Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are ...Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are restricted by the expensive monomer(1,4-cyclohexanedimethanol,CHDM).Direct upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate(DMCD)can promote the production of CHDM in large scale.In this work,a bifunctional Ru/UiO-66_(def)-SO_(3)H catalyst was synthesized and utilized in coupled methanolysis(of waste PET to dimethyl terephthalate(DMT))and hydrogenation(of DMT to DMCD)under mild condition.Characterizations revealed that Ru/UiO-66_(def)-SO_(3)H possessed mesopores(dominant channels of 2.72 and 3.44 nm),enlarged surface area(998 m^(2)·g^(–1)),enhanced acidity(580μmol·g^(–1)),and Ru nanoparticles(NPs)dispersed highly(45.1%)compared to those of Ru/UiO-66.These combined advantages could accelerate the methanolysis and hydrogenation reactions simultaneously,promoting the performance of direct upgrading of PET to DMCD in one pot.In particular,the conversion of PET and yield of DMCD over Ru/UiO-66_(def)-SO_(3)H reached 100%and 97.7%at 170℃and 3 MPa H_(2)within 6 h.Moreover,Ru/UiO-66_(def)-SO3H was also capable for the upcycling of waste PET-based products including beverage bottles,textile fiber and packaging film to DMCD.展开更多
The hydrothermal reaction of Zn（NO3）2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate （H6LI·H2O, cis-conformation LI： a,e,a,e,a,e） and 2,2＇-bpy yielded a new coordination polymer [Zn2（H2LII...The hydrothermal reaction of Zn（NO3）2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate （H6LI·H2O, cis-conformation LI： a,e,a,e,a,e） and 2,2＇-bpy yielded a new coordination polymer [Zn2（H2LII）（2,2＇-bpy）]·2H2O（trans-conformation LII： e,e,e,e,e,e）, which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD（X-ray powder diffraction）. This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922（5） nm, b=0.97291（8） nm, c=1.22184（9） nm, α=99.0020（10）°, β=99.1300（10）°, γ=99.1910（10）°, V= 0.76176（10） nm3 and Z=2. The structure is a three-dimensional supramolecular network based on linear coordination chains through π-π stacking and hydrogen bonding interactions. The confromation of the starting ligand H6LI transfromed to the H2LII. The complex emits strong luminescence at room temperature.展开更多
The hydrothermal reaction of Cd（OAc）2·2H2O, 4,4＇-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid （H4L） yields a three-dimensional （3D） coordination porous framework [Cd2LI（4,4＇-bpy）1.5（H2O）2]n·2...The hydrothermal reaction of Cd（OAc）2·2H2O, 4,4＇-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid （H4L） yields a three-dimensional （3D） coordination porous framework [Cd2LI（4,4＇-bpy）1.5（H2O）2]n·2nH2O, which was characterized by single-crystal X-ray diffraction （MoKα radiation, λ = 0.71073）, elemental analysis and IR. This complex crystallizes in the monoclinic system, space group C2/c with a = 25.951（3）, b = 11.6618（12）, c = 20.046（2） A, β = 114.863（2）o, V = 5504.4（10）A^3, Z = 8, Dc = 1.900 g/cm^3, Mr = 787.30, μ = 1.615 mm^-1, F（000） = 3128, the final R = 0.0978 and wR = 0.1780. The structure of the complex is a 3D coordination Cd-carboxylate framework consisting of 1D hexagonal channels along the c-axis filled with the bridging 4,4＇-bpy ligands. The 4,4＇-bpy ligands with two kinds of conformations are located alternately in the channels through coordination and hydrogen interactions to support the whole porous framework, in which the conformation-flexible cyclohexane-1,2,4,5-tetracarboxylate ligand adopts the I （e,a,a,e） conformation and acts as a pentadentate ligand to connect five Cd（Ⅱ） atoms via the carboxylate groups in different coordination modes.展开更多
目的探索酮还原酶家族1成员C3(aldo-keto reductase family 1 member C3,AKR1C3)对乳腺癌恶性细胞生物学行为的干预作用及对程序性细胞死亡蛋白/程序性死亡-配体1(programmed cell death protein1/programmed death-ligand1,PD-1/PD-L)...目的探索酮还原酶家族1成员C3(aldo-keto reductase family 1 member C3,AKR1C3)对乳腺癌恶性细胞生物学行为的干预作用及对程序性细胞死亡蛋白/程序性死亡-配体1(programmed cell death protein1/programmed death-ligand1,PD-1/PD-L)通路的影响。方法把MCF-7人乳腺癌细胞中NC组和AKR1C3组分别转染空质粒和AKR1C3质粒,采用MTT法检测转染后24 h、48 h、72 h细胞活力;采用流式细胞技术测定各组细胞的存活率以及早期、晚期凋亡比例;通过Transwell实验对各组细胞的迁移和侵袭能力进行检测;通过Western blot检测各组细胞PD-1、PD-L1、蛋白激酶B(protein kinase b,AKT)蛋白表达水平。使用C57BL/6小鼠构建荷瘤模型,将采用人乳腺癌MCF-7细胞转染NC质粒和AKR1C3质粒进行细胞荷瘤,每3 d测量瘤体积,持续21 d,绘制两组小鼠肿瘤生长曲线,并于实验终点测量肿瘤质量。结果相较于NC组,AKR1C3组细胞活力降低(P<0.05),并且具有时间依赖效应(P<0.05),迁移和侵袭能力降低(P<0.05),早期凋亡和晚期凋亡比例升高(P<0.05),PD-1、PD-L1、AKT蛋白表达水平降低(P<0.05)。动物实验表明,AKR1C3组小鼠肿瘤体积降低,肿瘤质量下降(P<0.05)。结论AKR1C3可以抑制人乳腺癌细胞恶性生物学行为,抑制PD-1/PDL1信号通路蛋白表达。展开更多
文摘Poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate)(PETG)possesses excellent properties and stability than traditional poly(ethylene terephthalate)(PET).However,the production and application of PETG are restricted by the expensive monomer(1,4-cyclohexanedimethanol,CHDM).Direct upgrading of waste PET to dimethyl cyclohexane-1,4-dicarboxylate(DMCD)can promote the production of CHDM in large scale.In this work,a bifunctional Ru/UiO-66_(def)-SO_(3)H catalyst was synthesized and utilized in coupled methanolysis(of waste PET to dimethyl terephthalate(DMT))and hydrogenation(of DMT to DMCD)under mild condition.Characterizations revealed that Ru/UiO-66_(def)-SO_(3)H possessed mesopores(dominant channels of 2.72 and 3.44 nm),enlarged surface area(998 m^(2)·g^(–1)),enhanced acidity(580μmol·g^(–1)),and Ru nanoparticles(NPs)dispersed highly(45.1%)compared to those of Ru/UiO-66.These combined advantages could accelerate the methanolysis and hydrogenation reactions simultaneously,promoting the performance of direct upgrading of PET to DMCD in one pot.In particular,the conversion of PET and yield of DMCD over Ru/UiO-66_(def)-SO_(3)H reached 100%and 97.7%at 170℃and 3 MPa H_(2)within 6 h.Moreover,Ru/UiO-66_(def)-SO3H was also capable for the upcycling of waste PET-based products including beverage bottles,textile fiber and packaging film to DMCD.
基金Supported by the National Natural Science Foundation of China(No.20901018)the Natural Science Foundation of Guangdong Province, China(No.9451009101003177)
文摘The hydrothermal reaction of Zn（NO3）2·4H2O, cyclohexane-1,2,3,4,5,6-hexacarboxylic acid hydrate （H6LI·H2O, cis-conformation LI： a,e,a,e,a,e） and 2,2＇-bpy yielded a new coordination polymer [Zn2（H2LII）（2,2＇-bpy）]·2H2O（trans-conformation LII： e,e,e,e,e,e）, which was characterized by single-crystal X-ray diffraction, elemental analysis, IR and XRPD（X-ray powder diffraction）. This complex crystallized in the triclinic system, with P1 space group and parameters a=0.66922（5） nm, b=0.97291（8） nm, c=1.22184（9） nm, α=99.0020（10）°, β=99.1300（10）°, γ=99.1910（10）°, V= 0.76176（10） nm3 and Z=2. The structure is a three-dimensional supramolecular network based on linear coordination chains through π-π stacking and hydrogen bonding interactions. The confromation of the starting ligand H6LI transfromed to the H2LII. The complex emits strong luminescence at room temperature.
基金Supported by the National Natural Science Foundation of China (No. 20901018)the Natural Science Foundation of Guangdong Province (No. 9451009101003177)
文摘The hydrothermal reaction of Cd（OAc）2·2H2O, 4,4＇-bpy and cyclohexane-1,2,4,5-tetracarboxylic acid （H4L） yields a three-dimensional （3D） coordination porous framework [Cd2LI（4,4＇-bpy）1.5（H2O）2]n·2nH2O, which was characterized by single-crystal X-ray diffraction （MoKα radiation, λ = 0.71073）, elemental analysis and IR. This complex crystallizes in the monoclinic system, space group C2/c with a = 25.951（3）, b = 11.6618（12）, c = 20.046（2） A, β = 114.863（2）o, V = 5504.4（10）A^3, Z = 8, Dc = 1.900 g/cm^3, Mr = 787.30, μ = 1.615 mm^-1, F（000） = 3128, the final R = 0.0978 and wR = 0.1780. The structure of the complex is a 3D coordination Cd-carboxylate framework consisting of 1D hexagonal channels along the c-axis filled with the bridging 4,4＇-bpy ligands. The 4,4＇-bpy ligands with two kinds of conformations are located alternately in the channels through coordination and hydrogen interactions to support the whole porous framework, in which the conformation-flexible cyclohexane-1,2,4,5-tetracarboxylate ligand adopts the I （e,a,a,e） conformation and acts as a pentadentate ligand to connect five Cd（Ⅱ） atoms via the carboxylate groups in different coordination modes.
