Physical Biology of the Materials–Microorganism Interface

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(6), P. 1978 - 1985

Published: Jan. 24, 2018

Future solar-to-chemical production will rely upon a deep understanding of the material-microorganism interface. Hybrid technologies, which combine inorganic semiconductor light harvesters with biological catalysis to transform light, air, and water into chemicals, already demonstrate wide product scope energy efficiencies surpassing that natural photosynthesis. But optimization economic competitiveness fundamental curiosity beg for answers two basic questions: (1) how do materials transfer charge microorganisms, (2) we design bio- chemocompatibility between these seemingly unnatural partners? This Perspective highlights state-of-the-art outlines future research paths inform cadre spectroscopists, electrochemists, bioinorganic chemists, material scientists, biologists who ultimately solve mysteries.

Language: Английский

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A machine learning approach for reliable prediction of amino acid interactions and its application in the directed evolution of enantioselective enzymes

Scientific Reports, Journal Year: 2018, Volume and Issue: 8(1)

Published: Nov. 7, 2018

Directed evolution is an important research activity in synthetic biology and biotechnology. Numerous reports describe the application of tedious mutation/screening cycles for improvement proteins. Recently, knowledge-based approaches have facilitated prediction protein properties identification improved mutants. However, epistatic phenomena constitute obstacle which can impair predictions engineering. We present innovative sequence-activity relationship (innov'SAR) methodology based on digital signal processing combining wet-lab experimentation computational design. In our machine learning approach, a predictive model developed to find resulting property when n single point mutations are permuted (2n combinations). The originality approach that only sequence information fitness mutants measured needed build models. illustrate case improving enantioselectivity epoxide hydrolase from Aspergillus niger. = 9 enzyme were experimentally assessed their used as dataset model. Based combinations (29), these 512 variants predicted, candidates checked: better with higher indeed found.

Language: Английский

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Noble−Metal Substitution in Hemoproteins: An Emerging Strategy for Abiological Catalysis

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 52(2), P. 326 - 335

Published: Jan. 29, 2019

ConspectusEnzymes have evolved to catalyze a range of biochemical transformations with high efficiencies and unparalleled selectivities, including stereoselectivities, regioselectivities, chemoselectivities, substrate while typically operating under mild aqueous conditions. These properties motivated extensive research identify or create enzymes reactivity that complements even surpasses the small-molecule catalysts for chemical reactions. One limitations preventing wider use in synthesis, however, is narrow bond constructions catalyzed by native enzymes. strategy overcome this limitation artificial metalloenzymes (ArMs) combine molecular recognition nature discovered chemists.This Account describes new approach generating ArMs formal replacement natural iron found porphyrin IX (PIX) hemoproteins noble metals. Analytical techniques coupled studies demonstrated expression apomyoglobins apocytochrome P450s (for which “apo-” denotes cofactor-free protein) followed reconstitution metal–PIX cofactors vitro creates proteins little perturbation structure, suggesting likely reside within active site. By means metal substitution strategy, large number been constructed contain varying metalloporphyrins mutations protein.The discussed encompass containing metals abiological chemoselectivity, enantioselectivity, diastereoselectivity, regioselectivity. include intramolecular intermolecular insertion carbenes into C–H, N–H, S–H bonds, cyclopropanation vinylarenes internal nonconjugated alkenes, insertions nitrenes C–H bonds. The rates bonds thermophilic P450 reconstituted an Ir(Me)–PIX cofactor are now comparable reactions and, date, 1000 times greater than those any previously reported ArM. This also encompasses selective carbene from ethyl diazoacetate over dimerization form class selectivity not occur catalysts. combined results highlight potential well-designed challenging achieve type catalyst. described herein should complement expand scope enzyme-catalyzed

Language: Английский

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Nature’s Machinery, Repurposed: Expanding the Repertoire of Iron-Dependent Oxygenases

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(20), P. 12239 - 12255

Published: Sept. 28, 2020

Iron is an especially important redox-active cofactor in biology because of its ability to mediate reactions with atmospheric O2. Iron-dependent oxygenases exploit this earth-abundant transition metal for the insertion oxygen atoms into organic compounds. Throughout astounding diversity transformations catalyzed by these enzymes, protein framework directs reactive intermediates toward precise formation products, which, many cases, necessitates cleavage strong C–H bonds. In recent years, members several iron-dependent oxygenase families have been engineered new-to-nature that offer advantages over conventional synthetic methods. Perspective, we first explore what known about reactivity heme-dependent cytochrome P450 and nonheme bearing 2-His-1-carboxylate facial triad reviewing mechanistic studies emphasis on how scaffold maximizes catalytic potential iron-heme iron cofactors. We then review cofactors repurposed abiological engineering frameworks enzymes. Finally, discuss contemporary challenges associated platforms comment their roles biocatalysis moving forward.

Language: Английский

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Synthetic chemistry in a water world. New rules ripe for discovery

Current Opinion in Green and Sustainable Chemistry, Journal Year: 2017, Volume and Issue: 11, P. 1 - 8

Published: Nov. 8, 2017

Language: Английский

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