Synthesis Of Three Deuterium Internal Standards And Their Application In Ambient Mass Spectrometry

Paper Spray Mass Spectrometry(PS-MS)was developed in 2009 as a new type of ambient MS.It can directly ionize compounds in the open atmospheric pressure environment without pretreatment or with few sample pretreatment steps.PS-MS has several advantages,such as simple sample preparation,rapid and high-throughput analysis.However,due to the influence of ion suppression for mass spectrometry,applications of PS-MS have been limited to qualitative and semi-quantitative analysis.Researchers have found that less ion suppression for mass spectrometry can be obtained by using isotope internal standards(ISs),and quantitative analysis can be achieved by PS-MS.In this study,three deuterated ISs were synthesized,and used for quantitative analysis of complex samples by PS-MS.In this work,three tasks were carried out,and the results are as follows:1.A paper spray mass spectrometry(PS-MS)method has been developed for the rapid quantification of benzoic acid(BA)and vitamin C(VC)in beverages.Using BA-ds as an IS to analyze BA and VC,the linearity of calibration curves was 0.9996 for BA and 0.9973 for VC.The limits of detection(LODs)and limits of quantitation(LOQs)were 0.1 ?g/mL and 0.3 ?g/mL for BA,0.3 ?g/mL and 1 ?g/mL for VC,respectively.The recovery ranged from 91.1-106.7%for BA,92.6-108.2%for VC.Compared with HPLC,there is no substantial difference in the quantification of BA and VC in samples,and the run time is far less than that of the HPLC method.The results indicated that PS-MS with deuterated ISs is a rapid and accurate method for the quantification of BA and VC.2.A PS-MS method has been developed for the rapid quantification of acetaminophen in tablets and blood.Using acetaminophen-ds as an IS to analyze acetaminophen,the linearity of calibration curves was 0.9997 for tablets and 0.9996 for blood.The LODs and LOQs were 0.1 ?g/mL and 0.3 ?g/mL for tablets,0.8 ?g/mL and 2.5 ?g/mL for blood,respectively.The recovery ranged from 96.0-100.8%for tablets,103.3-105.8%for blood.Compared with HPLC,there is no substantial difference in the quantification of acetaminophen in samples,and the run time is far less than that of the HPLC method.The results proved that PS-MS with deuterated ISs can be well applied to high-throughput screening of acetaminophen.3.A PS-MS method has been developed for the rapid quantification of Malachite Green(MG)in fish pond water.Using MG?d4 as an IS to analyze MG,the calibration curves ranged from 0.1-100 ?g/mL,and the linearity was 0.9996.The LODs and LOQs were 0.03 ?g/mL and 0.1?g/mL.The recovery ranged from 98.8-106.6%,and the intra-and inter-day precisions were 3.24%and 6.56%.Compared with LC-MS,there is no substantial difference in the quantification of MG in fish pond water,and the run time is far less than that of the LC-MS method.Based on deuterated ISs,PS-MS can quantitatively analyze the content of MG in fish pond water,with many advantages of few sample preparation,rapid and high-through features.In this study,Three deuterated ISs have been synthesized and applied to PS-MS.It confirmed that PS-MS cooperating with deuterated ISs has rapid and accurate advantage in complex sample analysis.