有机质谱学在蛇床子素、厚朴酚、和厚朴酚与鱼腥草素结构确定中的应用

有机质谱学在中药药效物质的结构确定中起到了至关重要的作用. 对中药药效物质质谱的确切解释需要对这些药效物质质谱的关键裂解规律有足够的了解. 应用有机质谱学规律对中药药效物质的结构确定进行了讨论. 这些中药的药效物质包括: 应用超临界二氧化碳从蛇床子中提取的蛇床子素和从厚朴中提取的厚朴酚与和厚朴酚; 应用水蒸汽蒸馏从鱼腥草中提取的鱼腥草素等. 具有较高丰度的质谱关键碎片峰 m/z 229 的出现是蛇床子素质谱的典型特征; 质谱关键碎片峰 m/z 169 的出现是鱼腥草素质谱的典型特征. 而质谱关键碎片峰 m/z 247 是否出现则是区分厚朴酚与和厚朴酚的质谱典型特征. 在此基础上, 尝试构建中药药效物质的有机质谱学平台.     

质谱技术在中药研究中的应用进展

中药是中华传统医学的瑰宝,在我国已广泛应用于疾病预防和治疗中,但其存在化学成分复杂、作用机制不明确等问题,制约了中药现代化及国际化的发展进程。质谱技术具有高灵敏度、高选择性、高稳定性及高通量的特点,特别适合于中药复杂成分及其代谢物的定性定量分析。该文综述了近年来质谱技术在中药成分鉴定及质量控制、中药代谢组学及中药药代动力学研究方面的典型应用,并对存在的问题及改进方法进行了展望。     

有机硅烷KH—550的气相色谱／质谱分析

对硅-550交联剂的组分进行了研究报道。通过GC对样品进行了研究分析,得到了七个分离很好的色谱峰以及样品中各组分的含量,再利用GC/MS联用技术和质谱裂解规律鉴定出样品各组分的分子结构。     

色谱-质谱联用技术在中药代谢组学研究中的应用

代谢组学是研究生物体被扰动后其代谢产物种类、数量及变化规律的科学,研究理念与中医药理论的整体、动态观念非常一致,目前很多工作已将代谢组学应用于中药药效物质基础、作用机制、复方及配伍规律等研究中,有望推动中医药现代化进程。色谱-质谱联用技术是代谢组学的主要分析技术平台,该文综述了近3年来色谱-质谱联用技术在中药代谢组学研究中的应用,重点介绍不同分离技术的特点及最新进展,并讨论了其存在的问题。     

GC/MS分析新疆大麻烟中的大麻类物质

大麻类物质是大麻制品及大麻植物的主要成分。本文采用GC／MS技术分析了新疆大麻烟中的大麻类物质。在莎车的麻烟中检测到16种大麻类组分，如CBD-C3、CBT、Δ^9THCV、CBL、CBD-C4、CBC、CBV、CBD、CBCR、Δ^10sTHC、CBE、Δ^3THC、Δ^9THC、DCBF、CBG和CBN。按照GC／MS鉴定的通用法则，推定了它们的结构。     

有机质谱在元素形态分析中的应用

应用于元素形态分析领域的有机质谱已经受到广泛的关注与重视,在环境监控,生物代谢机理研究和毒理药理分析方面都发挥了越来越重要的作用。本文归纳并评述了以有机质谱为基础的方法学在该领域的研究现状,总结了现有研究的特点,分析并展望了这一方法学的发展趋势。     

几种烟煤CS2萃取物的GC/MS分析

利用气相色谱－质谱联用（GC／MS）技术测定了平朔、大同和神府三种烟煤中CS2萃取物的成分，对其化学组成及结构特征进行了对比研究。结果表明，萃取物主要由脂肪烃、芳烃和含杂原子化合物三类成分组成。芳烃在萃取物整体中占绝对优势，以苯系、萘系、菲系和芘系的烷基取代芳烃为主要成分：脂肪烃除主要成份正构烷烃外，还有少量的类异戊二烯烃和萜烷；含杂原子化合物所占的比例很小，以含氧、氮和硫的化合物为主，在平朔和大同煤的CS2萃取还发现少量邻二氯苯。     

SPME-GC/MS在纺织品挥发性有害物质测定中的应用

建立了纺织品挥发性有害物质的测定方法,试样剪碎后置于体积分数为5%的甲醇的饱和NaCl溶液中,(40±1)℃超声处理10min,而后采用顶空固相微萃取和色质联用技术(HS SPME GC/MS)对目标化合物进行了测定,方法给出了相应的检测限量和适用范围,对几种主要的干洗剂检测限量均低于0.005mg/kg,回收率在90.6%～108.7%之间。     

诊断离子技术在中药质谱分析中的应用

诊断离子是指在质谱碰撞过程中产生的能够代表某一类成分特征裂解行为的碎片离子。以诊断离子为基础,通过手动或自动过滤的方式对复杂中药样品中化学成分的结构类型进行快速判断、辅助化学成分的鉴定,是目前广泛采用的数据后处理方法。相比于质量亏损过滤、中性丢失过滤和分子网络等数据处理技术,诊断离子技术可以鉴定含有未知取代基的成分,且可在一定程度上消除大量杂质和共流出成分产生的干扰,在中药非靶向鉴定中具有独特的优势。该文对近十年来诊断离子技术在黄酮类、生物碱类、苯丙素类、酚酸类、萜类、甾体类等中药不同类型化学成分质谱鉴定中的应用进行总结,并对其后续发展进行了讨论和展望。     

有机质谱人工智能解释——Z值二级族分类及在环境污染物质谱解释中的应用

本文叙述了环境污染物质谱人工智能解释计算机程序“DCP-AIMS-EP”.程序不仅基于质谱规则,而且基于依Z_i/Z_r值二级族分类构成的新型质谱知识库框架.程序在IBM486计算机上调试通过,并经225个环境污染物质谱和81个“非环境污染物”质谱验证评价,输出正确率达99.3%,置信度达95.3%.     

分别用鲜草与干草生产的鱼腥草注射液指纹图谱对比研究

采用GC-MS分析了21个厂家的鱼腥草注射液指纹图谱。结果发现,采用干草和鲜草生产的注射液的指纹图谱之间存在一定的差异。在药材干燥过程中发现,药材挥发油的含量及主要化合物的含量随干燥时间的变化与鱼腥草注射液的研究结果非常一致,结果说明鲜草注射液与干草注射液指纹图谱之间的差别主要是由于原药材的干燥程度所引起。在鱼腥草注射液指纹图谱标准制定中应该考虑到两类药材的影响。     

超声提取-气相色谱法测定鱼腥草中有机氯农药残留

提出了超声提取-气相色谱法测定鱼腥草中有机氯农药残留方法。采用丙酮-石油醚(1+1)混合溶剂超声提取30 min,然后浓硫酸净化、旋转蒸发浓缩,最后用气相色谱-电子捕获检测器(ECD)进行检测。有机氯农药的线性范围在0.001~0.20 mg·L-1之间,方法的检出限(3S/N)为0.023~0.29μg·kg-1,加标回收率在73.0%~115%之间,相对标准偏差(n=5)在1.4%~14%之间。本法与药典法对比,其回收率较高,适用于鱼腥草中有机氯农药的检测。     

Simultaneous determination of eight active components in Houttuynia cordata injection and its quality control in productive process

A simple, reliable and effective gas chromatography coupled with flame ionization detection method was developed for the simultaneous determination of eight components (α‐pinene, β‐pinene, myrcene, limonene, terpinen‐4‐ol, α‐terpineol, bornyl acetate and methyl‐n‐nonylketone) in Chinese medicine Houttuynia cordata and its injection. The chromatographic separation of all eight components, including undecylene as internal standard was performed on a DB‐1 column (30 m×0.25 mm, 0.25 μm). Excellent linear behaviors including herb and injection over the investigated concentration ranges were observed with the values of r² higher than 0.9990 for all analytes. Satisfactory intra‐day and inter‐day precisions were achieved with RSD less than 2% and the average recoveries for all analytes at three different concentrations obtained were in the range of 93.4–104.4%, with RSD ranging from 1.3 to 4.1%. The proposed method was successfully applied in the simultaneous determination of these active components in H. cordata and H. cordata injection (HCI), including the intermediate product of HCI in productive process, from different pharmaceutical factories and different production batches, indicating that the method in this paper was particularly suitable for the routine analysis of HCI and its quality control in productive process.     

Development and Verification of a Precolumn Derivatization LC-MS/MS Method for the Pharmacokinetic Study of Houttuynine of Houttuynia Essential Oil

Houttuynia essential oil (HEO) has excellent antiviral, anti-inflammatory, and other pharmacological effects, but the lack of effective analytical methods to quantify HEO in plasma has hindered its better clinical monitoring. Houttuynine (Hou) is one of the main active ingredients and quality control substances of HEO, so the pharmacokinetic study of HEO could be conducted by determining Hou blood concentration. Hou is active and not stable in plasma, which makes its blood concentration difficult to measure. In this work, a novel liquid chromatography tandem mass spectrometry (LC-MS/MS) method for Hou determination in rat blood was established that involves Hou being derivatized with 2, 4-dinitrophenylhydrazine to form a stable compound to prevent degradation. Herein, p-Tolualdehyde-2,4-dinitrophenylphenylhydrazone was selected as an internal standard substance and the LC-MS/MS method was evaluated for selectivity, precision, accuracy, calibration limit, matrix effect, recovery, and stability. Good linearity (r² = 0.998) was reached in the range of 2–2000 ng/mL, and the lower limit of quantification of Hou was determined to be 2 ng/mL. The mean intra-assay accuracy ranged from 77.7% to 115.6%, whereas the intra-assay precision (relative standard deviation, RSD) was below 11.42%. The matrix effect value for Hou in rat plasma was greater than 75%, and for the internal standard (IS) it was 104.56% ± 3.62%. The extraction recovery of Hou were no less than 90%, and for the IS it was 96.50% ± 4.68%. Our method is sensitive and reliable and has been successfully applied to the pharmacokinetic analysis of Hou in rats given HEO via gavage and injection.     

Software Assisted Multi-Tiered Mass Spectrometry Identification of Compounds in Traditional Chinese Medicine: Dalbergia odorifera as an Example

The complexity of metabolites in traditional Chinese medicine (TCM) hinders the comprehensive profiling and accurate identification of metabolites. In this study, an approach that integrates enhanced column separation, mass spectrometry post-processing and result verification was proposed and applied in the identification of flavonoids in Dalbergia odorifera. Firstly, column chromatography fractionation, followed by liquid chromatography–tandem mass spectrometry was used for systematic separation and detection. Secondly, a three-level data post-processing method was applied to the identification of flavonoids. Finally, fragmentation rules were used to verify the flavonoid compounds. As a result, a total of 197 flavonoids were characterized in D. odorifera, among which seven compounds were unambiguously identified in level 1, 80 compounds were tentatively identified by MS-DIAL and Compound Discoverer in level 2a, 95 compounds were annotated by Compound discoverer and Peogenesis QI in level 2b, and 15 compounds were exclusively annotated by using SIRIUS software in level 3. This study provides an approach for the rapid and efficient identification of the majority of components in herbal medicines.     

气相色谱-质谱联用结合化学计量学方法分析光照对鱼腥草挥发性成分的影响

采用色谱-质谱联用技术结合化学计量学方法对不同光照生长条件的鱼腥草挥发性成分进行分析。水蒸气蒸馏法提取鱼腥草挥发油,气相色谱-质谱进行分析。色谱指纹图谱结合主成分分析与相似度评价以探究不同光照挥发油成分的异同。直观推导式演进特征投影法(Heuristic evolving latent projections,HELP)分辨重叠色谱峰,NIST标准质谱库结合相关文献进行定性,峰面积归一化法定量,t-检验比较不同光照组成分含量间是否有显著性差异。3种光照下的鱼腥草挥发油指纹图谱存在一定的共性和差异,共鉴定出33种化合物,共有化合物26种。随着光照强度的减少,单萜类化合物含量减少,非萜类含量增多,倍半萜类变化不大。癸酰乙醛和甲基正壬酮在全光照组的含量明显低于遮光组的含量。研究结果表明,适度的遮光有利于鱼腥草挥发性有效成分含量的提高,鱼腥草药材挥发性成分种类及含量与生长条件密切相关。     

高分辨质谱技术在中药分析中的研究进展

中药分析涉及中药物质基础研究、药物代谢、中药质量控制等多个领域,是中药现代化研究的基础。随着现代化分析技术的发展,中药分析研究取得了极大的进展。针对中药成分复杂、代谢过程多样、目标物浓度低等难点,高分辨质谱技术凭借精确质量数、高分辨率及高灵敏度的优点在中药分析中具有显著优势。该文对高分辨质谱技术在中药分析中的应用进行了综述,重点介绍了四极杆飞行时间质谱、静电场轨道阱质谱、傅里叶变换离子回旋共振质谱和离子淌度串联质谱等质谱技术的发展,以及高分辨质谱在中药化学成分鉴定、中药化合物代谢研究、中药植物代谢组学研究以及中药有害化学成分检测中的研究进展。同时,对高分辨质谱在中药分析中的应用进行了展望,以期促进中药现代化发展。