The rational design of photochemical molecular device(PMD)and its hybrid system has great potential in improving the activity of photocatalytic hydrogen production.A series of Pd6L3 type metal-organic cages,denoted as...The rational design of photochemical molecular device(PMD)and its hybrid system has great potential in improving the activity of photocatalytic hydrogen production.A series of Pd6L3 type metal-organic cages,denoted as MOC-Py-M(M=H,Cu,and Zn),are designed for PMDs by combining metalloporphyrin-based ligands with catalytically active Pd^(2+)centers.These metal-organic cages(MOCs)are first successfully hybridized with graphitic carbon nitride(g-C_(3)N_(4))to form direct Z-scheme heterogeneous MOC-Py-M/g-C_(3)N_(4)(M=H,Cu,and Zn)photocatalysts via π-πinteractions.Benefiting from its better light absorption ability,the MOC-Py-Zn/g-C_(3)N_(4) catalyst exhibits high H_(2) production activity under visible light(10348μmol g^(-1) h^(-1)),far superior to MOC-Py-H/g-C_(3)N_(4) and MOC-Py-Cu/g-C_(3)N_(4).Moreover,the MOC-Py-Zn/g-C_(3)N_(4) system obtains an enhanced turn over number(TON)value of 32616 within 100 h,outperforming the homogenous MOC-Py-Zn(TON of 507 within 100 h),which is one of the highest photochemical hybrid systems based on MOC for visible-light-driven hydrogen generation.This confirms the direct Z-scheme heterostructure can promote effective charge transfer,expand the visible light absorption region,and protect the cages from decomposition in MOC-Py-Zn/g-C_(3)N_(4).This work presents a creative example that direct Z-scheme PMD-based systems for effective and persistent hydrogen generation from water under visible light are obtained by heterogenization approach using homogeneous porphyrin-based MOCs and g-C_(3)N_(4) semiconductors.展开更多
The orientation is the key factor to determine the physicochemical properties of the metal-organic framework(MOF)films.New strategies for oriented MOF films are of fundamental importance in the advancement of science ...The orientation is the key factor to determine the physicochemical properties of the metal-organic framework(MOF)films.New strategies for oriented MOF films are of fundamental importance in the advancement of science and technology.Here we report a unified approach to the synthesis of a large variety of porphyrin-based MOF films with different directions,chemistries and properties.This strategy is based on a general electrochemical regulation of coordination process of different metal cation(M_(1)=Zn,Co,Ni,Ce)and tetra(4-carboxyphenyl)porphyrin(M_(2)TCPP,M_(2)=H,Cu,Pt,Pd)on various conductive substrates.The cathode strategy relies on the reduction of M_(2)TCPP ligands and follows the electrochemical reaction mechanism to achieve effective control over crystallizing M_(1)-M_(2)TCPP MOF films oriented in the(110)direction.The highly oriented M_(1)-M_(2)TCPP MOF films are endowed with excellent crystalline,spatial network structure and hierarchical three-dimensional pore structure,which is conducive to charge transfer and material transmission and suitable for use as an electrochemical catalyst.The Zn-TCPP MOF films on conductive substrate could be used directly as an electrochemical sensor for electrocatalytic oxidation of NaNO2,and showed wide linear range,low limit of detection(0.24μM),high sensitivity(285.8 mA/(mM·cm2))and good anti-interference performance.We believe our methodology provides a simple and convenient route to a variety of oriented porphyrin-based MOF films for nanodevices with novel structure and function in nanotechnology.展开更多
Theranostics,integrating diagnostic and therapeutic functionalities,have emerged as advanced systems for timely cancer diagnosis and effective treatment.The development of versatile materials suitable for cancer thera...Theranostics,integrating diagnostic and therapeutic functionalities,have emerged as advanced systems for timely cancer diagnosis and effective treatment.The development of versatile materials suitable for cancer theranostics is intensifying.Porphyrin-based metal-organic frameworks(MOFs)leverage the structural diversity and designability inherent in MOFs,alongside the robust photophysical,catalytic,and biological properties of porphyrins.These materials enhance the solubility and stability of porphyrins and facilitate their stable functionalized assemblies,conferring the potential for multimodal imaging diagnostics and precision therapeutics.In this review,we summarized the potential of porphyrin-based MOFs as cancer theranostics platforms,focusing on recent advancements in porphyrin-based MOFs,and highlighting their functionalized strategies and developments in diagnostic imaging and synergistic therapies.Finally,we proposed the challenges and prospects of these emerging materials in cancer theranostics.展开更多
All-small-molecule organic solar cells (ASM OSCs) are promising for commercial application due to the well-defined chemical structures, convenient purifying process and low batch-to-batch variation. However, the simil...All-small-molecule organic solar cells (ASM OSCs) are promising for commercial application due to the well-defined chemical structures, convenient purifying process and low batch-to-batch variation. However, the similarity of molecule structures between small molecule donors and acceptors makes a hard regulation of their blend morphology, which will limit the efficiency.展开更多
Mitochondria are the power plants of the cell and play key roles in activating the apoptotic pathway in cancer cells,which are readily susceptible to cytotoxic reactive oxygen species and temperature elevations.Herein...Mitochondria are the power plants of the cell and play key roles in activating the apoptotic pathway in cancer cells,which are readily susceptible to cytotoxic reactive oxygen species and temperature elevations.Herein,we develop a"nanomissile"that targets mitochondria to enhance tumor treatment effects by facilitating mitochondrial dysfunction and releasing cytochrome C to activate the apoptotic pathway of cancer cells under 650-nm laser irradiation.Porphyringrafted polydopamine nanomaterial(PTPF-MitP)is designed as a nanomissile,with integrated O;-evolving photodynamic therapy and moderate photothermal therapy,which can selectively deliver to the mitochondria through a targeting unit,MitP.The cytotoxicity of PTPF-MitP to human lung tumor cells is twice as high as that of PTPF that does not have mitochondrial targeting units.In addition,it represents a realtime visualization and highly efficient treatment for tumor sites in vivo.This development represents a viable strategy for cancer therapy.展开更多
Single-atom catalysts were widely used to treat atmospheric pollution and alleviate energy crises through photocatalysis.However,how to prevent the aggregation of single atoms during the preparation and catalytic proc...Single-atom catalysts were widely used to treat atmospheric pollution and alleviate energy crises through photocatalysis.However,how to prevent the aggregation of single atoms during the preparation and catalytic processes remained a great challenge.Herein,a novel ultrathin two-dimensional porphyrin-based single-atom photocatalyst Ti-MOF(abbreviated as TMPd)obtained through a simple hydrothermal synthesis strategy was used for photocatalytic hydrogen evolution and NO removal,in which the singleatom Pd tightly anchored in the center of porphyrin to ensure single-atom Pd stable existence.Compared with most reported MOFs-based photocatalysts,the TMPd showed an excellent hydrogen evolution rate(1.32 mmol g^(-1)h^(-1))and the NO removal efficiency(62%)under visible light irradiation.Aberrationcorrected high-angle annular dark-field scanning transmission electron microscope(HAADF-STEM)and synchrotron-radiation-based X-ray absorption fine-structure spectroscopy(XAFS)proved that pd in TMPd existed in an isolated state,and the atomic force microscope(AFM)proved the ultrathin morphology of TMPd.DFT calculations had demonstrated that single-atom Pd could serve as the active center and more effectively achieve electron transfer,indicating that single-atom Pd played a vital role in photocatalytic hydrogen evolution.In addition,a possible photocatalytic pathway of NO removal was proposed based on ESR and in-situ infrared spectra,in which the catalysts anchored with single-atom Pd could produce more active substances and more effectively oxidize NO to NO_(2)^(-)or NO_(3)^(-).The results suggested that coordinating single-atom metal species as the active site in the center of porphyrin could be a feasible strategy to obtain various ultrathin porphyrin-based single-atom photocatalysts to acquire excellent photocatalytic performance further.展开更多
The deposition of tetrakis(4-sulonatophenyl)porphyrin(TPPS)thin film on optical fibers presents many possibilities for sensing applications.The J-form aggregation with a narrow and sharp spectral feature at about 490n...The deposition of tetrakis(4-sulonatophenyl)porphyrin(TPPS)thin film on optical fibers presents many possibilities for sensing applications.The J-form aggregation with a narrow and sharp spectral feature at about 490nm and its sensitivity to humidity have been discussed;a fast change of wavelength occurs according with variation in the humidity level.The reproducibility and high sensitivity of TPPS-coated fibers,along with the capabilities of optical fibers,suggest the device as a good candidate for humidity sensing in harsh environments.展开更多
文摘The rational design of photochemical molecular device(PMD)and its hybrid system has great potential in improving the activity of photocatalytic hydrogen production.A series of Pd6L3 type metal-organic cages,denoted as MOC-Py-M(M=H,Cu,and Zn),are designed for PMDs by combining metalloporphyrin-based ligands with catalytically active Pd^(2+)centers.These metal-organic cages(MOCs)are first successfully hybridized with graphitic carbon nitride(g-C_(3)N_(4))to form direct Z-scheme heterogeneous MOC-Py-M/g-C_(3)N_(4)(M=H,Cu,and Zn)photocatalysts via π-πinteractions.Benefiting from its better light absorption ability,the MOC-Py-Zn/g-C_(3)N_(4) catalyst exhibits high H_(2) production activity under visible light(10348μmol g^(-1) h^(-1)),far superior to MOC-Py-H/g-C_(3)N_(4) and MOC-Py-Cu/g-C_(3)N_(4).Moreover,the MOC-Py-Zn/g-C_(3)N_(4) system obtains an enhanced turn over number(TON)value of 32616 within 100 h,outperforming the homogenous MOC-Py-Zn(TON of 507 within 100 h),which is one of the highest photochemical hybrid systems based on MOC for visible-light-driven hydrogen generation.This confirms the direct Z-scheme heterostructure can promote effective charge transfer,expand the visible light absorption region,and protect the cages from decomposition in MOC-Py-Zn/g-C_(3)N_(4).This work presents a creative example that direct Z-scheme PMD-based systems for effective and persistent hydrogen generation from water under visible light are obtained by heterogenization approach using homogeneous porphyrin-based MOCs and g-C_(3)N_(4) semiconductors.
基金supported by the National Natural Science Foundation of China(Nos.21422102,21171049,21501045,21403054,and 22405072)Postdoctoral Fellowship Program of CPSF(No.GZC20230673)+3 种基金Program for Science&Technology Innovation Talents in Universities of Henan Province(No.13HASTIT009)Program for Changjiang Scholars and Innovative Research Team in University(No.PCS IRT1126)China Postdoctoral Science Foundation(No.2024M760782)Key Research Projects of Higher Education Institutions in Henan Province(No.24A150003).
文摘The orientation is the key factor to determine the physicochemical properties of the metal-organic framework(MOF)films.New strategies for oriented MOF films are of fundamental importance in the advancement of science and technology.Here we report a unified approach to the synthesis of a large variety of porphyrin-based MOF films with different directions,chemistries and properties.This strategy is based on a general electrochemical regulation of coordination process of different metal cation(M_(1)=Zn,Co,Ni,Ce)and tetra(4-carboxyphenyl)porphyrin(M_(2)TCPP,M_(2)=H,Cu,Pt,Pd)on various conductive substrates.The cathode strategy relies on the reduction of M_(2)TCPP ligands and follows the electrochemical reaction mechanism to achieve effective control over crystallizing M_(1)-M_(2)TCPP MOF films oriented in the(110)direction.The highly oriented M_(1)-M_(2)TCPP MOF films are endowed with excellent crystalline,spatial network structure and hierarchical three-dimensional pore structure,which is conducive to charge transfer and material transmission and suitable for use as an electrochemical catalyst.The Zn-TCPP MOF films on conductive substrate could be used directly as an electrochemical sensor for electrocatalytic oxidation of NaNO2,and showed wide linear range,low limit of detection(0.24μM),high sensitivity(285.8 mA/(mM·cm2))and good anti-interference performance.We believe our methodology provides a simple and convenient route to a variety of oriented porphyrin-based MOF films for nanodevices with novel structure and function in nanotechnology.
基金financially supported by Startup Foundation for Advanced Talents of Qingdao University(DC2400001387)National Natural Science Foundation of China(22074157)+3 种基金National Key R&D Program of China(2022YFA1103403)China Postdoctoral Science Foundation(2020M673541)Startup Foundation for Advanced Talents of Qingdao University(DC2100004477)State Key Laboratory of Bio-Fibers and Eco-Textiles of Qingdao University(RZ2200002491).
文摘Theranostics,integrating diagnostic and therapeutic functionalities,have emerged as advanced systems for timely cancer diagnosis and effective treatment.The development of versatile materials suitable for cancer theranostics is intensifying.Porphyrin-based metal-organic frameworks(MOFs)leverage the structural diversity and designability inherent in MOFs,alongside the robust photophysical,catalytic,and biological properties of porphyrins.These materials enhance the solubility and stability of porphyrins and facilitate their stable functionalized assemblies,conferring the potential for multimodal imaging diagnostics and precision therapeutics.In this review,we summarized the potential of porphyrin-based MOFs as cancer theranostics platforms,focusing on recent advancements in porphyrin-based MOFs,and highlighting their functionalized strategies and developments in diagnostic imaging and synergistic therapies.Finally,we proposed the challenges and prospects of these emerging materials in cancer theranostics.
基金The authors thank the National Natural Science Foundation of China(52103221,52172048)the Shandong Provincial Natural Science Foundation(ZR2021QB179,ZR2021QB024,ZR2021ZD06)the Fundamental Research Funds of Shandong University.
文摘All-small-molecule organic solar cells (ASM OSCs) are promising for commercial application due to the well-defined chemical structures, convenient purifying process and low batch-to-batch variation. However, the similarity of molecule structures between small molecule donors and acceptors makes a hard regulation of their blend morphology, which will limit the efficiency.
基金supported by the National Natural Science Foundation of China(21705117,22174110,21904095 and 22004089)the Elite Scholar Program of Tianjin University(2019XRG-0065)+2 种基金the Program of Tianjin Science and Technology Major Project and Engineering(19ZXYXSY00090)the Program for Chang Jiang Scholars and Innovative Research Team,Ministry of Education,China(IRT-16R61)the Special Fund Project for the Central Government to Guide Local Science and Technology Development(2020)。
文摘Mitochondria are the power plants of the cell and play key roles in activating the apoptotic pathway in cancer cells,which are readily susceptible to cytotoxic reactive oxygen species and temperature elevations.Herein,we develop a"nanomissile"that targets mitochondria to enhance tumor treatment effects by facilitating mitochondrial dysfunction and releasing cytochrome C to activate the apoptotic pathway of cancer cells under 650-nm laser irradiation.Porphyringrafted polydopamine nanomaterial(PTPF-MitP)is designed as a nanomissile,with integrated O;-evolving photodynamic therapy and moderate photothermal therapy,which can selectively deliver to the mitochondria through a targeting unit,MitP.The cytotoxicity of PTPF-MitP to human lung tumor cells is twice as high as that of PTPF that does not have mitochondrial targeting units.In addition,it represents a realtime visualization and highly efficient treatment for tumor sites in vivo.This development represents a viable strategy for cancer therapy.
基金supported by the National Natural Science Foundation of China(Nos.22001026,21502012)the Chongqing Science and Technology Commission(Nos.CSTB2022NSCQ-MSX1308,CSTB2023NSCQ-MSX0670)+4 种基金the Science and Technology Research Program of Chongqing Municipal Education Commission(No.KJZDK202300806)Graduate Innovation Program of Chongqing Technology and Business University(No.yjscxx2023–211–41)Student Development Assistance Program of Chongqing Technology and Business University(No.2021412237)Fund of National-local Joint Engineering Research Center for Road Engineering and Disaster Prevention and Reduction Technology in Mountainous Areas(No.SQDL-2021–01)Cultural Relics Protection Research Project of Chongqing Bureau of Cultural Relics(2022No.318)。
文摘Single-atom catalysts were widely used to treat atmospheric pollution and alleviate energy crises through photocatalysis.However,how to prevent the aggregation of single atoms during the preparation and catalytic processes remained a great challenge.Herein,a novel ultrathin two-dimensional porphyrin-based single-atom photocatalyst Ti-MOF(abbreviated as TMPd)obtained through a simple hydrothermal synthesis strategy was used for photocatalytic hydrogen evolution and NO removal,in which the singleatom Pd tightly anchored in the center of porphyrin to ensure single-atom Pd stable existence.Compared with most reported MOFs-based photocatalysts,the TMPd showed an excellent hydrogen evolution rate(1.32 mmol g^(-1)h^(-1))and the NO removal efficiency(62%)under visible light irradiation.Aberrationcorrected high-angle annular dark-field scanning transmission electron microscope(HAADF-STEM)and synchrotron-radiation-based X-ray absorption fine-structure spectroscopy(XAFS)proved that pd in TMPd existed in an isolated state,and the atomic force microscope(AFM)proved the ultrathin morphology of TMPd.DFT calculations had demonstrated that single-atom Pd could serve as the active center and more effectively achieve electron transfer,indicating that single-atom Pd played a vital role in photocatalytic hydrogen evolution.In addition,a possible photocatalytic pathway of NO removal was proposed based on ESR and in-situ infrared spectra,in which the catalysts anchored with single-atom Pd could produce more active substances and more effectively oxidize NO to NO_(2)^(-)or NO_(3)^(-).The results suggested that coordinating single-atom metal species as the active site in the center of porphyrin could be a feasible strategy to obtain various ultrathin porphyrin-based single-atom photocatalysts to acquire excellent photocatalytic performance further.
文摘The deposition of tetrakis(4-sulonatophenyl)porphyrin(TPPS)thin film on optical fibers presents many possibilities for sensing applications.The J-form aggregation with a narrow and sharp spectral feature at about 490nm and its sensitivity to humidity have been discussed;a fast change of wavelength occurs according with variation in the humidity level.The reproducibility and high sensitivity of TPPS-coated fibers,along with the capabilities of optical fibers,suggest the device as a good candidate for humidity sensing in harsh environments.
