以7-二乙胺基香豆素-3-羧酸、甘氨酸、组氨酸为原料,采用标准多肽合成法成功合成了水溶性的荧光探针分子香豆素-甘氨酸-甘氨酸-组氨酸(Coumarin-Gly-Gly-His,C-GGH),利用GGH三肽对Cu2+的络合作用形成C-GGH-Cu2+络合物,使探针分子C-GGH的荧光猝灭;然后,通过向体系中加入氰化物后,CN-对Cu2+的强络合作用形成稳定的络合物[Cu(CN)x]而使探针分子荧光逐渐恢复,以此实现对氰化物的定量检测。该法检测限为0.015μmol/L,远低于国家标准(GB85372008)中要求最严的矿泉水中氰化物的限量值0.01mg/L(相当于摩尔浓度0.385μmol/L),该探针分子对CN-的检测不受SCN-、F-、Cl-、Br-、I-、PO3- 4、N3-、NO3-、AcO-、SO2- 4、CO 2- 3等共存阴离子的影响。经对实际食物样品中氰化物进行检测,证明该方法的准确度与国标(GB/T5009.48-2003、GB/T5009.36-2003、GB/T8538-2008)方法一致,且更快捷、简单。
Cyanide is considered to be one of the most toxic species in food while the existing detection methods involve complex operationand will produce toxicity to inspectors. In this study, a water-soluble fluorescent probe(C-GGH) was synthesized by HOBT/DIC protocol in solution using 7-diethylaminoeoumarin-3-carboxylie acid, Glyeine and Histidine. Due to the presence of the recognition unit GGH, the probe C-GOH can conjugated with Cu2+ to formed non-fluorescent C- GGH Cu2+ complex. Due to the strong binding affinity of CN- to Cu24, CN can extract Cu2+from C--GGH-Cu2+complex, leading to the release of C-GGH and the recovery of fluorescent emission of the system. The probe allowed detection of cyanide in aqueous solution with a LOD (limit of detection) of 0.017 μmol/L which is much lower than the maximum contaminant level (0.385μmol/L) for cyanide in mineral water set by national standard (GB 8537 2008). The probe also displayed excellent specificity for CN-towards other anions, including F -, Cl- , Br- , I- , SCN- , PO3- 4 , N3- , NO3- , AcO- , SO2- 4 , and CO2-3. The method developed in this study received the same results as national standard method (GB/T 5009.48 2003, GB/T 5009.36-2003, GB/T 8538-2008), but more simple and quick in real sample detection.