In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properti...In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.展开更多
芝麻是八大类食物过敏原之一,快速准确识别芝麻过敏原对预防其过敏有重要意义。核酸适配体可以高效识别靶标过敏原,在过敏原检测中有良好的应用前景。为了获得芝麻主要过敏原Ses i 2的特异性核酸适体,本研究以Ses i 2为靶标,通过磁珠筛...芝麻是八大类食物过敏原之一,快速准确识别芝麻过敏原对预防其过敏有重要意义。核酸适配体可以高效识别靶标过敏原,在过敏原检测中有良好的应用前景。为了获得芝麻主要过敏原Ses i 2的特异性核酸适体,本研究以Ses i 2为靶标,通过磁珠筛选法(磁珠-SELEX)开展10轮筛选,经由高通量测序获得6条候补序列(S1~S6),并进行家族性、同源性分析及二级结构预测。结果表明,6条候选核酸适体的重复率可达46.38%,其自由能在-9.02到-2.47 kcal·moL^(-1)之间,根据自由能能量稳定原则,S1和S5吉布斯自由能最低最稳定,分别为-6.70和-9.02 kcal·moL^(-1)。利用ELISA试验进行亲和力测试,结果表明核酸适体S1和S2的亲和能力较强,S1:KD=67.02 nmol·L^(-1),R2=0.925 8,S2:KD=97.65 nmol·L^(-1),R2=0.795 1。核酸适体S1与过敏原Ses i 2的结合力和其他过敏原蛋白相比有显著差异,可视为具有特异性。本研究最终获得一条兼具良好亲和力和特异性的核酸适体S1,为芝麻过敏原快速检测提供了技术支撑。展开更多
目的探讨三酰甘油葡萄糖乘积(triglyceride-glucose index,TyG)指数和血浆致动脉粥样硬化指数(atherogenic index of plasma,AIP)与老年冠心病(coronary heart disease,CHD)合并2型糖尿病(type 2 diabetes mellitus,T2DM)患者冠状动脉...目的探讨三酰甘油葡萄糖乘积(triglyceride-glucose index,TyG)指数和血浆致动脉粥样硬化指数(atherogenic index of plasma,AIP)与老年冠心病(coronary heart disease,CHD)合并2型糖尿病(type 2 diabetes mellitus,T2DM)患者冠状动脉正性重构的关系。方法按照住院先后顺序选取2022年1月至2023年6月河南科技大学第一附属医院心血管内科收治的老年CHD合并T2DM患者120例,根据重构指数分为正性重构组47例和非正性重构组73例。比较2组临床资料;采用多因素logistic回归分析冠状动脉正性重构的危险因素;采用Spearman相关性分析TyG和AIP与冠状动脉正性重构的相关性;采用ROC曲线分析TyG和AIP对冠状动脉正性重构的预测价值。结果正性重构组吸烟、三酰甘油、糖化血红蛋白、TyG、AIP显著高于非正性重构组,高密度脂蛋白胆固醇、血钙水平显著低于非正性重构组(P<0.05,P<0.01)。单因素logistic回归分析显示,吸烟、三酰甘油、高密度脂蛋白胆固醇、糖化血红蛋白、血钙、TyG、AIP是老年CHD合并T2DM患者冠状动脉正性重构的危险因素(P<0.05,P<0.01)。多因素logistic回归分析显示,TyG(OR=7.253,95%CI:2.458~13.364,P=0.035)、AIP(OR=6.017,95%CI:2.205~12.025,P=0.030)是老年CHD合并T2DM患者冠状动脉正性重构的独立危险因素(P<0.05)。TyG、AIP预测老年CHD合并T2DM患者冠状动脉正性重构的曲线下面积分别为0.783、0.766,联合预测老年CHD合并T2DM患者冠状动脉正性重构的曲线下面积为0.868,显著优于单独预测(P<0.05)。结论TyG和AIP与老年CHD合并T2DM患者冠状动脉正性重构密切相关,可作为预测冠状动脉正性重构的有效指标,对临床早期识别高危患者及制定个体化干预策略具有重要意义。展开更多
文摘In this study, the first raw transition metals from V to Co complexes with benzene-1,2-dithiolate (L2-) ligand have been studied theoretically to elucidate the geometry, electronic structure and spectroscopic properties of the complexes. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods have been used. The ground state geometries, binding energies, spectral properties (UV-vis), frontier molecular orbitals (FMOs) analysis, charge analysis and natural bond orbital (NBO) have been investigated. The geometrical parameters are in good agreement with the available experimental data. The metal-ligand binding energies are 1 order of magnitude larger than the physisorption energy of a benzene-1, 2-dthiolate molecule on a metallic surface. The electronic structures of the first raw transition metal series from V to Co have been elucidated by UV-vis spectroscopic using DFT calculations. In accordance with experiment the calculated electronic spectra of these tris complexes show bands at 522, 565, 559, 546 and 863 nm for V3+, Cr3+, Mn3+, Fe3+ and Co3+ respectively which are mainly attributed to ligand to metal charge transfer (LMCT) transitions. The electronic properties analysis shows that the highest occupied molecular orbital (HOMO) is mainly centered on metal coordinated sulfur atoms whereas the lowest unoccupied molecular orbital (LUMO) is mainly located on the metal surface. From calculation of intramolecular interactions and electron delocalization by natural bond orbital (NBO) analysis, the stability of the complexes was estimated. The NBO results showed significant charge transfer from sulfur to central metal ions in the complexes, as well as to the benzene. The calculated charges on metal ions are also reported at various charge schemes. The calculations show encouraging agreement with the available experimental data.
文摘芝麻是八大类食物过敏原之一,快速准确识别芝麻过敏原对预防其过敏有重要意义。核酸适配体可以高效识别靶标过敏原,在过敏原检测中有良好的应用前景。为了获得芝麻主要过敏原Ses i 2的特异性核酸适体,本研究以Ses i 2为靶标,通过磁珠筛选法(磁珠-SELEX)开展10轮筛选,经由高通量测序获得6条候补序列(S1~S6),并进行家族性、同源性分析及二级结构预测。结果表明,6条候选核酸适体的重复率可达46.38%,其自由能在-9.02到-2.47 kcal·moL^(-1)之间,根据自由能能量稳定原则,S1和S5吉布斯自由能最低最稳定,分别为-6.70和-9.02 kcal·moL^(-1)。利用ELISA试验进行亲和力测试,结果表明核酸适体S1和S2的亲和能力较强,S1:KD=67.02 nmol·L^(-1),R2=0.925 8,S2:KD=97.65 nmol·L^(-1),R2=0.795 1。核酸适体S1与过敏原Ses i 2的结合力和其他过敏原蛋白相比有显著差异,可视为具有特异性。本研究最终获得一条兼具良好亲和力和特异性的核酸适体S1,为芝麻过敏原快速检测提供了技术支撑。
文摘目的探讨三酰甘油葡萄糖乘积(triglyceride-glucose index,TyG)指数和血浆致动脉粥样硬化指数(atherogenic index of plasma,AIP)与老年冠心病(coronary heart disease,CHD)合并2型糖尿病(type 2 diabetes mellitus,T2DM)患者冠状动脉正性重构的关系。方法按照住院先后顺序选取2022年1月至2023年6月河南科技大学第一附属医院心血管内科收治的老年CHD合并T2DM患者120例,根据重构指数分为正性重构组47例和非正性重构组73例。比较2组临床资料;采用多因素logistic回归分析冠状动脉正性重构的危险因素;采用Spearman相关性分析TyG和AIP与冠状动脉正性重构的相关性;采用ROC曲线分析TyG和AIP对冠状动脉正性重构的预测价值。结果正性重构组吸烟、三酰甘油、糖化血红蛋白、TyG、AIP显著高于非正性重构组,高密度脂蛋白胆固醇、血钙水平显著低于非正性重构组(P<0.05,P<0.01)。单因素logistic回归分析显示,吸烟、三酰甘油、高密度脂蛋白胆固醇、糖化血红蛋白、血钙、TyG、AIP是老年CHD合并T2DM患者冠状动脉正性重构的危险因素(P<0.05,P<0.01)。多因素logistic回归分析显示,TyG(OR=7.253,95%CI:2.458~13.364,P=0.035)、AIP(OR=6.017,95%CI:2.205~12.025,P=0.030)是老年CHD合并T2DM患者冠状动脉正性重构的独立危险因素(P<0.05)。TyG、AIP预测老年CHD合并T2DM患者冠状动脉正性重构的曲线下面积分别为0.783、0.766,联合预测老年CHD合并T2DM患者冠状动脉正性重构的曲线下面积为0.868,显著优于单独预测(P<0.05)。结论TyG和AIP与老年CHD合并T2DM患者冠状动脉正性重构密切相关,可作为预测冠状动脉正性重构的有效指标,对临床早期识别高危患者及制定个体化干预策略具有重要意义。
