基于表面增强拉曼光谱和顶空-气相色谱/氮磷检测技术的生氰糖苷类中成药中游离态氰化物含量测定

目的：分别建立表面增强拉曼光谱（SERS）和顶空-气相色谱/氮磷检测（HS-GC/NPD）2种技术方法，对生氰糖苷（简称氰苷）类中成药中的游离态氰化物进行含量测定和比对确认。方法：SERS方法结合在线裂解-吹扫捕集方式，对中成药中游离态氰化物进行提取转化，在785 nm激光（功率90 mW）、积分时间10 s下进行便携式SERS测定；GC-NPD方法则通过顶空进样的方式，采用HP-PLOT Q色谱柱（15 m×0.32 mm×20 μm）进行分离，程序升温（初始温度30℃，维持1.5 min，以35℃·min^-1速率升至190℃，维持1 min）。结果：SERS和GC-NPD 2种方法均能用于氰苷类中成药中游离态氰化物的含量测定，检测结果基本一致，分别在质量浓度0.1~2 mg·L^-1（r=0.997 0）和0.05~50 mg·L^-1（r=0.997 9）范围内呈良好的线性关系。对比不同厂家及批次的通宣理肺丸剂、片剂及口服液的检测结果表明：仅在丸剂中发现游离态氰化物，其中最高剂量相当于每次服用氰化物约0.18 mg（以HCN计），苦杏仁苷在样品处理条件下不影响游离态氰化物的准确测定。结论：针对氰苷类中成药中可能存在的游离态氰化物，提供了准确、灵敏的2种技术方法，并互为参照，SERS方法更适于快速检测。所获得的中成药中氰化物的数据可为相关中成药产品的质量控制和工艺优化提供依据。

Objective:To separately establish two methods using surface-enhanced Raman spectroscopy(SERS)and headspace/gas chromatography-nitrogen and phosphorus detection(HS/GC-NPD)for determination and comparison conformation of free cyanide in Chinese patent medicine of cyanogenic glycosides.Methods:SERS was combined with online lysis-purging and trapping approach.Cyanide was extracted and transformed from cyanide glycosides in Chinese patent medicine.Cyanide was then measured by portable SERS at 785 nm with laser power of 90 mW and integration time of 10 s.Meanwhile,GC-NPD was coupled with headspace sampling.The separation was performed on an HP-PLOT Q column(15 m×0.32 mm×20 μm)by temperature programming.The initial temperature was set at 30℃ for 1.5 min,and the temperature was increased to 190℃ at 35℃·min^-1,then maintained for 1 min.Results:Both SERS and GC-NPD methods could be used to determine the free cyanide in Chinese patent medicine of cyanogenic glycosides with similar detection results.The linear relationship was good in the range of 0.1-2 mg·L^-1(r=0.997 0)and 0.05-50 mg·L^-1(r=0.997 9),respectively.Different types of Chinese patent medicine,such as pills,tablets and oral liquid,were compared.Free cyanide was only found in the pills,of which the highest dose was equivalent to 0.18 mg of cyanide(based on HCN)per administration.Amygdalin did not affect the accurate determination of free cyanide under the sample pretreatment condition.Conclusion:As for the free cyanide in Chinese medicines of cyanogenic glycosides,both methods are accurate,sensitive,and can be mutual corroborated.The SERS method is more suitable for the on-site rapid detection.The data of cyanide in the Chinese patent medicine of cyanogenic glycosides provided fundamental basis for the quality control and optimization in the process of the related products.