Investigation Of Gold Nanoclusters With Dyes Involved Chemiluminescence Methods And Applications

In recent years,chemiluminescence analysis technology has become research hotspot in the spectrum field,due to its inherent merits of a wide calibration range,simple and rapid operation,and no background scattering light interference from external excitation light source.At present,the chemiluminescence method has been extensively used in biological tissue,clinical medicine,as well as the analysis and monitoring of environmental pollution.Compared with the quintessential luminol chemiluminescence,the research of dye chemicals as luminophor is relatively few,which captures scholars'considerable research interest.However,the study of chemiluminescence generally suffers from the drawbacks of weak CL signal and poor sensitivity.Currently,the research of CL is mainly focused on hunting for new CL reaction systems or combining traditional CL systems with new nanomaterials or techniques,which can not only improve the intensity and sensitivity of diverse CL reactions,but also expand the application fields.Nanomaterials is widely used as chemiluminescence energy receptor and reaction catalyst,because of their large specific surface area,favorable activity and high sensitivity.Metal nanoclusters are composed of several to hundreds of atoms,the particle size are usually less than 2 nm.Especially gold nanoclusters?Au NCs?have gained great attention on account of their remarkable features,such as easy synthesis,desirable water solubility,good photostability,large Stokes shift and nontoxicity.Up to now,the application of Au NCs is principally concentrated on fluorescence imaging and biological analysis field,less is involved in the application of chemical luminescence.Therefore,it is of great significance to further broaden the application scope of Au NCs in light analysis.This paper is divided into two parts.The first part is a review,which stated the research status of common dyes involved chemiluminescence,and the analytical application of nanomaterials in CL systems.The second part is a research report.The fluorescent Au NCs were introduced into the weak dyes chemiluminescence reaction systems,which constructs novel and simple chemiluminescence analysis in combination with flow-injection techniques for the determination of actual samples.The detailed content is as follows:1.Gold nanoclusters-catalyzed Rhodamine 6G–K₃Fe?CN?₆ chemiluminescence and its applicationAn ultra-facile flow injection chemiluminescence?CL?strategy was designed for bisphenol A?BPA?detection.It was based on the inhibition of Rhodamine 6G chemiluminescence by BPA on the gold nanoclusters?Au NCs?enhanced Rhodamine6G–K₃Fe?CN?₆ system in an alkaline medium for the first time.Furthermore,BSA-stabilized Au NCs were synthesized via a simple method with desirable reproducibility and stability.Under optimized conditions,the relative CL intensity was found to be proportional to the BPA concentration in the range of 2.0×10^-77 to1.0×10^-5mol/L,with a detection limit of 7.0×10^-8mol/L?S/N=3?.The effects of interfering substances on the detection of 1.0×10^-66 mol/L BPA were analyzed for confirming good selectivity.A brief discussion on the possible CL reaction mechanism was presented through the results of CL spectra,fluorescent spectra,UV-visible spectroscopy and radical scavenger reactions.Finally,this suggested method was used successfully to detect BPA in real samples with acceptable recovery values of 93.0-106.2%.2.Determination of catechol in water based on gold nanoclusters-catalyzed fluorescein-H₂O₂ chemiluminescenceIn this paper,a novel chemiluminescence?CL?system is introduced based on the reaction of fluorescein and H₂O₂ in alkaline medium.Gold nanoclusters?Au NCs?were synthesized using a facile BSA-stabilized method and were then applied to the fluorescein-H₂O₂ system for the first time,which effectively enhanced the CL intensity of reaction system.The addition of trace level of catechol into the CL system caused significant quenching of luminescence intensity.At optimal experimental conditions,the decreased CL intensity exhibited a favorable linear relation with catechol concentration.Based on this inhibitory phenomenon,a flow injection CL method with superior selectivity was developed for determining catechol.A possible reaction mechanism was also proposed according to the results of the kinetic curves of Au NCs in fluorescein-H₂O₂ CL system,radical scavengers and the spectra of CL,fluorescent and UV-visible.Finally,this method has been successfully used for the analysis of catechol in real water samples.3.Determination of fluvoxamine maleate in human urine and human serum using alkaline KMnO₄-Rhodamine B chemiluminescenceFlow injection chemiluminescence?FI-CL?behaviors of gold nanoclusters?Au NCs?-enhanced Rhodamine B-KMnO₄ system were studied in alkaline condition for the first time.In the present work,the as-prepared BSA-stabilized Au NCs showed excellent stability and reproducibility.Adding trace levels of fluvoxamine maleate?Flu?led to an obvious CL intensity decline from Rhodamine B-KMnO₄-Au NCs system,which could be used for quantitative detection of Flu.Under the optimized conditions,the proposed CL system exhibited favorable analytic performance for determination of Flu in the range of 2 to 100?g/mL.The detection limit for Flu measurement was 0.021?g/mL.Moreover,this newly-developed system revealed outstanding selectivity for the detection of Flu against a multitude of species,such as usual ions,uric acid and sectional hydroxy compounds.Additionally,CL spectra,UV-visible spectroscopy and fluorescent spectra were conducted to propose the possible reaction mechanism.Finally,this approach could detect Flu in human urine and human serum samples with desirable recoveries,which is indicative of its promising application under physiological conditions.