高效液相色谱-电感耦合等离子体质谱法测定卡铂和氯铂酸的含量

HPLC-ICP-MS Determination of Carboplatin and Chloroplatinic Acid

称取样品0.1000g,用水溶解后,根据被测物浓度不同加水定量稀释至合适浓度。在高效液相色谱分离中,选择PRP-X100为分离柱,由于固定相上键合有二乙烯基苯/三乙胺聚合物,对氯铂酸和卡铂的分离效果较好。用60mmol·L^-1硝酸铵溶液(预先用稀氨水或稀硝酸调节其酸度至pH5.5)为流动相,按等梯度程序进行洗脱。分离后的洗脱液按质谱仪器的工作条件进行测定。结果表明:氯铂酸和卡铂的线性范围依次为1.00~100μg·L^-1和500.0~1000μg·L^-1;检出限(3S/N)依次为0.1,0.01μg·L^-1。按标准加入法在实际样品基础上进行回收试验,测得氯铂酸的回收率为90.0%~98.8%,卡铂的回收率为98.5%~99.2%,两者测定值的相对标准偏差(n=6)依次为2.7%~3.4%和2.1%~2.8%。应用上述方法进行实际样品分析时还发现,当卡铂的检测量为1mg·L^-1时,未检测到氯铂酸,故该方法无需富集就能达到痕量铂的测定。

A portion of the sample (0.100 0 g) was dissolved in water and diluted to an appropriate volume according to the concentration of the analyte in sample. The ion-exchange column PRP-X100 was chosen as separation column, which was proved to have high efficiency in separation of chloroplatinic acid and carboplatin, due to bonding of polymer of divinylbenzene/triethylamine on the stationary phase. 60 mmol ·L^-1 NH4NO3 solution (pre-adjusted its acidity to pH 5.5 with dil. NH3·H2O or dil. HNO3) was used as mobile phase in the gradient elution program. Analyte in respective eluate was then determined by ICP-MS according to the prescribed procedure. As shown by the results, linearity ranges for chloroplatinic acid and carboplatin were found between 1.00 and 100 μg·L^-1 and between 500.0 and 1 000 μg·L^-1 with detection limits (3S/N) of 0.1 μg·L^-1 and 0.01 μg·L^-1 respectively. Testes for recovery were performed by standard addition method using a substantial sample as matrix, giving values of recovery of 90.0%.98.8% for chloroplatinic acid and of 98.5%-99.2% for carboplatin. Values of RSDs (n = 6) found was 2.7%-3.4 % for chloroplatinic acid and 2.1%.2.8% for carbonplatin. It was found that in the analysis of a substantial sample by the proposed method, as the concentration of carboplatin found was 1mg·L^-1 , H2[PtCl6 ] was not inspected in the same sample. Hence, inspection of traces of platinum(Ⅳ) was attained directly in the sample solution without any enrichment manipulation.