Radiotherapy is widely used clinically, but the toxic and side effects of nonselective killing of high-energy radiation limit its application. Finding biocompatible materials to assemble radiotherapy sensitizers and s...Radiotherapy is widely used clinically, but the toxic and side effects of nonselective killing of high-energy radiation limit its application. Finding biocompatible materials to assemble radiotherapy sensitizers and studying their sensitization patterns are of great significance for the clinical application. Here, biocompatible zinc porphyrin was chosen as sub-unit to construct various dimensional coordination frameworks. By employing top-down approach, suitable nanoframeworks with various dimensional zinc porphyrin were synthesized as radiosensitizers. The experimental data showed that high-dimensional zinc porphyrin nanoframeworks exhibit higher X-ray response performance.展开更多
We studied the excitation energies of zinc porphyrin（ZnP） and zinc porphyrin analogues（ZnP-R） with long-range corrected（LC） density functional theory. We compared three recent LC functionals, wB97XD, CAM-B3LYP, ...We studied the excitation energies of zinc porphyrin（ZnP） and zinc porphyrin analogues（ZnP-R） with long-range corrected（LC） density functional theory. We compared three recent LC functionals, wB97XD, CAM-B3LYP, LC-wPBE and functionals B3LYP with the experiments. It was lbund that the low energy excitation is well predicted for ZnP with the LC-wPBE functional based on 6-31G（d） basis set. Excited-state geometry optimiza- tions lbr all the compounds were carried out. It was shown that upon the photo-excitation nearly 1 e transferred to the acceptor unit[dodecafluorosubphthalocyanine, SubPc（F）12] and a highly polarized state formed in compound 5. But after the relaxation of the first excited state, the electron on the acceptor went back to the ZnP a little and then shifted from ZnP to the donor segment[bis（4-hexylphenyl）amino] partially. The computed excited-state radiative lifetime（r） for compound 5 is 943 μs, which shows a reasonable agreement with the experimental observation. According to the long-lived exciton in strong push-pull compound 5, we proposed that electron injection to semiconductor might occur alter vibrational relaxation of excited state.展开更多
Molecularly imprinted membrane-zinc porphyrin-mathacrylate（MIM-Zn-MAA）, a dual read-out sensor based on a molecularly imprinted membrane, was developed to recognize and detect dimethyl methylphosphonate （DMMP） as ...Molecularly imprinted membrane-zinc porphyrin-mathacrylate（MIM-Zn-MAA）, a dual read-out sensor based on a molecularly imprinted membrane, was developed to recognize and detect dimethyl methylphosphonate （DMMP） as an intermediate molecule of organophosphorus pesticides. The membranes were prepared via thermal polymerization of two functional monomers（zinc porphyrin and mathacrylate） on the surface of a glass slide functio- nalized with ethylene glycol dimethacrylate and azobisisobutyronitrile. The morphology of the as-synthesized MIM-Zn-MAA was determined with scanning electronic microscopy. The composite membranes exhibited macrovoid morphologies, which were affected by the functional monomers. These membranes were selectively adsorbed onto the template molecule and displayed higher adsorbing capacity toward DMMP compared with their structural analogs Changes in the fluorescent spectra were qualitatively and quantitatively monitored via fluorescence photometry. Dif- ference maps were also obtained using colorimetry before and after the reaction between MIM-Zn-MAA and DMMP at various concentrations. The maps showed a wide linear range varying from 0.1 lamol/L to 10 mmol/L with a low detection limit of 0.1 lamol/L. These preliminary results demonstrate that the as-fabricated dual read-out sensor dis- plays good sensitivity and selectivity toward DMMP, indicating its considerable potential in DMMP detection in practical applications.展开更多
The electronic structures, absorption spectra and intramolecular charge transfer properties of five push-pull zinc porphyrin analogs with different donor group and π bridge have been investigated by density functiona...The electronic structures, absorption spectra and intramolecular charge transfer properties of five push-pull zinc porphyrin analogs with different donor group and π bridge have been investigated by density functional theory（DFT） and TD（time-dependent）-DFT approach. The results show that the asymmetrical substituted diphenylamine group is favorable to the Q-band absorption of porphyrin dyes. The absence of the acetylenic bond in the π bridge part leads to the result that the B-band and the Q-band are blue-shifted and their absorption strength become weaker compared with that containing acetylenic bond, respectively. The introduction of the benzothiadiazole into the π bridge improves the intramolecular charge transfer.展开更多
Two new noble-metal-free molecular devices,[{Co(dmgH) 2 Cl}{Zn(PyTPP)}](1,dmgH = dimethyloxime,PyTPP = 5-(4pyridyl)-10,15,20-triphenylporphyrin) and [{Co(dmgH) 2 Cl}{Zn(apPyTPP)}](2,apPyTPP = 5-[4-(isonicotinamidyl)ph...Two new noble-metal-free molecular devices,[{Co(dmgH) 2 Cl}{Zn(PyTPP)}](1,dmgH = dimethyloxime,PyTPP = 5-(4pyridyl)-10,15,20-triphenylporphyrin) and [{Co(dmgH) 2 Cl}{Zn(apPyTPP)}](2,apPyTPP = 5-[4-(isonicotinamidyl)phenyl]10,15,20-triphenylporphyrin),for light-driven hydrogen generation were prepared and spectroscopically characterized.The zinc porphyrin photosensitizer and the Co III-based catalyst unit are linked by axial coordination of a pyridyl group in the periphery of zinc-porphyrin to the cobalt centre of catalyst with different lengths of bridges.The apparent fluorescence quenching and lifetime decays of 1 and 2 were observed in comparison with their reference chromophores,Zn(PyTPP)(3) and Zn(apPyTPP)(4),suggesting a possibility for an intramolecular electron transfer from the singlet excited state of zinc porphyrin unit to the cobalt centre in the molecular devices.Photochemical H2-evolving studies show that complexes 1 and 2 are efficient molecular photocatalysts for visible light-driven H2 generation from water with triethylamine as a sacrificial electron donor in THF/H2 O,with turnover numbers up to 46 and 35 for 1 and 2,respectively.In contrast to these molecular devices,the multicomponent catalyst of zinc porphyrin and [Co(dmgH) 2 PyCl] did not show any fluorescence quenching and as a consequence,no H2 gas was detected by GC analysis in the presence of triethylamine with irradiation of visible light.The plausible mechanism for the photochemical H2 generation with these molecular devices is discussed.展开更多
Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemi...Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipola- rizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic χ (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.展开更多
Abstract The effect of axial ligand 4-N,N-dimethyl aminopyridine (DMAP) on the fluorescence property of the second singlet excited state (S2) and first singlet excited state (S1) of 5,10,15, 20-tetra(p-methoxyl)phenyl...Abstract The effect of axial ligand 4-N,N-dimethyl aminopyridine (DMAP) on the fluorescence property of the second singlet excited state (S2) and first singlet excited state (S1) of 5,10,15, 20-tetra(p-methoxyl)phenyl zinc porphyrin has been investigated using steady-state absorption, fluorescence spectroscopy and picosecond time-resolved fluorescence spectroscopy. Hot fluores-cence is clearly observed and is then reasonably assigned to the higher vibronic level from S1 state. A further analysis of fluorescence kinetics results shows that the coordination of DMAP to the zinc ion results in a decrease of hot fluorescence lifetime and an increase of the relative con-tent of hot fluorescence. Similar phenomenon was observed with respects to S1 fluorescence upon the addition of DMAP in toluene. For a complete understanding of such an effect, a possible mechanism has been put forward and discussed in detail.展开更多
An inclusion complex of cyclic bis(zinc porphyrin) 1 with 5,15-dipyridylporphyrin derivative 3 has been designed and constructed. The complex formation is induced by Zn-N coordination, and is robust (Kassoc ~ 106 L/mo...An inclusion complex of cyclic bis(zinc porphyrin) 1 with 5,15-dipyridylporphyrin derivative 3 has been designed and constructed. The complex formation is induced by Zn-N coordination, and is robust (Kassoc ~ 106 L/mol) due to the presence of the cage effect of cyclic bis(zinc porphyrin). The cage-like complex as an entity is stable enough, and also convenient to achieve relative movement between the bis(zinc porphyrin) host and the dipyridylporphyrin guest connected by Zn-N coordination. The characteristics of these assemblies have been demonstrated by 1 H NMR, UV-vis, and fluorescence spectra. The results show its potential applications as a molecular gyroscope in molecular machines.展开更多
The binding conformations of bidentate ligand DABCO(1,4-diazobicyclo [2,2,2]octane) to a series of p'p type zinc porphyrin dimers covalently linked with flexible alkoxy chain - O(CH2)(n)O- (n=2-10) are described b...The binding conformations of bidentate ligand DABCO(1,4-diazobicyclo [2,2,2]octane) to a series of p'p type zinc porphyrin dimers covalently linked with flexible alkoxy chain - O(CH2)(n)O- (n=2-10) are described by H-1 NMR and UV-vis spectroscopy. DABCO can bind inside the cavities of porphyrin dimers and form a ternary sandwich complex as the alkoxy chain length is long enough. The thermodynamic parameters which control the binding behavior are investigated.展开更多
A preliminary study on a novel free base porphyrin dimer and a zinc prophyrin dimer by comparing their fluorescence properties with those of the corresponding monomers is presented. The fluorescence intensity of the f...A preliminary study on a novel free base porphyrin dimer and a zinc prophyrin dimer by comparing their fluorescence properties with those of the corresponding monomers is presented. The fluorescence intensity of the free base dimer is five times higher than that of the monomer, but the fluorescence intensity of the zinc porphyrin dimer is nearly similar to that of the zinc porphyrin monomer. The emission spectra show that energy transfer occurs between the two units.展开更多
基金supported by National Natural Science Foundation of China (Nos. 21877049, 22177038, 32171296)Guangdong Natural Science Foundation (Nos. 2020B1515120043, 2022A1515012235)+2 种基金Major Program for Tackling Key Problems of Industrial Technology in Guangzhou (Nos. 201902020013)Guangdong Pearl River Talent Program (No. 2017GC010354)Innovation Team Project in Guangdong Colleges and Universities (Nos. 2019KCXTD008, 2019KTSCX012)。
文摘Radiotherapy is widely used clinically, but the toxic and side effects of nonselective killing of high-energy radiation limit its application. Finding biocompatible materials to assemble radiotherapy sensitizers and studying their sensitization patterns are of great significance for the clinical application. Here, biocompatible zinc porphyrin was chosen as sub-unit to construct various dimensional coordination frameworks. By employing top-down approach, suitable nanoframeworks with various dimensional zinc porphyrin were synthesized as radiosensitizers. The experimental data showed that high-dimensional zinc porphyrin nanoframeworks exhibit higher X-ray response performance.
基金Supported by the National Natural Science Foundation of China（No.11179033）, the Program for New Century Excellent Talents in University of China（No.NCET- 10-0011）, the Beij ing Natural Science Foundation, China（N o.2132017 ） and Program for the Top Young Talents of Higher Learning Institutions of B eijing Municipality China.
文摘We studied the excitation energies of zinc porphyrin（ZnP） and zinc porphyrin analogues（ZnP-R） with long-range corrected（LC） density functional theory. We compared three recent LC functionals, wB97XD, CAM-B3LYP, LC-wPBE and functionals B3LYP with the experiments. It was lbund that the low energy excitation is well predicted for ZnP with the LC-wPBE functional based on 6-31G（d） basis set. Excited-state geometry optimiza- tions lbr all the compounds were carried out. It was shown that upon the photo-excitation nearly 1 e transferred to the acceptor unit[dodecafluorosubphthalocyanine, SubPc（F）12] and a highly polarized state formed in compound 5. But after the relaxation of the first excited state, the electron on the acceptor went back to the ZnP a little and then shifted from ZnP to the donor segment[bis（4-hexylphenyl）amino] partially. The computed excited-state radiative lifetime（r） for compound 5 is 943 μs, which shows a reasonable agreement with the experimental observation. According to the long-lived exciton in strong push-pull compound 5, we proposed that electron injection to semiconductor might occur alter vibrational relaxation of excited state.
基金Supported by the National Natural Science Foundation of China（No.31101284）, the Natural Science Foundation of Chongqing City, China（No.CSTC-2011BB1209）, the Fundamental Research Funds for the Central Universities of China （Nos.CQDXWL-2012-034, CQDXWL-2012-035, CDJPY1222 0001） and the Student Research Training Program in Chongqing University, China（Nos.CQU-SRTP-2015497, CQU-SRTP-2015502）.
文摘Molecularly imprinted membrane-zinc porphyrin-mathacrylate（MIM-Zn-MAA）, a dual read-out sensor based on a molecularly imprinted membrane, was developed to recognize and detect dimethyl methylphosphonate （DMMP） as an intermediate molecule of organophosphorus pesticides. The membranes were prepared via thermal polymerization of two functional monomers（zinc porphyrin and mathacrylate） on the surface of a glass slide functio- nalized with ethylene glycol dimethacrylate and azobisisobutyronitrile. The morphology of the as-synthesized MIM-Zn-MAA was determined with scanning electronic microscopy. The composite membranes exhibited macrovoid morphologies, which were affected by the functional monomers. These membranes were selectively adsorbed onto the template molecule and displayed higher adsorbing capacity toward DMMP compared with their structural analogs Changes in the fluorescent spectra were qualitatively and quantitatively monitored via fluorescence photometry. Dif- ference maps were also obtained using colorimetry before and after the reaction between MIM-Zn-MAA and DMMP at various concentrations. The maps showed a wide linear range varying from 0.1 lamol/L to 10 mmol/L with a low detection limit of 0.1 lamol/L. These preliminary results demonstrate that the as-fabricated dual read-out sensor dis- plays good sensitivity and selectivity toward DMMP, indicating its considerable potential in DMMP detection in practical applications.
基金Supported by the National Natural Science Foundation of China（Nos.21173096, 21203071） and the Natural Science Foundation of Jilin Province, China（No.201215031）.
文摘The electronic structures, absorption spectra and intramolecular charge transfer properties of five push-pull zinc porphyrin analogs with different donor group and π bridge have been investigated by density functional theory（DFT） and TD（time-dependent）-DFT approach. The results show that the asymmetrical substituted diphenylamine group is favorable to the Q-band absorption of porphyrin dyes. The absence of the acetylenic bond in the π bridge part leads to the result that the B-band and the Q-band are blue-shifted and their absorption strength become weaker compared with that containing acetylenic bond, respectively. The introduction of the benzothiadiazole into the π bridge improves the intramolecular charge transfer.
基金supported by the National Natural Science Foundation of China (20633020)the National Basic Research Program of China(2009CB220009)+2 种基金the Swedish Energy Agencythe Swedish Research Councilthe K & A Wallenberg Foundation
文摘Two new noble-metal-free molecular devices,[{Co(dmgH) 2 Cl}{Zn(PyTPP)}](1,dmgH = dimethyloxime,PyTPP = 5-(4pyridyl)-10,15,20-triphenylporphyrin) and [{Co(dmgH) 2 Cl}{Zn(apPyTPP)}](2,apPyTPP = 5-[4-(isonicotinamidyl)phenyl]10,15,20-triphenylporphyrin),for light-driven hydrogen generation were prepared and spectroscopically characterized.The zinc porphyrin photosensitizer and the Co III-based catalyst unit are linked by axial coordination of a pyridyl group in the periphery of zinc-porphyrin to the cobalt centre of catalyst with different lengths of bridges.The apparent fluorescence quenching and lifetime decays of 1 and 2 were observed in comparison with their reference chromophores,Zn(PyTPP)(3) and Zn(apPyTPP)(4),suggesting a possibility for an intramolecular electron transfer from the singlet excited state of zinc porphyrin unit to the cobalt centre in the molecular devices.Photochemical H2-evolving studies show that complexes 1 and 2 are efficient molecular photocatalysts for visible light-driven H2 generation from water with triethylamine as a sacrificial electron donor in THF/H2 O,with turnover numbers up to 46 and 35 for 1 and 2,respectively.In contrast to these molecular devices,the multicomponent catalyst of zinc porphyrin and [Co(dmgH) 2 PyCl] did not show any fluorescence quenching and as a consequence,no H2 gas was detected by GC analysis in the presence of triethylamine with irradiation of visible light.The plausible mechanism for the photochemical H2 generation with these molecular devices is discussed.
基金This work was supported by the NNSFC (20476034 NSFC/HKUST43)+1 种基金 NSF of Guangdong Province (000489) and SRF for ROCS State Education Ministry.
文摘Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipola- rizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic χ (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.
基金supported by the State Key Basis Research and Development Plans(Grant No.G1998010100)the National Natural Science Foundation of China(Grant Nos.39890390 and 20133020).
文摘Abstract The effect of axial ligand 4-N,N-dimethyl aminopyridine (DMAP) on the fluorescence property of the second singlet excited state (S2) and first singlet excited state (S1) of 5,10,15, 20-tetra(p-methoxyl)phenyl zinc porphyrin has been investigated using steady-state absorption, fluorescence spectroscopy and picosecond time-resolved fluorescence spectroscopy. Hot fluores-cence is clearly observed and is then reasonably assigned to the higher vibronic level from S1 state. A further analysis of fluorescence kinetics results shows that the coordination of DMAP to the zinc ion results in a decrease of hot fluorescence lifetime and an increase of the relative con-tent of hot fluorescence. Similar phenomenon was observed with respects to S1 fluorescence upon the addition of DMAP in toluene. For a complete understanding of such an effect, a possible mechanism has been put forward and discussed in detail.
基金Supported by the 973 Program (Grant No. 2006CB932900)National Natural Science Foundation of China (Grant Nos. 20802038 and 20721062)Tianjin Natural Science Foundation (Grant No. 07QTPTJC29700).
文摘An inclusion complex of cyclic bis(zinc porphyrin) 1 with 5,15-dipyridylporphyrin derivative 3 has been designed and constructed. The complex formation is induced by Zn-N coordination, and is robust (Kassoc ~ 106 L/mol) due to the presence of the cage effect of cyclic bis(zinc porphyrin). The cage-like complex as an entity is stable enough, and also convenient to achieve relative movement between the bis(zinc porphyrin) host and the dipyridylporphyrin guest connected by Zn-N coordination. The characteristics of these assemblies have been demonstrated by 1 H NMR, UV-vis, and fluorescence spectra. The results show its potential applications as a molecular gyroscope in molecular machines.
基金the National Natural Science Foundation (29871018) and Tianjin Science and Technology Committee Foundation (983602611) of China
文摘The binding conformations of bidentate ligand DABCO(1,4-diazobicyclo [2,2,2]octane) to a series of p'p type zinc porphyrin dimers covalently linked with flexible alkoxy chain - O(CH2)(n)O- (n=2-10) are described by H-1 NMR and UV-vis spectroscopy. DABCO can bind inside the cavities of porphyrin dimers and form a ternary sandwich complex as the alkoxy chain length is long enough. The thermodynamic parameters which control the binding behavior are investigated.
基金Supported by the National Natural Science Foundation of China(No. 20071014).
文摘A preliminary study on a novel free base porphyrin dimer and a zinc prophyrin dimer by comparing their fluorescence properties with those of the corresponding monomers is presented. The fluorescence intensity of the free base dimer is five times higher than that of the monomer, but the fluorescence intensity of the zinc porphyrin dimer is nearly similar to that of the zinc porphyrin monomer. The emission spectra show that energy transfer occurs between the two units.
