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
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
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
Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction us...Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction using H_(2)O as the reductant poses challenges is due to the difficulty in efficient cooperation among multiple functional moieties.Metal-organic frameworks(MOFs)are promising candidates for overall CO_(2)photoreduction due to their large surface area,diverse active sites,and excellent tailorability.In this study,we designed a metal-organic framework photocatalyst,named PCN-224(Zn)-Bpy(Ru),by integrating photoactive Zn(Ⅱ)-porphyrin and Ru(Ⅱ)-bipyridyl moieties.In comparison,two isostructural MOFs just with either Zn(Ⅱ)-porphyrin or Ru(Ⅱ)-bipyridyl moiety,namely PCN-224-Bpy(Ru)and PCN-224(Zn)-Bpy were also synthesized.As a result,PCN-224(Zn)-Bpy(Ru)exhibited the highest photocatalytic conversion rate of CO_(2)to CO,with a production rate of 7.6μmol·g^(-1)·h^(-1)in a mixed solvent of CH_(3)CN and H_(2)O,without the need for co-catalysts,photosensitizers,or sacrificial agents.Mass spectrometer analysis detected the signals of^(13)CO(m/z=29),^(13)C^(18)O(m/z=31),^(16)O^(18)O(m/z=34),and^(18)O_(2)(m/z=36),confirming that CO_(2)and H_(2)O acted as the carbon and oxygen sources for CO and O_(2),respectively,thereby confirming the coupling of photocatalytic CO_(2)reduction with H_(2)O oxidation.In contrast,using PCN-224-Bpy(Ru)or PCN-224(Zn)-Bpy as catalysts under the same conditions resulted in significantly lower CO production rates of only 1.5 and 0μmol·g^(-1)·h^(-1),respectively.Mechanistic studies revealed that the lowest unoccupied molecular orbital(LUMO)potential of PCN-224(Zn)-Bpy(Ru)is more negative than the redox potentials of CO_(2)/CO,and the highest occupied molecular orbital(HOMO)potential is more positive than that of H_(2)O/O_(2),satisfying the thermodynamic requirements for overall photocatalytic CO_(2)reduction.In comparison,the HOMO potential of PCN-224(Zn)-Bpy without Ru(II)-bipyridyl moieties is less positive than that of H_(2)O/O_(2),indicating that the Ru(II)-bipyridyl moiety is thermodynamically necessary for CO_(2)reduction coupled with H_(2)O oxidation.Additionally,photoluminescence spectroscopy revealed that the fluorescence of PCN-224(Zn)-Bpy(Ru)was almost completely quenched,and a longer average photoluminescence lifetime compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru)was observed.These suggest a low recombination rate of photogenerated carriers in PCN-224(Zn)-Bpy(Ru),which also supported by the higher photocurrent observed in PCN-224(Zn)-Bpy(Ru)compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru).In summary,the integrated Zn(II)-porphyrin and Ru(II)-bipyridyl moieties in PCN-224(Zn)-Bpy(Ru)play important roles of a photosensitizer and CO_(2)reduction as well as H_(2)O oxidation sites,and their efficient cooperation optimizes the band structure,thereby facilitating the coupling of CO_(2)reduction with H_(2)O oxidation and resulting in highperformance artificial photocatalytic CO_(2)reduction.展开更多
Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities.However,it is challenging to design molecular sensors for saccharides because this family of compounds i...Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities.However,it is challenging to design molecular sensors for saccharides because this family of compounds is hydromimetic in aqueous solutions and shares a similar chemical structure.In this review,research progress in the development of porphyrin-based saccharide sensors is described with representative examples.We focus on using porphyrin as the signal reporter because porphyrins exhibit unique advantages in high chemical stability,long emission wavelength,and multiple structural modification strategies.Reported literature results have been classified into mainly two sections according to the general working principles of the porphyrin sensor molecules.In the first section,recognition unit,design strategy and sensing performance of traditional porphyrin-based selective saccharide sensors are discussed.While in the second section,development of porphyrin-based sensor arrays for pattern recognition of saccharides has been summarized.Looking through the design strategy and sensing performance of reported achievements,it is reasonable to anticipate a bright future for designing practical porphyrin-based saccharide sensors.展开更多
Porphyrins and their derivatives are excellent photosensitizers in photodynamic therapy(PDT).The modification of porphyrin molecules into metal-organic cages(MOCs)is a viable strategy to improve their bioavailability....Porphyrins and their derivatives are excellent photosensitizers in photodynamic therapy(PDT).The modification of porphyrin molecules into metal-organic cages(MOCs)is a viable strategy to improve their bioavailability.In this work,MOC C66 based on porphyrin was synthesised by a one-pot self-assembly method.The three-dimensional structure of the metal-organic cage ameliorated the aggregation and selfquenching of porphyrins and increased the molar absorption coefficient in the visible light region,which enhanced the reactive oxygen species(ROS)yield of porphyrins and effectively improved the efficiency of photodynamic therapy.ROS generation ability tests in solution confirmed the improved reactive oxygen capacity of the cage,which showed greater phototoxicity to HeLa and MCF-7 cells in vitro,suggesting a new strategy for future modifications of the simple synthesis of porphyrins as photosensitizers.展开更多
Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitu...Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitution,as a strategy for improving the charge separation efficiency and increasing the amounts of active sites,has been designed and realized in a Hf-biphenyl dicarboxylic acid(BPDC)MOF.Specifically,a size and geometry matched meso-tetra(4-carboxyphenyl)porphyrin(TCPP)ligand was selected and doped into Hf-BPDC MOF by forming coordinating bonds with Hf centers,forming dualligand Hf-BPDC-TCPP MOF.The resultant Hf-BPDC-TCPP MOF showed significantly improved activity and chemical stability in the photocatalytic H_(2)generation(261μmol·g^(-1)·h^(-1))and tetracycline(TC)degradation reactions(95.8%),which was 48 and 1.47 folds higher than that of the Hf-BPDC MOF.Photophysical and electrochemical studies revealed that the introduction of porphyrin ligand could generate a stronger internal electric field for boosting the charge separation and transfer,increase the specific surface area for providing more active sites,and narrow the band gap to enhance the visible light absorption.This in situ ligand substitution method provides a promising approach to build a tunable platform for constructing high-performance MOF photocatalysts.展开更多
In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysi...In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysical properties which could be applicable in a wide range of areas[3–5].展开更多
Directed self-assembly has been used to create micro-nano scale patterns,including chiral periodic structures of organic molecules,for potential applications in optics,photonics,metamaterials,and medical and sensing t...Directed self-assembly has been used to create micro-nano scale patterns,including chiral periodic structures of organic molecules,for potential applications in optics,photonics,metamaterials,and medical and sensing technologies.This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques.The solution of tetrakis(4-sulfonatophenyl)porphyrin(TPPS)was induced by chiral amino acids(L/D-arginine and L/D-serine)to selfassemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate(SDS).The structures show precise line widths(5.5μm)and gaps(18μm).Using in situ optical microscopy and second harmonic generation(SHG)microscopy,the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated.It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies.This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.展开更多
Porphyrin and phthalocyanine compounds belong to a class of large and aromatic macrocyclic compounds.Owing to their unique structures and electronic properties,they have found widespread applications in optoelectronic...Porphyrin and phthalocyanine compounds belong to a class of large and aromatic macrocyclic compounds.Owing to their unique structures and electronic properties,they have found widespread applications in optoelectronic devices.In recent years,the doping of porphyrins and phthalocyanines into perovskite solar cells(PSCs)has emerged as an effective strategy to enhance device performance and stability.This doping strategy enables the modulation of perovskite film crystallization and surface defects,thereby improving charge transfer and enhancing the photo-conversion efficiency.As sensitizers,porphyrins and phthalocyanines absorb light in the visible and near-infrared spectral ranges,providing an advantage to the light absorption characteristics of PSCs.Additionally,their roles in interface modification and defect repair contribute to the long-term stability of the devices.The central metal of porphyrin can also adsorb ions and prevent the migration of harmful ions.This review summarizes the recent progress in the research on porphyrin and phthalocyanine-doped PSCs,empha-sizing their potential value in enhancing optoelectronic performance,increasing stability and expanding the application scope of these devices.展开更多
Redox-active organic electrode materials have emerged as a promising alternative to inorganic counter-parts in view of their low cost and easily tunable chemical/electrical/mechanical properties.However,practical issu...Redox-active organic electrode materials have emerged as a promising alternative to inorganic counter-parts in view of their low cost and easily tunable chemical/electrical/mechanical properties.However,practical issues of using these materials remain as a consequence of their electrically insulating character,limited specific capacity and cyclability.Porphyrin,a highly conjugated macrocyclic organic compound,is an appealing candidate due to its multi-electron transfer mechanism and its small energy barrier for rapid electron transfer.Here,a new class of copper(Ⅱ)meso-tetra(4-pyridyl)porphyrin(CuTPyP)was ob-tained by introducing copper ions into free-base H_(2) TPyP for regulation of redox activity and prevention of material dissolution,and was further hosted on conducting reduced graphene oxide(rGO)to enhance the redox activity.The resultant CuTPyP/rGO composites hence demonstrated a high reversible discharge capacity of 152 mAh g^(-1) after 200 cycles,with a capacity retention rate of 84.5% at 0.5 C,vastly superior to the bare CuTPyP(113 mAh g^(-1))and free-base H2 TPyP(62 mAh g^(-1)).A deep insight into the chemical states showed that electron-donating N atoms in the tetrapyridyl subunits behaved as the main charge storage sites during the charge and discharge state along with part contribution from the Cu(Ⅱ)/Cu(Ⅰ)conversion center.The high and stable electrochemical performance makes porphyrins a potential choice for real-use cathodes for long-term organic alkali metal batteries.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
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.
文摘Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction using H_(2)O as the reductant poses challenges is due to the difficulty in efficient cooperation among multiple functional moieties.Metal-organic frameworks(MOFs)are promising candidates for overall CO_(2)photoreduction due to their large surface area,diverse active sites,and excellent tailorability.In this study,we designed a metal-organic framework photocatalyst,named PCN-224(Zn)-Bpy(Ru),by integrating photoactive Zn(Ⅱ)-porphyrin and Ru(Ⅱ)-bipyridyl moieties.In comparison,two isostructural MOFs just with either Zn(Ⅱ)-porphyrin or Ru(Ⅱ)-bipyridyl moiety,namely PCN-224-Bpy(Ru)and PCN-224(Zn)-Bpy were also synthesized.As a result,PCN-224(Zn)-Bpy(Ru)exhibited the highest photocatalytic conversion rate of CO_(2)to CO,with a production rate of 7.6μmol·g^(-1)·h^(-1)in a mixed solvent of CH_(3)CN and H_(2)O,without the need for co-catalysts,photosensitizers,or sacrificial agents.Mass spectrometer analysis detected the signals of^(13)CO(m/z=29),^(13)C^(18)O(m/z=31),^(16)O^(18)O(m/z=34),and^(18)O_(2)(m/z=36),confirming that CO_(2)and H_(2)O acted as the carbon and oxygen sources for CO and O_(2),respectively,thereby confirming the coupling of photocatalytic CO_(2)reduction with H_(2)O oxidation.In contrast,using PCN-224-Bpy(Ru)or PCN-224(Zn)-Bpy as catalysts under the same conditions resulted in significantly lower CO production rates of only 1.5 and 0μmol·g^(-1)·h^(-1),respectively.Mechanistic studies revealed that the lowest unoccupied molecular orbital(LUMO)potential of PCN-224(Zn)-Bpy(Ru)is more negative than the redox potentials of CO_(2)/CO,and the highest occupied molecular orbital(HOMO)potential is more positive than that of H_(2)O/O_(2),satisfying the thermodynamic requirements for overall photocatalytic CO_(2)reduction.In comparison,the HOMO potential of PCN-224(Zn)-Bpy without Ru(II)-bipyridyl moieties is less positive than that of H_(2)O/O_(2),indicating that the Ru(II)-bipyridyl moiety is thermodynamically necessary for CO_(2)reduction coupled with H_(2)O oxidation.Additionally,photoluminescence spectroscopy revealed that the fluorescence of PCN-224(Zn)-Bpy(Ru)was almost completely quenched,and a longer average photoluminescence lifetime compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru)was observed.These suggest a low recombination rate of photogenerated carriers in PCN-224(Zn)-Bpy(Ru),which also supported by the higher photocurrent observed in PCN-224(Zn)-Bpy(Ru)compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru).In summary,the integrated Zn(II)-porphyrin and Ru(II)-bipyridyl moieties in PCN-224(Zn)-Bpy(Ru)play important roles of a photosensitizer and CO_(2)reduction as well as H_(2)O oxidation sites,and their efficient cooperation optimizes the band structure,thereby facilitating the coupling of CO_(2)reduction with H_(2)O oxidation and resulting in highperformance artificial photocatalytic CO_(2)reduction.
基金financially supported by the National Natural Science Foundation of China(Nos.22278229,22131005 and 21904066)333 High Level Talent Project of Jiangsu Province.
文摘Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities.However,it is challenging to design molecular sensors for saccharides because this family of compounds is hydromimetic in aqueous solutions and shares a similar chemical structure.In this review,research progress in the development of porphyrin-based saccharide sensors is described with representative examples.We focus on using porphyrin as the signal reporter because porphyrins exhibit unique advantages in high chemical stability,long emission wavelength,and multiple structural modification strategies.Reported literature results have been classified into mainly two sections according to the general working principles of the porphyrin sensor molecules.In the first section,recognition unit,design strategy and sensing performance of traditional porphyrin-based selective saccharide sensors are discussed.While in the second section,development of porphyrin-based sensor arrays for pattern recognition of saccharides has been summarized.Looking through the design strategy and sensing performance of reported achievements,it is reasonable to anticipate a bright future for designing practical porphyrin-based saccharide sensors.
基金supported by the National Natural Science Foundation of China(Nos.21977015 and 21820102001).
文摘Porphyrins and their derivatives are excellent photosensitizers in photodynamic therapy(PDT).The modification of porphyrin molecules into metal-organic cages(MOCs)is a viable strategy to improve their bioavailability.In this work,MOC C66 based on porphyrin was synthesised by a one-pot self-assembly method.The three-dimensional structure of the metal-organic cage ameliorated the aggregation and selfquenching of porphyrins and increased the molar absorption coefficient in the visible light region,which enhanced the reactive oxygen species(ROS)yield of porphyrins and effectively improved the efficiency of photodynamic therapy.ROS generation ability tests in solution confirmed the improved reactive oxygen capacity of the cage,which showed greater phototoxicity to HeLa and MCF-7 cells in vitro,suggesting a new strategy for future modifications of the simple synthesis of porphyrins as photosensitizers.
基金financially supported by the National Nature Science Foundation of China(Nos.22102064 and 21972058)supported by the Open Project Program of Fujian Provincial Key Laboratory of Ecology-Toxicological Effects and Control for Emerging Contaminants,Putian University。
文摘Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitution,as a strategy for improving the charge separation efficiency and increasing the amounts of active sites,has been designed and realized in a Hf-biphenyl dicarboxylic acid(BPDC)MOF.Specifically,a size and geometry matched meso-tetra(4-carboxyphenyl)porphyrin(TCPP)ligand was selected and doped into Hf-BPDC MOF by forming coordinating bonds with Hf centers,forming dualligand Hf-BPDC-TCPP MOF.The resultant Hf-BPDC-TCPP MOF showed significantly improved activity and chemical stability in the photocatalytic H_(2)generation(261μmol·g^(-1)·h^(-1))and tetracycline(TC)degradation reactions(95.8%),which was 48 and 1.47 folds higher than that of the Hf-BPDC MOF.Photophysical and electrochemical studies revealed that the introduction of porphyrin ligand could generate a stronger internal electric field for boosting the charge separation and transfer,increase the specific surface area for providing more active sites,and narrow the band gap to enhance the visible light absorption.This in situ ligand substitution method provides a promising approach to build a tunable platform for constructing high-performance MOF photocatalysts.
文摘In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysical properties which could be applicable in a wide range of areas[3–5].
基金funding from the National Natural Science Foundation of China(NSFC,Nos.22173112 and 91856121)Chinese Academy of Sciences for support(No.YJKYYQ20180014)。
文摘Directed self-assembly has been used to create micro-nano scale patterns,including chiral periodic structures of organic molecules,for potential applications in optics,photonics,metamaterials,and medical and sensing technologies.This study presents a straightforward approach for fabricating large-scale chiral grating porphyrin assemblies through template-assisted techniques.The solution of tetrakis(4-sulfonatophenyl)porphyrin(TPPS)was induced by chiral amino acids(L/D-arginine and L/D-serine)to selfassemble into highly ordered chiral grating structures with the assistance of sodium dodecyl sulfate(SDS).The structures show precise line widths(5.5μm)and gaps(18μm).Using in situ optical microscopy and second harmonic generation(SHG)microscopy,the chiral characteristics and dynamic evolution of the template-assisted self-assembly are investigated.It is found that the chirality of amino acids induced TPPS self-assembled into chiral structures and the liquid contraction interface significantly enhanced the chirality of the assemblies.This study is significant for understanding the mechanism of chiral evolution and designing novel micro-nano materials with predetermined chiral properties.
基金Funds for the Central Universities in China(zujbky-2021-ey10 and lzujbky-2022-it20)the National Natural Science Foundation of China(22371096 and 22075116).
文摘Porphyrin and phthalocyanine compounds belong to a class of large and aromatic macrocyclic compounds.Owing to their unique structures and electronic properties,they have found widespread applications in optoelectronic devices.In recent years,the doping of porphyrins and phthalocyanines into perovskite solar cells(PSCs)has emerged as an effective strategy to enhance device performance and stability.This doping strategy enables the modulation of perovskite film crystallization and surface defects,thereby improving charge transfer and enhancing the photo-conversion efficiency.As sensitizers,porphyrins and phthalocyanines absorb light in the visible and near-infrared spectral ranges,providing an advantage to the light absorption characteristics of PSCs.Additionally,their roles in interface modification and defect repair contribute to the long-term stability of the devices.The central metal of porphyrin can also adsorb ions and prevent the migration of harmful ions.This review summarizes the recent progress in the research on porphyrin and phthalocyanine-doped PSCs,empha-sizing their potential value in enhancing optoelectronic performance,increasing stability and expanding the application scope of these devices.
基金financially supported by the National Natural Science Foundation of China(No.52371248)the National Key R&D Program of China(No.2021YFB3802200)+1 种基金the Guangdong Basic and Applied Basic Research Foundation(No.2023A1515010905)the Scientific and Technological Innovation Foundation of Shunde Graduate School,USTB(No.BK22BE012).
文摘Redox-active organic electrode materials have emerged as a promising alternative to inorganic counter-parts in view of their low cost and easily tunable chemical/electrical/mechanical properties.However,practical issues of using these materials remain as a consequence of their electrically insulating character,limited specific capacity and cyclability.Porphyrin,a highly conjugated macrocyclic organic compound,is an appealing candidate due to its multi-electron transfer mechanism and its small energy barrier for rapid electron transfer.Here,a new class of copper(Ⅱ)meso-tetra(4-pyridyl)porphyrin(CuTPyP)was ob-tained by introducing copper ions into free-base H_(2) TPyP for regulation of redox activity and prevention of material dissolution,and was further hosted on conducting reduced graphene oxide(rGO)to enhance the redox activity.The resultant CuTPyP/rGO composites hence demonstrated a high reversible discharge capacity of 152 mAh g^(-1) after 200 cycles,with a capacity retention rate of 84.5% at 0.5 C,vastly superior to the bare CuTPyP(113 mAh g^(-1))and free-base H2 TPyP(62 mAh g^(-1)).A deep insight into the chemical states showed that electron-donating N atoms in the tetrapyridyl subunits behaved as the main charge storage sites during the charge and discharge state along with part contribution from the Cu(Ⅱ)/Cu(Ⅰ)conversion center.The high and stable electrochemical performance makes porphyrins a potential choice for real-use cathodes for long-term organic alkali metal batteries.
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.
