The mechanism, catalytic effect and solvent effect of the hetero-Diels-Alder reactions between 3-pyddinedithioesters and 1-phenylsulfanylbutadiene have been studied theoretically using density functional theory (DFT...The mechanism, catalytic effect and solvent effect of the hetero-Diels-Alder reactions between 3-pyddinedithioesters and 1-phenylsulfanylbutadiene have been studied theoretically using density functional theory (DFT) at the B3LYP/6-31G(d) level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C bond and the opposite results are found in other reactions. The BF3 catalyst may lower the activation barriers by changing the energies of LUMO for 3-pyridinedithioester. THF solvent has trivial influence on the potential energy surface of these reactions. With the BF3-catalyzed reactions, regioselectivity and stereoselectivity observed experimentally were predicted correctly by calculations and these results originate probably from C-H…F interaction in two transition states.展开更多
目的:对比三维多回波恢复梯度回波(3D MERGE)、三维可变反转角快速自旋回波(3D SPACE STIR)序列在腰椎间盘突出症(LDH)检查中的应用效果。方法:选择2020年1月~2022年11月收治的135例LDH患者,回顾性分析患者临床和磁共振成像(MRI)资料,...目的:对比三维多回波恢复梯度回波(3D MERGE)、三维可变反转角快速自旋回波(3D SPACE STIR)序列在腰椎间盘突出症(LDH)检查中的应用效果。方法:选择2020年1月~2022年11月收治的135例LDH患者,回顾性分析患者临床和磁共振成像(MRI)资料,所有患者均接受常规MRI扫描及3D MERGE、3D SPACE STIR序列扫描,对比3D MERGE、3D SPACE STIR序列测量神经根直径的一致性,评价两种序列的图像质量参数[信噪比(SNR)、对比噪声比(CNR)]、图像清晰度评分。结果:3D MERGE和3D SPACE STIR序列测量的L3~S1神经根直径比较差异无统计学意义(P>0.05),且两组序列测量的L3、L4、L5和S1直径均显示出较高相关性(r=0.957,0.986,0.975,0.972,P<0.05);3D MERGE序列的SNR及CNR均高于3D SPACE STIR序列,神经根显示分级、图像清晰度评分优于3D SPACE STIR序列,差异有统计学意义(P<0.05)。结论:3D MERGE、3D SPACE STIR序列在LDH神经根直径测量中具有极高一致性,3D MERGE序列较3D SPACE STIR序列能够更清晰显示神经跟的解剖形态,图像质量更好。展开更多
文摘The mechanism, catalytic effect and solvent effect of the hetero-Diels-Alder reactions between 3-pyddinedithioesters and 1-phenylsulfanylbutadiene have been studied theoretically using density functional theory (DFT) at the B3LYP/6-31G(d) level. The results show that all of these reactions proceed in a concerted but asynchronous way. In some reactions the formation of C-S bond is prior to that of C-C bond and the opposite results are found in other reactions. The BF3 catalyst may lower the activation barriers by changing the energies of LUMO for 3-pyridinedithioester. THF solvent has trivial influence on the potential energy surface of these reactions. With the BF3-catalyzed reactions, regioselectivity and stereoselectivity observed experimentally were predicted correctly by calculations and these results originate probably from C-H…F interaction in two transition states.
文摘目的:对比三维多回波恢复梯度回波(3D MERGE)、三维可变反转角快速自旋回波(3D SPACE STIR)序列在腰椎间盘突出症(LDH)检查中的应用效果。方法:选择2020年1月~2022年11月收治的135例LDH患者,回顾性分析患者临床和磁共振成像(MRI)资料,所有患者均接受常规MRI扫描及3D MERGE、3D SPACE STIR序列扫描,对比3D MERGE、3D SPACE STIR序列测量神经根直径的一致性,评价两种序列的图像质量参数[信噪比(SNR)、对比噪声比(CNR)]、图像清晰度评分。结果:3D MERGE和3D SPACE STIR序列测量的L3~S1神经根直径比较差异无统计学意义(P>0.05),且两组序列测量的L3、L4、L5和S1直径均显示出较高相关性(r=0.957,0.986,0.975,0.972,P<0.05);3D MERGE序列的SNR及CNR均高于3D SPACE STIR序列,神经根显示分级、图像清晰度评分优于3D SPACE STIR序列,差异有统计学意义(P<0.05)。结论:3D MERGE、3D SPACE STIR序列在LDH神经根直径测量中具有极高一致性,3D MERGE序列较3D SPACE STIR序列能够更清晰显示神经跟的解剖形态,图像质量更好。