Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safet...Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.展开更多
Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmeth...Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.展开更多
Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bip...Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine, and DMF = N,N＇-dimethylformamide） and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional（3D） layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional（2D） wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra（IR）, thermal gravimetric analyses（TGA） and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.展开更多
Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources.De-centralized production of hydrogen peroxide(H_(2)O_(2))from...Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources.De-centralized production of hydrogen peroxide(H_(2)O_(2))from water and oxygen of air is highly desirable for daily life and industry.We report an effective electrochemical refinery(e-refinery)for H_(2)O_(2)by means of electrocatalysis-controlled comproportionation reaction(2_(H)O+o→2HO),feeding pure water and oxygen only.Mesoporous nickel(Ⅱ)oxide(NiO)was used as electrocatalyst for oxygen evolution reaction(OER),producing oxygen at the anode.Conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)drove the oxygen reduction reaction(ORR),forming H_(2)O_(2)on the cathode.The reactions were evaluated in both half-cell and device configurations.The performance of the H_(2)O_(2)e-refinery,assembled on anion-exchange solid electrolyte and fed with pure water,was limited by the unbalanced ionic transport.Optimization of the operation conditions allowed a conversion efficiency of 80%.展开更多
A new Cd（Ⅱ） coordination polymer, namely, [Cd（1,3-bip）（3,5-pdc）]n （1,3-bip = 1,3-bis（imidazol）propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid） has been synthesized under hydrothermal conditions. Compou...A new Cd（Ⅱ） coordination polymer, namely, [Cd（1,3-bip）（3,5-pdc）]n （1,3-bip = 1,3-bis（imidazol）propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid） has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction （PXRD） and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 1.40178（7）, b = 1.72502（12）, c = 1.41635（6） ran, β = 92.653（4）°, V = 3.4212（3） nm3, Z = 4, C16HIsCdNsO4, Mr = 453.73, Dc = 1.762 g/cm3, F（000） = 1808,μ = 1.310 mm1, R = 0.0899 and wR = 0.1945. In compound 1, each 3,5-pdc ligand links three Cd（lI） ions and each Cd（Ⅱ） attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.展开更多
A new coordination polymer, [Cd2（NIPH）（L）2（H2O）]n（1, HL = 3-（2-pyridyl）pyrazole and H2NIPH = 5-nitroisophthalic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-...A new coordination polymer, [Cd2（NIPH）（L）2（H2O）]n（1, HL = 3-（2-pyridyl）pyrazole and H2NIPH = 5-nitroisophthalic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis, thermogravimetric analysis and fluorescence spectrum analysis. Complex 1 belongs to the triclinic system, space group P1 with a = 8.9539（6）, b = 11.6252（8）, c = 12.2472（8） A^°, α = 80.011（2）, β = 80.3850（10）, γ = 86.773（2）°, V = 1237.37（14） A^°3, Z = 2, Dc = 1.987 g/cm^3, μ = 1.780 mm^-1, Mr = 740.25, F（000） = 724, the final R = 0.0295 and wR = 0.1015 with I 〉 2σ（I）. Two H2NIPH as monodentate and bidentate ligands and two L ligands link four Cd（Ⅱ） ions to form a tetranuclear subunit. Each pair of the tetranuclear subunits is bridged by NIPH ligands to yield a one-dimensional double-chain structure. Furthermore, the 1D chains are linked into a 3D supramolecular framework with hydrogen bonds and π-π interactions. In addition, we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.展开更多
A new cadmium（II） polymer based on imidazole derivative, formulated as [Cd（Hiba）2]n 1, H2iba = 4-（1-H-imidazol-2-yl） benzoic acid）, has been synthesized under hydro- thermal conditions. The compound crystallize...A new cadmium（II） polymer based on imidazole derivative, formulated as [Cd（Hiba）2]n 1, H2iba = 4-（1-H-imidazol-2-yl） benzoic acid）, has been synthesized under hydro- thermal conditions. The compound crystallizes in triclinic system, space group P1 with a = 7.062（4）, b = 10.840（7）, c = 13.099（8） A, a = 98.102（7）, fl = 101.524（7）, y = I07.961（7）°, V= 912.3（10） A3, Z = 2, Mr = 486.75, Dc = 1.772 Mg/m3,/t = 1.234 mm-1, F（000） = 484, the final R = 0.0735 and wR = 0.1739 for 2154 observed reflections with 1 〉 20（I）. Polymer 1 consists of （Cd-Hiba）2 zigzag chains, which are further linked by hydrogen bonding to extend into a two-dimensional （2D） corrugated-shape sheet structure. The 2D structures are further connected into a 3D supramolecular edifice through hydrogen bonding. The polymer exhibits exceptional high thermal stability. The bulk purity of the materials of 1 was confirmed through the powder X-ray diffraction （PXRD） patterns. The luminescent property of polymer I has also been investigated.展开更多
Inverse emulsion polymerization was employed to synthesize inverse emulsion Cd（Ⅱ） imprinted polymers （IEⅡ P）. The morphology and functional groups of IEⅡP were characterized by SEM,FTIR and TG. Static adsorptio...Inverse emulsion polymerization was employed to synthesize inverse emulsion Cd（Ⅱ） imprinted polymers （IEⅡ P）. The morphology and functional groups of IEⅡP were characterized by SEM,FTIR and TG. Static adsorption experiments and competitive adsorption test were used to evaluate the adsorption ability of IEⅡP. The adsorption capacity of polymers could reach 86.7 mg·g^-1 under the optimal adsorption conditions. The pseudo second order kinetic model and Langmuir isotherm model could be used to analyze the experimental data well. The adsorption process of IEⅡP was chemical adsorption process and monomolecular type. Thermodynamic parameters showed that the adsorption process was endothermic and could occur spontaneously. The selectivity coefficients k of Cd^2＋/v, Cd^2＋/Zn^2＋ and Cd^2＋/Cu^2＋ were 2.4998, 1.2437 and 4.6882, respectively. The proposed method provides a new thought for removing Cd（Ⅱ） in water samples.展开更多
Two new coordination polymers {[Zn（Hbtc）（bpyb）]·H2O}n（1） and {[Cd（Hbtc）-（bpyb）（1.5）]·0.5 bpyb}n（2）（H3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis（4-pyridyl）benzene） have been synth...Two new coordination polymers {[Zn（Hbtc）（bpyb）]·H2O}n（1） and {[Cd（Hbtc）-（bpyb）（1.5）]·0.5 bpyb}n（2）（H3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis（4-pyridyl）benzene） have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H…N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H…N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.展开更多
基金The work was financially supported by the National Natural Science Foundation of China(No.52173135,22207024)Jiangsu Specially Appointed Professorship,Leading Talents of Innovation and Entrepreneurship of Gusu(ZXL2022496)the Suzhou Science and Technology Program(SKY2022039).
文摘Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.
文摘Two new coordination polymers,[Ni(Hpdc)(bib)(H_(2)O)]_(n)(1)and{[Ni(bib)_(3)](ClO_(4))_(2)}_(n)(2),were prepared by mixing Ni^(2+),3,5⁃pyrazoledicarboxylic acid(H3pdc)/p⁃nitrobenzoic acid and 1,4⁃bis(imidazol⁃1⁃ylmethyl)butane(bib)by a hydrothermal method,respectively.X⁃ray crystallography reveals a 2D network constructed by six⁃coordinated Ni(Ⅱ)centers,bib,and Hpdc2-ligands in complex 1,while a 2D network is built by Ni(Ⅱ)and bib ligands in 2.Furthermore,the quantum⁃chemical calculations have been performed on‘molecular fragments’extracted from the crystal structure of 1 using the PBE0/LANL2DZ method in Gaussian 16 and the VASP program.CCDC:2343794,1;2343798,2.
基金the National Natural Science Foundation of China(21501178)Natural Science Funds of Fujian Province(No.2014H0055)for financial support of this work
文摘Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine, and DMF = N,N＇-dimethylformamide） and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional（3D） layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional（2D） wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra（IR）, thermal gravimetric analyses（TGA） and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.
基金the competence centre Fun Mat-II funded by the Swedish Agency for Innovation Systems(Vinnova,grant no 2016-05156)Swedish Energy Agency(project no 42022-1)+3 种基金Swedish Research Council(VR 2021-04427,VR 2019-05577,VR 2016–05990)the Centre in Nanoscience and Technology(CeNano,Linkoping Institute of Technology(LiTH),Linkoping University,2020,2021)the Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University(Faculty Grant SFO-Mat-Li U No.2009-00971)the Knut and Alice Wal enberg Foundation(H2O2,KAW 2018.0058),for support
文摘Electrocatalysis enables the industrial transition to sustainable production of chemicals using abundant precursors and electricity from renewable sources.De-centralized production of hydrogen peroxide(H_(2)O_(2))from water and oxygen of air is highly desirable for daily life and industry.We report an effective electrochemical refinery(e-refinery)for H_(2)O_(2)by means of electrocatalysis-controlled comproportionation reaction(2_(H)O+o→2HO),feeding pure water and oxygen only.Mesoporous nickel(Ⅱ)oxide(NiO)was used as electrocatalyst for oxygen evolution reaction(OER),producing oxygen at the anode.Conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS)drove the oxygen reduction reaction(ORR),forming H_(2)O_(2)on the cathode.The reactions were evaluated in both half-cell and device configurations.The performance of the H_(2)O_(2)e-refinery,assembled on anion-exchange solid electrolyte and fed with pure water,was limited by the unbalanced ionic transport.Optimization of the operation conditions allowed a conversion efficiency of 80%.
基金Supported by the National Natural Science Foundation of China(No.21373132)the Science Foundation of Education Department of Shaanxi Provincial Government(No.12JK0637)
文摘A new Cd（Ⅱ） coordination polymer, namely, [Cd（1,3-bip）（3,5-pdc）]n （1,3-bip = 1,3-bis（imidazol）propane and 3,5-pdc = pyridine-3,5-dicarboxylic acid） has been synthesized under hydrothermal conditions. Compound 1 was characterized by infrared spectrum, elemental analysis, powder X-ray diffraction （PXRD） and single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 1.40178（7）, b = 1.72502（12）, c = 1.41635（6） ran, β = 92.653（4）°, V = 3.4212（3） nm3, Z = 4, C16HIsCdNsO4, Mr = 453.73, Dc = 1.762 g/cm3, F（000） = 1808,μ = 1.310 mm1, R = 0.0899 and wR = 0.1945. In compound 1, each 3,5-pdc ligand links three Cd（lI） ions and each Cd（Ⅱ） attaches to bip ligands to form a complicated 2D double-layer structure. In addition, the thermal stability and luminescent property of 1 have been studied in the solid state at room temperature.
基金supported by the Science and Technology Development Project of Jilin Provincial Science&Technology Department(201205080)the Science and Technology Research Projects of the Education Office of Jilin Province(No.2013.384)
文摘A new coordination polymer, [Cd2（NIPH）（L）2（H2O）]n（1, HL = 3-（2-pyridyl）pyrazole and H2NIPH = 5-nitroisophthalic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis, thermogravimetric analysis and fluorescence spectrum analysis. Complex 1 belongs to the triclinic system, space group P1 with a = 8.9539（6）, b = 11.6252（8）, c = 12.2472（8） A^°, α = 80.011（2）, β = 80.3850（10）, γ = 86.773（2）°, V = 1237.37（14） A^°3, Z = 2, Dc = 1.987 g/cm^3, μ = 1.780 mm^-1, Mr = 740.25, F（000） = 724, the final R = 0.0295 and wR = 0.1015 with I 〉 2σ（I）. Two H2NIPH as monodentate and bidentate ligands and two L ligands link four Cd（Ⅱ） ions to form a tetranuclear subunit. Each pair of the tetranuclear subunits is bridged by NIPH ligands to yield a one-dimensional double-chain structure. Furthermore, the 1D chains are linked into a 3D supramolecular framework with hydrogen bonds and π-π interactions. In addition, we analyzed Natural Bond Orbital（NBO） in using the PBE0/LANL2DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Cd（Ⅱ） ion.
基金supported by the National Natural Science Foundation of China (No. 21271098, 21071074 and 20871042)Specialized Research Fund for the Doctoral Program of Higher Education of China (No. 20104104110004)Natural Science Foundation of the Education Department of Henan Province (No 2011A150019 and 2008B430012)
文摘A new cadmium（II） polymer based on imidazole derivative, formulated as [Cd（Hiba）2]n 1, H2iba = 4-（1-H-imidazol-2-yl） benzoic acid）, has been synthesized under hydro- thermal conditions. The compound crystallizes in triclinic system, space group P1 with a = 7.062（4）, b = 10.840（7）, c = 13.099（8） A, a = 98.102（7）, fl = 101.524（7）, y = I07.961（7）°, V= 912.3（10） A3, Z = 2, Mr = 486.75, Dc = 1.772 Mg/m3,/t = 1.234 mm-1, F（000） = 484, the final R = 0.0735 and wR = 0.1739 for 2154 observed reflections with 1 〉 20（I）. Polymer 1 consists of （Cd-Hiba）2 zigzag chains, which are further linked by hydrogen bonding to extend into a two-dimensional （2D） corrugated-shape sheet structure. The 2D structures are further connected into a 3D supramolecular edifice through hydrogen bonding. The polymer exhibits exceptional high thermal stability. The bulk purity of the materials of 1 was confirmed through the powder X-ray diffraction （PXRD） patterns. The luminescent property of polymer I has also been investigated.
基金Supported by the National Natural Science Foundation of China(21276174)the Natural Science Foundation of Shanxi Province(2013011040-1)
文摘Inverse emulsion polymerization was employed to synthesize inverse emulsion Cd（Ⅱ） imprinted polymers （IEⅡ P）. The morphology and functional groups of IEⅡP were characterized by SEM,FTIR and TG. Static adsorption experiments and competitive adsorption test were used to evaluate the adsorption ability of IEⅡP. The adsorption capacity of polymers could reach 86.7 mg·g^-1 under the optimal adsorption conditions. The pseudo second order kinetic model and Langmuir isotherm model could be used to analyze the experimental data well. The adsorption process of IEⅡP was chemical adsorption process and monomolecular type. Thermodynamic parameters showed that the adsorption process was endothermic and could occur spontaneously. The selectivity coefficients k of Cd^2＋/v, Cd^2＋/Zn^2＋ and Cd^2＋/Cu^2＋ were 2.4998, 1.2437 and 4.6882, respectively. The proposed method provides a new thought for removing Cd（Ⅱ） in water samples.
基金supported by the National Natural Science Foundation of China(No.21373178)
文摘Two new coordination polymers {[Zn（Hbtc）（bpyb）]·H2O}n（1） and {[Cd（Hbtc）-（bpyb）（1.5）]·0.5 bpyb}n（2）（H3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis（4-pyridyl）benzene） have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H…N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H…N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.
