Castillo Alvaro, Greer Alexander
Department of Chemistry and Graduate Center, Brooklyn College, The City University of New York (CUNY), Brooklyn, NY 11210, USA.
Struct Chem. 2009 Jun 1;20(3):399-407. doi: 10.1007/s11224-009-9424-1.
Theoretical calculations have been used to examine singlet oxygen release from a naphthalene endoperoxide which bears a flexible (CH(2))(22) polymethylene "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, to (1)O(2) and 1,4-diicosa naphthalene. This study attempts to build a connection between (1)O(2) generation 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 of (1)O(2) from the naphthalene site.
理论计算已被用于研究一种带有柔性(CH₂)₂₂聚亚甲基“盖子”的萘内过氧化物的单线态氧释放。结合半经验和密度泛函理论的蒙特卡罗和ONIOM计算预测了聚亚甲基链在二氧杂双环[2.2.2]辛烷（1,4 - 二十二碳萘 - 1,4 - 内过氧化物）环化转化为单线态氧(¹O₂)和1,4 - 二十二碳萘过程中的构象影响。本研究试图建立¹O₂生成与二氧杂双环[2.2.2]辛烷“跳绳”动力学之间的联系。聚亚甲基链似乎起到了氧的守门人的作用。聚亚甲基桥不是完整地旋转一圈，而是进行半圆形旋转，从而保护过氧化物基团，限制¹O₂从萘位点解离。
