Photocatalytic Regeneration of Nicotinamide Cofactors by Quantum Dot–Enzyme Biohybrid Complexes

Brown, Katherine A.; Wilker, Molly B.; Boehm, Marko; Hamby, Hayden; Duković, Gordana; King, Paul W.

doi:10.1021/acscatal.5b02850

Cited by 95 publications

(90 citation statements)

References 29 publications

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“…Recent artificial light-harvesting strategies consist of bio-hydrid complexes of CdSe quantum dots and ferredoxin NADP + reductase for photocatalytic regeneration of NAD(P)H using visible light and ascorbic acid as electron donor 89 . Equally low turnover frequencies for NAD(P)H (7.4 h , displaying synthetic yields of approximately 30% in combination with a ketoreductase.…”

Section: Novel Chemistries and Other Trendsmentioning

confidence: 99%

Opportunities and challenges for combining chemo- and biocatalysis

et al. 2018

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N ature has evolved highly efficient systems in the form of cascade reactions, which assemble the metabolic networks that support life (growth and survival). The basic principle of cascade reactions is also frequently used in biocatalysis, using enzymes in isolation, as well as in combination with chemocatalysts (see Fig. 1 and Box 1 for definition of terms) [1][2][3][4][5][6][7] . As there is no need for purification and isolation of intermediates, operating time, production costs and waste are reduced, and concomitantly, overall yields are improved. In addition, the problem of unstable or difficult to handle intermediates can be overcome, and reactivity as well as selectivity can be enhanced by avoiding unfavourable reaction equilibria through the cooperative effects of multiple catalysts 8 . Starting in the 1980s, the early examples of the combination of chemo-and biocatalysts were reported by the van Bekkum group, who pioneered the development of a process to make the sugar substitute d-mannitol from readily available d-glucose through the combination of a heterogeneous metal-catalysed hydrogenation and an enzyme-catalysed isomerization 9 . The first broadly applied technology for the combination of enzyme and metalcatalysts, which was the research subject of many academic groups as well as industry, emerged in the 1990s from the Williams group 10,11 and aimed to achieve higher yields than classical kinetic resolution of racemates, thus overcoming the limitation of a maximum yield of 50% in the latter case. A prominent example of work that developed this theme is the combination of lipase-catalysed kinetic resolution via acylation of secondary alcohols with Pd-or Rh-catalysed racemization via reversible transfer hydrogenation to achieve a dynamic kinetic resolution (DKR) [12][13][14] . This example was facilitated in part because lipases are active and stable in organic solvents. Later, for instance, Turner's group combined a monoamine oxidase-catalysed imine formation with a chemical reduction 15 to achieve the 100% theoretical yield through a deracemization process. In addition to the combination of metalcatalysis with enzymes, organocatalysis, electrochemistry and light-induced reaction couples have since then been studied extensively, going far beyond the scope of a DKR.The challenges to combining chemo-and biocatalysis in cascades (see Box 1 for definitions and Table 1) can be daunting, not least the requirement for the chemical step to occur in the presence of water, the preferred solvent for enzymes 3 . This Review therefore highlights recent examples of the combination of chemo-and biocatalysts in aqueous multistep syntheses, and looks at how to overcome limitations by, for example, design of appropriate reaction conditions, protein engineering and advanced reactor concepts. Furthermore, trends such as the integration of transition metalcatalysis into microorganisms and the introduction of novel chemistry into engineered enzymes are discussed, and a critical assessment of the impact of this research ...

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Section: Novel Chemistries and Other Trendsmentioning

confidence: 99%

Opportunities and challenges for combining chemo- and biocatalysis

et al. 2018

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“…As an example relating to the reduction of carbonyl functionalities, Brown et al . achieved the conversion of aldehydes 37 with the aid of the commercially available Thermoanaerobium brockii alcohol dehydrogenase ( tb ADH, Scheme ).…”

Section: Photo‐biocatalysis By Application Of Isolated Enzymes or Celmentioning

confidence: 99%

“…The applied QDs are capped with mercaptopropionic acid, resulting in negatively charged QDs, and this allows for their binding at the positively charged FAD binding sites through electrostatic interactions. The photoenzymatic cascade can be extended to a multi‐enzyme cascade (not shown) through upstream decarboxylation of the corresponding keto acids with the aid of a keto acid decarboxylase from Lactococcus lactis to form the aldehydes 37 …”

Section: Photo‐biocatalysis By Application Of Isolated Enzymes or Celmentioning

confidence: 99%

“… Photoenzymatic reduction of aldehydes 37 by QD‐FNR/ tb ADH . [a] Turnover frequency (TOF) in mol 13 b per mol FNR per h.…”

Section: Photo‐biocatalysis By Application Of Isolated Enzymes or Celmentioning

confidence: 99%

“…As an example relating to the reduction of carbonyl functionalities, Brown et al [33] achieved the conversion of aldehydes 37 with the aid of the commercially available Thermoanaerobium brockii alcohol dehydrogenase (tbADH, Scheme 6). The required reducing equivalents of 13 b were photochemically re-generated with the aid of biohybrid complexes of the NADPHspecific ferredoxin NADP + -reductase (FNR) from Chlamydomonas reinhardtii and aC dSe QD photocatalyst.…”

Section: Reduction Of Carbonyl Functionalitiesmentioning

confidence: 99%

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Biocatalysis Fueled by Light: On the Versatile Combination of Photocatalysis and Enzymes

Seel

Gulder

2019

ChemBioChem

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Enzymes catalyze a plethora of highly specific transformations under mild and environmentally benign reaction conditions. Their fascinating performances attest to high synthetic potential that is often hampered by operational obstacles such as in vitro cofactor supply and regeneration. Exploiting light and combining it with biocatalysis not only helps in overcoming these drawbacks, but the fruitful liaison of these two fields of “green chemistry” also offers opportunities to unlock new synthetic reactivities. In this review we provide an overview of the wide variety of photo‐biocatalysis, ranging from the photochemical delivery of electrons required in redox biocatalysis and photochemical cofactor and reagent (re)generation to direct photoactivation of enzymes enabling reactions unknown in nature. We highlight synthetically relevant transformations such as asymmetric reactions facilitated by the combination of light as energy source and enzymes’ catalytic power.

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Nanocomposites Consisting of Chalcogenide Semiconductors and Gold

2019

Noble Metal‐Based Nanocomposites

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Photocatalytic Regeneration of Nicotinamide Cofactors by Quantum Dot–Enzyme Biohybrid Complexes

Cited by 95 publications

References 29 publications

Opportunities and challenges for combining chemo- and biocatalysis

Opportunities and challenges for combining chemo- and biocatalysis

Biocatalysis Fueled by Light: On the Versatile Combination of Photocatalysis and Enzymes

Nanocomposites Consisting of Chalcogenide Semiconductors and Gold

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