液相色谱-电感耦合等离子质谱和电喷雾电离质谱研究乙二胺二氯合钯与鸟嘌呤脱氧核糖核苷酸反应产物  

Analysis of Reaction Products of( Ethylenediamine) palladium(Ⅱ) Chloride and 5'-Deoxyguanylic Acid in Aqueous Solution by Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry and Electrospray Ionization Mass Spectrometry

作　　者：刘德晔[1] 朱峰[1] 马永建[1] 吉文亮[1] 刘华良[1] 

机构地区：[1]江苏省疾病预防控制中心,南京210009

出　　处：《分析化学》2015年第2期193-198,共6页Chinese Journal of Analytical Chemistry

基　　金：江苏省预防医学科研课题(No.Y20130053);江苏省医学领军人才项目(No.LJ201130);江苏省"十二.五"科教兴卫工程(No.ZX201109)项目资助

摘　　要：建立了基于HPLC-ICP-MS分离乙二胺二氯合钯[Pd(en)Cl2]与鸟嘌呤脱氧核糖核苷酸5'-d GMP反应产物的方法。方法得到两种能够随色谱流出的产物,产物在25 mmol/L磷酸盐缓冲液(pH 8.0)作为流动相时,得到的分离峰型良好。主产物保留时间为2.8 min,另一产物保留时间为3.2 min。主产物经富集后由ESI-MS(MS/MS)鉴定得到m/z为510,511,512,514和516的[M+1]+分子离子峰且丰度比与Pd同位素元素一致,再通过碎片推断结构为[Pd(en)(N1-5'-d GMP)],另一种产物经HPLC-DAD解析发现紫外吸收光谱与[Pd(en)(N1-5'-d GMP)]完全相同,HPLC-ICP-MS发现产物含Pd量也与[Pd(en)(N1-5'-d GMP)]相同,结合文献推断另一产物为[Pd(en)(N1-5'-d GMP)]的多聚物。研究表明,[Pd(en)(N1-5'-d GMP)]易在酸性条件下生成,其多聚物易在碱性条件下生成,在反应体系pH=6.0时,[Pd(en)(N1-5'-d GMP)]在12 h内生成且稳定存在。HPLC-ICP-MS图谱显示随着反应pH的增加两种产物的总量逐步减少。A method based on HPLC-ICP-MS was established to separate the reaction products of （ ethylenediamine） palladium（Ⅱ） chloride（[Pd （ en ） Cl2]）and 5’-deoxyguanylic acid （ 5’-dGMP）. Two reaction products were detected at pH 8. 0 with 25 mmol/L phosphate buffer solution as chromatography eluent. One was the main product with HPLC retention time of 2. 8 min, the other product’s retention time was 3.2 min. According to ESI-MS（MS/MS） study, m/z=510, 511, 512, 514, 516[M＋1]＋ parent ions （ abundances same to palladium isotopes） were detected. Further analysis showed that the main product was[Pd（ en） （ N1-5’-dGMP） ]. However the other product was hardly to be detected by ESI-MS. By using HPLC-DAD and HPLC-ICP-MS, we found that the two reaction products had the same UV absorption spectra and palladium percentage content. Combined with other groups’research, the other reaction product was deduced as dimmer, trimer or tetramer form of[Pd（ en） （ N1-5’-dGMP） ]. Further study revealed that[Pd（ en） （ N1-5’-dGMP） ] was easily formed in acid solution while its polymer form was generated in alkaline solution. At pH 6. 0, [Pd（en）（N1-5’-dGMP）] was formed within 12 hours with good stability. Research also revealed that the total amount of two reaction products declined as reaction pH climbed.

关 键 词：电感耦合等离子体质谱 液相色谱 鸟嘌呤脱氧核糖核苷酸 钯化合物 

分 类 号：O621.25[理学—有机化学] O657.63[理学—化学]