Photoinduced electron transfer process is a crucial step in photooxidation to obtain synthetic chemicals. How- ever, the driving forces of electron transfer as priority in all have been rarely studied in stepwise deta...Photoinduced electron transfer process is a crucial step in photooxidation to obtain synthetic chemicals. How- ever, the driving forces of electron transfer as priority in all have been rarely studied in stepwise detail. Herein, we report a series of BODIPY derivatives with an emphasis on the intramolecular charge transfer, enhancing the key step of photoinduced electron transfer process and photooxidation performances. A series of novel BODIPY photosensitizers （B-1--B-5） were prepared, wherein diethylamine amino of B-3 as charge injection group was conjugated to the 2,6-diiodo-styryl-BODIPY, and the electron transfer impetus was enhanced 1.6 times due to its more negative redox potentials. These results were also confirmed by the DFT/TDDFT calculation. Without pure oxygen, B-3 still can exhibit an exceptional performance in photoxidative aromatization of 1,4-DHP under mild condition. After irradiation for 28 rain, the conversion rate came to 98.2%.展开更多
AM1 method is employed to calculate the barriers against intramolecular proton transfer (IPT) of perylenequinone (PQ). The results obtained are as follows: (i) Barriers against the IPT reaction of ground state, single...AM1 method is employed to calculate the barriers against intramolecular proton transfer (IPT) of perylenequinone (PQ). The results obtained are as follows: (i) Barriers against the IPT reaction of ground state, singlet excited state and triplet excited state of PQ are 89.75, 55.40 and 83.97 kJ/mol, respectively. (ii) Barriers a-gainst the IPT process of anion of PQ in ground state and singlet excited state are 80.12 and 79. 91 kJ/mol, respectively, (iii) Barriers against the IPT of cation and anion radical of PQ (PQ,+ and PC,-) are 65. 94 and 59.29 kJ/ mol. (iv) The barrier against double proton transfer of PQ is 172.13 kJ/mol. (v) Two barriers against IPT of a type of perylenequinonoid photosensitizer (PQP), hypocrellin A (HA), are 89. 24 and 88. 07 kJ/mol. From these data conclusions can be drawn as follows: (i) IPT processes in ground state and excited state of PQ exist, but the transfer rate of excited state is much higher than that of ground state. (ii) It is almost impossible for PQ to transfer two protons simultaneously. (iii) IPT processes in anion, anion radical and cation radical of PQ still exist. (iv) The seven-membered side ring of HA has no marked influence on its barrier against IPT.展开更多
Using molecular mechanics method,values of the heat of formation (HF) of different conformations,of perylenequinonoid photosensitizes hypocrellin A (HA) and hypocrellin B (HB) were calculated and the variance of HF af...Using molecular mechanics method,values of the heat of formation (HF) of different conformations,of perylenequinonoid photosensitizes hypocrellin A (HA) and hypocrellin B (HB) were calculated and the variance of HF after phenolic protons' dissociation were calculated as well The following was found:(i) The HF values of lour conformational isomers of HA and HB are similar to each other,so the four isomcrs can transform to each other room temperature,(ii) There exists the difference between the ability of dissociation of phenolic protons of HA and that of HB,the former is higher than the latter (iii) There exist two intramolecular hydrogen bonds in HA and HB The bond energy is approximately 8 kJ/mol and the energy of conformation Ⅰ is lower than that of conformationⅡ The bond energy of HA is lower than that of HB.(iv) There exists a low energy snot when phenolic hydroxyl bond twists 180° from the position where hydrogen bond is formed,which suggests that this kind of conformation probably exists,(v) The phenolic hydrogen of HBMC forms hydrogen bond with the neighbouring nitrogen,which is its striticture basis of possessing photosensitizing activity.展开更多
The dependence on outer light source strongly hinders clinical applications of photodynamic therapy(PDT)to the deep-seated tumor.However,the majority of documented PDT systems that function without the external light ...The dependence on outer light source strongly hinders clinical applications of photodynamic therapy(PDT)to the deep-seated tumor.However,the majority of documented PDT systems that function without the external light source rely on either the chemiluminescence resonance energy transfer(CRET)or fluorescence resonance energy transfer(FRET)mechanism,which decreases the energy transfer efficiency and reproducibility of PDT.Herein,we developed a novel single-molecule triplet photosensitizer(iodoBodipy(IBDP)-L)that can be chemiexcited to triplet excited state to generate reactive oxygen species instead of outer light irradiation.The direct bonding of phthalhydrazid moiety to iodoBodipy fluorophore evoked valid intramolecular energy transfer(IET),and once phthalhydrazid part is activated by hydrogen peroxide,the released reaction energy could excite the iodoBodipy-phthalhydrazid conjugate as a whole.Reaction product IBDP-L-COOH showed high triplet state quantum yield(ΦT=65%)and large spin-orbit coupling.A large amount of reactive oxygen species(ROS)was produced in MCF-7 cells,thus inhibiting the cell growth both in vitro and in vivo after IBDP-L was formulated into nanoparticles(NPs)via nanoprecipitation.We believe that the synthesized IodoBodipy-phthalhydrazid conjugate based on the IET mechanism will open a new door in the molecular design of efficient triplet photosensitizers for treating deeply seated tumors in the future.展开更多
基金We thank the support of National Natural Science Foundation of China （Grant 21302224, 51172285, 21176259, 51303212, 51303202）, China Postdoctoral Science Foundation （2014M560590, 2015T80758）, Fundamental Research Funds for the Central Universities （15CX05010A）, Shandong Provincial Natural Science Foundation （ZR2013BQ028, ZR2013EMQ013）, Project of Science and Technology Program for Basic Research of Qingdao （14-2-4-47-jch） and the State Key Laboratory of Fine Chemicals （KF 1203）.
文摘Photoinduced electron transfer process is a crucial step in photooxidation to obtain synthetic chemicals. How- ever, the driving forces of electron transfer as priority in all have been rarely studied in stepwise detail. Herein, we report a series of BODIPY derivatives with an emphasis on the intramolecular charge transfer, enhancing the key step of photoinduced electron transfer process and photooxidation performances. A series of novel BODIPY photosensitizers （B-1--B-5） were prepared, wherein diethylamine amino of B-3 as charge injection group was conjugated to the 2,6-diiodo-styryl-BODIPY, and the electron transfer impetus was enhanced 1.6 times due to its more negative redox potentials. These results were also confirmed by the DFT/TDDFT calculation. Without pure oxygen, B-3 still can exhibit an exceptional performance in photoxidative aromatization of 1,4-DHP under mild condition. After irradiation for 28 rain, the conversion rate came to 98.2%.
文摘AM1 method is employed to calculate the barriers against intramolecular proton transfer (IPT) of perylenequinone (PQ). The results obtained are as follows: (i) Barriers against the IPT reaction of ground state, singlet excited state and triplet excited state of PQ are 89.75, 55.40 and 83.97 kJ/mol, respectively. (ii) Barriers a-gainst the IPT process of anion of PQ in ground state and singlet excited state are 80.12 and 79. 91 kJ/mol, respectively, (iii) Barriers against the IPT of cation and anion radical of PQ (PQ,+ and PC,-) are 65. 94 and 59.29 kJ/ mol. (iv) The barrier against double proton transfer of PQ is 172.13 kJ/mol. (v) Two barriers against IPT of a type of perylenequinonoid photosensitizer (PQP), hypocrellin A (HA), are 89. 24 and 88. 07 kJ/mol. From these data conclusions can be drawn as follows: (i) IPT processes in ground state and excited state of PQ exist, but the transfer rate of excited state is much higher than that of ground state. (ii) It is almost impossible for PQ to transfer two protons simultaneously. (iii) IPT processes in anion, anion radical and cation radical of PQ still exist. (iv) The seven-membered side ring of HA has no marked influence on its barrier against IPT.
基金Project supported by the National Natural Science Foundation of China
文摘Using molecular mechanics method,values of the heat of formation (HF) of different conformations,of perylenequinonoid photosensitizes hypocrellin A (HA) and hypocrellin B (HB) were calculated and the variance of HF after phenolic protons' dissociation were calculated as well The following was found:(i) The HF values of lour conformational isomers of HA and HB are similar to each other,so the four isomcrs can transform to each other room temperature,(ii) There exists the difference between the ability of dissociation of phenolic protons of HA and that of HB,the former is higher than the latter (iii) There exist two intramolecular hydrogen bonds in HA and HB The bond energy is approximately 8 kJ/mol and the energy of conformation Ⅰ is lower than that of conformationⅡ The bond energy of HA is lower than that of HB.(iv) There exists a low energy snot when phenolic hydroxyl bond twists 180° from the position where hydrogen bond is formed,which suggests that this kind of conformation probably exists,(v) The phenolic hydrogen of HBMC forms hydrogen bond with the neighbouring nitrogen,which is its striticture basis of possessing photosensitizing activity.
基金the National Natural Science Foundation of China(No.21925802)the Fundamental Research Fundamental Funds for the Central Universities(No.DUT22LAB601)+2 种基金Basic Research Fund for Free Exploration(No.2021Szvup019)NSFC-Liaoning United Fund(No.U1908202)All animal procedures were performed in accordance with the guidelines for Care and Use of Laboratory Animals of Dalian Medical University,and approved by the Dalian University of Technology Animal Care and Use Committee(No.DUT20230428).
文摘The dependence on outer light source strongly hinders clinical applications of photodynamic therapy(PDT)to the deep-seated tumor.However,the majority of documented PDT systems that function without the external light source rely on either the chemiluminescence resonance energy transfer(CRET)or fluorescence resonance energy transfer(FRET)mechanism,which decreases the energy transfer efficiency and reproducibility of PDT.Herein,we developed a novel single-molecule triplet photosensitizer(iodoBodipy(IBDP)-L)that can be chemiexcited to triplet excited state to generate reactive oxygen species instead of outer light irradiation.The direct bonding of phthalhydrazid moiety to iodoBodipy fluorophore evoked valid intramolecular energy transfer(IET),and once phthalhydrazid part is activated by hydrogen peroxide,the released reaction energy could excite the iodoBodipy-phthalhydrazid conjugate as a whole.Reaction product IBDP-L-COOH showed high triplet state quantum yield(ΦT=65%)and large spin-orbit coupling.A large amount of reactive oxygen species(ROS)was produced in MCF-7 cells,thus inhibiting the cell growth both in vitro and in vivo after IBDP-L was formulated into nanoparticles(NPs)via nanoprecipitation.We believe that the synthesized IodoBodipy-phthalhydrazid conjugate based on the IET mechanism will open a new door in the molecular design of efficient triplet photosensitizers for treating deeply seated tumors in the future.
