Synthetic Biology: Bottom-Up Assembly of Molecular Systems

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(21), P. 16294 - 16328

Published: Sept. 30, 2022

The bottom-up assembly of biological and chemical components opens exciting opportunities to engineer artificial vesicular systems for applications with previously unmet requirements. modular combination scaffolds functional building blocks enables the engineering complex biomimetic or new-to-nature functionalities. Inspired by compartmentalized organization cells organelles, lipid polymer vesicles are widely used as model membrane investigate translocation solutes transduction signals proteins. functionalization such compartments full control over their composition can thus provide specifically optimized environments synthetic processes. This review aims inspire future endeavors providing a diverse toolbox molecular modules, methodologies, different approaches assemble systems. Important technical practical aspects addressed selected presented, highlighting particular achievements limitations approach. Complementing cutting-edge technological achievements, fundamental also discussed cater inherently background target audience, which results from interdisciplinary nature biology. proteins modules use lipids block copolymers scaffold functionalized explored in detail. Particular emphasis is placed on ensuring controlled these into increasingly Finally, all descriptions presented greater context valuable biocatalysis, biosensing, bioremediation, targeted drug delivery.

Language: Английский

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Biomimetic Metallic Nanostructures for Biomedical Applications, Catalysis, and Beyond

Industrial & Engineering Chemistry Research, Journal Year: 2022, Volume and Issue: 61(22), P. 7547 - 7593

Published: May 16, 2022

Nature has inspired scientists to develop green and sustainable nanomaterials with biomimetic functions. Particularly, metallic nanostructures (biometal NPs) unique optical, catalytic, electrical properties have received tremendous attention in many fields, ranging from healthcare agriculture energy environmental sciences. Biometal NPs synthesized by various natural resources such as plant extracts, biomolecules, bacteria, even viruses possess functions including but not limited precise biorecognition, self-assembly, antibacterial/antiviral, enzymatic properties. In this report, we first review the bioinspired synthesis of industrially important metal nanoparticles, followed discussion on how different biological sources affect as-synthesized biometal NPs. Next, recent advancement applications these fields biomedical engineering catalysis, which include development nanobiosensors, imaging probes, nanotherapeutics (e.g., antimicrobial photodynamic/photothermal therapeutic agents), well design multifunctional nanozymes artificial metalloenzymes for chemical biopharmaceutical industries. Finally, highlight some latest advancements nanobiomimicry their emerging clean energy, electronic devices, data storage, shows game-changing role technological near future.

Language: Английский

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Expanding the Synthetic Toolbox through Metal–Enzyme Cascade Reactions

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(9), P. 5297 - 5346

Published: Jan. 10, 2023

The combination of metal-, photo-, enzyme-, and/or organocatalysis provides multiple synthetic solutions, especially when the creation chiral centers is involved. Historically, enzymes and transition metal species have been exploited simultaneously through dynamic kinetic resolutions racemates. However, more recently, linear cascades appeared as elegant solutions for preparation valuable organic molecules combining bioprocesses metal-catalyzed transformations. Many advantages are derived from this symbiosis, although there still bottlenecks to be addressed including successful coexistence both catalyst types, need compatible reaction media mild conditions, or minimization cross-reactivities. Therefore, here also provided by means coimmobilization, compartmentalization strategies, flow chemistry, etc. A comprehensive review presented focusing on period 2015 early 2022, which has divided into two main sections that comprise first use metals independent catalysts but working in an orchestral sequential manner, later their application bionanohybrid materials coimmobilization adequate supports. Each part classified different subheadings, based catalyzed catalyst, while development nonasymmetric stereoselective processes was considered section.

Language: Английский

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Learning from Protein Engineering by Deconvolution of Multi‐Mutational Variants

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 17, 2024

Abstract This review analyzes a development in biochemistry, enzymology and biotechnology that originally came as surprise. Following the establishment of directed evolution stereoselective enzymes organic chemistry, concept partial or complete deconvolution selective multi‐mutational variants was introduced. Early experiments led to finding mutations can interact cooperatively antagonistically with one another, not just additively. During past decade, this phenomenon shown be general. In some studies, molecular dynamics (MD) quantum mechanics/molecular mechanics (QM/MM) computations were performed order shed light on origin non‐additivity at all stages an evolutionary upward climb. Data used construct unique multi‐dimensional rugged fitness pathway landscapes, which provide mechanistic insights different from traditional landscapes. Along related line, biochemists have long tested result introducing two point enzyme for reasons, followed by comparison respective double mutant so‐called cycles, showed only additive effects, but more recently also uncovered cooperative antagonistic non‐additive effects. We conclude suggestions future work, call unified overall picture epistasis.

Language: Английский

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Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 143(1), P. 97 - 102

Published: Dec. 28, 2020

Intermolecular C–C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation olefins catalyzed by flavin-dependent 'ene'-reductases. Radical initiation occurs via photoexcitation rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone. This unique mechanism ensures radical formation only when both substrates present within protein active site. site can control terminating hydrogen atom transfer, enabling synthesis enantioenriched γ-stereogenic amides. work highlights potential for catalysis to enable new biocatalytic previously unknown electron transfer mechanisms.

Language: Английский

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Emerging strategies for expanding the toolbox of enzymes in biocatalysis

Current Opinion in Chemical Biology, Journal Year: 2020, Volume and Issue: 55, P. 45 - 51

Published: Jan. 11, 2020

Language: Английский

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Iron catalysts with N-ligands for carbene transfer of diazo reagents

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(14), P. 4867 - 4905

Published: Jan. 1, 2020

This review provides an overview of the catalytic activity iron complexes nitrogen ligands in driving carbene transfers towards CC, C–H and X–H bonds. The reactivity diazo reagents is discussed as well proposed reaction mechanisms.

Language: Английский

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Recent Advances in Biocatalysis with Chemical Modification and Expanded Amino Acid Alphabet

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(10), P. 6173 - 6245

Published: April 22, 2021

The two main strategies for enzyme engineering, directed evolution and rational design, have found widespread applications in improving the intrinsic activities of proteins. Although numerous advances been achieved using these ground-breaking methods, limited chemical diversity biopolymers, restricted to 20 canonical amino acids, hampers creation novel enzymes that Nature has never made thus far. To address this, much research devoted expanding protein sequence space via modifications and/or incorporation noncanonical acids (ncAAs). This review provides a balanced discussion critical evaluation applications, recent advances, technical breakthroughs biocatalysis three approaches: (i) modification cAAs, (ii) ncAAs, (iii) incorporated ncAAs. Furthermore, approaches result on functional properties mechanistic study are extensively reviewed. We also discuss design artificial with ncAAs incorporated. Finally, we current challenges future perspectives expanded acid alphabet.

Language: Английский

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Beyond the Second Coordination Sphere: Engineering Dirhodium Artificial Metalloenzymes To Enable Protein Control of Transition Metal Catalysis

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 52(3), P. 576 - 584

Published: March 4, 2019

ConspectusTransition metal catalysis is a powerful tool for chemical synthesis, standard by which understanding of elementary processes can be measured, and source awe those who simply appreciate the difficulty cleaving forming bonds. Each these statements amplified in cases where transition catalyst controls selectivity reaction. Enantioselective challenging but well-established phenomenon, regio- or site-selective increasingly common. On other hand, transition-metal-catalyzed reactions are typically conducted under highly optimized conditions. Rigorous exclusion air water common, it taken granted that only single substrate (of particular class) will present reaction, desired site achieved installing directing group, undesired reactivity blocked with protecting groups. These all reasonable synthetic strategies, they also highlight limits to control.The utility could greatly expanded if catalysts possessed ability regulate molecules encounter relative orientation molecules. The rapid widespread adoption stoichiometric bioorthogonal illustrates robust proceed high specificity mild reaction Expanding this capability beyond preprogrammed pairs via control therefore have an enormous impact on molecular science. Many metalloenzymes exhibit level control, directed evolution used rapidly improve catalytic properties systems. range catalyzed enzymes limited developed chemists. possibility imparting enzyme-like activity, selectivity, evolvability complexes has inspired creation artificial (ArMs). increasing levels exhibited ArMs date suggest systems constitute platform selective general.This Account outlines development new class based prolyl oligopeptidase (POP) scaffold. Studies POP containing covalently linked dirhodium cofactor shown impart enantioselectivity dirhodium-catalyzed reactions, increase rates, carbene intermediates targeted organic substrates over components cell lysate, including bulk water. Several design features enabled their random mutagenesis, revealed mutations throughout scaffold, second sphere cofactor, were important ArM activity selectivity. While was anticipated scaffold would capable encapsulating thus controlling bulky cofactors, dynamics studies conformational plays role its unique efficacy. advances selection, bioconjugation, form basis our ongoing efforts using protein scaffolds goal enabling capabilities, catalysis.

Language: Английский

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Intracellular Activation of Bioorthogonal Nanozymes through Endosomal Proteolysis of the Protein Corona

ACS Nano, Journal Year: 2020, Volume and Issue: 14(4), P. 4767 - 4773

Published: March 31, 2020

Bioorthogonal activation of prodrugs provides a strategy for on-demand on-site production therapeutics. Intracellular to localize therapeutics, potentially minimizing off-target effects. To this end, nanoparticles embedded with transition metal catalysts (nanozymes) were engineered generate either "hard" irreversible or "soft" reversible coronas in serum. The hard corona induced nanozyme aggregation, effectively inhibiting activity, whereas only modest loss activity was observed the nonaggregating soft nanozymes. In both cases complete restored by treatment proteases. mirrored reactivation: endogenous proteases endosome provided intracellular role reactivation verified through cells protease inhibitors, which prevented reactivation. This study demonstrates use proteolysis as localization therapeutic generation within cells.

Language: Английский

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