Recent DART Publications
Direct analysis in real time mass spectrometry and multivariate data analysis: A novel approach to rapid identification of analytical markers for quality control of traditional Chinese medicine preparation
Shanshan Zenga, Lu Wanga, Teng Chena, Yuefei Wangb, Huanbiao Moc, Haibin Qua,
Pharmaceutical Informatics Institute, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, China, State Key Laboratory of Modern Chinese Medicine, Tianjin University of Traditional Chinese Medicine, Tianjin 300193, China, Department of Nutrition and Food Sciences, Texas Woman's University, Denton, TX 76204-5888, USA
The paper presents a novel strategy to identify analytical markers of traditional Chinese medicine preparation (TCMP) rapidly via direct analysis in real time mass spectrometry (DART-MS). A commonly used TCMP, Danshen injection, was employed as a model. The optimal analysis conditions were achieved by measuring the contribution of various experimental parameters to the mass spectra. Salvianolic acids and saccharides were simultaneously determined within a single 1-min DART-MS run. Furthermore, spectra of Danshen injections supplied by five manufacturers were processed with principal component analysis (PCA). Obvious clustering was observed in the PCA score plot, and candidate markers were recognized from the contribution plots of PCA. The suitability of potential markers was then confirmed by contrasting with the results of traditional analysis methods. Using this strategy, fructose, glucose, sucrose, protocatechuic aldehyde and salvianolic acid A were rapidly identified as the markers of Danshen injections. The combination of DART-MS with PCA provides a reliable approach to the identification of analytical markers for quality control of TCMP.
The evaluation and implementation of direct analysis in real time quadrupole time-of-flight tandem mass spectrometry for characterization and quantification of geniposide in Re Du Ning Injections
Yan-Jing Li, Zhen-Zhong Wang, Yu-An Bi, Gang Ding, Long-Sheng Sheng, Jian-Ping Qin, Wei Xiao, Jia-Chun Li, Yong-Xiang Wang, Xue Wang. State Key Lab of New-tech for Chinese Medicine Pharmaceutical Processes, Lianyungang, ChinaJiangsu Kanion Pharmaceutical Co. Ltd., Nanjing, China, State Key Laboratory of Natural Medicines (China Pharmaceutical University), Nanjing, China
RATIONALE
The Direct Analysis in Real Time (DART) ionization source coupled with a quadrupole time-of-flight tandem mass spectrometry (Q-TOF MS/MS) system has the capability to desorb analytes directly from samples from complex Chinese herbal preparations without sample cleanup or chromatographic separation.
METHODS
In this work, a method based on DART/Q-TOF MS/MS has been developed for rapid determination of geniposide present in 'Re Du Ning Injections', a Chinese herbal preparation. The method has been evaluated for both qualitative and quantitative analysis of geniposide in Re Du Ning Injections.
RESULTS
Variables including polarity for ion detection, DART gas heater temperature, matrix effect and sample presentation speed were investigated. The quantitative method was validated with respect to linearity, sensitivity, repeatability, precision and accuracy by using both internal and external standards. A comparison of the results obtained using the DART-based method was made with those obtained using a conventional High-Performance Liquid Chromatography/Diode-Array Detector (HPLC/DAD) by analyzing geniposide in four batches of Re Du Ning Injections.
CONCLUSIONS
The DART/Q-TOF MS/MS-based method provides a rapid, efficient and powerful method to analyze compounds from complex Traditional Chinese Medicines with limited sample preparation thus reducing time and complexity of quality control for those materials.
Rapid control of Chinese star anise fruits and teas for neurotoxic anisatin by Direct Analysis in Real Time (DART) high resolution mass spectrometry
Yao Shena, Teris A. van Beeka, Frank W. Claassena, Han Zuilhofa, Bo Chenb, Michel W.F. Nielena,
Laboratory of Organic Chemistry, Wageningen University, Dreijenplein 8, 6703 HB Wageningen, The Netherlands, Key Laboratory of Chemical Biology & Traditional Chinese Medicine Research, Ministry of Education, Hunan Normal University, Changsha 410081, China, RIKILT Institute of Food Safety, P.O. Box 230, 6700 AE Wageningen, The Netherlands
After ingestion, products containing Chinese star anise (Illicium verum) contaminated or adulterated with Japanese star anise (Illicium anisatum) or other Illicium species, can cause epilepsy, hallucinations, and nausea due to the rare neurotoxic sesquiterpene dilactone anisatin that is present in Japanese star anise. Thus a rapid, simple and unambiguous method for distinguishing between the morphologically similar Chinese star anise and toxic Japanese star anise is important for food safety issues. Direct Analysis in Real Time (DART) ambient ionisation coupled with orbitrap high resolution mass spectrometry allowed the recording of mass spectra of anisatin in solid star anise fruits in seconds without any prior sample pretreatment. Spectra could be obtained in both positive ([M+NH4]+ at m/z 346.1496, C15H24NO8) and negative mode ([M−H]− at m/z 327.1074, C15H19O8) and gave the same outcome provided a mass resolution of at least 27,000 is available. The anisatin signal was typically >1000 times larger in Japanese star anise than in Chinese star anise thus allowing an unequivocal qualitative determination. Herbal teas containing star anise fragments too small to be visually recognised, could be analysed by preparing a tea in 6 min and subsequently sampling ∼2 μL of tea on a glass rod. None of the 8 investigated retail teas contained significant quantities of anisatin. Spiking a complex herbal tea containing Chinese star anise with an equally concentrated tea prepared from Japanese star anise provided a linear calibration curve (R2 ≥ 0.995) after normalising on a native constituent of Chinese star anise (standard addition method). This showed that adulteration down to 1% (w/w) is still measurable. Compared with existing PCR, TLC, GC-MS and HPLC-ESI-MS/MS procedures, the proposed DART-HRMS procedure is faster and simpler and moreover measures the actual biotoxin.
|
