It is of great significance to study the relationship between the excited state intramolecular proton transfer(ESIPT)properties and antioxidant activities of compounds in the field of life sciences.In this work,two no...It is of great significance to study the relationship between the excited state intramolecular proton transfer(ESIPT)properties and antioxidant activities of compounds in the field of life sciences.In this work,two novel compounds 5HF-OMe and 5HF-NH2 are designed through introducing a methoxy-and amino-group into the structure of 5-hydroxyflavone(5HF)respectively.The relationship between the ESIPT reaction and antioxidant activities of the three compounds is studied via the density functional theory(DFT)and time-dependent DFT(TD-DFT)methods.The calculated potential energy curves suggest that the rate of ESIPT reaction will gradually slow down from 5HF to 5HF-OMe and 5HF-NH2.In addition,the antioxidant activities of the three compounds gradually enhance from 5HF to 5HF-OMe and 5HF-NH2,which can be seen from the calculated energy gaps and ionization potential values.Interestingly,the above results imply that the rate of ESIPT reaction has a negative relationship with the antioxidant activities of the compounds,i.e.,the slower rate of ESIPT reaction will reflect the higher antioxidant activity of the compound,which will provide valuable reference for detecting the antioxidant activity of compound via the photophysical method.展开更多
We theoretically investigate the excited state intramolecular proton transfer(ESIPT) behavior of the novel fluorophore bis-imine derivative molecule HNP which was designed based on the intersection of 1-(hydrazonometh...We theoretically investigate the excited state intramolecular proton transfer(ESIPT) behavior of the novel fluorophore bis-imine derivative molecule HNP which was designed based on the intersection of 1-(hydrazonomethyl)-naphthalene-2-ol and 1-pyrenecarboxaldehyde. Especially, the density functional theory(DFT) and time-dependent density functional theory(TDDFT) methods for HNP monomer are introduced. Moreover, the "our own n-layered integrated molecular orbital and molecular mechanics"(ONIOM) method(TDDFT:universal force field(UFF)) is used to reveal the aggregation-induced emission(AIE) effect on the ESIPT process for HNP in crystal. Our results confirm that the ESIPT process happens upon the photoexcitation for the HNP monomer and HNP in crystal, which is distinctly monitored by the optimized geometric structures and the potential energy curves. In addition, the results of potential energy curves reveal that the ESIPT process in HNP will be promoted by the AIE effect. Furthermore, the highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) for the HNP monomer and HNP in crystal have been calculated. The calculation demonstrates that the electron density decrease of proton donor caused by excitation promotes the ESIPT process. In addition, we find that the variation of atomic dipole moment corrected Hirshfeld population(ADCH) charge for proton acceptor induced by the AIE effect facilitates the ESIPT process. The results will be expected to deepen the understanding of ESIPT dynamics for luminophore under the AIE effect and provide insight into future design of high-efficient AIE compounds.展开更多
The influences of the substituent base position on the excited state intramolecular proton transfer fluorescence properties were explored in 2-(2'-hydroxyphenyl)imidazo[1,2-a]-pyridine(HPIP)and HPIP's derivati...The influences of the substituent base position on the excited state intramolecular proton transfer fluorescence properties were explored in 2-(2'-hydroxyphenyl)imidazo[1,2-a]-pyridine(HPIP)and HPIP's derivatives(5'Br-HPIP and 6'BrHPIP).And the density functional theory(DFT)and time-dependent DFT(TD-DFT)methods were used to calculate the molecule structures.The calculated results showed that the influence of 5'Br-HPIP on the fluorescence intensity is stronger than that of 6'Br-HPIP.The fluorescence emission peak of 5'Br-HPIP occurred a blue shift compared with HPIP,and 6'BrHPIP exhibited an opposite red shift.The change of the fluorescence emission peak was attributed to the decrease of the energy gap from 6'Br-HPIP to 5'Br-HPIP.Our work on the substituent position influence could be helpful to design and develop new materials.展开更多
基金Project supported by the National Basic Research Program of China(Grant No.2019YFA0307701)the National Natural Science Foundation of China(Grant No.11874180)the Science and Technology Development Project of Jilin Province of China(Grant No.20190103101JH).
文摘It is of great significance to study the relationship between the excited state intramolecular proton transfer(ESIPT)properties and antioxidant activities of compounds in the field of life sciences.In this work,two novel compounds 5HF-OMe and 5HF-NH2 are designed through introducing a methoxy-and amino-group into the structure of 5-hydroxyflavone(5HF)respectively.The relationship between the ESIPT reaction and antioxidant activities of the three compounds is studied via the density functional theory(DFT)and time-dependent DFT(TD-DFT)methods.The calculated potential energy curves suggest that the rate of ESIPT reaction will gradually slow down from 5HF to 5HF-OMe and 5HF-NH2.In addition,the antioxidant activities of the three compounds gradually enhance from 5HF to 5HF-OMe and 5HF-NH2,which can be seen from the calculated energy gaps and ionization potential values.Interestingly,the above results imply that the rate of ESIPT reaction has a negative relationship with the antioxidant activities of the compounds,i.e.,the slower rate of ESIPT reaction will reflect the higher antioxidant activity of the compound,which will provide valuable reference for detecting the antioxidant activity of compound via the photophysical method.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11574115 and 11704146)
文摘We theoretically investigate the excited state intramolecular proton transfer(ESIPT) behavior of the novel fluorophore bis-imine derivative molecule HNP which was designed based on the intersection of 1-(hydrazonomethyl)-naphthalene-2-ol and 1-pyrenecarboxaldehyde. Especially, the density functional theory(DFT) and time-dependent density functional theory(TDDFT) methods for HNP monomer are introduced. Moreover, the "our own n-layered integrated molecular orbital and molecular mechanics"(ONIOM) method(TDDFT:universal force field(UFF)) is used to reveal the aggregation-induced emission(AIE) effect on the ESIPT process for HNP in crystal. Our results confirm that the ESIPT process happens upon the photoexcitation for the HNP monomer and HNP in crystal, which is distinctly monitored by the optimized geometric structures and the potential energy curves. In addition, the results of potential energy curves reveal that the ESIPT process in HNP will be promoted by the AIE effect. Furthermore, the highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) for the HNP monomer and HNP in crystal have been calculated. The calculation demonstrates that the electron density decrease of proton donor caused by excitation promotes the ESIPT process. In addition, we find that the variation of atomic dipole moment corrected Hirshfeld population(ADCH) charge for proton acceptor induced by the AIE effect facilitates the ESIPT process. The results will be expected to deepen the understanding of ESIPT dynamics for luminophore under the AIE effect and provide insight into future design of high-efficient AIE compounds.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11874180 and 11704146)the Program of Science and Technology Development Plan of Jilin Province,China(Grant Nos.20190201138TC and 20190103101JH)。
文摘The influences of the substituent base position on the excited state intramolecular proton transfer fluorescence properties were explored in 2-(2'-hydroxyphenyl)imidazo[1,2-a]-pyridine(HPIP)and HPIP's derivatives(5'Br-HPIP and 6'BrHPIP).And the density functional theory(DFT)and time-dependent DFT(TD-DFT)methods were used to calculate the molecule structures.The calculated results showed that the influence of 5'Br-HPIP on the fluorescence intensity is stronger than that of 6'Br-HPIP.The fluorescence emission peak of 5'Br-HPIP occurred a blue shift compared with HPIP,and 6'BrHPIP exhibited an opposite red shift.The change of the fluorescence emission peak was attributed to the decrease of the energy gap from 6'Br-HPIP to 5'Br-HPIP.Our work on the substituent position influence could be helpful to design and develop new materials.
