| Cis-diol substances are widely distributed in organisms,such as ribonucleosides,glycoproteins/glycopeptides,neurotransmitters and sugars,etc.They participate in and regulate various life activities and are closely related to the physiological state of the human body,and are often used as biomarkers for diseases such as cancer,diabetes,neuroendocrine and cardiovascular diseases.Therefore,cis-diol substances play an important role in life health and clinical medicine.However,the content of cis-diol substances is usually very low in biological systems,and there is a high abundance of interference matrices in biological samples,which will interfere with the detection and analysis process.Therefore,selective enrichment is crucial for the analysis of cis-diol compounds.Many studies have shown that metal oxides(such as zirconia)have good enrichment ability for cis-diols in alkaline environments(based on lewis acid-base interactions)and are excellent materials for the extraction of cis-diol compounds.However,traditional metal oxide enrichment methods often require a laborious and time-consuming separation process.Therefore,it is necessary to develop a simple and rapid method for the analysis of cis-diol compounds in biological samples.In recent years,magnetic solid-phase extraction is a novel pretreatment technique that enables fast,simple,and efficient extraction of target analytes from complex matrices.Compared with other solid-phase extraction methods,its main advantage is that it only requires a magnet to separate the adsorbed material from the sample solution,and it is simple to operate and easy to achieve phase separation.At present,magnetic solid phase extraction has been widely used.At the same time,the rapid analysis of four endogenous ribonucleotides in human urine was successfully achieved by introducing Nanoelectrospray Tandem Mass Spectrometry(nESI-MS/MS)in in our previous research.The whole analysis process takes only 10 min,and the detection time of nESIMS/MS is less than 1 min,which provides a new idea for the rapid detection of cis-diol compounds.In this paper,based on the specific interaction between zirconia and cis-diols,using the characteristics of rapid separation of magnetic nanomaterials,combined with nESI-MS/MS detection,A simple and rapid analysis of endogenous and exogenous cisdiols in urine was realized andThe first part,magnetic-zirconia nanocomposites solid-phase extraction combined with nanoelectrospray ionization-tandem mass spectrometry for quantitation of dopamine in human urine:Fe3O4-ZrO2 magnetic nanomaterials were synthesized by co-precipitation method,and the synthesized materials were characterized by scanning electron microscope,specific surface area analyzer and other characterization methods.The results confirmed that the material had loose porous structure and large specific surface area,which provided an important basis for the enrichment of cis-diol compounds.In this study,Fe3O4-ZrO2 enrichment combined with nESI-MS/MS was used to detect spiked dopamine in artificial urine.The experimental conditions such as the amount of Fe3O4-ZrO2,adsorption and elution time were optimized,and then the method was evaluated.The whole analysis process takes only 4 minutes,the standard curve has a good linear range(4-100 ng mL-1),the correlation coefficient R2=0.9915,and the limit of detection(LOD)is 1.3 ng mL-1.Finally,the method was successfully used for quantitative analysis of endogenous dopamine in three real urine samples,and the results were consistent with the concentration range of healthy human urine.The results showed that Fe3O4-ZrO2 extraction combined with nESI-MS/MS was a simple and rapid method for the analysis of dopamine in biological fluids.The second part,magnetic-zirconia nanocomposites solid-phase extraction combined with nanoelectrospray ionization-tandem mass spectrometry for quantitation of nadolol in human urine:we used magnetic sorbent Fe3O4-ZrO2 enrichment combined with nESI-MS/MS to achieve quantitative analysis of the stimulant nadolol in urine.The experimental parameters such as the amount of magnetic adsorbent used,pH value,adsorption time,and desorption solvent types were systematically optimized.Under the optimal experimental conditions,the whole analysis process took only 5 min,and the limit of detection was 0.084 ng mL-1.The sensitivity of the magnetic solid phase extraction method was 17 times higher than that of the detection before extraction,which also met the requirements of the World Anti-Doping Agency.In addition,this method also quantified two exogenous cis-diol drugs,6-hydroxydopamine and methyldopa,with the sensitivity increased by 9.5 and 14 times,respectively.The experimental results show that the coupling of magnetic solid-phase extraction and nanoelectrospray ionization tandem mass spectrometry can realize the simple and rapid analysis of three exogenous cis-diol compounds in urine,and has a broad application prospect in the analysis of cis-diol compounds in biological samples. |
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