Analysis Of Metal Elements In Anti-cancer Traditional Chinese Medicine By Inductively Coupled Plasma Mass Spectrometry

In recent years,the safety of Traditional Chinese Medicine?TCM?has attracted public attention.The contents of heavy metal elements which are harmful to human health is an important factor that limits the sales and exportation of TCMs.China has a large-scale production and exportation of TCMs.The large amount use of pesticide and fertilizer during TCM cultivation,the metal elements in the soil,water and air and the elements during the process of TCMs' decoction would make the content of heavy metals exceede limitation.Therefore,accurate analysis of heavy metals in Chinese Herbal Medicine is of great importance.In this paper,inductively coupled plasma mass spectrometry?ICP-MS?was used to determine beneficial elements and harmful heavy metal elements in some anti-cancer TCMs.The results were accurate and highly credible.Objective:1.A method was established to determine magnesium,manganese,iron,copper and zinc in single drug Scutellaria barbata,Rhizoma imperatae and anti-gastric cancer compound by inductively coupled plasma mass spectrometry?ICP-MS?.The purpose was to establish a scientific and accurate analytical method for the analysis of metal elements in anti-cancer TCMs.2.A method was established to determine lithium,manganese,aluminum,titanium,vanadium,chromium,manganese,iron,cobalt,nickel,cadmium and lead in Citrus reticulata by inductively coupled plasma mass spectrometry?ICP-MS?.The purpose was to establish an accurate analytical method,laying the foundation for the further studies of Citrus reticulata in the clinical application.3.Flow injection-inductively was coupled with inductively coupled plasma mass spectrometry?FI-ICP-MS?to determine cadmium,mercury and lead in Chrysanthemi indici,Rhizoma Coptidis,Panax notoginseng,Clematis chinensis,Glycyrrhiza uralensis,Smilax glabra,Atractylodes macrocephala,and Scutellaria baicalensis.The aim was to reduce the influence of matrix effects on the instrument sensitivity,improve the accuracy of analysis,and provide a basis for the determination of the three heavy metal elements in TCMs.4.Dynamic reaction cell-inductively coupled plasma mass spectrometry?DRC-ICP-MS?was established to analyze heavy metal elements chromium,arsenic,cadmium and lead in Jerusalem artichoke.The aim was to reduce the interference of polyatomic ions in ICP-MS,and improve the accuracy.Methods:1.The samples were pretreated by HNO₃-HCl-HClO4-HF acid digestion system.24 Mg,55Mn,57 Fe,65Cu and 66 Zn were used as detection isotopes,45 Sc as the internal standard isotope to reduce the matrix interferences and instrument drift.2.The sample were pretrated by HNO₃-HCl-HCl O4-HF acid digestion system.7Li,24 Mg,27Al,47 Ti,51V,52 Cr,55Mn,57 Fe,59Co,60 Ni,111Cd and 208 Pb were used as detection isotopes,45 Sc,115In and 209 Bi as the internal standard isotope to reduce the matrix interferences and instrument drift.3.The samples were pretreated by HNO₃-HCl-H₂O₂-HF acid digestion system.The experiment parameters for FI-ICP-MS were optimized.111 Cd,202Hg and 208 Pb were used as the detection isotopes and 115 In,209Bi as internal standard isotopes.4.The samples were pretreated by HNO₃-HCl-H₂O₂-HF acid digestion system.Cr and As were determined by DRC-ICP-MS,and Cd and Pb were determined by standard ICP-MS.As the reaction gas,CH4 was poured into the dynamic reaction cell to eliminate the interferences.52 Cr,75As,111 Cd and 208 Pb were used as the detection isotopes,and 115 In and 209 Bi as internal standard to correct the matrix interferences and instrument drift.Results:1.The content of each element in single-agent and compound was determined by ICP-MS.The differences of elements content among the single-agent and compound,raw materials,decoction,residue and soluble were analyzed.And the ratio of different elements in different dosage forms were studied.With the optimized experimental conditions,the detection limits of instruments and methods were 0.004-0.150 ng/mL and 0.009-0.312 ?g/g,with the relative standard deviation in the range of 1.2-1.6%.The contents of the five elements in GBW 07603 national standard shrub leaves material were analyzed with the established method.The results were in good agreements with the standard values.2.The content of each elements in Citrus reticulata was determined by ICP-MS.With the optimized experimental conditions,the detection limits of instruments and methods were0.001-0.120 ng/mL and 0.0008-0.090 ?g/g,with the relative standard deviation in the range of1.27-2.59%.The contents of the twelve elements in GBW 07602 national standard shrub leaves material were analyzed with the established method.The results were in good agreements with the standard values.3.The elements of cadmium,mercury and lead in eight kinds of anti-cancer TCMs were determined by FI-ICP-MS method.The results showed that the analytical performance of ICP-MS was improved remarkably.With the optimized experimental conditions,the detection limits of instruments and methods were 0.006-0.010 ng/mL and 0.0016-0.0053 ?g/g with the relative standard deviation in the range of 1.8-2.9%.The contents of Cd,Hg and Pb in 8 kinds of Chinese Herbal Medicine were in the range of 0.004-1.10 ?g/g,0.012-0.11 ?g/g and0.90-3.30 ?g/g,respectively.Except Cd in Scutellaria barbata and Rhizoma Coptidis,all the other elements meet the requirements of "Medicinal Plants and Preparations Import and Export of Green Industry Standards".4.Chromium and arsenic in Jerusalem artichoke were determined by DRC-ICP-MS.With the optimized experimental conditions,the detection limits of instruments and methods are 0.007-0.019 ng/mL,0.0042-0.0187 ?g/g,with the relative standard deviation was in the range of 2.1-3.7%.The recovery of the four elements was in the range of 89-110% by adding a certain amount of standard solution to the Jerusalem artichoke samples.The content of the four heavy metal elements in GBW 07604 national standard poplar leaves material were analyzed with the established method.The results were in good agreements with the standard values.Conclutions:ICP-MS could be used for the determination of metal elements in anti-cancer traditional Chinese medicine.Flow injection and dynamic reaction cell coupled to inductively coupled plasma mass spectrometry,played an important role in decreasing the matrix effects and instrument drift to a certain extent.Its were goodful for the instrument sensitivity and the accuracy of the results.The flow injection also decreased the influence of the salt with high concentration on the instrument at lower dilution factor,effectively reducing the cleaning times for sampling cone and skimmer cone.As a result,the life time of instrument was improved and the costs decreased.ICP-MS could be widely used in the analysis of heavymetal elements in anti-cancer TCMs,which is of large merits for the Traditional Chinese Medicines.