Light-Driven, Quantum Dot-Mediated Regeneration of FMN To Drive Reduction of Ketoisophorone by Old Yellow Enzyme

Burai, Tarak Nath; Panay, Aram J.; Zhu, Haiming; Lian, Tianquan; Lutz, Stefan

doi:10.1021/cs300085h

Cited by 49 publications

(35 citation statements)

References 26 publications

(36 reference statements)

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“…Using methylviologen as an electron mediator along with a dehydrogenase homologue related to the "old yellow enzyme", improvements in the reduction of ketoisophorone could be achieved by irradiating a CdSe QD. 1025 The enzyme was first allowed to interact with a flavin cofactor attached to the QD surface to establish the functional assembly. Although the efficiency of the initial transfer to the methylviologen was only 5%, the use of QDs in this configuration was found to be far more efficient than traditional Ru-based photosensitizers.…”

Section: Relaying Electrons To Enzymes and Cofactorsmentioning

confidence: 99%

Energy Transfer with Semiconductor Quantum Dot Bioconjugates: A Versatile Platform for Biosensing, Energy Harvesting, and Other Developing Applications

Spillmann²,

et al. 2016

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Luminescent semiconductor quantum dots (QDs) are one of the more popular nanomaterials currently utilized within biological applications. However, what is not widely appreciated is their growing role as versatile energy transfer (ET) donors and acceptors within a similar biological context. The progress made on integrating QDs and ET in biological configurations and applications is reviewed in detail here. The goal is to provide the reader with (1) an appreciation for what QDs are capable of in this context, (2) how this field has grown over a relatively short time span, and, in particular, (3) how QDs are steadily revolutionizing the development of new biosensors along with a myriad of other photonically active nanomaterial-based bioconjugates. An initial discussion of QD materials along with key concepts surrounding their preparation and bioconjugation is provided given the defining role these aspects play in the QDs ability to succeed in subsequent ET applications. The discussion is then divided around the specific roles that QDs provide as either Förster resonance energy transfer (FRET) or charge/electron transfer donor and/or acceptor. For each QD-ET mechanism, a working explanation of the appropriate background theory and formalism is articulated before examining their biosensing and related ET utility. Other configurations such as incorporation of QDs into multistep ET processes or use of initial chemical and bioluminescent excitation are treated similarly. ET processes that are still not fully understood such as QD interactions with gold and other metal nanoparticles along with carbon allotropes are also covered. Given their maturity, some specific applications ranging from in vitro sensing assays to cellular imaging are separated and discussed in more detail. Finally a perspective on how this field will continue to evolve is provided.

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Section: Relaying Electrons To Enzymes and Cofactorsmentioning

confidence: 99%

Energy Transfer with Semiconductor Quantum Dot Bioconjugates: A Versatile Platform for Biosensing, Energy Harvesting, and Other Developing Applications

Spillmann²,

et al. 2016

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“…Through spectroscopic and (photo)electrochemical analyses,w ee lucidated the capability of N-CDs to deliver photoexcited electrons to M and different photochemical reduction behaviors of NAD + and mNAD + s. Initial rates and yields of regeneration were in the order of NADH > mNH 2 H > mBuH > mCOOHH, which we ascribe to different reduction peak potentials of cofactors.The coupling of photochemical regeneration of mNADHs with a TsOYEdriven reaction allowed for the efficient synthesis of (R)-2- CdSe-sensitized regeneration of methyl viologen [19] YqjM 23.3 [b] 8.0 [b] 12 [b] Au-TiO 2 -sensitized regeneration of free FMN [20] TsOYE Through spectroscopic and (photo)electrochemical analyses,w ee lucidated the capability of N-CDs to deliver photoexcited electrons to M and different photochemical reduction behaviors of NAD + and mNAD + s. Initial rates and yields of regeneration were in the order of NADH > mNH 2 H > mBuH > mCOOHH, which we ascribe to different reduction peak potentials of cofactors.The coupling of photochemical regeneration of mNADHs with a TsOYEdriven reaction allowed for the efficient synthesis of (R)-2- CdSe-sensitized regeneration of methyl viologen [19] YqjM 23.3 [b] 8.0 [b] 12 [b] Au-TiO 2 -sensitized regeneration of free FMN [20] TsOYE…”

Section: Angewandte Chemiementioning

confidence: 99%

Biocatalytic C=C Bond Reduction through Carbon Nanodot‐Sensitized Regeneration of NADH Analogues

et al. 2018

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Light-driven activation of redox enzymes is an emerging route for sustainable chemical synthesis. Among redox enzymes, the family of Old Yellow Enzyme (OYE) dependent on the nicotinamide adenine dinucleotide cofactor (NADH) catalyzes the stereoselective reduction of α,β-unsaturated hydrocarbons. Here, we report OYE-catalyzed asymmetric hydrogenation through light-driven regeneration of NADH and its analogues (mNADHs) by N-doped carbon nanodots (N-CDs), a zero-dimensional photocatalyst. Our spectroscopic and photoelectrochemical analyses verified the transfer of photo-induced electrons from N-CDs to an organometallic electron mediator (M) for highly regioselective regeneration of cofactors. Light triggered the reduction of NAD and mNAD s with the cooperation of N-CDs and M, and the reduction behaviors of cofactors were dependent on their own reduction peak potentials. The regenerated cofactors subsequently delivered hydrides to OYE for stereoselective conversions of a broad range of substrates with excellent biocatalytic efficiencies.

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“…Full conversion of substrates 41 b and 41 g , containing a 1,2‐ and a 1,1‐disubstituted C=C double bond, respectively, was observed. When CdSe quantum dots were used as the photosensitizer, an electron mediator such as 23 was required, and product 42 a was produced with only moderate enantioselectivity (64 % ee ). The filling of the electron hole by the sacrificial electron donor TEA ( 24 ) was determined to be the rate‐limiting step.…”

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

confidence: 99%

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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Light-Driven, Quantum Dot-Mediated Regeneration of FMN To Drive Reduction of Ketoisophorone by Old Yellow Enzyme

Cited by 49 publications

References 26 publications

Energy Transfer with Semiconductor Quantum Dot Bioconjugates: A Versatile Platform for Biosensing, Energy Harvesting, and Other Developing Applications

Energy Transfer with Semiconductor Quantum Dot Bioconjugates: A Versatile Platform for Biosensing, Energy Harvesting, and Other Developing Applications

Biocatalytic C=C Bond Reduction through Carbon Nanodot‐Sensitized Regeneration of NADH Analogues

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

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