Copper model complexes of lytic polysaccharide monooxygenases

溶解多糖单加氧酶的铜模型复合物

• 批准号: 1795205
• 金额: --
• 依托单位: University of York
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2016
• 资助国家: 英国
• 起止时间: 2016 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-1795205
• 关键词: Copper; model; complexes; lytic; polysaccharide

The LPMOs are a new class of copper-containing enzymes which are capable of oxidising C-H of around 100 kcal/mol. The copper active site of these enzymes contains the copper coordinated by a 'histidine brace' where the amino terminus of the protein is used to coordinate to the copper ion. Such coordination is extremely rare in bioinorganic chemistry and many questions are posed as to what the role of this group is in allowing the copper complex to generate highly oxidising species.This PhD will concentrate on preparing and studying two types of small molecule complexes and examining their spectroscopic and structural properties in the context of LPMOs. The first class of complexes will contain either an NH2 or and NH group as part of the copper's coordination set to examine whether the hydrogen atoms are important in the chemistry of the copper ion. The second class will contain deprotonated amide/amine in the coordination set to examine whether such a similar species could exist in LPMOs. In both cases the complexes will be studied spectroscopically and structurally. The reactivity of the Cu(I) forms of these complexes will also be studied, with a view to understanding more about the analogous reactivity in LPMOs.The principal spectroscopic techniques will be multi-frequency EPR, visible absorption spectroscopy and magnetic circular dichroism. These techniques will be augmented with a theoretical approach to interpreting the related spin-Hamiltonian parameters and the orbital energetics. The latter will be determined using density functional calculations. It is anticipated that new theoretical methods may need to be deployed in the interpretation of EPR data of Cu complexes. As such, new approaches which use DFT energetics alongside sum-over-states perturbative calculations will be examined.

LPMOS是一类新型的含铜酶，能够氧化约100千卡/摩尔的C-H。这些酶的铜活性部位含有由组氨酸支架配位的铜，在组氨酸支架上，蛋白质的氨基末端被用来与铜离子配位。这种配位在生物无机化学中是极其罕见的，对于这个基团在使铜配合物产生高氧化性物种方面所起的作用提出了许多问题。本博士学位论文将集中在制备和研究两种类型的小分子配合物，并在LPMOS的背景下考察它们的光谱和结构性质。第一类络合物将包含NH2或和NH基团，作为铜的配位集的一部分，以检查氢原子在铜离子的化学中是否重要。第二类将在配位集中包含去质子酰胺/胺，以检查这种类似物种是否可能存在于LPMO中。在这两种情况下，都将对络合物进行光谱和结构研究。还将研究这些配合物的铜(I)形式的反应性，以期更多地了解LPMO中类似的反应性。主要的光谱技术将是多频EPR、可见吸收光谱和磁圆二色谱。这些技术将被一种解释相关自旋哈密顿参数和轨道能量学的理论方法所增强。后者将使用密度泛函计算来确定。可以预见，可能需要采用新的理论方法来解释铜配合物的EPR数据。因此，我们将考察使用DFT能量学和状态总和微扰计算的新方法。