•MOFs with different dimensionalities are a versatile host platform for the effective enzymes immobilization.•Dimensionality of MOFs significantly affects performance of enzyme@MOF ...composites.•Preparation approaches of enzyme@MOF composites with different dimensionalities are evaluated.•There will be great demand on enzyme@MOF composites with diverse functionality.
Metal-organic frameworks (MOFs) are an emerging class of porous materials with well-defined pore and crystal structure, favorable biocompatibility, good chemo-/machinal stability and high surface area, which endow them as ideal host matrix to develop enzyme@MOF composites. Most of the enzyme@MOF composites exhibit excellent catalysis performances performance and increased stability. In the past decade, many efforts have been made to develop enzyme@MOF composites with potential applications. The dimensionality of the MOFs has a significant effect on the catalytic performance of enzyme@MOF composites. However, there have been few reviews on enzyme@MOF composites with different dimensionalities. This review aims to describe the contemporary advances in the development of enzyme@MOF composites with different dimensionalities. Synthesizing strategies of enzyme@MOF composites with different dimensionalities are summarized. The interaction between enzymes and MOFs with different dimensionalities from the aspects of activity, stability, and reusability are discussed. Furthermore, the application and potential research direction of enzyme@MOF composites are introduced. We believe this work will be helpful for readers to understand the fundamental research and applications of enzyme@MOF composites with different dimensionalities.
Vinyl and p‐nitrophenyl esters have emerged as alternative substrates for the LovD9 acylation mechanism, showing product yields as high as those obtained by ...α‐dimethylbutyryl‐S‐methyl‐3‐mercaptopropionate (DMB‐SMMP), the thioester for which LovD9 was evolved. More information can be found in the Research Article by G. Jiménez‐Osés, F. López‐Gallego and co‐workers (DOI: 10.1002/chem.202300911).
A chemoenzymatic cascade process for the sustainable production of pyrroles has been developed. Pyrroles were synthesized by exploiting the previously unexplored aromatizing activity of monoamine ...oxidase enzymes (MAO-N and 6-HDNO). MAO-N/6-HDNO whole cell biocatalysts are able to convert 3-pyrrolines into pyrroles under mild conditions and in high yields. Moreover, MAO-N can work in combination with the ruthenium Grubbs catalyst, leading to the synthesis of pyrroles from diallylamines/-anilines in a one-pot cascade metathesis–aromatization sequence.
Enzymatic carbon dioxide fixation is one of the most important metabolic reactions as it allows the capture of inorganic carbon from the atmosphere and its conversion into organic biomass. However, ...due to the often unfavorable thermodynamics and the difficulties associated with the utilization of CO
, a gaseous substrate that is found in comparatively low concentrations in the atmosphere, such reactions remain challenging for biotechnological applications. Nature has tackled these problems by evolution of dedicated CO
-fixing enzymes, i.e., carboxylases, and embedding them in complex metabolic pathways. Biotechnology employs such carboxylating and decarboxylating enzymes for the carboxylation of aromatic and aliphatic substrates either by embedding them into more complex reaction cascades or by shifting the reaction equilibrium via reaction engineering. This review aims to provide an overview of natural CO
-fixing enzymes and their mechanistic similarities. We also discuss biocatalytic applications of carboxylases and decarboxylases for the synthesis of valuable products and provide a separate summary of strategies to improve the efficiency of such processes. We briefly summarize natural CO
fixation pathways, provide a roadmap for the design and implementation of artificial carbon fixation pathways, and highlight examples of biocatalytic cascades involving carboxylases. Additionally, we suggest that biochemical utilization of reduced CO
derivates, such as formate or methanol, represents a suitable alternative to direct use of CO
and provide several examples. Our discussion closes with a techno-economic perspective on enzymatic CO
fixation and its potential to reduce CO
emissions.
The development of mild, efficient, and enantioselective methods for preparing chiral building blocks from simple, renewable carbon units has been a long-term goal of the sustainable chemical ...industry. Mandelate derivatives are valuable pharmaceutical intermediates and chiral resolving agents, but their manufacture relies heavily on highly toxic cyanide. Herein, we report (S)-4-hydroxymandelate synthase (HmaS)-centered biocatalytic cascades for the synthesis of mandelates from benzaldehydes and glycine. We show that HmaS can be engineered to perform R-selective hydroxylation by single-point mutation, empowering the stereodivergent synthesis of both (S)- and (R)-mandelate derivatives. These biocatalytic cascades enabled the production of various mandelate derivatives with high atom economy as well as excellent yields (up to 98 %) and ee values (up to >99 %). This methodology offers an effective cyanide-free technology for greener and sustainable production of mandelate derivatives.
A ball‐and‐stick Houk‐style view of islatravir, the target of the total synthesis described in this work, is depicted in the cover image. Islatravir is on top of a “caged” Human Immunodeficiency ...Virus to indicate that the molecule is an HIV translocation‐transcriptase inhibitor. In the center of the picture is a circle showing the three key catalytic steps of the synthesis; a biocatalytic cascade, an enantioselective alkynylation, and an ozonolysis deprotection cascade. More information can be found in the Full Paper by H. C. Johnson, A. M. Whittaker, et al. on page 14118.
•Requirements for future sustainable bulk chemical production identified•Examples of biocatalytic processes to bulk-chemical/fuels, including production of biodiesel, furfurals and amines.•Future ...process-based research fields requiring increased attention identified.
The design and development of new routes for the production of sustainable bulk-chemicals requires focus on feedstock, conversion technology and downstream product recovery. This brief article discusses some of the constraints with using fermentation and suggests the removal of some constraints by using microbial biocatalysis or enzyme biocatalysis, which give a number of benefits in the context of the requirements for bulk-chemical production. Some potential process concepts are described, for products in the suitable low-price range. These examples (biodiesel, furfurals and amines) are used to illustrate the power of biocatalysis. Suggestions for future research efforts beyond molecular biology, involving process-based concepts, are also discussed.
Ionic liquids have unique chemical properties that have fascinated scientists in many fields. The effects of adding ionic liquids to biocatalysts are many and varied. The uses of ionic liquids in ...biocatalysis include improved separations and phase behaviour, reduction in toxicity, and stabilization of protein structures. As the ionic liquid state of the art has progressed, concepts of what can be achieved in biocatalysis using ionic liquids have evolved and more beneficial effects have been discovered. In this review ionic liquids for whole-cell and isolated enzyme biocatalysis will be discussed with an emphasis on the latest developments, and a look to the future.
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