Artificial Metalloenzyme for Enantioselective Sulfoxidation Based on Vanadyl-Loaded Streptavidin

Pordea, Anca; Creus, Marc; Panek, Jarosław J.; Duboc, Carole; Mathis, Déborah; Novič, Marjana; Ward, Thomas R.

doi:10.1021/ja8017219

Cited by 151 publications

(109 citation statements)

References 59 publications

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“…4). [156][157][158][159][160][161][162] As previously described, in natural evolution, the use of alternative metal ions can greatly change the specific activity of a metalloenzyme with different substrates. As the use of bioavailable metal ions is not a concern in the artificial design of metalloenzymes, many unique chemical reactions can take place through the use of precious metal ions instead, opening up the potential to harness the vast catalytic scope of transition metals in the design of novel enzymatic catalysts.…”

Section: Engineering Metalloenzymes For Novel Functions Using Lessonsmentioning

confidence: 99%

The Evolution of New Catalytic Mechanisms for Xenobiotic Hydrolysis in Bacterial Metalloenzymes

et al. 2016

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An increasing number of bacterial metalloenzymes have been shown to catalyse the breakdown of xenobiotics in the environment, while others exhibit a variety of promiscuous xenobiotic-degrading activities. Several different evolutionary processes have allowed these enzymes to gain or enhance xenobiotic-degrading activity. In this review, we have surveyed the range of xenobiotic-degrading metalloenzymes, and discuss the molecular and catalytic basis for the development of new activities. We also highlight how our increased understanding of the natural evolution of xenobiotic-degrading metalloenzymes can be been applied to laboratory enzyme design.

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Section: Engineering Metalloenzymes For Novel Functions Using Lessonsmentioning

confidence: 99%

The Evolution of New Catalytic Mechanisms for Xenobiotic Hydrolysis in Bacterial Metalloenzymes

et al. 2016

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“…This insight led to an expansion of Ward's research ranging from asymmetric transfer hydrogenation of prochiral ketones and imines, catalyzed by d 6 piano-stool complexes (Scheme 2); [12] and palladiumcatalyzed asymmetric allylic alkylation (Scheme 3) [13] towards oxidation reactions including the vanadyl-catalyzed sulfoxidation of prochiral sulfides (Scheme 4) [14] and the dihydroxylation of olefins.…”

Section: Artificial Metalloenzymes: Enantioselective Catalysis and Bementioning

confidence: 99%

Bioorganic and Bioinorganic Chemistry

Constable¹,

Housecroft²,

Creus³

et al. 2010

Chimia

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The interdisciplinary projects in bioinorganic and bioorganic chemistry of the Department of Chemistry, University of Basel led to the preparation of new systems that mimic biologically important processes and to the discovery of compounds from natural sources which are very promising with respect to medical applications. The advances in these areas are reported here. The Constable-Housecroft group is involved in biomimetic and bioinspired chemistry primarily relating to the fundamental processes in nature with a target of designing functional systems of sufficient robustness for practical application. This overview concentrates upon chemical approaches to the splitting of water into H 2 and O 2 based upon biomimetic or bioinspired principles. Other activities within the group involve the tagging of biomolecules with luminescent metal complexes for intracellular studies (with Prof. Matthias Wymann, Department of Biomedicine) and the deployment of nanoparticles functionalised with laccase for water purification (with Prof. Uwe Pieles, FHNW). The group has adopted a general strategy of mimicking the biological membrane by using two-dimensional control of the self-assembly of multiple components at solid-liquid or solid-air interfaces.The ultimate aim for energy production is a coupled water-splitting reaction using solar energy to generate H 2 and O 2 followed by recombination of the two diatomics in a fuel cell. The formal process is presented in Fig. 1 which serves to highlight the features that need to be controlled. Water oxidation and reduction reactions will take place at spatially separated sites and the kinetics of charge separation will be critical in controlling the success of the devices. The device can be purely molecular or the oxidation and reduction equivalents could be holes and electrons in the valence and conduction bands of a semiconductor or a combination of both approaches.For the water reduction process the group has taken inspiration from the Fe 2 S 2 structural motif found in Fe-Fe hydrogenases and invested significant synthetic Biomimetic Splitting of WaterEdwin C. Constable and Catherine E. Housecroft Evolutionary Rules for Metalloenzyme Design Marc CreusCurrent work within the newlyestablished Creus group is based on the concept that direct metal coordination to non-catalytic proteins may lead to nascent metalloenzymes, which can form a basis for further evolution. Conceptually, the dual ideas of 'emergence' and 'evolution' of metalloenzymes correspond to two extremes of an evolutionary process: i) a qualitative step, involving a new function reached through innovation (e.g. acquisition of catalytic activity from previously inactive form) and ii) a quantitative step (e.g. the improvement of a weak, but detectable function). Directed evolution, despite its limitations in practical terms, [1] provides a powerful tool for the second type (or quantitative) step. [2] Although the study of intermediate steps of improvement of metalloenzymes is likely to contribute greatly to the ...

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“…[9][10][11][12][13] For the localization of an organometallic moiety within a macromolecular host, three anchoring strategies can be envisaged: covalent, dative or supramolecular. [5] Using such approaches, enantioselective artificial metalloenzymes have been created for hydrolysis, [12] hydrogenation, [14][15][16][17] transfer hydrogenation, [18] allylic alkylation, [19] sulfoxidation, [20][21][22][23][24] epoxidation, [25,26] dihydroxylation, [27] Diels-Alder, [28,29] trans-amination, [30] Michael addition [31] and fluorination. [32] Comparatively, supramolecular anchoring appears as the most appealing, since it allows separate variation of both biological and chemical components, followed by straightforward combination of the organometallic moiety and the macromolecular host.…”

mentioning

confidence: 99%

Artificial Metalloenzymes for Enantioselective Catalysis Based on the Biotin–Avidin Technology

Mao

Ward

2009

Bio-Inspired Catalysts

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Artificial metalloenzymes, based on the incorporation of a biotinylated catalytically active organometallic moiety within streptavidin, offer an attractive alternative to homogeneous, heterogeneous and enzymatic catalysis. In this account, we outline our recent results and implications in the developments of such artificial metalloenzymes for various asymmetric transformations, including hydrogenation, transfer hydrogenation, allylic alkylation and sulfoxidation.

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Artificial Metalloenzyme for Enantioselective Sulfoxidation Based on Vanadyl-Loaded Streptavidin

Cited by 151 publications

References 59 publications

The Evolution of New Catalytic Mechanisms for Xenobiotic Hydrolysis in Bacterial Metalloenzymes

The Evolution of New Catalytic Mechanisms for Xenobiotic Hydrolysis in Bacterial Metalloenzymes

Bioorganic and Bioinorganic Chemistry

Artificial Metalloenzymes for Enantioselective Catalysis Based on the Biotin–Avidin Technology

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