Study On Rapid Analysis Of Corni Fructus By Ambient Mass Spectrometry

As the treasure of Chinese nation’s cultural heritage,traditional Chinese medicines(TCMs) integrate practical experience,clinical efficacy and an integral theoretical system,and become more and more popular around the world.However,a number of counterfeits of TCMs are illegally sold in herb markets.Therefore,quality evaluation of the active components and species distinction is vital for ensuring the efficiency and safety of TCMs.Following the introduction and application,ambient ionization mass spectrometric(AMS) methods have seen rapid development because of their ultra-fast nature and high structural selectivity.More than thirty of ambient ionisation modes have been developed and applied in different fields,such as environmental monitoring,food inspection,and drug metabolism.In this paper,using the advantages of ambient mass spectrometry,the quality control and species distinction analysis of Corni fructus was carried out,including its qualitative,quantitative and biological activity analysis.In chapter one,the research progress of Corni fructus is reviewed,including its component,pharmacological effect,species distinction and quality control.The research situation of ambient mass spectrometry is introduced,especially the principle and application of paper spray mass spectrometry.The detection of the activity of acetylcholinesterase and its activity inhibition by Corni fructus is briefly described.Chapter two is a foundation chapter.Using high performance liquid chromatography(HPLC) method for the fingerprint analysis of Corni fructus and chemometrics for species distinction,the material basis was established;using liquid chromatography-mass spectrometry(HPLC) for the analysis of fourteen chemical constituents of Corni fructus and electrospray ionization(ESI)-MS for mass spectra,the theoretical basis was established.In chapter three,the mass spectra of Corni fructus was studied using paper spray mass spectrometry(PS-MS).Quality control and species distinction of Corni fructus was successfully achieved by ambient mass spectrometry.Using reference material of Corni fructus,the PS-MS operating conditions in the positive and negative ion modes were optimized,and the PS-MS chemical profile of Corni fructus was constructed.Based on ingredients analysis of Corni fructus in the previous chapter,the active constituents in the PS-MS chemical profile of Corni fructus were identified.Mass spectra profiles of 23 batches of Corni fructus and 10 batches of Crataegi fructus were distinguished by chemometrics,and both the positive and negative ion modes obtained good results.Using genipin as internal standard,semi-quantitative analysis of loganin and morroniside was determined.In chapter four,the rapid detection method of acetylcholinesterase by PS-MS was established for screening the bioactivity of Corni fructus.The dilution ratio,buffer solution,paper substrate,cone voltage and spray voltage was optimized.Using HPLC-MS as a benchmark method,the PS-MS method was validated.The linearity of both methods were 0.9999.The precision was less than 4% and recoveries were between 99.98%-100.38%.The method was successfully applied to the determination of acetylcholinesterase activity in human plasma and the rapid screening of bioactivity of Corni fructus.With the advantages of high specificity,low matrix effect,ultra-speed and high throughput,the PS-MS method can be used as a reference method for the rapid monitoring of other enzymes by ambient mass spectrometry.