Despite decades of efforts,state-of-the-art synthetic burn dressings to treat partial-thickness burns are still far from ideal.Current dressings adhere to the wound and necessitate debridement.This work describes the ...Despite decades of efforts,state-of-the-art synthetic burn dressings to treat partial-thickness burns are still far from ideal.Current dressings adhere to the wound and necessitate debridement.This work describes the first“supramolecular hybrid hydrogel(SHH)”burn dressing that is biocompatible,self-healable,and on-demand dissoluble for easy and trauma-free removal,prepared by a simple,fast,and scalable method.These SHHs leverage the interactions of a custom-designed cationic copolymer via host-guest chemistry with cucurbit[7]uril and electrostatic interactions with clay nanosheets coated with an anionic polymer to achieve enhanced mechanical properties and fast on-demand dissolution.The SHHs show high mechanical strength(>50 kPa),self-heal rapidly in~1 min,and dissolve quickly(4-6 min)using an amantadine hydrochloride(AH)solution that breaks the supramolecular interactions in the SHHs.Neither the SHHs nor the AH solution has any adverse effects on human dermal fibroblasts or epidermal keratinocytes in vitro.The SHHs also do not elicit any significant cytokine response in vitro.Furthermore,in vivo murine experiments show no immune or inflammatory cell infiltration in the subcutaneous tissue and no change in circulatory cytokines compared to sham controls.Thus,these SHHs present excellent burn dressing candidates to reduce the time of pain and time associated with dressing changes.展开更多
By changing the solvents, three polyoxometalate（POM）-based supramolecular hybrids, [Co2 L3][SiW（12）O（40）]·17 H2 O（1）,[Co2 L2（H2 O）4][SiW（12）O（40）].2 EtOH·2 H2 O（2） and [Co2 L3][SiW（12）O（40...By changing the solvents, three polyoxometalate（POM）-based supramolecular hybrids, [Co2 L3][SiW（12）O（40）]·17 H2 O（1）,[Co2 L2（H2 O）4][SiW（12）O（40）].2 EtOH·2 H2 O（2） and [Co2 L3][SiW（12）O（40）]·9 DMA·6 H2 O（3）, have been synthesized under hydrothermal or solvothermal conditions. All three hybrids show various supramolecular structures, which contain two kinds of different metal-organic motifs. A kind of metal-organic cationic cage [Co2 L3]^4＋ is formed in the presence of H2 O for 1, DMA/H2 O for 3, and a metalorganic cationic circle [Co2 L2]^（4＋） is constructed in the presence of EtOH/H2 O for 2. That is to say, the solvents show a key role in tuning the architectures of metal-organic fragments and the final POM-based supramolecular structures. The adsorption properties of 1-3 for different organic dyes have also been investigated.展开更多
A novel supramolecular structural inorganic-organic hybrid [（4-bromoanilimiun）（[18]crown-6）]3[PMo（12）O40]·CH3 CN has been synthesized through standard solvent evaporated method. The structure of the title c...A novel supramolecular structural inorganic-organic hybrid [（4-bromoanilimiun）（[18]crown-6）]3[PMo（12）O40]·CH3 CN has been synthesized through standard solvent evaporated method. The structure of the title compound was determined through single-crystal X-ray diffraction analysis. It crystallizes in monoclinic system with P21/n space group. The crystal data are a = 18.9529（4）, b = 26.4444（5）, c = 19.0985（4） A, β = 90.132（6）o, V = 9572.1（3） A^3, Z = 4, Dc= 2.203 g·cm^（–1）, μ = 14.956 mm^（–1）, F（000） = 6192, S = 1.098, the final R = 0.0859 and w R（I 〉 2σ（I）） = 0.2100. Supramolecular cations are constructed through strong N–H…O hydrogen bonding interaction between the six oxygen atoms of [18]crown-6 molecule and nitrogen atom of（4-bromoanilimiun） cation. Three kinds of different arranged supramolecular cations exist in the title compound, which are filled into the large space formed by [PMo（12）O40] polyoxoanions. Thermogravimentic differential thermal analysis revealed that hydrogen bonding interaction and intermolecular interaction play an important role in maintaining the stability of the title compound.展开更多
A novel organic-inorganic hybrid, Na2（Hmorph）2[MosO26]·2H2O （1, Hmorph = morpholine）, has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray diffract...A novel organic-inorganic hybrid, Na2（Hmorph）2[MosO26]·2H2O （1, Hmorph = morpholine）, has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray diffraction, IR, UV/Vis spectrum, elemental analysis and thermogravimetric analysis （TGA）. Single-crystal X-ray analysis reveals that the title compound crystallizes in the monoclinic system, space group P21/c with a = 8.0194（4）, b = 16.1398（8）, c = 12.5893（6） A, fl = 92.824（4）°, V = 1627.47（14） A3, Mr = 1439.78, Z = 2, Dc = 2.938 g/cm3, p = 3.116 mm-1, F（000） = 1364, the final R = 0.0250, wR = 0.0628 and S = 1.027 for 3209 observed reflections with I 〉 2σ（/）. In compound 1, the polyanions are stacked through electrostatic interactions, coordination of Na＋ ions and hydrogen bonds to form a novel 3-D extended supramolecular ＂host＂ network with 1-D channels encapsulating organic ＂guests＂.展开更多
A Keggin-type tungstosilicate compound [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O 1 （bipy = bipyridine） was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed ...A Keggin-type tungstosilicate compound [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O 1 （bipy = bipyridine） was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 （C40H40Co2N8O44SiW12） crystallizes in the triclinic system, space group P1 with a = 10.4979（6）, b = 13.3946（7）, c = 13.5756（8）A, α= 70.0769（18）, β = 68.910（3）, γ = 74.186（4）°, V = 1649.84（16）A^3, Mr = 3688.95, Z = 1, Dc = 3.713 mg·m^-3, μ = 21.432 mm^-1, F（000） = 1644, S = 1.058, the final R = 0.0511 and wR =0.1023 for 6523 observed reflections （I 〉 2σ（I））. Compound 1 consists of two coordinated cation fragments [Co^Ⅱ（2,2′-bipy）2（H2O）]^2＋, one normal Keggin polyanion unit [SiW^Ⅵ12O40]^4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photoluminescence property in the solid state at room temperature.展开更多
Reactions of NaAcebiim （NaAcebiim = 1-acetic acid-2, 2＇-biimidazote monoso- dium salt） and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd（Acebiim）（NO3）（H20）]n （1） and 0D [Z...Reactions of NaAcebiim （NaAcebiim = 1-acetic acid-2, 2＇-biimidazote monoso- dium salt） and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd（Acebiim）（NO3）（H20）]n （1） and 0D [Zn（Acebiim）2（H20）2]＇2H20 （2） in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group Pi, and 2 is of monoclinic system, space group P2 1/n. In 1, two nitrate groups link two Cd（Ⅱ） ions forming [Cd2（NO3）2（H20）2] as secondary building units that are interconnected by the Acebiim ligand into an infinite ladder. In2, the hydrogen-bonded synthon R22（16） between the N-H moieties and carboxylic acid link [Zn（Acebiim）2（H20）2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.展开更多
The orsano-inorganic hybrid compound [ Ni（phen）3] [ （H2W12O40） { Ni（phen）2H2O} { Ni（trien） } ]·2H2O was synthesized from Na2 WO4·2H2O, NiSO4·6H2O, CH3COOK, triethylenetetramine and 1,10-phenanth...The orsano-inorganic hybrid compound [ Ni（phen）3] [ （H2W12O40） { Ni（phen）2H2O} { Ni（trien） } ]·2H2O was synthesized from Na2 WO4·2H2O, NiSO4·6H2O, CH3COOK, triethylenetetramine and 1,10-phenanthroline in water by the hydrothermal reaction, and characterized by IR, X-ray single crystal diffraction, and TG-DTA analysis. This compound crystallized in the monoclinic system, space group P2 （1）/n, with lattice constants： a =1.80998 （6） nm, b =2.36504（8） nm, c =2.29199（7） nm,β= 110.2220（10）°, V=9.2065（5） nm, Z=4. Final R indices R1=0.0532. ωR2=0.1295. The compound is decomposed at 593℃.展开更多
基金This research was supported partially by grants from the National Institutes of Health(NIH 5R21GM136002,NIH 1R21GM141683,and NIH 5R01HL145031)National Science Foundation(NSF Grant CHE-1904465 and EEC-1941543)a Massachusetts General Hospital(MGH)Executive Committee on Research(ECOR)Interim Support Fund,and a Shriners Hospital Research Grant(SHC 85125,and 85128).
文摘Despite decades of efforts,state-of-the-art synthetic burn dressings to treat partial-thickness burns are still far from ideal.Current dressings adhere to the wound and necessitate debridement.This work describes the first“supramolecular hybrid hydrogel(SHH)”burn dressing that is biocompatible,self-healable,and on-demand dissoluble for easy and trauma-free removal,prepared by a simple,fast,and scalable method.These SHHs leverage the interactions of a custom-designed cationic copolymer via host-guest chemistry with cucurbit[7]uril and electrostatic interactions with clay nanosheets coated with an anionic polymer to achieve enhanced mechanical properties and fast on-demand dissolution.The SHHs show high mechanical strength(>50 kPa),self-heal rapidly in~1 min,and dissolve quickly(4-6 min)using an amantadine hydrochloride(AH)solution that breaks the supramolecular interactions in the SHHs.Neither the SHHs nor the AH solution has any adverse effects on human dermal fibroblasts or epidermal keratinocytes in vitro.The SHHs also do not elicit any significant cytokine response in vitro.Furthermore,in vivo murine experiments show no immune or inflammatory cell infiltration in the subcutaneous tissue and no change in circulatory cytokines compared to sham controls.Thus,these SHHs present excellent burn dressing candidates to reduce the time of pain and time associated with dressing changes.
基金financially supported by the National Natural Science Foundation of China(Nos. 21671025, 21471021, 21501013,21401010)Program for Distinguished Professor of Liaoning Province(No. 2015399)
文摘By changing the solvents, three polyoxometalate（POM）-based supramolecular hybrids, [Co2 L3][SiW（12）O（40）]·17 H2 O（1）,[Co2 L2（H2 O）4][SiW（12）O（40）].2 EtOH·2 H2 O（2） and [Co2 L3][SiW（12）O（40）]·9 DMA·6 H2 O（3）, have been synthesized under hydrothermal or solvothermal conditions. All three hybrids show various supramolecular structures, which contain two kinds of different metal-organic motifs. A kind of metal-organic cationic cage [Co2 L3]^4＋ is formed in the presence of H2 O for 1, DMA/H2 O for 3, and a metalorganic cationic circle [Co2 L2]^（4＋） is constructed in the presence of EtOH/H2 O for 2. That is to say, the solvents show a key role in tuning the architectures of metal-organic fragments and the final POM-based supramolecular structures. The adsorption properties of 1-3 for different organic dyes have also been investigated.
基金thank the foundation of Wuhan Textile University(No.165002)Hubei Key Laboratory of Biomass Fibers and Eco-dyeing&Finishing for supporting this work
文摘A novel supramolecular structural inorganic-organic hybrid [（4-bromoanilimiun）（[18]crown-6）]3[PMo（12）O40]·CH3 CN has been synthesized through standard solvent evaporated method. The structure of the title compound was determined through single-crystal X-ray diffraction analysis. It crystallizes in monoclinic system with P21/n space group. The crystal data are a = 18.9529（4）, b = 26.4444（5）, c = 19.0985（4） A, β = 90.132（6）o, V = 9572.1（3） A^3, Z = 4, Dc= 2.203 g·cm^（–1）, μ = 14.956 mm^（–1）, F（000） = 6192, S = 1.098, the final R = 0.0859 and w R（I 〉 2σ（I）） = 0.2100. Supramolecular cations are constructed through strong N–H…O hydrogen bonding interaction between the six oxygen atoms of [18]crown-6 molecule and nitrogen atom of（4-bromoanilimiun） cation. Three kinds of different arranged supramolecular cations exist in the title compound, which are filled into the large space formed by [PMo（12）O40] polyoxoanions. Thermogravimentic differential thermal analysis revealed that hydrogen bonding interaction and intermolecular interaction play an important role in maintaining the stability of the title compound.
基金supported by the Science and Technology Development Foundation of Jilin Province(201201105,201215171)
文摘A novel organic-inorganic hybrid, Na2（Hmorph）2[MosO26]·2H2O （1, Hmorph = morpholine）, has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray diffraction, IR, UV/Vis spectrum, elemental analysis and thermogravimetric analysis （TGA）. Single-crystal X-ray analysis reveals that the title compound crystallizes in the monoclinic system, space group P21/c with a = 8.0194（4）, b = 16.1398（8）, c = 12.5893（6） A, fl = 92.824（4）°, V = 1627.47（14） A3, Mr = 1439.78, Z = 2, Dc = 2.938 g/cm3, p = 3.116 mm-1, F（000） = 1364, the final R = 0.0250, wR = 0.0628 and S = 1.027 for 3209 observed reflections with I 〉 2σ（/）. In compound 1, the polyanions are stacked through electrostatic interactions, coordination of Na＋ ions and hydrogen bonds to form a novel 3-D extended supramolecular ＂host＂ network with 1-D channels encapsulating organic ＂guests＂.
基金Hubei Natural Science Foundation (Grant No.2018CFB402)the Foundation of Wuhan Textile University (Grant No.165002)Hubei Key Laboratory for Processing and Application of Catalytic Materials (Grant No.201829203)~~
基金Supported by the Natural Science Foundation of Fujian Province (2007J0216, U0750004)the Ministry of Education of China (No. 208066)+1 种基金the Education Department of Fujian Province (JA07029)the State Key Laboratory of Structural Chemistry (No. 20080053)
文摘A Keggin-type tungstosilicate compound [Co^Ⅱ（2,2′-bipy）2（H2O）]2[SiW^Ⅵ12O40]·2H2O 1 （bipy = bipyridine） was prepared by a hydrothermal method for the first time. Single-crystal X-ray diffraction revealed that 1 （C40H40Co2N8O44SiW12） crystallizes in the triclinic system, space group P1 with a = 10.4979（6）, b = 13.3946（7）, c = 13.5756（8）A, α= 70.0769（18）, β = 68.910（3）, γ = 74.186（4）°, V = 1649.84（16）A^3, Mr = 3688.95, Z = 1, Dc = 3.713 mg·m^-3, μ = 21.432 mm^-1, F（000） = 1644, S = 1.058, the final R = 0.0511 and wR =0.1023 for 6523 observed reflections （I 〉 2σ（I））. Compound 1 consists of two coordinated cation fragments [Co^Ⅱ（2,2′-bipy）2（H2O）]^2＋, one normal Keggin polyanion unit [SiW^Ⅵ12O40]^4- and two lattice water molecules. To be noted, each polyanion unit is linked to two cation fragments by its two surface terminal oxygen atoms and two cobalt atoms of two cation fragments forming an organic-inorganic hybrid unit in 1. Furthermore, the compound shows strong photoluminescence property in the solid state at room temperature.
基金supported by the National Natural Science Foundation of China(No.#21003125,21073190)the Natural Science Foundation of Fujian Province(2010 J01057)
文摘Reactions of NaAcebiim （NaAcebiim = 1-acetic acid-2, 2＇-biimidazote monoso- dium salt） and cadmium or zinc nitrate produce two supramolecular architectures, namely, 1D [Cd（Acebiim）（NO3）（H20）]n （1） and 0D [Zn（Acebiim）2（H20）2]＇2H20 （2） in acidic aqueous solutions. Single-crystal X-ray diffraction analysis reveals that complex 1 crystallizes in the triclinic system, space group Pi, and 2 is of monoclinic system, space group P2 1/n. In 1, two nitrate groups link two Cd（Ⅱ） ions forming [Cd2（NO3）2（H20）2] as secondary building units that are interconnected by the Acebiim ligand into an infinite ladder. In2, the hydrogen-bonded synthon R22（16） between the N-H moieties and carboxylic acid link [Zn（Acebiim）2（H20）2], generating a 1D-extended ribbon. Moreover, hydrogen bonds and π-π interactions further stabilize the 3D supramolecular architecture.
文摘The orsano-inorganic hybrid compound [ Ni（phen）3] [ （H2W12O40） { Ni（phen）2H2O} { Ni（trien） } ]·2H2O was synthesized from Na2 WO4·2H2O, NiSO4·6H2O, CH3COOK, triethylenetetramine and 1,10-phenanthroline in water by the hydrothermal reaction, and characterized by IR, X-ray single crystal diffraction, and TG-DTA analysis. This compound crystallized in the monoclinic system, space group P2 （1）/n, with lattice constants： a =1.80998 （6） nm, b =2.36504（8） nm, c =2.29199（7） nm,β= 110.2220（10）°, V=9.2065（5） nm, Z=4. Final R indices R1=0.0532. ωR2=0.1295. The compound is decomposed at 593℃.
