Department of Analytical Chemistry, Nutrition and Food Science, University of Alicante, P.O. Box 99, 03080 Alicante, Spain.
J Chromatogr A. 2012 Nov 2;1262:70-6. doi: 10.1016/j.chroma.2012.08.084. Epub 2012 Sep 5.
The potential of high temperature liquid chromatography (HTLC) with detection by inductively coupled plasma mass spectrometry (ICP-MS) for the determination of arsenosugars in marine organisms was examined for the first time. The retention behavior of four naturally occurring dimethylarsinoylribosides was studied on a graphite column using plain water as mobile phase. An aqueous solution of pH 8, ionic strength 13.8mM and containing 2% (v/v) of methanol, along with a column temperature of 120°C and a liquid flow rate of 1.0 mL/min, were selected as the optimal conditions, as they allowed the separation of the four arsenosugars in less than 18 min, without any interferences due to other common arsenic species (arsenite, arsenate, dimethylarsinate, methylarsonate and arsenobetaine). The run time could be further decreased to 12 min by working at 1.5 mL/min, although with a 3-4 times loss of sensitivity. The procedural limits of detection were 0.03-0.04 μg As/g dry mass, and the precision of the procedure ranged from 4% for arsenosugar glycerol to 18% for arsenosugar sulfate (RSD%, n=5). The developed method was applied to a number of representative biological samples, such as algae and crustaceans, providing results consistent with previous studies. In the red algae samples, the most of extracted arsenic was as arsenosugars (81-97%), mainly arsenosugar phosphate (56-94%). On the other hand, lower concentrations of these compounds were found in the crustacean, accounting for about 15% of the extracted arsenic.
首次考察了高温液相色谱（HTLC）与电感耦合等离子体质谱（ICP-MS）联用检测法在海洋生物中检测砷糖的潜力。研究了四种天然二甲基砷酰基核糖苷在石墨柱上的保留行为，以纯水为流动相。选择 pH 值为 8、离子强度为 13.8mM 并含有 2%（v/v）甲醇的水溶液，柱温为 120°C，液体流速为 1.0mL/min 作为最佳条件，因为这些条件可以在不到 18 分钟内分离出四种砷糖，而不会受到其他常见砷物种（亚砷酸盐、砷酸盐、二甲基砷酸酯、甲基砷酸酯和砷甜菜碱）的干扰。通过以 1.5mL/min 的速度运行，可以进一步将运行时间缩短至 12 分钟，但灵敏度会降低 3-4 倍。该方法的检出限为 0.03-0.04μg As/g 干质量，该方法的精密度范围为 0.04%（砷糖甘油）至 18%（砷糖硫酸盐）（RSD%，n=5）。该方法应用于多种代表性生物样品，如藻类和甲壳类动物，结果与先前的研究一致。在红藻样品中，提取的砷大部分以砷糖的形式存在（81-97%），主要是砷糖磷酸盐（56-94%）。另一方面，在甲壳类动物中这些化合物的浓度较低，占提取砷的约 15%。
