Redox Biocatalysis in Lidocaine-Based Hydrophobic Deep Eutectic Solvents: Non-Conventional Media Outperform Aqueous Conditions.

Redox biocatalysis is an essential pillar of the chemical industry. Yet, the enzymes' nature restricts most reactions to aqueous conditions, where the limited substrate solubility leads to unsustainable diluted biotranformations. Non-aqueous media represent a strategic solution to conduct intensified biocatalytic routes.

Development of a Human Recombinant Collagen for Vat Polymerization-Based Bioprinting.

In light-based 3D-bioprinting, gelatin methacrylate (GelMA) is one of the most widely used materials, as it supports cell attachment, and shows good biocompatibility and degradability in vivo. However, as an animal-derived material, it also causes safety concerns when used in medical applications. Gelatin is a partial hydrolysate of collagen, containing high amounts of hydroxyproline.

Antimicrobial properties and biocompatibility of semi-synthetic carbohydrate-based ionic hydrogels.

Hydrogels have gained significant interest in the last decades, especially in the medical sector, due to their versatile properties. While hydrogels from naturally occurring polysaccharides ( cellulose) are well-known, those produced from polymerizable carbohydrate-based monomers remain underexplored. However, these semi-synthetic hydrogels offer the great advantage of having adjustable properties for customization depending on their application.

Intensified, Kilogram-Scaled, and Environment-Friendly: Chemoenzymatic Synthesis of Bio-Based Acylated Hydroxystyrenes.

Lignin-derived styrene derivatives are versatile building blocks for the manufacture of biobased polymers. As shown previously, phenol-protected hydroxystyrenes are accessible under industrially sound conditions (>100 g L, >95% yield) by subjecting biogenic phenolic acids to enzymatic decarboxylation and base-catalyzed acylation in nonaqueous media (wet cyclopentyl methyl ether, CPME). Herein, we demonstrate the production of 1 kg of 4-acetoxy-3-methoxy-styrene in a 10 L reactor and present practical adjustments to the up- and downstream processing that warrant a straightforward process and high isolated yields.

Integrated preservation of water activity as key to intensified chemoenzymatic synthesis of bio-based styrene derivatives.

The valorization of lignin-derived feedstocks by catalytic means enables their defunctionalization and upgrading to valuable products. However, the development of productive, safe, and low-waste processes remains challenging. This paper explores the industrial potential of a chemoenzymatic reaction performing the decarboxylation of bio-based phenolic acids in wet cyclopentyl methyl ether (CPME) by immobilized phenolic acid decarboxylase from Bacillus subtilis, followed by a base-catalyzed acylation.

Biocatalysis in Water or in Non-Conventional Media? Adding the CO Production for the Debate.

Biocatalysis can be applied in aqueous media and in different non-aqueous solutions (non-conventional media). Water is a safe solvent, yet many synthesis-wise interesting substrates cannot be dissolved in aqueous solutions, and thus low concentrations are often applied. Conversely, non-conventional media may enable higher substrate loadings but at the cost of using (fossil-based) organic solvents.

Correction: 3D printed and stimulus responsive drug delivery systems based on synthetic polyelectrolyte hydrogels manufactured digital light processing.

Correction for '3D printed and stimulus responsive drug delivery systems based on synthetic polyelectrolyte hydrogels manufactured digital light processing' by Sonja Vaupel , 2023, DOI: https://doi.org/10.1039/d3tb00285c.

Robust Light Driven Enzymatic Oxyfunctionalization via Immobilization of Unspecific Peroxygenase.

Unspecific peroxygenases have attracted interest in synthetic chemistry, especially for the oxidative activation of C-H bonds, as they only require hydrogen peroxide (H O ) instead of a cofactor. Due to their instability in even small amounts of H O , different strategies like enzyme immobilization or in situ H O production have been developed to improve the stability of these enzymes. While most strategies have been studied separately, a combination of photocatalysis with immobilized enzymes was only recently reported.

3D printed and stimulus responsive drug delivery systems based on synthetic polyelectrolyte hydrogels manufactured digital light processing.

Hydrogels are three-dimensional hydrophilic polymeric networks absorbing up to and even more than 90 wt% of water. These superabsorbent polymers retain their shape during the swelling process while enlarging their volume and mass. In addition to their swelling behavior, hydrogels can possess other interesting properties, such as biocompatibility, good rheological behavior, or even antimicrobial activity.

Crosslinked Aggregates of Fusion Enzymes in Microaqueous Organic Media.

Baeyer-Villiger monooxygenases (BVMOs) are attractive for selectively oxidizing various ketones using oxygen into valuable esters and lactones. However, the application of BVMOs is restrained by cofactor dependency and enzyme instability combined with water-related downsides such as low substrate loading, low oxygen capacity, and water-induced side reactions. Herein, we described a redox-neutral linear cascade with in-situ cofactor regeneration catalyzed by fused alcohol dehydrogenase and cyclohexanone monooxygenase in aqueous and microaqueous organic media.

Process intensification in continuous flow biocatalysis by up and downstream processing strategies.

In this review, we focus on the holistic continuous enzymatic production and put special emphasis on process intensification by up- and downstream processing in continuous flow biocatalysis. After a brief introduction, we provide an overview of current examples of enzyme immobilization as an upstream process for flow biocatalysis. Thereafter, we provide an overview of unit operations as downstream processing strategies, namely continuous (i) liquid-liquid extraction, (ii) adsorptive downstream processing, and (iii) crystallization and precipitation.

Immobilization and Application of Fatty Acid Photodecarboxylase in Deep Eutectic Solvents.

Since its discovery in 2017, the fatty acid decarboxylase (FAP) photoenzyme has been the focus of extensive research, given its ability to convert fatty acids into alka(e)nes using merely visible blue light. Unfortunately, there are still some drawbacks that limit the applicability of this biocatalyst, such as poor solubility of the substrates in aqueous media, poor photostability, and the impossibility of reusing the catalyst for several cycles. In this work, we demonstrate the use of FAP in non-conventional media as a free enzyme and an immobilized preparation.

Transmembrane Shuttling of Photosynthetically Produced Electrons to Propel Extracellular Biocatalytic Redox Reactions in a Modular Fashion.

Many biocatalytic redox reactions depend on the cofactor NAD(P)H, which may be provided by dedicated recycling systems. Exploiting light and water for NADPH-regeneration as it is performed, e.g.

A holistic carrier-bound immobilization approach for unspecific peroxygenase.

Unspecific peroxygenases (UPOs) are among the most studied enzymes in the last decade and their well-deserved fame owes to the enzyme's ability of catalyzing the regio- and stereospecific hydroxylation of non-activated C-H bonds at the only expense of HO. This leads to more direct routes for the synthesis of different chiral compounds as well as to easier oxyfunctionalization of complex molecules. Unfortunately, due to the high sensitivity towards the process conditions, UPOs' application at industrial level has been hampered until now.

Design of fusion enzymes for biocatalytic applications in aqueous and non-aqueous media.

Biocatalytic cascades play a fundamental role in sustainable chemical synthesis. Fusion enzymes are one of the powerful toolboxes to enable the tailored combination of multiple enzymes for efficient cooperative cascades. Especially, this approach offers a substantial potential for the practical application of cofactor-dependent oxidoreductases by forming cofactor self-sufficient cascades.

Transmembrane Shuttling of Photosynthetically Produced Electrons to Propel Extracellular Biocatalytic Redox Reactions in a Modular Fashion.

Many biocatalytic redox reactions depend on the cofactor NAD(P)H, which may be provided by dedicated recycling systems. Exploiting light and water for NADPH-regeneration as it is performed, e.g.

Exploring the Temperature Effect on Enantioselectivity of a Baeyer-Villiger Biooxidation by the 2,5-DKCMO Module: The SLM Approach.

Temperature is a crucial parameter for biological and chemical processes. Its effect on enzymatically catalysed reactions has been known for decades, and stereo- and enantiopreference are often temperature-dependent. For the first time, we present the temperature effect on the Baeyer-Villiger oxidation of rac-bicyclo[3.

A Deep Eutectic Solvent Thermomorphic Multiphasic System for Biocatalytic Applications.

The applicability of a thermomorphic multiphasic system (TMS) composed of a hydrophobic deep eutectic solvent (DES) and an aqueous potassium phosphate buffer with a lower critical solution temperature (LCST) phase change for homogeneous biocatalysis was investigated. A lidocaine-based DES with the fatty acid oleic acid as a hydrogen-bond donor was studied. Phase diagrams were determined and presented within this study.

Enzymatic Cascade for the Synthesis of 2,5-Furandicarboxylic Acid in Biphasic and Microaqueous Conditions: 'Media-Agnostic' Biocatalysts for Biorefineries.

5-hydroxymethylfurfural (HMF) is produced upon dehydration of C6 sugars in biorefineries. As the product, it remains either in aqueous solutions, or is in situ extracted to an organic medium (biphasic system). For the subsequent oxidation of HMF to 2,5-furandicarboxylic acid (FDCA), 'media-agnostic' catalysts that can be efficiently used in different conditions, from aqueous to biphasic, and to organic (microaqueous) media, are of interest.

Enzyme immobilization in hydrogels: A perfect liaison for efficient and sustainable biocatalysis.

Biocatalysis is an established chemical synthesis technology that has by no means been restricted to research laboratories. The use of enzymes for organic synthesis has evolved greatly from early development to proof-of-concept - from small batch production to industrial scale. Different enzyme immobilization strategies contributed to this success story.

Expression and activity of heterologous hydroxyisocaproate dehydrogenases in sp. PCC 6803 Δ.

Exploiting light to drive redox reactions is currently a hot topic since light is considered as an environmentally friendly source of energy. Consequently, cyanobacteria, which can use light e.g.

Photobioreactors for cultivation and synthesis: Specifications, challenges, and perspectives.

Due to their versatility and the high biomass yield produced, cultivation of phototrophic organisms is an increasingly important field. In general, open ponds are chosen to do it because of economic reasons; however, this strategy has several drawbacks such as poor control of culture conditions and a considerable risk of contamination. On the other hand, photobioreactors are an attractive choice to perform cultivation of phototrophic organisms, many times in a large scale and an efficient way.

Comparison and Validation of Force Fields for Deep Eutectic Solvents in Combination with Water and Alcohol Dehydrogenase.

Deep eutectic solvents (DESs) have become popular as environmental-friendly solvents for biocatalysis. Molecular dynamics (MD) simulations offer an in-depth analysis of enzymes in DESs, but their performance depends on the force field chosen. Here, we present a comprehensive validation of three biomolecular force fields (CHARMM, Amber, and OPLS) for simulations of alcohol dehydrogenase (ADH) in DESs composed of choline chloride and glycerol/ethylene glycol with varying water contents.

Internal Illumination to Overcome the Cell Density Limitation in the Scale-up of Whole-Cell Photobiocatalysis.

Cyanobacteria have the capacity to use photosynthesis to fuel their metabolism, which makes them highly promising production systems for the sustainable production of chemicals. Yet, their dependency on visible light limits the cell-density, which is a challenge for the scale-up. Here, it was shown with the example of a light-dependent biotransformation that internal illumination in a bubble column reactor equipped with wireless light emitters (WLEs) could overcome this limitation.

Divorce in the two-component BVMO family: the single oxygenase for enantioselective chemo-enzymatic Baeyer-Villiger oxidations.

Two-component flavoprotein monooxygenases consist of a reductase and an oxygenase enzyme. The proof of functionality of the latter without its counterpart as well as the mechanism of flavin transfer remains unanswered beyond doubt. To tackle this question, we utilized a reductase-free reaction system applying purified 2,5-diketocamphane-monooxygenase I (2,5-DKCMO), a FMN-dependent type II Baeyer-Villiger monooxygenase, and synthetic nicotinamide analogues (NCBs) as dihydropyridine derivatives for FMN reduction.