Krishan Kumar’s research while affiliated with University of the Basque Country and other places

Enzyme-polymer hybrids combine the resources provided by nature – enzymes – with a chemical toolbox – synthetic polymers – in the laboratory for carrying out complex chemical reactions with high selectivity outside of cellular machinery. Recent advances in polymer chemistry have opened new opportunities for imparting novel, adjustable functionalities into enzymes, which act as an anchoring site for precise accommodation of inorganic catalysts (nanoparticles, nanoclusters, and single atoms) and give rise to the creation of artificial multicatalytic systems. This book chapter summarizes the latest progress in designing supramolecular catalytic hybrid materials with applications in chemoenzymatic reactions. Additionally, it discusses the challenges and limitations in this field, along with potential future directions.

Modifying the coordination or local environments of single‐, di‐, tri‐, and multi‐metal atom (SMA/DMA/TMA/MMA)‐based materials is one of the best strategies for increasing the catalytic activities, selectivity, and long‐term durability of these materials. Advanced sheet materials supported by metal atom‐based materials have become a critical topic in the fields of renewable energy conversion systems, storage devices, sensors, and biomedicine owing to the maximum atom utilization efficiency, precisely located metal centers, specific electron configurations, unique reactivity, and precise chemical tunability. Several sheet materials offer excellent support for metal atom‐based materials and are attractive for applications in energy, sensors, and medical research, such as in oxygen reduction, oxygen production, hydrogen generation, fuel production, selective chemical detection, and enzymatic reactions. The strong metal–metal and metal–carbon with metal–heteroatom (i.e., N, S, P, B, and O) bonds stabilize and optimize the electronic structures of the metal atoms due to strong interfacial interactions, yielding excellent catalytic activities. These materials provide excellent models for understanding the fundamental problems with multistep chemical reactions. This review summarizes the substrate structure‐activity relationship of metal atom‐based materials with different active sites based on experimental and theoretical data. Additionally, the new synthesis procedures, physicochemical characterizations, and energy and biomedical applications are discussed. Finally, the remaining challenges in developing efficient SMA/DMA/TMA/MMA‐based materials are presented.

The entrapment of deep eutectic solvents (DES) and eutectic systems into porous scaffolds renders a new class of soft and nonvolatile materials called eutectogels that have recently stepped into the spotlight in different areas ranging from electronics to drug delivery. Recent progress in the use of DES in biocatalysis, where they have been demonstrated to improve substrate supply, conversion, and enzyme stability, has opened an unparalleled opportunity to exploit the merits of eutectogels for immobilizing biological catalysts. The resulting functional materials could outperform traditional hydrogels and ionic liquid gels, offering fresh perspectives to broaden the application scope of many enzymes. In this perspective, we go into the potential of eutectogels as innovative scaffolds that support biocatalytic reactions and discuss different applications where these systems could show plain benefits compared to traditional materials. Future directions for this newly developed technology are highlighted.

The inorganic content and the catalytic performance pose metal‐loaded enzyme nanoflowers as promising candidates for developing bioelectrodes capable of functioning without the external addition of a redox mediator. However, these protein‐inorganic hybrids have yet to be successfully applied in combination with electrode materials. Herein, the synthesis procedure of these bionanomaterials is reproposed to precisely control the morphology, composition, and performance of this particular protein‐mineral hybrid, formed by glucose oxidase and cobalt phosphate. This approach aims to enhance the adherence and electron mobility between the enzyme and a carbon electrode. The strategy relies on dressing the protein in a tailored thin nanogel with multivalent chemical motifs. The functional groups of the polymer facilitate the fast protein sequence‐independent biomineralization. Furthermore, the engineered enzymes enable the fabrication of robust cobalt‐loaded enzyme inorganic hybrids with exceptional protein loads, exceeding 90% immobilization yields. Notably, these engineered biohybrids can be readily deposited onto flat electrode surfaces without requiring chemical pre‐treatment. The resulting bioelectrodes are robust and exhibit electrochemical responses even without the addition of a redox mediator, suggesting that cobalt complexes promote electron wiring between the active site of the enzyme and the electrode.

Utilizing stimuli-responsive polymers for surface modification of nanoparticle allows the adjustment of properties for individual system; however, limited research explores the impact of ionic liquid-modified gold nanoparticles (AuNPs) on the conformational phase transition of block copolymers. Herein, we synthesized poly(N-isopropylacrylamide)-b-poly(acryloylmorpholine) (PNIPAM-b-PACMO) copolymers by reversible addition − fragmentation chain-transfer polymerization and investigated the effect of ionic-liquid modified AuNPs (IL-AuNPs) on the aggregation behavior of the copolymer. Copolymerization of PNIPAM with PACMO shifted the lower critical solution temperature (LCST) towards higher temperature in comparison to LCST value of PNIPAM. Addition of IL-AuNPs further raises the transition temperature in concentration dependent manner. A more significant alteration in the transition temperature was observed in the presence of IL-AuNPs with a higher alkyl chain length. The variation in transition temperature of the copolymer by different IL-AuNPs yields benefits in the temperature responsive properties which can helpful for various applications.

Metalloenzymes represent exemplary systems in which an organic scaffold combines with a functional inorganic entity, resulting in excellent redox catalysts. Inspired by these natural hybrid biomolecules, biomolecular templates have garnered significant attention for the controlled synthesis of inorganic nanostructures. These nanostructures ultimately benefit from the protection and colloidal stabilization provided by the biomacromolecule. In this study, we have employed this strategy to prepare nanozymes with redox capabilities, utilizing the versatile catalytic profile of Pt-loaded nanomaterials. Thus, we have investigated protein-templated Pt-based nanoclusters of different sizes and compositions, which exhibit remarkable oxidase, catalase, and reductase-like activities. The interplay between the composition and catalytic activity highlighted the size of the nanocluster as the most prominent factor in determining the performance of the nanozymes. Additionally, we have demonstrated the use of protein-templated nanozymes as potential co-catalysts in combination with enzymes for coupled reactions, under both sequential and concurrent one-pot conditions. This study provides valuable insights into nanozyme design and its wide range of applications in the design of complex catalytic systems.