| Objective The aim of this study was to set up a rapid quantitative method for the chemicals illegally added in some traditional Chinese medicine products using rapid high resolution liquid chromatography-triple quadrupole mass spectrometry system(RRLC-QQQ-MS).Methods 1.The chromatographic separation of ephedrine hydrochloride,sibutramine hydrochloride and furosemide was performed on Agilent SB-C18 column(2.1mm×50mm,5μm)with acetonitrile(containing 0.1%formic acid)and 0.1%formic acid solution as mobile phase by gradient elution at flow rate of 0.2mL·min-1;The Mass Spectrometry(MS)conditions:The positive,negative and multiple reaction monitoring(MRM)mode were used to detect contents of chemicals illegally added in seven kinds of diet pills,with electrospray ionization source(ESI).2.The detection for five kinds of glucocorticoids(prednisone acetate;hydrocortisone acetate;dexamethasone acetate;budesonide;methylprednisolone)was performed on Agilent Poroshell 120 EC-C18 column(3mm X 50mm,2.7μm),with gradient elution of acetonitrile(containing 0.1%formic acid)and 0.1%formic acid solution at flow rate of 0.3mL·min-1.The MS conditions:The positive and MRM mode were used to detect prohibited substances in snake wines quantitatively and quantitatively.3.The determination of seven kinds of glucocorticoids(prednisone acetate;hydrocortisone acetate;dexamethasone acetate;methylprednisolone;triamcinolone acetate;fluoxyprednisolone and prednisolone)was performed on Agilent Poroshell 120 EC-C1g(3mmx 100mm,2.7μm)at the column temperature of 35℃.Acetonitrile(containing 0.1%formic acid)and 0.1%formic acid solution as mobile phase by gradient elution at flow rate of 0.3mL·min-1;The MS conditions:The positive and MRM mode was used to detect glucocorticoids in four categories of twenty kinds of cosmetics.Results 1.A quantitative analysis method of sibutramine hydrochloride,furosemide and ephedrine hydrochloride based on RRLC-QQQ-MS was established.We selected the m/z for ephedrine hydrochloride was 166.1-148.1,sibutramine hydrochloride was 280.1-124.9 and furosemide was 329.0-284.9 to detect sibutramine hydrochloride,furosemide and ephedrine hydrochloride in seven kinds of diet pills,which were bought from the market.Sibutramine hydrochloride and ephedrine hydrochloride were detected in all seven diet pills.The concentration range of two substances were 0.39～4.29μg·g-1 and 1.63～8984.18μg·g-1 respectively.One drug had furosemide,with the content was 8.71μg·g-1.2.To establish a mass spectrometric method for the analysis of prednisone acetate,hydrocortisone acetate,dexamethasone acetate,budesonide and methylprednisolone based on RRLC-QQQ-MS.We used nitrogen to dry samples and re-dissolved them in methanol,and the m/z for prednisone acetate was 401.2-383.1,hydrocortisone acetate was 405.3-327.2,dexamethasone acetate was 435.3-309.2,budesonide was 431.2-413.1 and methylprednisolone was 375.2-357.3 for detection respectively.This method made it possible to achieve rapid quantification detection of prednisone acetate,hydrocortisone acetate,dexamethasone acetate,budesonide and methylprednisolone in ten kinds of snake wines.The results showed that prohibited components were detected in eight samples.The contents of prednisone acetate,hydrocortisone acetate and methylprednisolone were 1.94～323.Oμg·mL-1,7.23～454.18μg·mL-1 and 2.45～31.19μg·mL-1 respectively,and the content of dexamethasone acetate was 0.51～6.37μg·mL-1,budesonide was found in one sample with content of 0.93μg·mL-1.3.The quantitative method for prednisone acetate,hydrocortisone acetate,dexamethasone acetate,methylprednisolone acetate,triamcinolone acetate,fluoxyprednisolone and prodnisolone based on RRLC-QQQ-MS was set in consideration of matrix effect,according to the different types of cosmetics(toner,lotion,cream and powder).Samples were pretreated by vacuum freeze-drying and re-dissolved in methanol to extract the target components effectively.And the m/z of prednisone acetate was 401.2-383.1,hydrocortisone acetate was 405.3-327.2,dexamethasone acetate was 435.3-309.2,methylprednisolone was 375.2-357.1,triamcinolone acetonide was 395.2-357.1,triamcinolone acetonide acetate was 477.1-439.2 and prednisolone was 361.2-343.4.This rapid quantitative method was carried out to detect glucocorticoids in twenty kinds of cosmetics.Eighteen samples were detected with prohibited components,and a variety of prohibited ingredients were detected in samples,moreover the contents of prednisone acetate,hydrocortisone acetate,methylprednisolone,prednisolone and triamcinolone acetonide were 4.37～40.11μg·g-3.18～83.88μg·g-1,1.51-765.44μg·g-1,1.66～8.77μg·g-1 and 2.45～31.19μg·g-1 respectively,and the contents of dexamethasone acetate and triamcinolone acetonide were 1.64～16.77μg·g-1 and 1.26～21.20μg·g-1.In addition,we also analyzed the cracking mode of seven glucocorticoids,according to the secondary mass spectrum.Conclusion 1.By optimizing the sample pretreatment conditions and chromatographic conditions,the separation of the standard was significantly increased.The qualitative analysis was based on the retention time and the parent ion,and the quantitative analysis was carried out by the characteristic smaller ion.This method improved the specificity and accuracy of the substance significantly,and it could provide a scientific basis for the market supervision department.2.The method established was fast,convenient,high accurate,low detection limit and widely used,and it was suitable for rapid detection of chemicals in some traditional Chinese medicine products quantitatively and qualitatively.3.Chemicals were found in many batches of products,so we could infer that chemicals illegally added were commonly existed in current part of the traditional Chinese medicine products.Compared to the past,the illegal addition has been single to more species,large to less dose,this phenomenon should cause the attention of relevant market supervision departments and consumers. |
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