雄黄及含雄黄复方中砷含量、形态和晶形分析

Arsenic Content,Species and Crystal Construct Analysis of Realgar and Prescriptions Containing Realgar

目的对雄黄及含雄黄复方制剂中的砷含量、砷形态和雄黄晶形进行分析。方法采用微波消解-原子荧光法测定雄黄和复方制剂中的总砷含量,人工胃液提取-原子荧光法测定可溶性砷,离子树脂交换分离-原子荧光法测定可溶性三价砷(AsⅢ)和五价砷(AsⅤ),X衍射荧光法对雄黄粉末进行物相(晶形)分析,X荧光光谱法进行雄黄粉末的全元素分析。结果受试雄黄含硫化砷97.3%,主成分是β-雄黄(As4S4)和α-雄黄(AsS)的混合物,同时含有少量二硫化二砷(As2S2)和雌黄(As2S3)。As/S(摩尔数之比)为1.00001。还含有少量A l、S i、K、Ca、Ti、Fe、Sb、N i、Cu、W等杂质。在雄黄及含雄黄复方制剂的人工胃液提取液中均检出了可溶性砷、AsⅢ和AsⅤ;且不同来源的雄黄,可溶性砷以及两种价态的砷的比例也不同。雄黄中可溶性砷百分含量为0.62%,其中AsⅢ和AsⅤ比例为2.30∶1。结论雄黄及含雄黄复方中混杂存在三价和五价无机砷。有必要加强对雄黄药材的质量监控。

Objectlve To determine arsenic contents and species in Realgar and prescriptions containing Realgar, and analyze crystal construct of Realgar. Methods Total arsenic in medicines was determined by fluorescence spectrometry （AFS） with microwave digestion. Soluble arsenic was determined by AFS after artificial gastric juice extract treatment. Two soluble inorganic arsenic species（ As^Ⅱ and As^Ⅴ ） were separated by ion-exchange resin and tested by AFS. Crystal construct of Realgar was tested by X-ray diffraction, and element composition was tested by X-fluorescence spectrometry. Results The amount of arsenic sulfide in Realgar was 97.3%. The experiments indicated that Realgar was a mixture of β-Realgar（ As4S4 ）and α-Realgar（ AsS）, also containing a little As2S2 and As2S3. The mole ratio of arsenic and sulphur （As/S） was 1. 00001. Other elements （ Al, Si, K, Ca, Ti, Fe, Sb, Ni, Cu and W） amounted 1.99%, Soluble arsenic could be detected in the artificial gastric juice extract of Realgar and prescriptions. The contents of soluble arsenic,As^Ⅱ and As^Ⅴ varied with different sources of Realgar. The amount of soluble arsenic in Realgar was 0.62% ,including 0.42% As^Ⅱ and 0.18% As^Ⅴ respectively. Conclusion Two soluble inorganic arsenic species（ As^Ⅱ and As^Ⅴ ） exit in Realgar and prescriptions containing Realgar. It is necessary to improve quality control of Realgar.