Tang Xinxing, Gu Yuan, Cai Shang, Xu Meiling, Wang Chang
School of Radiation Medicine and Protection, Medical College of Soochow University, Suzhou 215123, China.
Se Pu. 2012 Jul;30(7):696-704. doi: 10.3724/sp.j.1123.2012.01037.
A robust and sensitive high performance liquid chromatography-electrospray tandem mass spectrometry (HPLC-ESI MS/MS) method was developed with solid phase extraction (SPE) sample preparation. It was optimized for the analysis of various amino acids in rat plasma. Silica-based strong cationic exchange SPE cartridges were used to extract amino acids and minimize the ion-suppression effect. The SPE cleanup protocol was optimized and it was found that the sample loading pH was very critical for the recovery and reproducibility. When the plasma sample was mixed with 0.1 mol/L acetic acid (pH 2.8) and loaded on SPE cartridge, the recoveries and repeatability for most of the amino acids were satisfactory. The method was fully validated. The analytical characteristics such as total recoveries (33.6%-107.7%, except lysine and ornithine), linearities (r > 0.99 except arginine), intra-day precisions (relative standard deviation (RSD) < 9.0%) and inter-day precisions (RSD < 19.1%) were satisfactory for most of the amino acids. Furthermore, the method was successfully applied to study the ionizing radiation exposure induced changes in amino acid concentration of plasma samples from rats. Experimental results showed that the ionization radiation could lead to metabolism disorder of plasma amino acids, and the degree of disorder was related with the degree of injury by the ionization radiation injury. Some of the amino acids may be potential biomarkers of ionization radiation injury. These results provide experimental basis for screening of new markers of the acute radiation damage.
建立了一种采用固相萃取(SPE)样品前处理的稳健且灵敏的高效液相色谱 - 电喷雾串联质谱(HPLC - ESI MS/MS)方法。该方法针对大鼠血浆中多种氨基酸的分析进行了优化。采用基于硅胶的强阳离子交换SPE柱来提取氨基酸并最小化离子抑制效应。对SPE净化方案进行了优化,发现样品上样pH对回收率和重现性至关重要。当血浆样品与0.1 mol/L乙酸(pH 2.8)混合并加载到SPE柱上时,大多数氨基酸的回收率和重复性令人满意。该方法经过了全面验证。大多数氨基酸的分析特性,如总回收率(赖氨酸和鸟氨酸除外,为33.6% - 107.7%)、线性(精氨酸除外,r > 0.99)、日内精密度(相对标准偏差(RSD)< 9.0%)和日间精密度(RSD < 19.1%)均令人满意。此外,该方法成功应用于研究电离辐射暴露诱导的大鼠血浆样品中氨基酸浓度变化。实验结果表明,电离辐射可导致血浆氨基酸代谢紊乱,且紊乱程度与电离辐射损伤程度相关。一些氨基酸可能是电离辐射损伤的潜在生物标志物。这些结果为筛选急性辐射损伤新标志物提供了实验依据。