We theoretically investigate the excited state intramolecular proton transfer(ESIPT) behavior of the novel fluorophore bis-imine derivative molecule HNP which was designed based on the intersection of 1-(hydrazonometh...We theoretically investigate the excited state intramolecular proton transfer(ESIPT) behavior of the novel fluorophore bis-imine derivative molecule HNP which was designed based on the intersection of 1-(hydrazonomethyl)-naphthalene-2-ol and 1-pyrenecarboxaldehyde. Especially, the density functional theory(DFT) and time-dependent density functional theory(TDDFT) methods for HNP monomer are introduced. Moreover, the "our own n-layered integrated molecular orbital and molecular mechanics"(ONIOM) method(TDDFT:universal force field(UFF)) is used to reveal the aggregation-induced emission(AIE) effect on the ESIPT process for HNP in crystal. Our results confirm that the ESIPT process happens upon the photoexcitation for the HNP monomer and HNP in crystal, which is distinctly monitored by the optimized geometric structures and the potential energy curves. In addition, the results of potential energy curves reveal that the ESIPT process in HNP will be promoted by the AIE effect. Furthermore, the highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) for the HNP monomer and HNP in crystal have been calculated. The calculation demonstrates that the electron density decrease of proton donor caused by excitation promotes the ESIPT process. In addition, we find that the variation of atomic dipole moment corrected Hirshfeld population(ADCH) charge for proton acceptor induced by the AIE effect facilitates the ESIPT process. The results will be expected to deepen the understanding of ESIPT dynamics for luminophore under the AIE effect and provide insight into future design of high-efficient AIE compounds.展开更多
目的初探纵向弛豫时间定量成像(T1 mapping)和酰胺质子转移加权(amide proton transfer weighted,APTw)成像鉴别慢性肾病(chronic kidney disease,CKD)患者与健康人群的价值。材料与方法回顾性分析2019年8月至2020年10月行3.0 T MRI检查...目的初探纵向弛豫时间定量成像(T1 mapping)和酰胺质子转移加权(amide proton transfer weighted,APTw)成像鉴别慢性肾病(chronic kidney disease,CKD)患者与健康人群的价值。材料与方法回顾性分析2019年8月至2020年10月行3.0 T MRI检查的CKD患者病例资料共21例(女6例,男15例),所有患者均经大连医科大学附属第一医院肾内科医师依据CKD临床实践指南确诊;同时收集24例健康志愿者临床资料作为对照组。将所有原始图像导入ISP工作站,生成伪彩图。由两名影像科诊断医师采用双盲法分别从肾的上极、中部、下极各选择一个层面并于皮质和髓质中分别放置感兴趣区(region of interest,ROI),面积约10~20 mm^(2),避开肾窦、大血管及肾周组织。测量所得皮髓质T1值与APT值应用SPSS 26.0软件进行统计学分析:应用组内相关系数(intra-class correlation coefficients,ICC)进行观察者间测量结果一致性检验;根据数据正态分布情况,采用独立样本t检验或Mann-Whitney U检验分析两组间参数值差异,P<0.05为差异具有统计学意义;采用受试者工作特征(receiver operating characteristic,ROC)曲线分析各参数诊断效能,根据最大约登指数得到相对应的阈值、敏感度和特异度,并计算曲线下面积(area under the curve,AUC)值。结果两位观察者间测量结果一致性良好(ICC>0.75)。CKD组双肾皮质T1值和皮质APT值显著高于健康对照组(P<0.05);左肾皮质T1值鉴别CKD的AUC值为0.887,敏感度66.7%,特异度100.0%;左肾皮质APT值鉴别CKD的AUC值为0.966,敏感度95.2%,特异度95.8%;右肾皮质T1值鉴别CKD的AUC值为0.960,敏感度76.2%,特异度100.0%;右肾皮质APT值鉴别CKD的AUC值为0.921,敏感度85.7%,特异度91.7%。结论T1 mapping与APTw成像可无创有效鉴别CKD,基于二者的定量参数在一定程度上反映了单侧肾脏各自结构与功能的改变,有望为临床疾病诊断提供一定的参考价值。展开更多
用量子力学与分子力学组合的ONIOM(MP2/6-311++G(3df,3pd):UFF)//ONIOM(CAM-B3LYP/6-31+G(d,p):UFF)方法,研究了标题反应的机理.分子结构计算表明:Sα-Ala·2H2O@SWCNT(8,8)和Sα-Ala·3H2O@SWCNT(8,8)中,季碳与其上面氢的键长...用量子力学与分子力学组合的ONIOM(MP2/6-311++G(3df,3pd):UFF)//ONIOM(CAM-B3LYP/6-31+G(d,p):UFF)方法,研究了标题反应的机理.分子结构计算表明:Sα-Ala·2H2O@SWCNT(8,8)和Sα-Ala·3H2O@SWCNT(8,8)中,季碳与其上面氢的键长分别是0.11055和0.11100(nm),比Sα-Ala·1H2O@SWCNT(8,8)的季碳与其上面氢的键长0.10991nm明显长;环形过渡态TS1·2H2O@SWCNT(8,8)和TS1·3H2O@SWCNT(8,8)的氢键键角比TS1·1H2O@SWCNT(8,8)的明显增大.势能面计算发现:在SWCNT(8,8)内以1个、2个和3个H2O分子为氢转移媒介,α-Ala的质子从季碳向羰基氧迁移的能垒是208.6、160.9和154.4(k J·mol-1).比α-Ala限域在SWCNT(8,8)内质子从季碳向羰基氧迁移的能垒322.7 k J·mol-1大幅降低.结果表明:SWCNT(8,8)与水的复合环境对α-Ala的质子从季碳向羰基氧迁移具有较好的催化作用.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11574115 and 11704146)
文摘We theoretically investigate the excited state intramolecular proton transfer(ESIPT) behavior of the novel fluorophore bis-imine derivative molecule HNP which was designed based on the intersection of 1-(hydrazonomethyl)-naphthalene-2-ol and 1-pyrenecarboxaldehyde. Especially, the density functional theory(DFT) and time-dependent density functional theory(TDDFT) methods for HNP monomer are introduced. Moreover, the "our own n-layered integrated molecular orbital and molecular mechanics"(ONIOM) method(TDDFT:universal force field(UFF)) is used to reveal the aggregation-induced emission(AIE) effect on the ESIPT process for HNP in crystal. Our results confirm that the ESIPT process happens upon the photoexcitation for the HNP monomer and HNP in crystal, which is distinctly monitored by the optimized geometric structures and the potential energy curves. In addition, the results of potential energy curves reveal that the ESIPT process in HNP will be promoted by the AIE effect. Furthermore, the highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) for the HNP monomer and HNP in crystal have been calculated. The calculation demonstrates that the electron density decrease of proton donor caused by excitation promotes the ESIPT process. In addition, we find that the variation of atomic dipole moment corrected Hirshfeld population(ADCH) charge for proton acceptor induced by the AIE effect facilitates the ESIPT process. The results will be expected to deepen the understanding of ESIPT dynamics for luminophore under the AIE effect and provide insight into future design of high-efficient AIE compounds.
文摘目的初探纵向弛豫时间定量成像(T1 mapping)和酰胺质子转移加权(amide proton transfer weighted,APTw)成像鉴别慢性肾病(chronic kidney disease,CKD)患者与健康人群的价值。材料与方法回顾性分析2019年8月至2020年10月行3.0 T MRI检查的CKD患者病例资料共21例(女6例,男15例),所有患者均经大连医科大学附属第一医院肾内科医师依据CKD临床实践指南确诊;同时收集24例健康志愿者临床资料作为对照组。将所有原始图像导入ISP工作站,生成伪彩图。由两名影像科诊断医师采用双盲法分别从肾的上极、中部、下极各选择一个层面并于皮质和髓质中分别放置感兴趣区(region of interest,ROI),面积约10~20 mm^(2),避开肾窦、大血管及肾周组织。测量所得皮髓质T1值与APT值应用SPSS 26.0软件进行统计学分析:应用组内相关系数(intra-class correlation coefficients,ICC)进行观察者间测量结果一致性检验;根据数据正态分布情况,采用独立样本t检验或Mann-Whitney U检验分析两组间参数值差异,P<0.05为差异具有统计学意义;采用受试者工作特征(receiver operating characteristic,ROC)曲线分析各参数诊断效能,根据最大约登指数得到相对应的阈值、敏感度和特异度,并计算曲线下面积(area under the curve,AUC)值。结果两位观察者间测量结果一致性良好(ICC>0.75)。CKD组双肾皮质T1值和皮质APT值显著高于健康对照组(P<0.05);左肾皮质T1值鉴别CKD的AUC值为0.887,敏感度66.7%,特异度100.0%;左肾皮质APT值鉴别CKD的AUC值为0.966,敏感度95.2%,特异度95.8%;右肾皮质T1值鉴别CKD的AUC值为0.960,敏感度76.2%,特异度100.0%;右肾皮质APT值鉴别CKD的AUC值为0.921,敏感度85.7%,特异度91.7%。结论T1 mapping与APTw成像可无创有效鉴别CKD,基于二者的定量参数在一定程度上反映了单侧肾脏各自结构与功能的改变,有望为临床疾病诊断提供一定的参考价值。
文摘用量子力学与分子力学组合的ONIOM(MP2/6-311++G(3df,3pd):UFF)//ONIOM(CAM-B3LYP/6-31+G(d,p):UFF)方法,研究了标题反应的机理.分子结构计算表明:Sα-Ala·2H2O@SWCNT(8,8)和Sα-Ala·3H2O@SWCNT(8,8)中,季碳与其上面氢的键长分别是0.11055和0.11100(nm),比Sα-Ala·1H2O@SWCNT(8,8)的季碳与其上面氢的键长0.10991nm明显长;环形过渡态TS1·2H2O@SWCNT(8,8)和TS1·3H2O@SWCNT(8,8)的氢键键角比TS1·1H2O@SWCNT(8,8)的明显增大.势能面计算发现:在SWCNT(8,8)内以1个、2个和3个H2O分子为氢转移媒介,α-Ala的质子从季碳向羰基氧迁移的能垒是208.6、160.9和154.4(k J·mol-1).比α-Ala限域在SWCNT(8,8)内质子从季碳向羰基氧迁移的能垒322.7 k J·mol-1大幅降低.结果表明:SWCNT(8,8)与水的复合环境对α-Ala的质子从季碳向羰基氧迁移具有较好的催化作用.
