Dubey Archana, Heinonen Olle
Department of Physics and Astronomy, University of Central Florida, Orlando, FL, USA.
Biometals. 2013 Dec;26(6):1003-12. doi: 10.1007/s10534-013-9677-4. Epub 2013 Sep 25.
We have determined the structure and coordination chemistry of rhizoferrin (Rf), which is a particular type of siderophore, and its Fe(III) complexes using density functional theory calculations. Our results show that the Fe(III) ion binds in an octahedral coordination, with a low-spin (S = 1/2) charge-neutral chiral complex having the largest binding energy of the investigated complexes. We have also calculated nuclear magnetic resonance parameters, such as chemical shifts for (1)H and (13)C, and indirect nuclear spin-spin couplings for (1)H-(1)H and (13)C-(1)H in free Rf and in a low-spin neutral Rf metal complex, as well as nuclear quadrupole interaction parameters, such as asymmetry parameter and nuclear quadrupole coupling constants for (14)N. Our calculated values for the chemical shifts for free Rf are in excellent agreement with experimental data while the calculated NMR parameters for Fe(III) complexes are predictions for future experimental work.
我们利用密度泛函理论计算确定了根际铁载体（Rf）及其铁（III）配合物的结构和配位化学，根际铁载体是一种特殊类型的铁载体。我们的结果表明，铁（III）离子以八面体配位方式结合，所研究的配合物中具有最低自旋（S = 1/2）电荷中性手性配合物的结合能最大。我们还计算了核磁共振参数，如游离Rf以及低自旋中性Rf金属配合物中（1）H和（13）C的化学位移，以及（1）H-（1）H和（13）C-（1）H的间接核自旋-自旋耦合，此外还计算了核四极相互作用参数，如（14）N的不对称参数和核四极耦合常数。我们计算得到的游离Rf化学位移值与实验数据高度吻合，而铁（III）配合物的计算核磁共振参数则是对未来实验工作的预测。
