Firefly Inspired Degradation Reaction:a New Strategy For Chemiluminescence Materials

Bioluminescence has the advantages of no external stimulus,low noise and high sensitivity,and has a wide range of applications in life science research.As bioluminescence system is complicated,for many bioluminescence systems,people don't have a clear understanding about the mechanism of luminescence and structure of substrates;even for the known bioluminescence systems,due to lack the knowledge for the key structure of the substrate,the modification of the luciferin structure is very limited.In order to further meet the practical needs,It is the urgent need to explore the key factor for degradation of substrate with luminescence and development new luminescent materials to meet the actual requirements.Among the known bioluminescence systems,for different bioluminescent system,although the substrates structure and mechanism of luminescence were different,by summarizing the luminescence mechanism of these bioluminescent systems,we found that their similarity is enol-substrate reacted with oxygen giving out light,so it is of great importance to make clear the factor for enol-substrate degradation luminescence.In the second chapter of this paper,we explored the key factors of enol-degradation luminescence,one of the key elements is the path of enol-degradation,enol-dagradation give out light only by third path,another key factor is the fluorescence of degradation product.It was found that the degradation path of the intermediate dioxetane has a certain relationship with the luminescence by comparing mechanism of enol-luciferin degradation luminescence with enol-methyl ketone degradation.We synthesized the methyl ester molecules based on methyl ketone,the enol-methyl ester was degradated with luminescence.we analyzed the degradation products of enol-methyl ketone and enol-methyl ester molecule by mass spectrometry and 1H NMR,the results demonstrate that ketone and ester with different degradation path,femtosecond laser spectroscopy traced the process of degradation of ketone and ester,which further prove that the two kinds of molecules with different degradation path.The above evidences confirmed that the degradation path is one of the key factors for enol-dagradation luminescence.We also find the fluorescence of the degradation products is another factor for luminescence,the energy transfer phenomenon in this system was discovered.In the third chapter of this paper,we explored the factor influence the luminescence efficiency from the molecule structure and external environment aspects.The electronic-donated substitute contributes to improve the luminescence efficiency,while the electronic-accepted substitute is not.To some extent,luminescence efficiency depends upon the fluorescence quantum yield of degradation products,in addition,external environment was considered.In this paper,the research of the key factor for enol-degradation glowing not only provides a new method for making new chemiluminescence materials,but also provides a new idea for exploring known and unknown bioluminescence systems.