Theoretical Chemistry Section, Bhabha Atomic Research Centre, Mumbai 400 085, India.
J Phys Chem A. 2012 May 3;116(17):4388-95. doi: 10.1021/jp3015194. Epub 2012 Apr 20.
The feasibility of using cucurbituril host molecule as a probable actinyl cation binders candidate is investigated through density functional theory based calculations. Various possible binding sites of the cucurbit[5]uril host molecule to uranyl are analyzed and based on the binding energy evaluations, μ(5)-binding is predicted to be favored. For this coordination, the structure, vibrational spectra, and binding energies are evaluated for the binding of three actinyls in hexa-valent and penta-valent oxidation states with functionalized cucurbiturils. Functionalizing cucurbituril with methyl and cyclohexyl groups increases the binding affinities of actinyls, whereas fluorination decreases the binding affinities as compared to the native host molecule. Surprisingly hydroxylation of the host molecule does not distinguish the oxidation state of the three actinyls.
通过基于密度泛函理论的计算，研究了将葫芦[5]脲主分子用作可能的锕酰阳离子结合剂候选物的可行性。分析了葫芦[5]脲主分子与铀酰的各种可能结合位点，并基于结合能评估，预测μ(5)-结合是有利的。对于这种配位，评估了六价和五价氧化态的三种锕系元素与功能化葫芦[5]脲的结合的结构、振动光谱和结合能。与天然主分子相比，用甲基和环己基官能化葫芦[5]脲增加了锕系元素的结合亲和力，而氟化则降低了结合亲和力。令人惊讶的是，主体分子的羟基化并不能区分三种锕系元素的氧化态。
