Sonodynamic therapy(SDT)is garnering considerable attention as a promising treatment for deep-seated tumors because of its strong tissue penetration ability,non-invasiveness,and controllability.However,the SDT efficie...Sonodynamic therapy(SDT)is garnering considerable attention as a promising treatment for deep-seated tumors because of its strong tissue penetration ability,non-invasiveness,and controllability.However,the SDT efficiency of traditional sonosensitizers including porphyrins and their derivatives are limited due to their poor water dissolubility,high aggregation,and low reactive oxygen species(ROS)production efficiency.Consequently,it is crucial to develop novel sonosensitizers with high yields of ROS,outstanding water solubility,and good biocompatibility.Herein,we constructed a new platform for SDT based on unimolecular porphyrin derivatives OPV-C_(3)-TPP.The probe OPV-C_(3)-TPP was synthesized by covalently linking conjugated oligomers(OPV)with 5,10,15,20-tetra(4-aminophenyl)porphyrin(TAPP).The introduction of OPV greatly improves the water solubility of the porphyrins and reduces the self-aggregation of the porphyrins.In addition,OPV-C_(3)-TPP has good intramolecular energy transfer efficiency,thus enhancing the yield of ROS.The experimental results show that OPV-C_(3)-TPP exhibits excellent ROS generation capacity under ultrasound(US)irradiation,which leads to apoptosis and necrosis of tumor cells.In vivo tumor growth is also significantly inhibited in the OPV-C_(3)-TPP t US group,exhibiting better SDT effects than TAPP.Therefore,the unimolecular OPV-C_(3)-TPP can be used as a potential sonosensitizer,providing a promising SDT for deep-tissue tumors.展开更多
The adsorption properties of a magnesium porphyrin(MgP)molecule on Au(111)surface covered with up to three lay-ers of sodium chloride(NaCl)were investigated by means of first-principles calculations.The most stable ad...The adsorption properties of a magnesium porphyrin(MgP)molecule on Au(111)surface covered with up to three lay-ers of sodium chloride(NaCl)were investigated by means of first-principles calculations.The most stable adsorption configuration of MgP on the NaCl/Au(111)heterosurfaces was found to be at the Cl-top site with a 20°angle between the[110]lattice direction of NaCl and the Mg–N bond of the molecule.Compared with MgP molecule adsorbed on bare Au(111),the inclusion of NaCl lay-ers can lead to a significant decrease in the adsorption energy of the MgP molecule.The exis-tence of NaCl layers also reduced the charge transfer between the molecule and the surface.For heterosurfaces with two or three monolayers of NaCl,the charge transfer was almost com-pletely suppressed.The obtained partial density of states(PDOS)showed that hybridization between the electronic structures of the adsorbed MgP molecule and the metal surface can be significantly suppressed when NaCl layers were added.For the heterosurface with three lay-ers of NaCl,the PDOS around the Fermi level was almost identical with that of the free molecule,suggesting the electronic structure of the MgP molecule was nicely preserved.Influ-ence of the NaCl layers on the electronic structure of the MgP molecule was mainly found for molecular orbitals(MOs)away from the Fermi level as a result of the large band gap of the NaCl layers.展开更多
The fabrication of bioreceptor-free method for accurate and sensitive detection of ochratoxin A(OTA) in cereal is critical, but still a significant challenge to mitigate risks to food industries and public health. In ...The fabrication of bioreceptor-free method for accurate and sensitive detection of ochratoxin A(OTA) in cereal is critical, but still a significant challenge to mitigate risks to food industries and public health. In this study, a smartphone-ratiometric fiuorescence sensor for the ultrasensitive detection of OTA is developed based on a porphyrinic metal-organic framework and silica nanoparticle composite(Zr-MOF/Si NPs)away from the use of antibodies and aptamers. Due to the excellent recognition ability of Zr-MOF and good storage stability of Si NPs, OTA is detected by Zr-MOF/Si NPs with a wide linear range of 0.05–1000 ng/m L and low detection limit of 0.016 ng/m L. Moreover, the red–blue ratio values of the fiuorescence images are extracted through the smartphone color recognizer application with a limit of detection of 1.74 ng/m L, lower than the permissible content of OTA in cereal prescribed by World Health Organization. This sensing platform has been successfully applied in maize samples with superior repeatability and satisfactory recoveries, providing a novel way for simple and label-free analysis of OTA in cereal.展开更多
Selective dinitrogen(N_(2))capture from coalbed methane(CBM)is significant in chemical industries,but it remains a challenge because of similar physicochemical properties of N_(2) and CH_(4).Herein,the adsorption of t...Selective dinitrogen(N_(2))capture from coalbed methane(CBM)is significant in chemical industries,but it remains a challenge because of similar physicochemical properties of N_(2) and CH_(4).Herein,the adsorption of them on the 2D porphyrin sheets doped with various 3d transition metal ions(marked as MPor,M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn)were comparatively investigated by using density functional theory to screen a suitable adsorbent for CBM separation.Though systematical comparison of adsorption energies of gas molecules and Gibbs free energy change the N_(2) desorption process on all MPor surfaces,FePor is confirmed to be a promising adsorbent because of its undemanding regeneration conditions and modest chemical bonding state with N_(2) molecule.Further mechanism analysis reveals that the charge transferred from lone pair of N_(2) molecule to d_(z2)orbital of Fe ion and back-donated from d_(xz)and d_(yz)orbitals of Fe ion to the unoccupiedπ*orbital of N_(2) molecule.Such hybridization of orbitals improves the selective adsorption of N_(2) from CBM.展开更多
The generation of reactive intermediates is a pivotal step during photocatalytic redox elimination of organic micropollutants in water.The UV/S(Ⅳ)-based water treatment system has garnered significant attention as an...The generation of reactive intermediates is a pivotal step during photocatalytic redox elimination of organic micropollutants in water.The UV/S(Ⅳ)-based water treatment system has garnered significant attention as an efficient advanced reduction process for pollutant abatement.However,as a reductive system,the conventional UV/S(Ⅳ)approach exhibits limited efficacy in removing electron-rich micropollutants.Our study uncovered that meso–tetrakis(4-chlorophenyl)porphyrin-Fe(Ⅲ)chloride(TPPFe,a typical iron(Ⅲ)porphyrin)catalyzed the conversion of SO_(3)^(2-)into SO_(3)^(·-)under UV365irradiation without generating of eaq-and H·,leading to the formation of diverse oxidizing species.Additionally,the introduction of TPPFe induced an absorption redshift,broadening the range of applicable UV wavelengths.An in-depth photocatalytic cycle mechanism for TPPFe^(Ⅲ)Cl-[TPPFe^(Ⅱ)Cl]-was introduced and verified by density functional theory(DFT)calculations.Furthermore,quantum chemistry calculations via transition state were conducted to assess the oxidizing reactivity of the reactive species with micropollutants.Both·OH and SO_(4)^(·-)demonstrate a strong propensity to react with carbamazepine(CMZ,a model micropollutant).Meanwhile,1O2exhibits a distinct reaction mechanism with CMZ.Consequently,the radical-and ^(1)O_(2)-mediated distinct degradation pathways were elucidated.This study provides an experimental/theoretical exploration of reactive intermediate generation and their interactions with CMZ,shedding valuable insights into the mechanisms of electron-shuttling photosensitizers catalyzing the UV/S(Ⅳ)oxidation process.展开更多
Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the r...Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the reaction material,and exhibits high delocalization energy to significantly enhance thermal stability.The nitrogen in the azo bond improves the adsorption capacity for ORR and OER catalytic intermediates,while the-ph-NH_(2)group further increases the electron cloud density at the Co-N_(4)center in A-PpazoPorCo.Density functional theory(DFT)calculations reveal that the strong electron-donating-ph-NH_(2)groups and the electron-donating azo bonds form an electron donor-π-electron acceptor(D-π-A)structure,which further enhances the electron cloud density.The strongπ-πinteraction between A-PpazoPorCo and three-dimensional graphene(3D-G)significantly boosts the oxygen catalytic performance of the A-PpazoPorCo/3D-G.The catalytic ORR half-wave potential(E_(1/2))of A-PpazoPorCo/3D-G can reach 0.880 V vs.RHE.The total overpotential(ΔE=E_(j=10)-E_(1/2))is 0.617 V,demonstrating excellent bifunctional oxygen catalytic performance.The efficient oxygen catalytic performance indicates that A-PpazoPorCo/3D-G has the potential for application in fuel cells cathodes and overall water splitting anodes.展开更多
Protoporphyrin IX (PPIX) fluorescence-guided brain tumor resection, using 5-aminolevulinic acid (5-ALA), is among the most valuable tools for determining tumor removal area. However, PPIX fluorescence is not necessari...Protoporphyrin IX (PPIX) fluorescence-guided brain tumor resection, using 5-aminolevulinic acid (5-ALA), is among the most valuable tools for determining tumor removal area. However, PPIX fluorescence is not necessarily achieved during an operation visually even when 5-ALA is used, and we do not know until tumor exposure to the excitation light of the ultraviolet region whether PPIX fluorescence has been achieved. When a particular biopsy and frozen section diagnosis is made, the reason for lack of PPIX fluorescence in the tissue cannot be judged. We do not know whether the tumor fails to fluoresce or no fluorescence is seen because it is not the main body of the tumor. We investigated whether the presence or absence of tumor fluorescence could be predicted by examining urinary porphyrin before surgery, at the time of intraoperative fluorescence diagnosis using 5-ALA. The urine of brain tumor patients 2 hours after 5-ALA administration was irradiated with a 405 ± 1 nm laser light. The patients were divided into a fluorescent urine group and negative fluorescent urine group. Red fluorescence was observed in response to the 405 ± 1 nm laser beam for all tumors in the fluorescent urine group. Clear red fluorescence was not observed even with 405 ± 1 nm laser beam irradiation in any tumors in the negative fluorescent urine group. Preoperative prediction of the intraoperative fluorescence of PPIX can be achieved by observation of urine 2 hours after 5-ALA administration with exposure to a 405 ± 1 nm laser light.展开更多
A new porphyrin-fluorescein hybrid 2 (Fl-PPTPP) has been synthesized and characterized by UV-Vis, IR, H-NMR, ESI-MS and elemental analysis. The supramolecular 1 self-assembly of Fl-PPTPP with amino-porphyrinatomangane...A new porphyrin-fluorescein hybrid 2 (Fl-PPTPP) has been synthesized and characterized by UV-Vis, IR, H-NMR, ESI-MS and elemental analysis. The supramolecular 1 self-assembly of Fl-PPTPP with amino-porphyrinatomanganese [Mn (p-APTPP)Cl] by hydrogen-bonding was studied using fluorescence spectroscopic titration and ESI-MS.展开更多
Four ＂picket fence＂ porphyrin atropisomers were respectively synthesized from the four corresponding atropisomers of meso-tetra（o-aminophenyl）porphyrin that had been chromatographed on a column eluted with petrole...Four ＂picket fence＂ porphyrin atropisomers were respectively synthesized from the four corresponding atropisomers of meso-tetra（o-aminophenyl）porphyrin that had been chromatographed on a column eluted with petroleum ether and ethyl acetate. Results show that each atropisomer could be successfully synthesized by controlling the acylation temperature at 0 ℃. They were characterized by 1H NMR, HRMS, IR, UV-Vis and Langmuir-Blodgett（LB） film analyses. Although the results of HRMS, IR, UV-Vis analyses indicate there is no remarkable difference among the atropisomers, the results of the 1H NMR and the mean molecular areas obtained by LB film technique imply that the atropisomers are significantly discrepant. The former shows that the chemical shifts of the methyl and amide protons of each atropisomer are distinct, while the later presents that the different atropisomer molecules can occupy the different surface areas at the air/water interface.展开更多
The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic acti...The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic activity of molecular catalysts has been widely studied in H-cells;their less studied capabilities in more efficient flow cell reactors have the potential to rival that of heterogeneous catalysts.In this work,a comparative study of amino functionalized iron-tetraphenylporphyrins(amino-Fe-TPPs) immobilized onto carbonaceous materials in both H-cells and flow cells was conducted to selectively reduce CO_(2) to CO.In a flow cell set up operating in alkaline media,the resulting hybrid catalyst exhibits 87% faradaic efficiency(FE) with extraordinary current density(j) of 119 mA/cm^(2) and turnover frequency(TOF) of 14 s^(-1) at-1.0 V vs.RHE.This remarkable catalytic activity was achieved through thoughtful combination of molecular and flow cell design that provides an effective strategy for future immobilized heterogeneous approaches toward CO_(2) reduction reactions(CO_(2) RRs).展开更多
A mono-funtionalised tetraphenylporphyrin (TPP) bearing valine moiety at the phenylring was synthesized for photocytotoxicity examination in four steps, starting from regiospecificmono-nitration of TPP at the phenyl r...A mono-funtionalised tetraphenylporphyrin (TPP) bearing valine moiety at the phenylring was synthesized for photocytotoxicity examination in four steps, starting from regiospecificmono-nitration of TPP at the phenyl ring. The in vitro photocytotoxicitic effect against SPC-Aladenocarcinona cell line was tested.展开更多
A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed...A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.展开更多
ω -Bromopropylporphyrin ether synthesized from the raction of 1,3-dibromopropane as the bridge-linked reagent and 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin (H_2MHTPP) as the matrix reacts with 5,15-di(4- hydrox...ω -Bromopropylporphyrin ether synthesized from the raction of 1,3-dibromopropane as the bridge-linked reagent and 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin (H_2MHTPP) as the matrix reacts with 5,15-di(4- hydroxyphenyl)-10,20-diphenyl porphyrin( trans -H_2DHDPP) to give the title nanometer porphyrin trimer. The characterization was carried out by means of elemental analyses,UV-Vis,IR, 1H NMR and XRD.展开更多
Photodynamic inactivation of microorganisms known as antibacterial photodynamic therapy(APDT)is one of the most promising and innovative approaches for the destruction of pathogenic microorganisms.Among the photosensi...Photodynamic inactivation of microorganisms known as antibacterial photodynamic therapy(APDT)is one of the most promising and innovative approaches for the destruction of pathogenic microorganisms.Among the photosensitizers(PSs),compounds based on cationic porphyrins/metalloporphyrins are most successfully used to inactivate microorganisms.Series of meso-substituted cationic pyridylporphyrins and metalloporphyrins with various peripheral groups in the third and fourth positions of the pyrrole ring have been synthesized in Armenia.The aim of this work was to determine and test the most e®ective cationic porphyrins and metalloporphyrins with high photoactivity against Gram negative and Gram positive microorganisms.It was shown that the synthesized cationic pyridylporphyrins/metalloporphyrins exhibit a high degree of phototoxicity towards both types of bacteria,including the methicillinresistant S.aureus strain.Zinc complexes of porphyrins are more phototoxic than metal-free porphyrin analogs.The e®ectiveness of these Zn–metalloporphyrins on bacteria is consistent with the level of singlet oxygen generation.It was found that the high antibacterial activity of the studied cationic porphyrins/metalloporphyrins depends on four factors:the presence in the porphyrin macrocycle of a positive charge(+4),a central metal atom(Zn2þÞand hydrophobic peripheral functional groups as well as high values of quantum yields of singlet oxygen.The results indicate that meso-substituted cationic pyridylporphyrins/metalloporphyrins cannd wider application in photoinactivation of bacteria than anionic or neutral PSs usually used in APDT.展开更多
The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a...The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a?2d with Merrifield’s peptide resin obtained 3a?3d. The compounds 3a?3d reacted with methyl iodide respectively gave 4a?4d. New complexes 4a?4d have been identified by IR, UV-visible spectra, and AES.展开更多
The water soluble tetra p sulfonatophenylporphyrinatolanthanide, [Ln·TPPS·OH ·2imidazole] ·3H 2O(Ln=Tb～Yb), were synthesized and characterized. Their stability and complex constants were...The water soluble tetra p sulfonatophenylporphyrinatolanthanide, [Ln·TPPS·OH ·2imidazole] ·3H 2O(Ln=Tb～Yb), were synthesized and characterized. Their stability and complex constants were also studied and determined. The structural formula of the lanthanide porphyrins was proposed too. The lanthanide atom is sitting above the porphyrin plane. For the lanthanide porphyrin complexes, the complex becomes more stable and the reduction potential has a slight shift to more positive values as the atomic number increases from Tb to Yb. The mechanism of electrode processes for these lanthanidee porphyrin complexes were investigated in details.展开更多
基金supported by the National Natural Science Foundation of China(22274095 and 21974084)the Fundamental Research Funds for the Central Universities(GK202302004).
文摘Sonodynamic therapy(SDT)is garnering considerable attention as a promising treatment for deep-seated tumors because of its strong tissue penetration ability,non-invasiveness,and controllability.However,the SDT efficiency of traditional sonosensitizers including porphyrins and their derivatives are limited due to their poor water dissolubility,high aggregation,and low reactive oxygen species(ROS)production efficiency.Consequently,it is crucial to develop novel sonosensitizers with high yields of ROS,outstanding water solubility,and good biocompatibility.Herein,we constructed a new platform for SDT based on unimolecular porphyrin derivatives OPV-C_(3)-TPP.The probe OPV-C_(3)-TPP was synthesized by covalently linking conjugated oligomers(OPV)with 5,10,15,20-tetra(4-aminophenyl)porphyrin(TAPP).The introduction of OPV greatly improves the water solubility of the porphyrins and reduces the self-aggregation of the porphyrins.In addition,OPV-C_(3)-TPP has good intramolecular energy transfer efficiency,thus enhancing the yield of ROS.The experimental results show that OPV-C_(3)-TPP exhibits excellent ROS generation capacity under ultrasound(US)irradiation,which leads to apoptosis and necrosis of tumor cells.In vivo tumor growth is also significantly inhibited in the OPV-C_(3)-TPP t US group,exhibiting better SDT effects than TAPP.Therefore,the unimolecular OPV-C_(3)-TPP can be used as a potential sonosensitizer,providing a promising SDT for deep-tissue tumors.
基金supported by the National Natural Science Foundation of China(No.22373084,No.62201494)Hebei Natural Science Foundation(B2022203007)the Cultivation Project for Basic Research and Innovation of Yanshan University(2024LGZD002).
文摘The adsorption properties of a magnesium porphyrin(MgP)molecule on Au(111)surface covered with up to three lay-ers of sodium chloride(NaCl)were investigated by means of first-principles calculations.The most stable adsorption configuration of MgP on the NaCl/Au(111)heterosurfaces was found to be at the Cl-top site with a 20°angle between the[110]lattice direction of NaCl and the Mg–N bond of the molecule.Compared with MgP molecule adsorbed on bare Au(111),the inclusion of NaCl lay-ers can lead to a significant decrease in the adsorption energy of the MgP molecule.The exis-tence of NaCl layers also reduced the charge transfer between the molecule and the surface.For heterosurfaces with two or three monolayers of NaCl,the charge transfer was almost com-pletely suppressed.The obtained partial density of states(PDOS)showed that hybridization between the electronic structures of the adsorbed MgP molecule and the metal surface can be significantly suppressed when NaCl layers were added.For the heterosurface with three lay-ers of NaCl,the PDOS around the Fermi level was almost identical with that of the free molecule,suggesting the electronic structure of the MgP molecule was nicely preserved.Influ-ence of the NaCl layers on the electronic structure of the MgP molecule was mainly found for molecular orbitals(MOs)away from the Fermi level as a result of the large band gap of the NaCl layers.
基金funding from the National Natural Science Foundation of China (No. 31871877)the National Key Research and Development Program of China (No. 2019YFC1606303)。
文摘The fabrication of bioreceptor-free method for accurate and sensitive detection of ochratoxin A(OTA) in cereal is critical, but still a significant challenge to mitigate risks to food industries and public health. In this study, a smartphone-ratiometric fiuorescence sensor for the ultrasensitive detection of OTA is developed based on a porphyrinic metal-organic framework and silica nanoparticle composite(Zr-MOF/Si NPs)away from the use of antibodies and aptamers. Due to the excellent recognition ability of Zr-MOF and good storage stability of Si NPs, OTA is detected by Zr-MOF/Si NPs with a wide linear range of 0.05–1000 ng/m L and low detection limit of 0.016 ng/m L. Moreover, the red–blue ratio values of the fiuorescence images are extracted through the smartphone color recognizer application with a limit of detection of 1.74 ng/m L, lower than the permissible content of OTA in cereal prescribed by World Health Organization. This sensing platform has been successfully applied in maize samples with superior repeatability and satisfactory recoveries, providing a novel way for simple and label-free analysis of OTA in cereal.
基金Supported by the National Natural Science Foundation of China(Nos.52476170 and 51906232)the Natural Science Foundation of Shanxi Province of China(Nos.202303021211156,202203021212140)Project of Science and Technology Innovation Team of Shanxi Province(No.202204051002023)。
文摘Selective dinitrogen(N_(2))capture from coalbed methane(CBM)is significant in chemical industries,but it remains a challenge because of similar physicochemical properties of N_(2) and CH_(4).Herein,the adsorption of them on the 2D porphyrin sheets doped with various 3d transition metal ions(marked as MPor,M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn)were comparatively investigated by using density functional theory to screen a suitable adsorbent for CBM separation.Though systematical comparison of adsorption energies of gas molecules and Gibbs free energy change the N_(2) desorption process on all MPor surfaces,FePor is confirmed to be a promising adsorbent because of its undemanding regeneration conditions and modest chemical bonding state with N_(2) molecule.Further mechanism analysis reveals that the charge transferred from lone pair of N_(2) molecule to d_(z2)orbital of Fe ion and back-donated from d_(xz)and d_(yz)orbitals of Fe ion to the unoccupiedπ*orbital of N_(2) molecule.Such hybridization of orbitals improves the selective adsorption of N_(2) from CBM.
基金financially supported by the National Key R&D Program of China(No.2023YFE0112100)the XMU Training Program of Innovation and Entrepreneurship of Undergraduates(No.2024Y1328)。
文摘The generation of reactive intermediates is a pivotal step during photocatalytic redox elimination of organic micropollutants in water.The UV/S(Ⅳ)-based water treatment system has garnered significant attention as an efficient advanced reduction process for pollutant abatement.However,as a reductive system,the conventional UV/S(Ⅳ)approach exhibits limited efficacy in removing electron-rich micropollutants.Our study uncovered that meso–tetrakis(4-chlorophenyl)porphyrin-Fe(Ⅲ)chloride(TPPFe,a typical iron(Ⅲ)porphyrin)catalyzed the conversion of SO_(3)^(2-)into SO_(3)^(·-)under UV365irradiation without generating of eaq-and H·,leading to the formation of diverse oxidizing species.Additionally,the introduction of TPPFe induced an absorption redshift,broadening the range of applicable UV wavelengths.An in-depth photocatalytic cycle mechanism for TPPFe^(Ⅲ)Cl-[TPPFe^(Ⅱ)Cl]-was introduced and verified by density functional theory(DFT)calculations.Furthermore,quantum chemistry calculations via transition state were conducted to assess the oxidizing reactivity of the reactive species with micropollutants.Both·OH and SO_(4)^(·-)demonstrate a strong propensity to react with carbamazepine(CMZ,a model micropollutant).Meanwhile,1O2exhibits a distinct reaction mechanism with CMZ.Consequently,the radical-and ^(1)O_(2)-mediated distinct degradation pathways were elucidated.This study provides an experimental/theoretical exploration of reactive intermediate generation and their interactions with CMZ,shedding valuable insights into the mechanisms of electron-shuttling photosensitizers catalyzing the UV/S(Ⅳ)oxidation process.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22172093 and 21776167)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2023MB061)。
文摘Fully conjugated covalent organic frameworks(COFs)are widely used in electrocatalysis.The COF with-ph-NH_(2)edge poly(1,4-phenyldiazo porphyrin cobalt)(A-PpazoPorCo)is synthesized by adjusting the molar ratio of the reaction material,and exhibits high delocalization energy to significantly enhance thermal stability.The nitrogen in the azo bond improves the adsorption capacity for ORR and OER catalytic intermediates,while the-ph-NH_(2)group further increases the electron cloud density at the Co-N_(4)center in A-PpazoPorCo.Density functional theory(DFT)calculations reveal that the strong electron-donating-ph-NH_(2)groups and the electron-donating azo bonds form an electron donor-π-electron acceptor(D-π-A)structure,which further enhances the electron cloud density.The strongπ-πinteraction between A-PpazoPorCo and three-dimensional graphene(3D-G)significantly boosts the oxygen catalytic performance of the A-PpazoPorCo/3D-G.The catalytic ORR half-wave potential(E_(1/2))of A-PpazoPorCo/3D-G can reach 0.880 V vs.RHE.The total overpotential(ΔE=E_(j=10)-E_(1/2))is 0.617 V,demonstrating excellent bifunctional oxygen catalytic performance.The efficient oxygen catalytic performance indicates that A-PpazoPorCo/3D-G has the potential for application in fuel cells cathodes and overall water splitting anodes.
文摘Protoporphyrin IX (PPIX) fluorescence-guided brain tumor resection, using 5-aminolevulinic acid (5-ALA), is among the most valuable tools for determining tumor removal area. However, PPIX fluorescence is not necessarily achieved during an operation visually even when 5-ALA is used, and we do not know until tumor exposure to the excitation light of the ultraviolet region whether PPIX fluorescence has been achieved. When a particular biopsy and frozen section diagnosis is made, the reason for lack of PPIX fluorescence in the tissue cannot be judged. We do not know whether the tumor fails to fluoresce or no fluorescence is seen because it is not the main body of the tumor. We investigated whether the presence or absence of tumor fluorescence could be predicted by examining urinary porphyrin before surgery, at the time of intraoperative fluorescence diagnosis using 5-ALA. The urine of brain tumor patients 2 hours after 5-ALA administration was irradiated with a 405 ± 1 nm laser light. The patients were divided into a fluorescent urine group and negative fluorescent urine group. Red fluorescence was observed in response to the 405 ± 1 nm laser beam for all tumors in the fluorescent urine group. Clear red fluorescence was not observed even with 405 ± 1 nm laser beam irradiation in any tumors in the negative fluorescent urine group. Preoperative prediction of the intraoperative fluorescence of PPIX can be achieved by observation of urine 2 hours after 5-ALA administration with exposure to a 405 ± 1 nm laser light.
基金We are gratefully acknowledged financial support of this work by the National Natural ScienceFoundation of China (2007 1034) the N.S.F of Guangdong Province of China.
文摘A new porphyrin-fluorescein hybrid 2 (Fl-PPTPP) has been synthesized and characterized by UV-Vis, IR, H-NMR, ESI-MS and elemental analysis. The supramolecular 1 self-assembly of Fl-PPTPP with amino-porphyrinatomanganese [Mn (p-APTPP)Cl] by hydrogen-bonding was studied using fluorescence spectroscopic titration and ESI-MS.
基金Supported by the National Natural Science Foundation of China(No.20806025)
文摘Four ＂picket fence＂ porphyrin atropisomers were respectively synthesized from the four corresponding atropisomers of meso-tetra（o-aminophenyl）porphyrin that had been chromatographed on a column eluted with petroleum ether and ethyl acetate. Results show that each atropisomer could be successfully synthesized by controlling the acylation temperature at 0 ℃. They were characterized by 1H NMR, HRMS, IR, UV-Vis and Langmuir-Blodgett（LB） film analyses. Although the results of HRMS, IR, UV-Vis analyses indicate there is no remarkable difference among the atropisomers, the results of the 1H NMR and the mean molecular areas obtained by LB film technique imply that the atropisomers are significantly discrepant. The former shows that the chemical shifts of the methyl and amide protons of each atropisomer are distinct, while the later presents that the different atropisomer molecules can occupy the different surface areas at the air/water interface.
基金supported by NSERC DG 2016-06122 and 201606589 through Discovery Grants to HBK and X.A.Z.,respectivelyby the Canada Foundation for Innovation,Canada Research Chair,and the Ontario Research Fund。
文摘The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic activity of molecular catalysts has been widely studied in H-cells;their less studied capabilities in more efficient flow cell reactors have the potential to rival that of heterogeneous catalysts.In this work,a comparative study of amino functionalized iron-tetraphenylporphyrins(amino-Fe-TPPs) immobilized onto carbonaceous materials in both H-cells and flow cells was conducted to selectively reduce CO_(2) to CO.In a flow cell set up operating in alkaline media,the resulting hybrid catalyst exhibits 87% faradaic efficiency(FE) with extraordinary current density(j) of 119 mA/cm^(2) and turnover frequency(TOF) of 14 s^(-1) at-1.0 V vs.RHE.This remarkable catalytic activity was achieved through thoughtful combination of molecular and flow cell design that provides an effective strategy for future immobilized heterogeneous approaches toward CO_(2) reduction reactions(CO_(2) RRs).
文摘A mono-funtionalised tetraphenylporphyrin (TPP) bearing valine moiety at the phenylring was synthesized for photocytotoxicity examination in four steps, starting from regiospecificmono-nitration of TPP at the phenyl ring. The in vitro photocytotoxicitic effect against SPC-Aladenocarcinona cell line was tested.
基金Supported by the National Natural Science Foundation of China （20776003, 20576005） and the Key Project of Natural Science Foundation of Beijing （2061001）.
文摘A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.
文摘ω -Bromopropylporphyrin ether synthesized from the raction of 1,3-dibromopropane as the bridge-linked reagent and 5-(4-hydroxyphenyl)-10,15,20-triphenylporphyrin (H_2MHTPP) as the matrix reacts with 5,15-di(4- hydroxyphenyl)-10,20-diphenyl porphyrin( trans -H_2DHDPP) to give the title nanometer porphyrin trimer. The characterization was carried out by means of elemental analyses,UV-Vis,IR, 1H NMR and XRD.
基金the Decree of the Government of the Russian Federation No.220 of April 9,2010(Agreement No.075-15-2021-615 of June 4,2021).
文摘Photodynamic inactivation of microorganisms known as antibacterial photodynamic therapy(APDT)is one of the most promising and innovative approaches for the destruction of pathogenic microorganisms.Among the photosensitizers(PSs),compounds based on cationic porphyrins/metalloporphyrins are most successfully used to inactivate microorganisms.Series of meso-substituted cationic pyridylporphyrins and metalloporphyrins with various peripheral groups in the third and fourth positions of the pyrrole ring have been synthesized in Armenia.The aim of this work was to determine and test the most e®ective cationic porphyrins and metalloporphyrins with high photoactivity against Gram negative and Gram positive microorganisms.It was shown that the synthesized cationic pyridylporphyrins/metalloporphyrins exhibit a high degree of phototoxicity towards both types of bacteria,including the methicillinresistant S.aureus strain.Zinc complexes of porphyrins are more phototoxic than metal-free porphyrin analogs.The e®ectiveness of these Zn–metalloporphyrins on bacteria is consistent with the level of singlet oxygen generation.It was found that the high antibacterial activity of the studied cationic porphyrins/metalloporphyrins depends on four factors:the presence in the porphyrin macrocycle of a positive charge(+4),a central metal atom(Zn2þÞand hydrophobic peripheral functional groups as well as high values of quantum yields of singlet oxygen.The results indicate that meso-substituted cationic pyridylporphyrins/metalloporphyrins cannd wider application in photoinactivation of bacteria than anionic or neutral PSs usually used in APDT.
文摘The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru3(CO)12], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a?2d respectively. Treatment of 2a?2d with Merrifield’s peptide resin obtained 3a?3d. The compounds 3a?3d reacted with methyl iodide respectively gave 4a?4d. New complexes 4a?4d have been identified by IR, UV-visible spectra, and AES.
文摘The water soluble tetra p sulfonatophenylporphyrinatolanthanide, [Ln·TPPS·OH ·2imidazole] ·3H 2O(Ln=Tb～Yb), were synthesized and characterized. Their stability and complex constants were also studied and determined. The structural formula of the lanthanide porphyrins was proposed too. The lanthanide atom is sitting above the porphyrin plane. For the lanthanide porphyrin complexes, the complex becomes more stable and the reduction potential has a slight shift to more positive values as the atomic number increases from Tb to Yb. The mechanism of electrode processes for these lanthanidee porphyrin complexes were investigated in details.
