Co‐immobilization of an Enzyme and a Metal into the Compartments of Mesoporous Silica for Cooperative Tandem Catalysis: An Artificial Metalloenzyme

Engström, Karin; Johnston, Eric V.; Verho, Oscar; Gustafson, Karl P. J.; Shakeri, Mozaffar; Tai, Cheuk‐Wai; Bäckvall, Jan‐E.

doi:10.1002/anie.201306487

Cited by 211 publications

(162 citation statements)

References 37 publications

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“…These are very versatile enzymes with successful results in different processes using non-natural substrates [13] and they are commercially available in large amounts. Recently, these enzymes have been combined with metals in the preparation of several hybrids catalysts [14][15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

2016

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Heterogeneous catalysts have been synthesized by the conjugation of Hoveyda-Grubbs second-generation catalyst with a lipase. The catalytic properties of the organometallic compound in solution were firstly optimized, evaluating the activity of Ru in the ring-closing metathesis of diethyldiallymalonate at 25 • C at different solvents and in the presence of different additives. The best result was found using tetrahydrofuran as a solvent. Some additives such as phenylboronic acid or polyetheneglycol slightly improved the activity of the Ru catalyst whereas others, such as pyridine or dipeptides affected it negatively. The organometallic compound immobilized on functionalized-surface materials activated with boronic acid or epoxy groups (around 50-60 µg per mg support) and showed 50% conversion at 24 h in the ring-closing metathesis. Cross-linked enzyme aggregates (CLEA's) of the Hoveyda-Grubbs second-generation catalyst with Candida antarctica lipase (CAL-B) were prepared, although low Ru catalyst was found to be translated in low conversion. Therefore, a sol-gel preparation of the Hoveyda-Grubbs second-generation and CAL-B was performed. This catalyst exhibited good activity in the metathesis of diethyldiallymalonate in toluene and in aqueous media. Finally, a new sustainable approach was used by the conjugation lipase-Grubbs in solid phase in aqueous media. Two strategies were used: one using lipase previously covalently immobilized on an epoxy-Sepharose support (hydrophilic matrix) and then conjugated with grubbs; and in the second, the free lipase was incubated with organometallic in aqueous solution and then immobilized on epoxy-Sepharose. The different catalysts showed excellent conversion values in the ring-closing metathesis of diethyldiallymalonate in aqueous media at 25 • C.

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Section: Introductionmentioning

confidence: 99%

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

2016

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“…In a recent approach, Bäckvall and co-workers (Engström et al, 2013) created a heterogeneous hybrid catalyst by co-immobilizing CAL-B and Pd nanoparticles in mesocelullar foam (MCF), so that each pore of it contains both an anzymatic and a metal component. This "artificial metalloenzyme" was able to efficiently catalyze the DKR of 1-phenylethylamine, thus presenting a "deracemase" activity, which is not displayed by any known natural enzyme.…”

Section: Dynamic Kinetic Resolution Of Amines Catalyzed By Lipases Anmentioning

confidence: 99%

Lipases: Valuable catalysts for dynamic kinetic resolutions

Miranda

Souza

2015

Biotechnology Advances

187

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“…Several methods have also been applied for improving enzymes as biocatalysts. Immobilization of enzymes on heterogeneous catalysts [104][105][106] and preparation of cross-linked enzyme aggregates [107] are well-developed methods to improve the activity and stability of enzymes at extreme conditions, and to facilitate enzyme recycling. In addition, engineering enzymes by rational design [108,109] and directed evolution [110] are alternative ways to obtain enzyme mutants with improved properties and new functions.…”

Section: Future Prospects and Conclusionmentioning

confidence: 99%

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

Wang

Zhao

2016

Catalysts

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Abstract:The application of biocatalysts in the synthesis of fine chemicals and medicinal compounds has grown significantly in recent years. Particularly, there is a growing interest in the development of one-pot tandem catalytic systems combining the reactivity of a chemical catalyst with the selectivity engendered by the active site of an enzyme. Such tandem catalytic systems can achieve levels of chemo-, regio-, and stereo-selectivities that are unattainable with a small molecule catalyst. In addition, artificial metalloenzymes widen the range of reactivities and catalyzed reactions that are potentially employable. This review highlights some of the recent examples in the past three years that combined transition metal catalysis with enzymatic catalysis. This field is still in its infancy. However, with recent advances in protein engineering, catalyst synthesis, artificial metalloenzymes and supramolecular assembly, there is great potential to develop more sophisticated tandem chemoenzymatic processes for the synthesis of structurally complex chemicals.

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Co‐immobilization of an Enzyme and a Metal into the Compartments of Mesoporous Silica for Cooperative Tandem Catalysis: An Artificial Metalloenzyme

Cited by 211 publications

References 37 publications

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

Design of Heterogeneous Hoveyda–Grubbs Second-Generation Catalyst–Lipase Conjugates

Lipases: Valuable catalysts for dynamic kinetic resolutions

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

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