A Review of the Current State of Magnetic Force Microscopy to Unravel the Magnetic Properties of Nanomaterials Applied in Biological Systems and Future Directions for Quantum Technologies

Nanomaterials, Год журнала: 2023, Номер 13(18), С. 2585 - 2585

Опубликована: Сен. 18, 2023

Magnetism plays a pivotal role in many biological systems. However, the intensity of magnetic forces exerted between bodies is usually low, which demands development ultra-sensitivity tools for proper sensing. In this framework, force microscopy (MFM) offers excellent lateral resolution and possibility conducting single-molecule studies like other single-probe (SPM) techniques. This comprehensive review attempts to describe paramount importance applications by highlighting MFM's main advantages but also intrinsic limitations. While working principles are described depth, article focuses on novel micro- nanofabrication procedures MFM tips, enhance response signal tested biomaterials compared commercial nanoprobes. work depicts some relevant examples where can quantitatively assess performance nanomaterials involved systems, including magnetotactic bacteria, cryptochrome flavoproteins, nanoparticles that interact with animal tissues. Additionally, most promising perspectives field highlighted make reader aware upcoming challenges when aiming toward quantum technologies.

Язык: Английский

---

Atomic-level design of metalloenzyme-like active pockets in metal–organic frameworks for bioinspired catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 53(1), С. 137 - 162

Опубликована: Ноя. 29, 2023

Natural metalloenzymes with astonishing reaction activity and specificity underpin essential life transformations. Nevertheless, enzymes only operate under mild conditions to keep sophisticated structures active, limiting their potential applications. Artificial that recapitulate the catalytic of can not circumvent enzymatic fragility but also bring versatile functions into practice. Among them, metal-organic frameworks (MOFs) featuring diverse site-isolated metal sites supramolecular have emerged as promising candidates for move toward unparalleled properties behaviour enzymes. In this review, we systematically summarize significant advances in MOF-based metalloenzyme mimics a special emphasis on active pocket engineering at atomic level, including primary secondary coordination spheres. Then, deep understanding mechanisms advanced applications are discussed. Finally, perspective emerging frontier research is provided advance bioinspired catalysis.

Язык: Английский

---

Ion‐Selective Microporous Polymer Membranes with Hydrogen‐Bond and Salt‐Bridge Networks for Aqueous Organic Redox Flow Batteries

Advanced Materials, Год журнала: 2023, Номер 35(12)

Опубликована: Янв. 12, 2023

Redox flow batteries (RFBs) have great potential for long-duration grid-scale energy storage. Ion-conducting membranes are a crucial component in RFBs, allowing charge-carrying ions to transport while preventing the cross-mixing of redox couples. Commercial Nafion widely used but their unsatisfactory ionic and molecular selectivity, as well high costs, limit performance widespread deployment this technology. To extend longevity reduce cost RFB systems, inexpensive ion-selective that concurrently deliver low resistance selectivity toward redox-active species highly desired. Here, high-performance fabricated from blends carboxylate- amidoxime-functionalized polymers intrinsic microporosity, which exploit beneficial properties both polymers. The enthalpy-driven formation cohesive interchain interactions, including hydrogen bonds salt bridges, facilitates microscopic miscibility blends, ionizable functional groups within sub-nanometer pores allow optimization membrane ion-transport functions. resulting microporous demonstrate fast cation conduction with crossover species, enabling improved power ratings reduced capacity fade aqueous RFBs using anthraquinone ferrocyanide

Язык: Английский

---

Choose Your Own Adventure: A Comprehensive Database of Reactions Catalyzed by Cytochrome P450 BM3 Variants

ACS Catalysis, Год журнала: 2024, Номер 14(8), С. 5560 - 5592

Опубликована: Март 29, 2024

Cytochrome P450 BM3 monooxygenase is the topic of extensive research as many researchers have evolved this enzyme to generate a variety products. However, abundance information on increasingly diversified variants that catalyze broad array chemistry not in format enables easy extraction and interpretation. We present database categorizes by their catalyzed reactions includes details about substrates provide reaction context. This >1500 downloadable machine-readable instructions maximize ease gathering information. The allows rapid identification commonly reported substitutions, aiding who are unfamiliar with identifying starting points for engineering. For those actively engaged engineering BM3, database, along review, provides powerful user-friendly platform understand, predict, identify attributes variants, encouraging further enzyme.

Язык: Английский

---

Bioinspired Catalyst Design Principles: Progress in Emulating Properties of Enzymes in Synthetic Catalysts

ACS Catalysis, Год журнала: 2023, Номер 13(18), С. 11883 - 11901

Опубликована: Авг. 25, 2023

Catalysis enables many aspects of modern life, including fuels, products, plastics, and medicines. Recent advances in catalysis have enabled us to realize higher efficiencies new processes. Ideally, we seek achieve high rates selective conversions using catalysts derived from abundantly available elements operating under mild conditions, specifically lower reaction temperatures pressures. Such could enable decentralized, on-demand synthesis chemicals energy carriers. Nature has demonstrated the feasibility this approach with enzymes, which showcase catalytic processes at low pressures nonprecious metals. Current thinking holds that addition active site, complexity enzyme structure, protein scaffold, is also critical achieving performance. Recreating environment been a long-standing scientific goal. However, still understand functions enzymes better than de novo design mimic features, while retaining their activity selectivity more demanding conditions. In Perspective, will critically examine four key areas catalyst incorporate chemical structural properties into synthetic catalysts: (i) use confinement enhance activity, (ii) tailoring around (iii) proton transport, (iv) bifunctionality cooperativity.

Язык: Английский

---

From random to rational: improving enzyme design through electric fields, second coordination sphere interactions, and conformational dynamics

Chemical Science, Год журнала: 2023, Номер 14(40), С. 10997 - 11011

Опубликована: Янв. 1, 2023

A forward-looking perspective on optimizing enzyme design through synergizing electric fields, coordination spheres, and dynamics.

Язык: Английский

---

Engineering an Oxygen‐Binding Protein for Photocatalytic CO₂Reductions in Water

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(20)

Опубликована: Март 14, 2023

Abstract While native CO 2 ‐reducing enzymes display remarkable catalytic efficiency and product selectivity, few artificial biocatalysts have been engineered to allow understanding how the work. To address this issue, we report cobalt porphyrin substituted myoglobin (CoMb) as a homogeneous catalyst for photo‐driven conversion in water. The activity selectivity were optimized by varying pH concentrations of enzyme photosensitizer. Up 2000 TON(CO) was attained at low with (15 %), while 74 % reached increasing loading but compromised TON(CO). generation overall further improved introducing positively charged residues (Lys or Arg) near active stie CoMb, which demonstrates value tuning secondary coordination sphere enhance performance protein‐based photocatalytic system.

Язык: Английский

---

Evaluating the Transition State Stabilization/Destabilization Effects of the Electric Fields from Scaffold Residues by a QM/MM Approach

The Journal of Physical Chemistry B, Год журнала: 2023, Номер 127(19), С. 4245 - 4253

Опубликована: Май 8, 2023

The protein scaffolds of enzymes not only provide structural support for the catalytic center but also exert preorganized electric fields electrostatic catalysis. In recent years, uniform oriented external (OEEFs) have been widely applied to enzymatic reactions mimic effects environment. However, exerted by individual residues in proteins may be quite heterogeneous across active site, with varying directions and strengths at different positions site. Here, we propose a QM/MM-based approach evaluate scaffold. particular, heterogeneity residue effect native environment can properly accounted this QM/MM approach. A case study O–O heterolysis reaction cycle TyrH shows that (1) scaffold are relatively far from field site is very significant stabilization/destabilization due each well approximated interaction energy between QM region dipole; (2) near highly along breaking bond. such case, approximating as misrepresent overall residue. present residues' impact on reactions, which useful computational optimization boost enzyme

Язык: Английский

---

Biomimetic-Structured Cobalt Nanocatalyst Suppresses Aortic Dissection Progression by Catalytic Antioxidation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(25), С. 17201 - 17210

Опубликована: Июнь 14, 2024

As one of the most lethal cardiovascular diseases, aortic dissection (AD) is initiated by overexpression reactive oxygen species (ROS) in aorta that damages vascular structure and finally leads to massive hemorrhage sudden death. Current drugs used clinics for AD treatment fail efficiently scavenge ROS a large extent, presenting undesirable therapeutic effect. In this work, nanocatalytic antioxidation concept has been proposed elevate efficacy constructing cobalt nanocatalyst with biomimetic can pathological an efficient sustainable manner. Theoretical calculations demonstrate reaction catalyzed redox transition between hydroxocobalt(III) oxo-hydroxocobalt(V) accompanied inner-sphere proton-coupled two-electron transfer, forming nonassociated activation catalytic cycle. The action region effectively alleviates oxidative stress, which further modulates inflammatory microenvironment promoting phenotype macrophages. Consequently, smooth muscle cells are also protected from inflammation meantime, suppressing progression. This study provides approach other diseases.

Язык: Английский

---

Using BpyAla to generate Copper Artificial Metalloenzymes: a catalytic and structural study

Catalysis Science & Technology, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Artificial metalloenzymes (ArMs) have emerged as a promising avenue in the field of biocatalysis, offering new reactivity. However, their design remains challenging due to limited understanding protein dynamics and how introduced cofactors alter scaffold structure. Here we present structures catalytic activity novel copper ArMs capable (

Язык: Английский

---