time to the analysis of the impurities in deuterium. The chromatographic conditions were optimized. The results indicated the retention time of all the impurities in D2 was less than 76. 0 s, the resolution of each component was larger than 1. 5 with the relative standard deviation (RSD) less than 1. 0%, and the detection limit of each component was less than 7. 0 μL / L. The method can quickly realize the separation and accurate quantitative analysis of the impurities in deuterium, and meet the analysis requirements of impurity in gas of deuterium and tritium fuel in fusion reactor. © 2021, Youke Publishing Co.,Ltd. All rights reserved.     

Pyrolysis Process of Plant Fibers北大核心CSCD

The natural plant fiber has a large molecular weight and complex structure and composition,and its thermal cracking products and the composition distribution are also more complex. The fast pyrolysiscomprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry（Py-GC×GC-TOF/MS）,thermogravimetry-Fourier transform infrared spectroscopy（TG-FT-IR）,and in situ Fourier transform infrared spectroscopy（in situ FT-IR）methods were used to study the thermal pyrolysis process of six different natural fibers. The distribution of thermal pyrolysis products of different fibers under different pyrolysis temperatures was investigated and the product form was fully discussed. The research results show that the products of fiber pyrolysis mainly include alcohols,aldehydes,ketones,acids,esters,hydrocarbons, dehydrated sugars and CO2,etc. The types of pyrolysis products of different natural plant fibers are obviously different,and the main product types obtained are all different. At the same time,the results of in situ infrared spectroscopy and mass spectrometry show that pyrolysis products are closely related to the pyrolysis temperature. The results of in situ infrared experiments show that when the pyrolysis temperature is lower than 100 °C,the adsorbed water on the surface of the fiber structure is desorbed,but the fiber structure does not change significantly. When the pyrolysis temperature range is 100~200 °C,the temperature has little effect toward the pyrolysis process. When the temperature exceeds 300 °C,the fiber pyrolysis reaction intensifies and the surface structure changes significantly,and the main products are aldehydes and ketones. © 2022, Science Press (China). All rights reserved.     

Determination of mannose in honey by isotope dilution gas chromatography mass spectrometryEI北大核心CSCD

建立了一种同位素稀释-气相色谱/质谱(GC-MS)测定蜂蜜中甘露糖含量的方法。选择了一种新型化合物[13C;D]-D-甘露糖作为蜂蜜中甘露糖检测的同位素内标,优化了甘露糖及其内标的气相色谱分离条件和质谱参数。蜂蜜样品经70%乙醇水溶液溶解后加入同位素内标,采用两步衍生法对蜂蜜中糖组分进行衍生化,即先加入2.5%盐酸羟胺-吡啶溶液进行肟化衍生,再加入N,O-双(三甲基硅基)三氟乙酰胺(BSTFA)进行硅烷化衍生,采用GC-MS对甘露糖进行定性分析和定量检测。结果表明,以洋槐蜜、油菜蜜、荆条蜜和椴树蜜为代表性样品基质,甘露糖的检出限均为6 mg/kg,定量限为20 mg/kg,在20,40,200 mg/kg 3个添加水平下方法的平均回收率在66.1%~91.7%之间,相对标准偏差不超过20%。该方法适用于不同类型蜂蜜中甘露糖含量的测定。     

毛细管电泳-质谱技术在手性化合物分离分析中的研究进展北大核心CSCD

目前使用的绝大多数药物为手性化合物,它们具有相似的物理和化学性质,但药理活性不同,且常以外消旋混合物的形式存在,因此对手性化合物的分离在生物、环境、食品和医药等领域一直备受关注。与广泛使用的液相色谱-质谱(LC-MS)相比,毛细管电泳-质谱(CE-MS)作为一种新型分离分析技术,具有分离效率高、样品和试剂消耗量低、选择性高和分离模式多样化等诸多优势,已经发展成为手性分析领域中有广阔应用前景的分析方法之一。CE-MS结合了CE的高分离效率和低样品消耗以及MS的高灵敏度和强结构解析能力,在蛋白质组学和代谢组学等领域发挥了重要作用。CE杰出的手性拆分能力与MS优势的结合,亦使CE-MS成为实现手性化合物高效分离分析的完美组合。在过去的十几年里,基于不同CE-MS分离模式的高性能手性分析体系层出不穷,如电动色谱-质谱(EKC-MS)、胶束电动色谱-质谱(MEKC-MS)和毛细管电色谱-质谱(CEC-MS)等,并成功应用于医药、生物、食品和环境科学等领域的手性化合物分析。该文主要综述了2011~2021年,CE-MS在手性化合物分析领域的技术、手性选择剂(如改性环糊精和聚合物表面活性剂等)的使用以及在医药等领域应用方面的研究进展,并讨论了不同手性分析模式的局限性,为未来的CE-MS手性分离分析技术发展及应用提供借鉴。     

Quantitative analysis of NP-10 and BS-12 in binary mixed systemEI北大核心CSCD

A method for the determination of two surfactants in binary mixtures of nonylphenolpolyoxyethylene ether NP-10and dodecyl dimethyl betaineBS-12was developed. The content of NP-10 in NP-10/BS-12 binary mixed system could be accurately detected by UV spectroscopy. The effect of BS-12 on the absorbance of NP-10 at the maximum absorption wavelength of 223 nm is negligible. When the concentration of NaCl in the solution was 10-100 mg/Lthis method could still accurately detect the content of NP-10 in the binary mixed systemand the recoveries of NP-10 were 99.4%-100.9%. The content of BS-12 in NP-10/BS-12 binary mixed system could be accurately detected by colorimetryand the interference of NP-10 on the detection of BS-12 could be also ignored. When the NaCl concentration in the solution was 10-100 mg/Lthe recoveries of BS-12 detected by colorimetry in NP-10/BS-12 binary mixed system were 98.3%-101.7%. The method can be used to detect the contents of NP-10 and BS-12 in the binary mixed system. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Preparation and application of novel polymer nanoparticles in the detection of copper ion and cysteineEI北大核心CSCD

A novel amphiphilic copolymer,dipropenoxystyrene anthracene and acrylic acid copolymer（BASA-AA） was designed and synthesized based on divinyl anthracene. The polymer self-assembled rapidly in water to create polymer nanoparticles（BASA-AA NPs）with a uniform size of 45 nm,no dye leakage,and great brightness（Φ= 36%）. Because of the enormous number of carboxyl groups on the surface of the particles,it can disperse extremely well in water,and can be used for the rapid detection of copper ion and cysteine（Cys）in pure water, with the limit of detection of 45 nmol/L. The fluorescent intensity of the nanoparticles will be greatly reduced after the introduction of copper ion,realizing the detection of copper ion with high selectivity and sensitivity. A composite probe made of BASA-AA NPs and copper ion can detect Cys in the range of 0.1-10 µμmol/L,with the detection limit of 84 nmol/L,due to the high binding capacity of the sulfhydryl group and copper ion. The method is simple and rapid in material synthesis and preparation,and shows high selectivity and sensitivity in pure water. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Study on the interference elimination of trace cadmium in superalloy by ICP-MS / MSEI北大核心CSCD

A triple quadrupole inductively coupled plasma mass spectrometry (ICP-MS / MS) method was developed for the determination of trace Cd in superalloys. Meanwhile, the interference elimination effects of different collision / reaction gases (He, O2 and NH3) in single quadrupole mode (SQ) and double quadrupole mode (QQQ) were investigated. The results indicated that the modes of QQQ-O2 and QQQ-NH3 possessed satisfactory interference elimination effect than the others. The optimal flow rates of O2 and NH3 were 0. 75 mL / min and 0. 50 mL / min, respectively. In order to verify the interference elimination effect, the recovery rate of 0. 1 μg / g Cd in 0. 10 mg / g to 100 mg / g Mo content solutions, as well as the determination results of superalloy standard substance and the actual sample were investigated. The measured value was within the range of the standard value, and the measured value of the actual sample was consistent with that of the hydride generation atomic fluorescence method. Therefore, the proposed method can eliminate the polyatomic ions interference of Mo on trace Cd. © 2022, Youke Publishing Co.,Ltd. All rights reserved.     

Determination of perfluorooctane sulfonic acid in cosmetics by high-perfor⁃ mance liquid chromatography-tandem mass spectrometryEI北大核心CSCD

A high performance liquid chromatography-tandem mass spectrometry（HPLC-MS/MS）method was developed for the determination of perfluorooctane sulfonic acid （PFOS）in cosmetics. The cosmetic samples were extracted with methanol by ultrasonication,and PFOS was quantified by HPLC-MS/MS. The samples were detected in negative multiple reaction monitoring（MRM）mode using an Agilent Poroshell 120 EC-C18 （100 mm× 2.1 mm,2.7 µμm）column with a gradient elution using 0.1% formic acid aqueous solution（A）-methanol（B）as the mobile phase. The results showed that the linearity of PFOS was good in the range of 1-100 µμg/L with the correlation coefficient r2 larger than 0.9998;the limits of detection and limits of quantification were 0.015 and 0.050 mg/kg,respectively. The average recoveries were 98.7%-112.5%,and the relative standard deviations （RSDs）were less than 5%. The method is suitable for the determination of PFOS in cosmetics. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Determination of the migration of fourteen endocrine disruptors in food packaging materials by liquid chromatography-tandem mass spectrometryEI北大核心CSCD

A method for the determination of the migration of 14 endocrine disruptors（bisphenol A,bisphenol E,bisphenol F,bisphenol S,bisphenol B,bisphenol Z,bisphenol AF,bisphenol AP,tetrabromobisphenol A, tetrachlorobisphenol A,octylphenol,4-n-octylphenol,4-nonylphenol and 4-n-nonylphenol）in food packaging materials by liquid chromatography-tandem mass spectrometry was developed. The samples were soaked in water,4% acetic acid solution,10% ethanol solution,50% ethanol solution,olive oil,simulated sweat and simulated saliva. The soakings were purified by solvent extraction or Oasis HLB solid phase extraction. After separation by a Waters Atlantis™ T3 column,the samples were determined by multiple reaction monitoring mode with electrospray negative ion source,and quantified by matrix external standard method. The linear correlation coefficients of 14 endocrine disruptors were 0.9901-0.9986,the recoveries were 82.3%-108.7% with the relative standard deviations of 0.8%-6.8%,the limits of detection were 0.1-0.5 μµg/L and the limits of quantification were 0.3-1.5 μµg/L. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Research Progress on the Continuous Cropping Obstacles of Ginseng from Soil Improvement北大核心CSCD

The unique black soil resources and natural environment of Jilin province provide the proper conditions for the growth of ginseng-the king of herb. Ginseng industry has effectively promoted the development of medical and health industry,and brought considerable economic income for ginseng farmers. However,long-term continuous cropping of ginseng causes the chemical,biological,and physical properties deterioration of soil,which influences the yield and the quanlity of ginseng,and results in the occurrence of replant obstacle. Identifying the malignant soil factors in continuous cropping obstacles,then analyzing the evolution process,and putting forward the improvement strategies is the primary task of ginseng research at present. This paper reviews the influence of ginseng cultivation on the physicochemical property,nutrient, enzyme activity,microecology and ecotoxicity of the soil,and the achievements of improving ginseng soil by chemical and biological techniques and methods in recent 10 years. © 2022, Science Press (China). All rights reserved.     

Recent advancements in analytical methods of phosphodiesterase 5 inhibitors and their metabolitesEI北大核心CSCD

磷酸二酯酶5抑制剂(PDE5i)用于治疗勃起功能障碍和肺动脉高压等疾病。因PDE5i类药物种类繁多,理化性质各异,在体内代谢迅速且具有多种代谢途径,故生物样本检验难度大。本文介绍了PDE5i类药物及其代谢物,总结了生物样本中该类物质的沉淀蛋白法、液-液萃取法、固相萃取法和固相微萃取法等前处理方法,综述了高效液相色谱法、液相色谱质谱联用法、荧光光谱法和电化学分析法等检测方法,展望了PDE5i及其代谢物分析的未来发展方向,以期为PDE5i的药物监测和法庭科学毒物检验提供参考。     

Determination of the migration of 8 benzophenones in food contact materials and products by HPLC-MS / MSEI北大核心CSCD

建立了高效液相色谱-串联质谱法测定食品接触材料及制品中8种二苯甲酮类物质迁移量的方法。样品经过食品模拟物浸泡后,水、4%乙酸、10%乙醇、20%乙醇、50%乙醇模拟物直接进样,95%乙醇模拟物用水按照1:4比例稀释后进样,橄榄油和异辛烷模拟物用甲醇-水混合溶液萃取后进样。采用C₁₈柱分离,用甲醇-0.1%甲酸水溶液为流动相梯度洗脱,质谱采用正离子多反应监测（MRM）模式运行。本方法在8种食品模拟物中的定量限为0.01～0.20 mg/kg;在0.04～0.80 mg/kg, 0.2～2.0 mg/kg, 0.6～3.0 mg/kg线性范围内相关系数良好（R≥0.9958）;加标实验结果显示相对标准偏差（RSD）为0.61%～7.8%。该方法可用于食品接触材料及制品中二苯甲酮类物质迁移量的测定。     

Synthesis of Ruthenium-Graphene Quantum Dots Artificial Oxidase and Its Application in Colorimetric Detection of Phoxim in Carrots北大核心CSCD

The histidine functionalized graphene quantum dots（His-GQDs）react with ruthenium trichloride to form a stable ruthenium complex. This complex is treated in a N2 atmosphere at 600 ℃ for 1 h to obtain a ruthenium-graphene quantum dot composite （Ru-His-GQD）. The results of scanning electron microscopy （SEM）and transmission electron microscopy（TEM）analysis demonstrate that Ru-His-GOD has one three-dimensional structure. The diameter of ruthenium nanoparticles is between 40 and 60 nm. Ru-His-GQD is rich in functional groups and has high oxidase-like activity. Based on Ru-His-GQD catalyzed oxidation of 3,3′,5,5′-tetramethylbenzidine（TMB）to produce blue compounds,a photometric method for the determination of phoxim in carrots is established. Phoxim can inhibit the activity of Ru-His-GQD oxidase,resulting in a decrease in the absorbance of the blue compound. When the concentration of phoxim is between 30～240 μg/ L,the absorbance of the oxidation product of TMB at 652 nm decreases linearly with the increase of phoxim concentration. The detection limit of the method reaches 7. 33 μg/L（S/N=3）,and the sensitivity is higher than those in literature. It has been successfully applied to the detection of phoxim in carrots. © 2022, Science Press (China). All rights reserved.     

Determination of Seven Major Ginsenosides in Different Parts of Panax quinquefolius L.（American Ginseng） with Different Ages

Ginsenosides Rgl, Re, Rb1, Rc, Rb2, Rb3, and Rd in different parts of the American ginseng plant were investigated. The extraction process was a pressurized microwave-assisted extraction（PMAE）. The seven ginsenosides were separated and determined by high-performance liquid chromatography（HPLC） with a ultraviolet（UV） detector, at 203 nm. The experiment results showed significant variations in the individual ginsenoside contents of the American ginseng in different parts and ages of the plant. The results demonstrated that the leaves, root hairs, and rhizomes of Panax quinquefolius L. contained higher ginsenoside contents, followed by the main roots and stems. The leaves contained dramatically higher levels of ginsenoside Rg1 Rb3, and Rd than the other four parts. Higher contents of Rb1 and Re were present in the main roots, root hairs, and rhizomes. The amount of ginsenoside content in the stems was the lowest. The total content of the seven ginsenosides in main roots, root hairs and rhizomes increased with the age of the plant. In contrast, the ginsenoside contents in the leaves and stems decreased with a year of growth.