Theoretical studies of a singlet oxygen-releasing dioxapaddlane (1,4-diicosa naphthalene-1,4-endoperoxide).
Theoretical studies of a singlet oxygen-releasing dioxapaddlane (1,4-diicosa naphthalene-1,4-endoperoxide).
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单线态氧释放二氧杂环己烷（1,4-二二十二萘-1,4-内过氧化物）的理论研究。
DOI：
10.1007/s11224-009-9424-1
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发表时间：
2009
影响因子：
1.7
通讯作者：
Greer,Alexander
中科院分区：
文献类型：
--
作者：
Castillo,Alvaro;Greer,Alexander
理论计算已经被用来检验从一个具有柔性（CH2）22聚乙烯“盖子”的萘内过氧化物中释放的单线态氧。结合半经验理论和密度泛函理论的蒙特卡罗和ONIOM计算预测了聚亚甲基链对二氧杂环烷、1,4-二硫代萘-1,4-内过氧化物、二氧化二硫代萘和1,4-二硫代萘环还原的构象影响。本研究试图建立122代与二叠纪“跳绳”动力学之间的联系。聚亚甲基链似乎起着氧气守门人的作用。聚乙烯桥的半圆旋转保护了过氧化物基团，限制了102与萘位点的解离，而不是一个完整的圆。
Theoretical calculations have been used to examine singlet oxygen release from a naphthalene endoperoxide which bears a flexible (CH2)22polymethylene “lid”. Monte Carlo and ONIOM calculations that incorporated semi-empirical and density functional theory predicted the conformational influence of the polymethylene chain in the cycloreversion of dioxapaddlane, 1,4-diicosa naphthalene-1,4-endoperoxide, to1O2and 1,4-diicosa naphthalene. This study attempts to build a connection between1O2generation and “jump rope” dynamics of the dioxapaddlane. The polymethylene chain appears to function as a gatekeeper for the oxygen. Instead of coming full circle, a semi-circle rotation of the polymethylene bridge protected the peroxide group, limiting the dissociation of1O2from the naphthalene site.