Protein-Polymer Conjugates as Biocompatible and Recyclable ATRP Catalysts.

Atom transfer radical polymerization (ATRP) is a leading method for creating polymers with precise control over molecular weight, yet its reliance on metal catalysts limits its application in metal-sensitive and environmental contexts. Addressing these limitations, we have developed a recyclable, biocompatible, robust, and tunable ATRP catalyst composed of a protein-polymer-copper conjugate, synthesized by polymerizing an -proline-based monomer onto bovine serum albumin and complexing with Cu(II). The use of this conjugate catalyst maintains ATRP's precision while ensuring biocompatibility with both and HEK 293 cells, and its high molecular weight allows for easy recycling through dialysis.

A Supramolecular Approach to Engineering Living Cells with Enzymes for Adaptive and Recyclable Cascade Synthesis.

Biocatalytic transformation in nature is inherently dynamic, spontaneous, and adaptive, enabling complex chemical synthesis and metabolism. These processes often involve supramolecular recognition among cells, enzymes, and biomacromolecules, far surpassing the capabilities of isolated cells and enzymes used in industrial synthesis. Inspired by nature, here we design a supramolecular approach to equip living cells with these capacities, enabling recyclable, efficient cascade reactions.

Combining Liposomal Photocatalysts with Whole-Cell Catalysts for One-pot Photobiocatalysis.

Cooperative photobiocatalytic processes have seen extensive potentials for the synthesis of both bulk and fine chemicals owing to their versatility, eco-friendliness, and cost-effectiveness. Nevertheless, developing a universal and effective synthetic strategy compatible with both catalytic systems remains challenging. In this study, we explored cationic liposomes as biocompatible photocatalyst encapsulation systems and combined them with bacteria overexpressing enzymes for two-step and three-step cascade reactions.

Enzyme-particle Complexes Facilitate Pickering Interfacial Biocatalysis.

Pickering interfacial biocatalysis (PIB), where biocatalysts stabilize emulsions through carrier coupling or polymer grafting, has emerged as a powerful platform for organic synthesis due to its ability to accommodate water-insoluble substrates within enzymatic cascade reactions. PIB provides a large interfacial area for two-phase reactions, reducing diffusional resistance and enhancing transformation efficiency. The performance of PIB relies heavily on enzyme-particle conjugates, which serve a dual function: stabilizing the emulsion and acting as the active biocatalysts in the system.

Pickering Emulsions Biocatalysis: Recent Developments and Emerging Trends.

Biocatalysis within biphasic systems is gaining significant attention in the field of synthetic chemistry, primarily for its ability to solve the problem of incompatible solubilities between biocatalysts and organic compounds. By forming an emulsion from these two-phase systems, a larger surface area is created, which greatly improves the mass transfer of substrates to the biocatalysts. Among the various types of emulsions, Pickering emulsions stand out due to their excellent stability, compatibility with biological substances, and the ease with which they can be formed and separated.

Integrating Enzymes with Supramolecular Polymers for Recyclable Photobiocatalytic Catalysis.

Chemical modifications of enzymes excel in the realm of enzyme engineering due to its directness, robustness, and efficiency; however, challenges persist in devising versatile and effective strategies. In this study, we introduce a supramolecular modification methodology that amalgamates a supramolecular polymer with Candida antarctica lipase B (CalB) to create supramolecular enzymes (SupEnzyme). This approach features the straightforward preparation of a supramolecular amphiphilic polymer (β-CD@SMA), which was subsequently conjugated to the enzyme, resulting in a SupEnzyme capable of self-assembly into supramolecular nanoparticles.

Enzyme-Polymer-Conjugate-Based Pickering Emulsions for Cell-Free Expression and Cascade Biotransformation.

In this study, we addressed the limitations of conventional enzyme-polymer-conjugate-based Pickering emulsions for interfacial biocatalysis, which traditionally suffer from nonspecific and uncontrollable conjugation positions that can impede catalytic performance. By introducing a non-canonical amino acid (ncAA) at a specific site on target enzymes, we enabled precise polymer-enzyme conjugation. These engineered conjugates then acted as biocatalytically active emulsifiers to stabilize Pickering emulsions, while encapsulating a cell-free protein synthesis (CFPS) system in the aqueous phase for targeted enzyme expression.

Metal Alloys-Structured Electrocatalysts: Metal-Metal Interactions, Coordination Microenvironments, and Structural Property-Reactivity Relationships.

Metal alloys-structured electrocatalysts (MAECs) have made essential contributions to accelerating the practical applications of electrocatalytic devices in renewable energy systems. However, due to the complex atomic structures, varied electronic states, and abundant supports, precisely decoding the metal-metal interactions and structure-activity relationships of MAECs still confronts great challenges, which is critical to direct the future engineering and optimization of MAECs. Here, this timely review comprehensively summarizes the latest advances in creating the MAECs, including the metal-metal interactions, coordination microenvironments, and structure-activity relationships.

Electronic Structure-Dependent Water-Dissociation Pathways of Ruthenium-Based Catalysts in Alkaline H -Evolution.

Ruthenium (Ru)-based catalysts have displayed compelling hydrogen evolution activities, which hold the promising potential to substitute platinum in alkaline H -evolution. In the challenging alkaline electrolytes, the water-dissociation process involves multistep reactions, while the profound origin and intrinsic factors of diverse Ru species on water-dissociation pathways and reaction principles remain ambiguous. Here the fundamental origin of water-dissociation pathways of Ru-based catalysts in alkaline media to be from their unique electronic structures in complex coordination environments are disclosed.

Cell-free metabolic engineering enables selective biotransformation of fatty acids to value-added chemicals.

Fatty acid-derived products such as alkanes, fatty aldehydes, and fatty alcohols have many applications in the chemical industry. These products are predominately produced from fossil resources, but their production processes are often not environmentally friendly. While microbes like have been engineered to convert fatty acids to corresponding products, the design and optimization of metabolic pathways in cells for high productivity is challenging due to low mass transfer, heavy metabolic burden, and intermediate/product toxicity.

Tailoring Protein-Polymer Conjugates as Efficient Artificial Enzymes for Aqueous Asymmetric Aldol Reactions.

Artificial enzymes are becoming a powerful toolbox for selective organic syntheses. Herein, we first propose an advanced artificial enzyme by polymeric modularity as an efficient aldolase mimic for aqueous asymmetric aldol reactions. Based on an in-depth understanding of the aldolase reaction mechanism and our previous work, we demonstrate the modular design of protein-polymer conjugates by co-incorporating l-proline and styrene onto a noncatalytic protein scaffold with a high degree of controllability.

Biocatalytic Synthesis Using Self-Assembled Polymeric Nano- and Microreactors.

Biocatalysis is increasingly being explored for the sustainable development of green industry. Though enzymes show great industrial potential with their high efficiency, specificity, and selectivity, they suffer from poor usability and stability under abiological conditions. To solve these problems, researchers have fabricated nano- and micro-sized biocatalytic reactors based on the self-assembly of various polymers, leading to highly stable, functional, and reusable biocatalytic systems.

Copper-Containing Artificial Polyenzymes as a Clickase for Bioorthogonal Chemistry.

Artificial polyenzymes (ArPoly) are tailored combinations of universal protein scaffolds and polymers newly proposed as promising alternatives to natural enzymes to expand the biocatalyst toolbox. The concept of ArPoly has been continuously extended to metal-containing ArPoly to overcome the drawbacks faced by conventional artificial metalloenzymes. Herein, we present a sustainable route to synthesize a novel water-soluble metalloenzyme for copper-catalyzed azide-alkyne cycloadditions in water with remarkable selectivity.

Cationic Covalent Organic Polymer Thin Film for Label-free Electrochemical Bacterial Cell Detection.

Numerous species of bacteria pose a serious threat to human health and cause several million deaths annually. It is therefore essential to have quick, efficient, and easily operable methods of bacterial cell detection. Herein, we synthesize a novel cationic covalent organic polymer (COP) named through the Menshutkin reaction and evaluate its potential as an impedance sensor for cells.

Artificially sporulated Escherichia coli cells as a robust cell factory for interfacial biocatalysis.

The natural bacterial spores have inspired the development of artificial spores, through coating cells with protective materials, for durable whole-cell catalysis. Despite attractiveness, artificial spores developed to date are generally limited to a few microorganisms with their natural endogenous enzymes, and they have never been explored as a generic platform for widespread synthesis. Here, we report a general approach to designing artificial spores based on Escherichia coli cells with recombinant enzymes.

Designing Modular Cell-free Systems for Tunable Biotransformation of l-phenylalanine to Aromatic Compounds.

Cell-free systems have been used to synthesize chemicals by reconstitution of expressed enzymes. However, coexpression of multiple enzymes to reconstitute long enzymatic pathways is often problematic due to resource limitation/competition (e.g.

Responsive Emulsions for Sequential Multienzyme Cascades.

Multienzyme cascade biocatalysis is an efficient synthetic process, avoiding the isolation/purification of intermediates and shifting the reaction equilibrium to the product side.. However, multienzyme systems are often limited by their incompatibility and cross-reactivity.

Tailoring Particle-Enzyme Nanoconjugates for Biocatalysis at the Organic-Organic Interface.

Nonaqueous Pickering emulsions (PEs) are a powerful platform for catalysis design, offering both a large interface contact and a preferable environment for water-sensitive synthesis. However, up to now, little progress has been made to incorporate insoluble enzymes into the nonaqueous system for biotransformation. Herein, we present biocatalytically active nonaqueous PEs, stabilized by particle-enzyme nanoconjugates, for the fast transesterification and esterification, and eventually for biodiesel synthesis.

Cell-free protein synthesis enables one-pot cascade biotransformation in an aqueous-organic biphasic system.

Biocatalytic cascade reactions have become increasingly important and useful for chemical synthesis. However, biocatalysts are often incompatible with organic solvents, which prohibits many cascade reactions involving nonpolar substrates. In this study, we used cell-free protein synthesis (CFPS) to express enzymes in an aqueous-organic biphasic system for the construction of an artificial enzymatic pathway.

Facile Synthesis of Enzyme-Embedded Metal-Organic Frameworks for Size-Selective Biocatalysis in Organic Solvent.

immobilization of enzyme into metal-organic frameworks (MOFs) is performed through a one-step and facile method. lipase B (CalB) is directly embedded in zeolitic imidazolate framework (ZIF)-8 by simply mixing an aqueous solution of 2-methylimidazole and zinc nitrate hexahydrate [Zn(NO)⋅6HO] containing CalB at room temperature. Due to the intrinsic micropores of ZIF-8, the obtained CalB@ZIF composite is successfully applied in size-selective transesterification reaction in organic solvent.

Association of Serum Lipoprotein-Associated Phospholipase A2 and A379V Gene Polymorphisms with Carotid Plaques.

Lipoprotein-associated phospholipase A2 (LP-PLA2) is closely related to the development of atherosclerosis. The A379V gene polymorphism, located in exon 11 of the gene, can affect LP-PLA2 levels and the inflammatory response. However, the association between the A379V polymorphism and formation of carotid plaques is unclear.

Gastrodin Attenuates Neuronal Apoptosis and Neurological Deficits after Experimental Intracerebral Hemorrhage.

Objective: Gastrodin, a glucoside of gastrodigenin, inhibits cerebral oxidant stress and apoptosis in multiple central nervous system injury, but its effect in intracerebral hemorrhage (ICH) remains unclear. This study investigated the effect of gastrodin on neuronal apoptosis and neurological deficits in rat ICH model.

Methods: In vitro experiments were performed using hematoma lysate-induced cell damage model in primary cortical neurons.

Living whole-cell catalysis in compartmentalized emulsion.

Whole-cell biocatalysis plays an important role in biotransformation with unique features such as good tolerance of solvents and easy recycling. However, the relatively low catalytic efficiency limits their use in real production. In this study, a multi-compartmentalized emulsion in organic solvent was constructed to encapsulate living cells for enhanced catalytic performance.