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Green analytical approaches for contaminants: Sustainable alternatives to conventional chromatographic methods 污染物的绿色分析方法:传统色谱法的可持续替代方法
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-28 DOI: 10.1016/j.chroma.2025.465921
Víctor Cutillas, Carmen Ferrer, María Jesús Martínez-Bueno, Amadeo R. Fernández-Alba
The growing importance of environmental sustainability has driven advancements in analytical chemistry, particularly in the development of green chromatographic techniques. This review explores various chromatographic methods that align with green chemistry principles, offering environmentally friendly alternatives to traditional gold-standard approaches. Techniques such as supercritical fluid chromatography (SFC), miniaturized liquid chromatography (LC), and gas chromatography (GC) with alternative carrier gases (e.g., hydrogen and nitrogen) are discussed in depth for their ability to reduce solvent consumption, minimize waste, and improve operational efficiency. These methods not only maintain high sensitivity and accuracy but also reduce the ecological impact of contaminant analysis. By comparing these sustainable approaches to conventional techniques, this review highlights their potential to meet regulatory standards while supporting eco-friendly practices within routine analysis laboratories.
环境可持续性日益增长的重要性推动了分析化学的进步,特别是在绿色色谱技术的发展。本综述探讨了与绿色化学原理相一致的各种色谱方法,为传统的金标准方法提供了环境友好的替代品。超临界流体色谱(SFC)、小型化液相色谱(LC)、气相色谱(GC)等可选载气(如氢气和氮气)的技术可以减少溶剂消耗,减少浪费,提高操作效率。这些方法不仅保持了较高的灵敏度和准确性,而且减少了污染物分析对生态的影响。通过将这些可持续方法与传统技术进行比较,本综述强调了它们在满足监管标准的同时支持常规分析实验室中环保实践的潜力。
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引用次数: 0
Sulfonic acid-functionalized covalent organic framework@Ti3C2Tx as efficient solid-phase microextraction blade coating for the extraction of monoamine neurotransmitters in rat serum samples 磺酸功能化共价有机framework@Ti3C2Tx作为高效固相微萃取叶片涂层提取大鼠血清中单胺类神经递质
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-28 DOI: 10.1016/j.chroma.2025.465919
Cheng Yang , Nian Yang , Di Zhao , Zhiyu Zhang , Junying Song , Zhenqiang Zhang , Kai Hu , Shusheng Zhang
Herein, a sulfonic-functionalized covalent organic framework@Ti3C2Tx nanocomposite (SO3HCOF@Ti3C2Tx) was synthesized and employed as solid phase microextraction (SPME) coating for isolation and extraction of monoamine neurotransmitters (MNTs) from rat serum samples. The resultant composite can combine the characteristics of hydrophilic Ti3C2Tx and SO3HCOF, which endow it has multiple adsorption sites and can provide multiple interactions such as cation exchange, hydrogen bonding and π-π with the target MNTs. The synthesized SO3HCOF@Ti3C2Tx SPME blades have excellent protein exclusion capability, ensuring high adsorption efficiency for MNTs. Under the optimized conditions, the proposed SO3HCOF@Ti3C2Tx blades-based SPME-HPLC method exhibited good linearities (r2≥0.9963), low limits of detection (0.015–0.030 ng mL-1) and low matrix effect (0.83 %-17.36 %). The recoveries of MNTs in the rat serum were in range of 90.3 %-118.3 %, with RSDs <10.8 %. The SPME-HPLC method was successfully applied for the analysis of 4 MNTs in the serum of depression model rats. This work not only details the development of a multi-functional composite, but it also presents an effective strategy for the determination of trace MNTs in serum sample.
本文合成了一种磺化共价有机framework@Ti3C2Tx纳米复合材料(SO3HCOF@Ti3C2Tx),并将其用作固相微萃取(SPME)涂层,用于分离和提取大鼠血清样品中的单胺类神经递质(MNTs)。该复合材料结合了Ti3C2Tx和SO3HCOF亲水性的特点,具有多个吸附位点,并能与目标MNTs进行阳离子交换、氢键和π-π等多种相互作用。合成的SO3HCOF@Ti3C2Tx SPME叶片具有优异的蛋白质排除能力,保证了MNTs的高吸附效率。在优化条件下,SO3HCOF@Ti3C2Tx叶片型SPME-HPLC法线性良好(r2≥0.9963),检出限低(0.015 ~ 0.030 ng mL-1),基质效应低(0.83% ~ 17.36%)。mnt在大鼠血清中的加样回收率为90.3% ~ 118.3%,rsd为10.8%。采用SPME-HPLC法对抑郁症模型大鼠血清中4种mnt进行了分析。这项工作不仅详细介绍了多功能复合材料的开发,而且还提出了一种测定血清样品中痕量mnt的有效策略。
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引用次数: 0
Fabrication and evaluation of a dual-zwitterionic functionalized hydrophilic monolith for chromatographic separation 色谱分离用双两性离子功能化亲水单体的制备与评价
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-28 DOI: 10.1016/j.chroma.2025.465917
Liang Lai , Hongying Lan , Hui Huang , Tong Li , Kesara Ar-sanork , Jia-Huan Qu , Dongsheng Xu , Zhengjin Jiang
In this study, the chromatographic performance of a novel dual-zwitterionic hydrophilic stationary phase were investigated. Three zwitterionic HILIC monoliths were prepared using 3-(4-((methacryloyloxy)methyl)-1-methylpiperidin-1-ium-1-yl)propane-1-sulfonate (MAMMPS), 2-methacryloyloxyethyl phosphorylcholine (MPC), and a combination of MAMMPS and MPC (1:1, molar ratio) with N,N'-methylenebisacrylamide (MBA), separately. The monoliths exhibited good repeatability and stability. A high column efficiency of 120,000 plates/m was reached on the novel dual-zwitterionic functionalized poly(MAMMPS@MPC-co-MBA) monolith. Through the analysis and testing with different standards, the poly(MAMMPS@MPC-co-MBA) monolith exhibited the strongest retention capacity for negatively charged benzoic acid derivatives due to its high hydrophilicity and weak electronegativity. In contrast, the poly(MPC-co-MBA) monolith, functionalized with a single zwitterion, facilitated electrostatic interactions with negatively charged analytes. Baseline separation was achieved on all three monoliths for selected nucleobases, nucleosides, phenol derivatives, and amine compounds. However, their retention strength was mainly related to the hydrophilicity of the stationary phases, while hydrogen bonding and electrostatic interactions played secondary roles. Among the monoliths, the poly(MAMMPS-co-MBA) monolith demonstrated the best separation for neutral, acidic, and alkaline compounds. These findings offer valuable insights for the future selection and application of dual-zwitterionic HILIC monoliths for chromatographic separations.
本文研究了一种新型双两性离子亲水固定相的色谱性能。采用3-(4-(甲基丙烯酰氧基)甲基)-1-甲基哌啶-1- 1-酰基)丙烷-1-磺酸盐(MAMMPS)、2-甲基丙烯酰氧基乙基磷酸胆碱(MPC)以及分别以1:1摩尔比与N,N'-亚甲基双丙烯酰胺(MBA)的混合物制备了3个两性离子HILIC单体。样品重复性好,稳定性好。在新型双两性离子功能化聚(MAMMPS@MPC-co-MBA)整体柱上达到了120,000板/m的高柱效率。通过不同标准的分析和测试,聚(MAMMPS@MPC-co-MBA)单体具有较高的亲水性和较弱的电负性,对带负电荷的苯甲酸衍生物的保留能力最强。相反,聚(MPC-co-MBA)单体,用一个两性离子功能化,促进了与带负电荷的分析物的静电相互作用。在选定的核碱基、核苷、酚衍生物和胺类化合物的所有三个单体上实现基线分离。然而,它们的保留强度主要与固定相的亲水性有关,氢键和静电相互作用次要。在这些单体中,聚(MAMMPS-co-MBA)单体对中性、酸性和碱性化合物的分离效果最好。这些发现为今后双两性离子HILIC单体色谱分离的选择和应用提供了有价值的见解。
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引用次数: 0
Development of a highly sensitive field-amplified capillary electrophoresis tandem triple quadrupole mass spectrometry for the quantification of trace methamphetamine in sewage 高灵敏度场放大毛细管电泳串联三重四极杆质谱法测定污水中痕量甲基苯丙胺的建立
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-28 DOI: 10.1016/j.chroma.2025.465920
Yanping Wei , Yujie Zhang , Yueting Hu , Fan Shui , Jia Tang , Yiyang Yu , Guocan Zheng , Jing Zeng
Accurate quantification of trace levels of illicit drugs in wastewater, such as methamphetamine (MAMP), is crucial for sewage epidemiology. In this study, we developed a novel method that integrates field-amplified sample injection capillary electrophoresis with triple quadrupole mass spectrometry (FASI-CE-QQQ MS). This method enables simultaneous on-line preconcentration and separation, coupled with highly sensitive detection. Validation demonstrated excellent linearity within the range of 1 to 200 ng/L (R² = 0.9996), a limit of detection (LOD) of 0.1 ng/L (S/N = 12.3), high accuracy (RE < 6.4 %) and precision (RSD < 11.4 %). It was successfully applied to quantify MAMP in two unknown water samples, yielding average concentrations of 3.70 ng/L and 84.73 ng/L, respectively. These results were consistent with those obtained from an interlaboratory comparison exercise across China using on-line solid-phase extraction coupled with ultra-high performance liquid chromatography tandem triple quadrupole mass spectrometry (on-line SPE-UHPLC-QQQ MS). Finally, a comprehensive comparison between the newly developed FASI-CE-QQQ MS and the on-line SPE-UHPLC-QQQ MS methods revealed that the FASI-CE-QQQ MS offers significant advantages in terms of sensitivity, rapidity, and reduced solvent and sample consumption, making it a promising approach for the accurate determination of trace drugs in water.
准确量化废水中痕量非法药物,如甲基苯丙胺(MAMP),对污水流行病学至关重要。在这项研究中,我们开发了一种将场放大样品注射毛细管电泳与三重四极杆质谱(FASI-CE-QQQ MS)相结合的新方法。该方法可同时在线富集和分离,并具有高灵敏度的检测。结果表明,该方法在1 ~ 200 ng/L范围内线性良好(R²= 0.9996),检出限(LOD)为0.1 ng/L (S/N = 12.3),准确度高(RE <;6.4%)和精密度(RSD <;11.4%)。它成功地应用于定量两个未知水样中的MAMP,平均浓度分别为3.70 ng/L和84.73 ng/L。这些结果与在中国使用在线固相萃取-超高效液相色谱串联三重四极杆质谱(在线SPE-UHPLC-QQQ MS)进行的实验室间比较一致。最后,将新建立的FASI-CE-QQQ质谱法与在线SPE-UHPLC-QQQ质谱法进行了综合比较,结果表明FASI-CE-QQQ质谱法在灵敏度、快速、减少溶剂和样品消耗等方面具有显著优势,有望用于水中痕量药物的准确测定。
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引用次数: 0
Ion exchange- and enrichment-based technology applied to large-scale plasma proteomic analysis of breast cancer neoadjuvant chemotherapy 离子交换和富集技术应用于乳腺癌新辅助化疗的大规模血浆蛋白质组学分析
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-27 DOI: 10.1016/j.chroma.2025.465914
Xiaozhen Cui , Zhihua Zhong , Sen Xu , Yini Pan , Xi Wang , Luobin Zhang , An He , Xueting Ye , Hua Cao , Weibing Zhang , Ruijun Tian
Mass spectrometry (MS) based proteomics provides unbiased quantification of all proteins in plasma, which can dynamically reflect individual health states in real time. However, large-scale proteomics studies are constrained by the excessive dynamic range of plasma proteome and low throughput. Herein, two kinds of magnetic metal-organic frameworks (MOFs) modified with ion exchange functional groups (denoted as MHP-UiO-66-SAX and MHP-HKUST-1-SCX) were designed and fabricated to exhibit large protein adsorption capability, which were combined with an automated Liquid-handling System, thus realizing in-depth, high-throughput and automated proteomics studies. The constructed workflow could automatically complete the sample preparation before MS within only six hours and nearly a thousand protein groups per sample could be quantified. In the cohort study of nearly one hundred breast cancer neoadjuvant chemotherapy (NC) plasma samples, two differentially expressed proteins previously reported as biomarkers were related with the pathological complete response (PCR) of the breast cancer, demonstrating the feasibility of the developed technology for preparing large-scale clinical samples and exhibiting the potential application in monitoring the effect of chemotherapy.
基于质谱(MS)的蛋白质组学提供了对血浆中所有蛋白质的无偏定量,可以实时动态地反映个体的健康状态。然而,大规模的蛋白质组学研究受到血浆蛋白质组动态范围过大和低通量的限制。本文设计并制备了两种离子交换功能基团修饰的磁性金属有机框架(mof),分别为MHP-UiO-66-SAX和MHP-HKUST-1-SCX,具有较大的蛋白质吸附能力,并与自动化液体处理系统相结合,实现了深入、高通量和自动化的蛋白质组学研究。构建的工作流程可在6小时内自动完成质谱前的样品制备,每个样品可定量近千个蛋白质组。在近100例乳腺癌新辅助化疗(NC)血浆样本的队列研究中,两种差异表达蛋白作为生物标志物与乳腺癌的病理完全反应(PCR)相关,证明了所开发的技术制备大规模临床样本的可行性,以及在化疗效果监测方面的潜在应用。
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引用次数: 0
Model-based analysis of a hydrophobic interaction chromatography for antibody-drug conjugate purification 抗体-药物偶联物纯化的疏水相互作用层析模型分析
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-27 DOI: 10.1016/j.chroma.2025.465916
Tobias Hahn , Fara Lyu , Pia Graf , Steve Richter , Jorge Gandarilla , Dean Clyne , Lei Cao , Chen Wang
Antibody-drug conjugates (ADCs) are a class of biopharmaceutical drugs designed as a targeted therapy for treating cancer while sparing healthy cells. ADCs are complex molecules composed of an antibody linked to a biologically active cytotoxic drug. The drug-to-antibody ratio (DAR), which represents the number of drugs conjugated to an antibody, is an important quality attribute of ADCs. The conjugation process typically yields a complex DAR profile, which requires further purification to remove undesired DAR species. Separation of DAR species post conjugation reaction can be achieved using hydrophobic interaction chromatography (HIC). HIC utilizes the hydrophobicity differences of different drug-loaded ADCs to separate them by reversible interaction between the proteins and the hydrophobic stationary phase. The buffer greatly influences the binding interaction between hydrophobic proteins and a HIC resin, but the process is also sensitive to variations in temperature, resin attributes, and the solid-liquid ratio of the column. A mechanistic model that captures these critical process parameters and material and column properties was established from calibration studies using multiple well-characterized HIC columns and resin lots. This model enabled in-silico characterization of the HIC process and facilitated understanding of unexpected process performance observations. It revealed the importance of controlling resin-specific hydrophobic capacity to minimize the DAR separation variations. It led to identifying an effective process control strategy to ensure a consistent DAR profile.
抗体-药物偶联物(adc)是一类生物制药药物,设计用于治疗癌症,同时保留健康细胞的靶向治疗。adc是一种复杂的分子,由与生物活性细胞毒性药物相连接的抗体组成。DAR (drug-to-antibody ratio,药抗比)是adc的重要质量属性,它代表了与抗体结合的药物数量。共轭过程通常产生复杂的DAR轮廓,需要进一步纯化以去除不需要的DAR物种。疏水相互作用色谱法(HIC)可以实现DAR类化合物共轭反应后的分离。HIC利用不同载药adc的疏水性差异,通过蛋白质与疏水固定相的可逆相互作用将其分离。缓冲液极大地影响疏水蛋白与HIC树脂之间的结合相互作用,但该过程对温度、树脂属性和柱的固液比的变化也很敏感。通过使用多个表征良好的HIC色谱柱和树脂批次进行校准研究,建立了一个捕获这些关键工艺参数、材料和色谱柱特性的机制模型。该模型实现了HIC过程的硅表征,并促进了对意外过程性能观察的理解。这揭示了控制树脂特异性疏水能力以最小化DAR分离变化的重要性。它导致确定一个有效的过程控制策略,以确保一致的DAR配置文件。
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引用次数: 0
Off-line in-tube solid-phase microextraction of some herbicides based on poly(styrene-divinylbenzene) coated Fe3O4 nanoparticles 基于聚苯乙烯-二乙烯基苯包被Fe3O4纳米颗粒的管内固相微萃取除草剂
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-26 DOI: 10.1016/j.chroma.2025.465910
Maedeh Saadat , Yadollah Yamini , Nasser Nikfarjam , Hanieh Kefayati
Triazines are a class of persistent micropollutants in environmental areas with high toxicity. Because of their general usage and poisonous and stability of their deteriorated products, extraction and determination trace amounts of triazines are important. Off-line in-tube solid phase microextraction efficiently used for extraction of trace amounts of analytes. In addition, magnetic field was used to keep the nanoparticles in the tube and also to enhance preconcentration of the analytes. Magnetic nanoparticles can be utilized as a reusable sorbent with high surface area, strong interaction, chemical stability and high selectivity.
A novel approach was introduced using a magnetic nanocomposite of cross-linked poly(styrene-divinylbenzene) for the in-tube solid-phase microextraction of triazine herbicides. The prepared material was characterized using various techniques. High performance liquid chromatography-ultraviolet detection was used to separate and determine the analytes. The effects of pH (6), extraction time (20 min), type and volume of elution solvent (500 µL methanol) and extraction flow rate (2 mL min-1), desorption flow rate (50 µL min-1) and salt addition (15%) and applying magnetic field on the extraction efficiency of the triazines were investigated. Under optimum conditions, calibration curves were found to be linear in the range of 0.3-500 µg L−1 for cyanazine, simazine, and propazine with a coefficient of determination (R2) of 0.9951, 0.9984, and 0.9984, respectively. The LODs were 0.1 µg L−1 for all of the analytes. The method was successfully used for the extraction and determination of triazine herbicides in fruit juice samples.
Magnetic nano particles illustrate minimum back pressure in tube due to elimination of filters, high surface-to-volume ratio and lot of active sites favorable for the adsorption of the analytes. Despite the limitations imposed by the chemical conditions of extraction on the application of nanoparticles and polymeric sorbents, variables such as pH, concentration, and surface charges do not influence the magnetic interactions of MNPs. By applying magnetic field, the magnetic nature of the analytes is effective on the preconcentration of them.
三嗪类是一类高毒性环境区域的持久性微污染物。由于其用途广泛,变质产物的毒性和稳定性,微量三嗪的提取和测定具有重要意义。离线管内固相微萃取有效地用于萃取痕量分析物。此外,利用磁场将纳米颗粒保持在管中,并增强分析物的预富集。磁性纳米颗粒具有高表面积、强相互作用、化学稳定性和高选择性等特点,是一种可重复使用的吸附剂。采用交联聚苯乙烯-二乙烯基苯磁性纳米复合材料制备了一种管内固相微萃取三嗪类除草剂的方法。用各种方法对所制备的材料进行了表征。采用高效液相色谱-紫外检测对分析物进行分离测定。考察了pH(6)、提取时间(20 min)、洗脱溶剂种类和体积(500µL甲醇)、提取流速(2 mL min-1)、解吸流速(50µL min-1)、加盐量(15%)和外加磁场对三嗪类化合物提取效率的影响。在最佳条件下,在0.3 ~ 500µg L−1范围内,氰嗪、西玛嗪和丙嗪的校准曲线均呈线性,决定系数(R2)分别为0.9951、0.9984和0.9984。所有分析物的lod均为0.1µg L−1。该方法可用于果汁样品中三嗪类除草剂的提取和测定。磁性纳米颗粒由于消除了过滤器、高表面体积比和大量有利于被分析物吸附的活性位点而具有最小的管内背压。尽管萃取的化学条件对纳米颗粒和聚合物吸附剂的应用施加了限制,但诸如pH值、浓度和表面电荷等变量并不影响MNPs的磁相互作用。通过施加磁场,分析物的磁性对其富集是有效的。
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引用次数: 0
An injection filling method for packing chromatography devices 一种用于包装色谱装置的注射填充方法
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-26 DOI: 10.1016/j.chroma.2025.465913
Raja Ghosh, Justin Bernar
An injection filling method for packing resin media in a chromatography device for protein separation is discussed in this paper. The method is first demonstrated by packing anion exchange resin within a cuboid chromatography device and a squat column, both having 7.5 mL bed volume. The method is further demonstrated by packing size exclusion chromatography media in a 50 mL cuboid chromatography device. Overall, the packing method is simple and is less demanding in terms of requirement for operator skill and experience. The devices packed using the injection filling method had excellent separation efficiency attributes. Flow through and eluted protein peaks obtained using a device with an intentional minor indentation on the inner surface of the chromatography device showed pre-peaks (or fronting) and these peaks were wider than those obtained with a device without such an indentation. Surface imperfections had a greater impact on eluted peaks than on flow-through peaks. Size exclusion chromatography experiment carried out at high flow rates showed that protein separation obtained with the 50 mL cuboid device packed using the injection filling method was superior to that obtained with a conventional 50 mL column packed with the same media. At a high flow rate. the resin-bed within the column compacted very significantly while no such compaction was observed in the cuboid device.
本文讨论了一种在蛋白质分离色谱装置中填充树脂介质的注射填充方法。该方法首先通过在长方体色谱装置和深柱内填充阴离子交换树脂进行验证,两者都具有7.5 mL床容积。在50ml长方体色谱装置中,用填料尺寸排除色谱介质进一步验证了该方法。总的来说,这种包装方法简单,对操作人员的技能和经验要求较低。采用注射填充法包装的器件具有优良的分离效率属性。使用在色谱装置的内表面有意有微小压痕的装置获得的流动和洗脱的蛋白质峰显示出预峰(或前缘),并且这些峰比没有这种压痕的装置获得的峰宽。表面缺陷对洗脱峰的影响大于对流动峰的影响。在高流速下进行的尺寸排除色谱实验表明,用注射填充法填充的50 mL长方体装置获得的蛋白质分离优于用相同介质填充的传统50 mL柱获得的蛋白质分离。在高流速下。柱内的树脂床压实非常明显,而在长方体装置中没有观察到这种压实。
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引用次数: 0
Study of the aberrant retention behavior of a semi-crystalline polyamide in reversed-phase liquid chromatography 半晶聚酰胺在反相液相色谱中的异常保留行为研究
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-26 DOI: 10.1016/j.chroma.2025.465887
Jordy D. Kruijswijk , Stefan Wijker , Harry J.A. Philipsen , Peter J. Schoenmakers , Govert W. Somsen
The elution behavior of semi-crystalline polyamides (PAs) in reversed-phase liquid chromatography (RPLC) was examined. RPLC of the aliphatic polyamide 4,6 (PA46) yielded a single broad peak. However, the partly aromatic polyamide X (PAX) displayed a deviating elution profile, encompassing early- and late-eluting portions, which changed in relative abundance when varying injection and gradient conditions. These bands were suspected to be due to formation of amorphous and crystalline phases, respectively. RPLC fractions of the PAs were subjected to the same RPLC system and to size-exclusion chromatography. The presumed amorphous PAX portion showed two bands in RPLC, suggesting that (largely) amorphous and crystalline phases are formed upon sample injection. Differential scanning calorimetry (DSC) demonstrated that reducing the crystallinity of PAX decreased the relative abundance of the late-eluting fraction, approaching the behavior of aliphatic polyamides. X-ray diffraction and static-light-scattering analyses confirmed the semi-crystallinity of the two solid PA samples. Although both small particles and larger aggregates were observed in solution, these findings could not be correlated to the differences in elution profile of the PAs. Cloud-point measurements indicated that the solubility of both PA46 and PAX was almost independent of temperature. Strikingly, at low column temperatures (i.e. below the depressed melting point), PAX eluted as a single broad PAX peak. To conclude, the semi-crystallinity of PAX influences its RPLC-elution behavior, and by ensuring complete dissolution of the crystalline phase useful chemical information can be extracted from the obtained chromatograms.
研究了半结晶聚酰胺(PAs)在反相液相色谱(RPLC)中的洗脱行为。脂族聚酰胺4,6 (PA46)的RPLC显示单峰宽。然而,部分芳香族聚酰胺X (PAX)表现出偏离洗脱曲线,包括早期和晚期洗脱部分,其相对丰度随着注射和梯度条件的变化而变化。这些条带被怀疑分别是由于非晶相和结晶相的形成。PAs的RPLC馏分采用相同的RPLC体系和排色层析。假定的非晶PAX部分在RPLC中显示出两条条带,表明样品注入后(大部分)形成了非晶相和结晶相。差示扫描量热法(DSC)表明,降低PAX的结晶度降低了后期洗脱部分的相对丰度,接近脂肪族聚酰胺的行为。x射线衍射和静态光散射分析证实了两种固体PA样品的半结晶性。虽然在溶液中观察到小颗粒和较大的聚集体,但这些发现不能与PAs洗脱剖面的差异相关。浊点测量表明PA46和PAX的溶解度几乎与温度无关。引人注目的是,在较低的柱温下(即低于降低的熔点),PAX作为一个单一的PAX峰被洗脱。综上所述,PAX的半结晶度影响其hplc洗脱行为,通过确保晶体相完全溶解,可以从获得的色谱中提取有用的化学信息。
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引用次数: 0
Thermal transformation of CBD, CBDA, and Δ9-THC during e-cigarette vaping: Identification of conversion products by GC–MS 电子烟蒸发过程中CBD、CBDA和Δ9-THC的热转化:转化产物的GC-MS鉴定
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2025-03-25 DOI: 10.1016/j.chroma.2025.465909
Eun Jae Kim , Eunjung Kwon , Seo Jung Oh , Mi Ran Choi , Sang-Rae Lee , Byung Hwa Jung , Wonwoong Lee , Jongki Hong
The use of electronic cigarettes (e-cigarettes) has gained popularity worldwide for reducing the unpleasant odors and flavors of smoking marijuana. However, due to the high vaporization temperature of the heating coil in e-cigarettes, cannabinoids could be converted into secondary cannabinoid products, potentially causing unintended psychological and harmful effects. A lab-built impinger and aerosol collection device was prepared to study the thermal transformation of cannabinoids during e-cigarette vaping, optimizing collection conditions according to variations in coil wattage, cartridge oil, and collection solvents. Thermal conversion of individual cannabidiolic acid (CBDA), cannabidiol (CBD), and Δ9-tetrahydrocannabinol (Δ9-THC) in e-cartridge liquid was performed with increasing coil power from 45 W to 105 W. Collected aerosol solution was derivatized with trimethylsilyl reagents and analyzed by gas chromatography-mass spectrometry (GC-MS) scan mode. Thermal vaping profiles of individual authentic cannabinoids were studied according to the variation of coil power of the e-cigarette. During the CBDA vaping process of the e-cigarette, most of the acidic CBDA was converted to neutral CBD through thermal decarboxylation and further degraded to produce several thermal products. Several interesting psychoactive Δ8-iso and Δ9-THC isomers, and cannabichromene (CBC) and CBD quinone (CBDQ) were observed from the vaping process of CBDA and CBD. In the case of Δ9-THC vaping, psychoactive hexahydrocannabinol (HHC) derivatives and cannabinol (CBN), were produced via thermal reduction and oxidation. These thermal products were identified by comparing retention times and mass spectra of authentic standards and interpreting their mass spectra. The amounts of most thermal products were increased with increasing coil power from 45 W to 105 W. In contrast, potentially harmful CBDQ was found to be highest amount at 45 W and decreased with increasing coil power. From the profile data and identification results, thermal transformation pathways of cannabinoids during the vaping process are proposed. This study will provide important information on the formation mechanism of thermal conversion products and basic guidance for risk assessment of Cannabis oil vaping by e-cigarette.
电子烟(电子烟)的使用在世界范围内受到欢迎,因为它减少了吸食大麻的难闻气味和味道。然而,由于电子烟加热线圈的高蒸发温度,大麻素可能转化为二次大麻素产品,可能造成意想不到的心理和有害影响。为了研究大麻素在电子烟蒸发过程中的热转化,制备了一种撞击气溶胶收集装置,并根据线圈功率、药筒油和收集溶剂的变化对收集条件进行了优化。当线圈功率从45 W增加到105 W时,对电子药筒液中单个大麻二酸(CBDA)、大麻二酚(CBD)和Δ9-tetrahydrocannabinol (Δ9-THC)进行热转化。收集的气溶胶溶液用三甲基硅基试剂衍生化,采用气相色谱-质谱(GC-MS)扫描模式进行分析。根据电子烟线圈功率的变化,研究了个体大麻素的热蒸发特性。在电子烟CBDA蒸发过程中,大部分酸性CBDA通过热脱羧转化为中性CBD,并进一步降解生成多种热产物。从CBDA和CBD的蒸发过程中观察到几个有趣的精神活性Δ8-iso和Δ9-THC异构体,以及大麻色胺(CBC)和CBD醌(CBDQ)。在Δ9-THC雾化的情况下,通过热还原和氧化产生具有精神活性的六氢大麻酚(HHC)衍生物和大麻酚(CBN)。通过比较正品标准品的保留时间和质谱,并对其质谱进行解释,确定了这些热产物。随着线圈功率从45w增加到105w,大多数热产物的数量都有所增加。相反,潜在有害的CBDQ在45 W时最高,并随着线圈功率的增加而降低。根据剖面数据和鉴定结果,提出了大麻素在蒸发过程中的热转化途径。本研究将为大麻油电子烟热转化产物的形成机制提供重要信息,并为大麻油电子烟雾化风险评估提供基础指导。
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Journal of Chromatography A
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