Peptidic Scaffolds Enable Rapid and Multivariate Secondary Sphere Evolution for an Abiotic Metallocatalyst
| العنوان: | Peptidic Scaffolds Enable Rapid and Multivariate Secondary Sphere Evolution for an Abiotic Metallocatalyst |
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| المؤلفون: | Sabari Ghosh, Phuong Nguyen Tran, Dan McElheny, Juan J. Perez, Andy I. Nguyen |
| المصدر: | Inorganic Chemistry. 61:6679-6687 |
| بيانات النشر: | American Chemical Society (ACS), 2022. |
| سنة النشر: | 2022 |
| مصطلحات موضوعية: | Inorganic Chemistry, Coordination Complexes, Metalloproteins, Physical and Theoretical Chemistry, Ligands, Peptides, Catalysis |
| الوصف: | Metalloenzymes have benefited from the iterative process of evolution to achieve the precise arrangements of secondary sphere non-covalent interactions that enhance metal-centered catalysis. Iterative synthesis of scaffolds that display complex secondary sphere elements in abiotic systems can be highly challenging and time-intensive. To overcome this synthetic bottleneck, we developed a highly modular and rapid synthetic strategy, leveraging the efficiency of solid-phase peptide synthesis and conformational control afforded by non-canonical residues to construct a ligand platform displaying up to four unique residues of varying electronics and sterics in the secondary coordination sphere. As a proof-of-concept that peptidic secondary sphere can cooperate with the metal complex, we applied this scaffold to a well-known, modestly active C-H oxidizing Fe catalyst to evolve specific non-covalent interactions that is more than double its catalytic activity. Solution-state NMR structures of several catalyst variants suggest that higher activity is correlated with a hydrophobic pocket above the Fe center that may enhance the formation of a catalyst-substrate complex. Above all, we show that peptides are a convenient, highly modular, and structurally defined ligand platform for creating secondary coordination spheres that comprise multiple, diverse functional groups. |
| تدمد: | 1520-510X 0020-1669 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::b92c37582da500fade5c991305771b39 https://doi.org/10.1021/acs.inorgchem.2c00901 |
| حقوق: | CLOSED |
| رقم الأكسشن: | edsair.doi.dedup.....b92c37582da500fade5c991305771b39 |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 1520510X 00201669 |
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