It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(...It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.展开更多
目的探讨糖类抗原19-9(carbohydrate antigen 19-9,CA19-9)、中性粒细胞/淋巴细胞比值(neutrophil to lymphocyte ratio,NLR)在胆囊癌根治手术后患者疾病转归中的临床意义。方法选取2015年1月至2021年12月于临沂市中心医院行胆囊癌根治...目的探讨糖类抗原19-9(carbohydrate antigen 19-9,CA19-9)、中性粒细胞/淋巴细胞比值(neutrophil to lymphocyte ratio,NLR)在胆囊癌根治手术后患者疾病转归中的临床意义。方法选取2015年1月至2021年12月于临沂市中心医院行胆囊癌根治术且均完成1年随访的72例胆囊癌患者为胆囊癌组,其中,男39例,女33例,年龄(63.19±3.85)岁。根据1∶1配对原则,另选取同期72例胆囊息肉患者为对照组,其中,男37例,女35例,年龄(62.54±3.52)岁。比较两组入院时血清CA19-9水平、NLR,比较入院时、术后1周不同疾病转归胆囊癌患者血清CA19-9水平、NLR,比较不同病理学参数胆囊癌患者血清CA19-9水平、NLR。Spearman分析入院时血清CA19-9水平、NLR与病理学参数及疾病转归的相关性。采用受试者操作特征曲线(receiver operating characteristic curve,ROC)分析入院时、术后1周血清CA19-9水平、NLR联合检测对胆囊癌患者转归不良的预测价值。结果入院时,胆囊癌组血清CA19-9水平、NLR均高于对照组[(237.14±38.41)U/ml比(31.87±6.43)U/ml、(4.02±1.25)比(1.84±0.43);均P<0.05]。转归不良患者入院时、术后1周血清CA19-9水平、NLR均高于转归良好患者[(261.71±25.33)U/ml比(218.56±24.52)U/ml、(4.73±1.02)比(3.48±0.75),(181.64±28.58)U/ml比(85.43±12.19)U/ml、(3.37±0.48)比(2.24±0.53);均P<0.05]。不同病理参数胆囊癌患者血清CA19-9水平、NLR比较:中高分化患者低于低分化患者[(208.41±22.83)U/ml比(294.60±23.18)U/ml、(3.14±0.47)比(5.78±0.69)],Ⅰ~Ⅱ期患者低于Ⅲ~Ⅳ期患者[(188.43±25.63)U/ml比(276.11±23.08)U/ml、(2.95±0.57)比(4.88±0.64)],无淋巴结转移的患者低于有淋巴结转移的患者[(206.93±24.25)U/ml比(287.49±16.64)U/ml、(3.38±0.49)比(5.09±0.73)],且两指标水平与组织分化程度(r=-0.698、-0.533)呈负相关,与临床分期(r=0.742、0.659)、淋巴结转移(r=0.701、0.634)、疾病转归(r=0.588、0.719)均呈正相关(均P<0.05)。入院时、术后1周血清CA19-9水平、NLR联合预测胆囊癌患者转归不良的曲线下面积(area under the curve,AUC)分别为0.776(95%CI 0.718~0.839)、0.834(95%CI 0.768~0.906),最佳预测灵敏度分别为87.10%、93.55%,最佳预测特异度分别为68.29%、73.17%。结论CA19-9、NLR在胆囊癌根治术后转归不良患者血清中表达上调,两指标与临床病理参数及疾病转归均有一定相关性。两者联合检测对转归情况具有一定预测价值,可作为临床预测根治术后患者转归情况的辅助指标。展开更多
基金supported by the National Key Research and Development Program of China(Nos.2022YFB3504100,2022YFB3506200)the National Natural Science Foundation of China(Nos.22208373,22376217)+1 种基金the Beijing Nova Program(No.20220484215)the Science Foundation of China University of Petroleum,Beijing(No.2462023YJRC030)。
文摘It is urgent to develop catalysts with application potential for oxidative coupling of methane(OCM)at relatively lower temperature.Herein,three-dimensional ordered macro porous(3 DOM)La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)(A_(2)B_(2)O_(7)-type)catalysts with disordered defective cubic fluorite phased structure were successfully prepared by a colloidal crystal template method.3DOM structure promotes the accessibility of the gaseous reactants(O2and CH4)to the active sites.The co-doping of Ca and Sr ions in La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts improved the formation of oxygen vacancies,thereby leading to increased density of surface-active oxygen species(O_(2)^(-))for the activation of CH4and the formation of C2products(C2H6and C2H4).3DOM La_(2-x)Sr_(x)Ce_(2-y)CayO_(7-δ)catalysts exhibit high catalytic activity for OCM at low temperature.3DOM La1.7Sr0.3Ce1.7Ca0.3O7-δcatalyst with the highest density of O_(2)^(-)species exhibited the highest catalytic activity for low-temperature OCM,i.e.,its CH4conversion,selectivity and yield of C2products at 650℃are 32.2%,66.1%and 21.3%,respectively.The mechanism was proposed that the increase in surface oxygen vacancies induced by the co-doping of Ca and Sr ions boosts the key step of C-H bond breaking and C-C bond coupling in catalyzing low-temperature OCM.It is meaningful for the development of the low-temperature and high-efficient catalysts for OCM reaction in practical application.
文摘目的探讨糖类抗原19-9(carbohydrate antigen 19-9,CA19-9)、中性粒细胞/淋巴细胞比值(neutrophil to lymphocyte ratio,NLR)在胆囊癌根治手术后患者疾病转归中的临床意义。方法选取2015年1月至2021年12月于临沂市中心医院行胆囊癌根治术且均完成1年随访的72例胆囊癌患者为胆囊癌组,其中,男39例,女33例,年龄(63.19±3.85)岁。根据1∶1配对原则,另选取同期72例胆囊息肉患者为对照组,其中,男37例,女35例,年龄(62.54±3.52)岁。比较两组入院时血清CA19-9水平、NLR,比较入院时、术后1周不同疾病转归胆囊癌患者血清CA19-9水平、NLR,比较不同病理学参数胆囊癌患者血清CA19-9水平、NLR。Spearman分析入院时血清CA19-9水平、NLR与病理学参数及疾病转归的相关性。采用受试者操作特征曲线(receiver operating characteristic curve,ROC)分析入院时、术后1周血清CA19-9水平、NLR联合检测对胆囊癌患者转归不良的预测价值。结果入院时,胆囊癌组血清CA19-9水平、NLR均高于对照组[(237.14±38.41)U/ml比(31.87±6.43)U/ml、(4.02±1.25)比(1.84±0.43);均P<0.05]。转归不良患者入院时、术后1周血清CA19-9水平、NLR均高于转归良好患者[(261.71±25.33)U/ml比(218.56±24.52)U/ml、(4.73±1.02)比(3.48±0.75),(181.64±28.58)U/ml比(85.43±12.19)U/ml、(3.37±0.48)比(2.24±0.53);均P<0.05]。不同病理参数胆囊癌患者血清CA19-9水平、NLR比较:中高分化患者低于低分化患者[(208.41±22.83)U/ml比(294.60±23.18)U/ml、(3.14±0.47)比(5.78±0.69)],Ⅰ~Ⅱ期患者低于Ⅲ~Ⅳ期患者[(188.43±25.63)U/ml比(276.11±23.08)U/ml、(2.95±0.57)比(4.88±0.64)],无淋巴结转移的患者低于有淋巴结转移的患者[(206.93±24.25)U/ml比(287.49±16.64)U/ml、(3.38±0.49)比(5.09±0.73)],且两指标水平与组织分化程度(r=-0.698、-0.533)呈负相关,与临床分期(r=0.742、0.659)、淋巴结转移(r=0.701、0.634)、疾病转归(r=0.588、0.719)均呈正相关(均P<0.05)。入院时、术后1周血清CA19-9水平、NLR联合预测胆囊癌患者转归不良的曲线下面积(area under the curve,AUC)分别为0.776(95%CI 0.718~0.839)、0.834(95%CI 0.768~0.906),最佳预测灵敏度分别为87.10%、93.55%,最佳预测特异度分别为68.29%、73.17%。结论CA19-9、NLR在胆囊癌根治术后转归不良患者血清中表达上调,两指标与临床病理参数及疾病转归均有一定相关性。两者联合检测对转归情况具有一定预测价值,可作为临床预测根治术后患者转归情况的辅助指标。
