| The detection of clinical drugs and biochemical markers plays an extremely important role in drug analysis,clinical medical examination and exploration of related biological processes.The development of highly sensitive,selective,fast and simple analytical sensing methods and analytical platform tools is the key node to realize the key technologies from laboratory research to practical application,and is still a hot spot in the field of analytical sensing research.Gold nanocluster is a new type of nanomaterial,which has the advantages of low toxicity,high biocompatibility,unique optical properties,surface easily modified,etc.,and has been successfully used in sensor construction and analytical applications.However,most Au NCs have low quantum yield,low material stability and complicated modification and separation steps,which restrict their practical application and popularization.It is of great research value to develop a probe with simple operation,friendly environment,fast response and strong luminescence gold nanocluster,and develop an efficient and sensitive method for drug and biochemical marker analysis.In this thesis,based on the investigation of the synthesis and application of metal nanoclusters,faced with the requirements of complex sample analysis,the main work is carried out in two aspects:one is to explore the combination of Zn2+with different ligands,regulate the synthesis of gold nanoclusters aggregation state and its luminescence properties,develop simple and rapid,high sensitivity,strong stability,good selectivity fluorescence sensing methods,and develop its analytical applications;The second is to explore the diligand scheme of one-step synthesis of intense fluorescence gold nanoclusters,explore the role of reactive oxygen species（H2O2,·OH）and gold nanoclusters,and on this basis to develop a new method for the analysis of biochemical markers;Specific work contents are as follows:1.The effect of Zn2+on the fluorescence and morphology of gold nanoclusters synthesized with 6-mercaptocaprolic acid（6-MHA）ligand was explored.The results showed that short rod-like and strongly fluorescent gold nanoclusters GCA could be obtained under the condition of 24h synthesis.Based on the complexation and coordination effects of CQ and Zn2+,a simple,rapid,highly sensitive,highly selective and environmentally friendly method was developed for the detection of chloroiodoquinoline（CQ）.Under optimized experimental conditions,good linearity was obtained in the range of 0.01-1μM and 1-5μM,and the detection limit was as low as 2n M.The detection system showed good selectivity,and was successfully applied to the determination of CQ content in chloroiodoquine cream.2.The effect of Zn2+on the fluorescence and morphology of gold nanoclusters synthesized with 3-mercaptopropionic acid（3-MPA）ligand was investigated.The results showed that dandelion like gold nanoclusters with strong fluorescence could be obtained under the condition of 24h synthesis.Based on the differences between pyrophosphate（PPi）,phosphate(PO43-)and Zn2+binding,a GNC-PPi fluorescence sensing platform was constructed for quantitative analysis of PPase.Under the optimal experimental conditions,PPase obtained good linearity in the range of 0.5-80m U/m L,the detection limit was as low as 0.2m U/m L,and was successfully applied to the determination of PPase in serum samples,the recovery was between 98.34-103.59%.The method is simple,highly sensitive and selective.The synthesis of the probe and the establishment of the sensing platform have successfully expanded the synthesis methods and analytical applications of strong fluorescent gold nanomaterials.3.The effects of oligarginine peptide functionalized gold nanoclusters（CR9-Au NCs）on reactive oxygen species（H2O2,·OH）were investigated.The results showed that high reactive oxygen·OH had a good quenching effect on the gold nanoclusters.Combined with Fenton reaction and specific oxidase,a new method was developed for the determination of H2O2and oxidase-related biochemical markers using CR9-Au NCs as fluorescence indicator.Under the optimal conditions,the concentration of H2O2in the range of 0.2-10μM and 10-100μM has good linearity.Glucose,uric acid and cholesterol had good linearity in the range of 1.0-50μM,0.2-50μM and 1.0-80μM,and the detection limits were as low as 0.34,0.12 and 0.26μM,respectively.The results showed that CR9-Au NCs could be used to determine blood glucose in human serum.The establishment of the sensor system has successfully expanded the application of gold nanoclusters in biomarker detection. |
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