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
目的探究纤维蛋白原样蛋白1(fibrinogen-like protein 1,FGL1)和膜联蛋白A11(annexin A11,ANXA11)对肺癌手术患者效用评估价值及与预后的相关性。方法将本院2020年1月至2023年12月接诊的98例肺癌患者纳入肺癌组,另选取98例健康人作为对...目的探究纤维蛋白原样蛋白1(fibrinogen-like protein 1,FGL1)和膜联蛋白A11(annexin A11,ANXA11)对肺癌手术患者效用评估价值及与预后的相关性。方法将本院2020年1月至2023年12月接诊的98例肺癌患者纳入肺癌组,另选取98例健康人作为对照组。受试者入院后分别于空腹状态下采取6 mL肘静脉血,采用ELISA法检测血清ANXA11水平,采用实时荧光定量PCR技术检测ANXA11表达水平。根据术后1个月肿瘤标志物变化、影像学表现和免疫功能指标变化情况分为治疗有效组(n=68)和无效组(n=30)。患者出院后均行12~36个月的随访,根据患者预后情况分为预后良好组(n=63)和预后不良组(n=35)。对比对照组和肺癌组/有效组和无效组/预后FGL1、ANXA11表达差异;ROC分析FGL1、ANXA11单一及联合检测对肺癌手术患者临床效用评估价值;Spearman分析FGL1、ANXA11表达与预后的关系。结果肺癌组FGL1和ANXA11表达水平明显高于对照组(均P<0.05);无效组FGL1和ANXA11表达水平明显高于有效组(均P<0.05);ROC结果显示FGL1、ANXA11单独及联合检测对肺癌手术患者效用评估的曲线线下面积分别为0.928,并且联合检测具有较高的特异性(95.59%)以及敏感度(90.00%),诊断价值显著高于单独检测ROC曲线线下面积(均P<0.05);预后不良组FGL1和ANXA11表达水平明显高于预后良好组(均P<0.05);Spearman相关性结果显示FGL1、ANXA11与肺癌手术患者预后呈显著正相关(r=0.771、0.793,均P<0.05)。结论肺癌患者的FGL1与ANXA11表达水平高于健康人,治疗无效者高于有效者,预后不良者高于良好者,二者单独及联合检测对患者手术治疗效用评估均有价值,且其与预后相关性显著。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.
文摘目的探究纤维蛋白原样蛋白1(fibrinogen-like protein 1,FGL1)和膜联蛋白A11(annexin A11,ANXA11)对肺癌手术患者效用评估价值及与预后的相关性。方法将本院2020年1月至2023年12月接诊的98例肺癌患者纳入肺癌组,另选取98例健康人作为对照组。受试者入院后分别于空腹状态下采取6 mL肘静脉血,采用ELISA法检测血清ANXA11水平,采用实时荧光定量PCR技术检测ANXA11表达水平。根据术后1个月肿瘤标志物变化、影像学表现和免疫功能指标变化情况分为治疗有效组(n=68)和无效组(n=30)。患者出院后均行12~36个月的随访,根据患者预后情况分为预后良好组(n=63)和预后不良组(n=35)。对比对照组和肺癌组/有效组和无效组/预后FGL1、ANXA11表达差异;ROC分析FGL1、ANXA11单一及联合检测对肺癌手术患者临床效用评估价值;Spearman分析FGL1、ANXA11表达与预后的关系。结果肺癌组FGL1和ANXA11表达水平明显高于对照组(均P<0.05);无效组FGL1和ANXA11表达水平明显高于有效组(均P<0.05);ROC结果显示FGL1、ANXA11单独及联合检测对肺癌手术患者效用评估的曲线线下面积分别为0.928,并且联合检测具有较高的特异性(95.59%)以及敏感度(90.00%),诊断价值显著高于单独检测ROC曲线线下面积(均P<0.05);预后不良组FGL1和ANXA11表达水平明显高于预后良好组(均P<0.05);Spearman相关性结果显示FGL1、ANXA11与肺癌手术患者预后呈显著正相关(r=0.771、0.793,均P<0.05)。结论肺癌患者的FGL1与ANXA11表达水平高于健康人,治疗无效者高于有效者,预后不良者高于良好者,二者单独及联合检测对患者手术治疗效用评估均有价值,且其与预后相关性显著。
