Graphene oxide membrane as an efficient extraction and ionization substrate for spray-mass spectrometric analysis of malachite green and its metabolite in fish samples

A graphene oxide (GO) nanosheet-modified N+-nylon membrane (GOM) has been prepared and used as an extraction and spray-ionization substrate for robust mass spectrometric detection of malachite green (MG), a highly toxic disinfectant in liquid samples and fish meat. The GOM is prepared by self-deposition of GO thin film onto an N+-nylon membrane, which has been used for efficient extraction of MG in aquaculture water samples or homogenized fish meat samples. Having a dissociation constant of 2.17 × 10−9 M−1, the GOM allows extraction of approximately 98% of 100 nM MG. Coupling of the GOM-spray with an ion-trap mass spectrometer allows quantitation of MG in aquaculture freshwater and seawater samples down to nanomolar levels. Furthermore, the system possesses high selectivity and sensitivity for the quantitation of MG and its metabolite (leucomalachite green) in fish meat samples. With easy extraction and efficient spray ionization properties of GOM, this membrane spray-mass spectrometry technique is relatively simple and fast in comparison to the traditional LC-MS/MS methods for the quantitation of MG and its metabolite in aquaculture products.