A biohybrid strategy for enabling photoredox catalysis with low-energy light

Cesana, Paul T.; Li, Beryl X.; Shepard, Samuel G.; Ting, Stephen I.; Hart, S. R.; Olson, Courtney M.; Alvarado, Jesus I. Martinez; Son, Minjung; Steiman, Talia J.; Castellano, Felix N.; Doyle, Abigail G.; MacMillan, David W. C.; Schlau‐Cohen, Gabriela S.

doi:10.1016/j.chempr.2021.10.010

Cited by 32 publications

(43 citation statements)

References 80 publications

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“…Instead of energy transfer between different metal centres, the photocatalyst [Ru(bpy) 3 ] 2+ was coupled to the light-harvesting protein R-phycoerythrin (RPE), which exhibits strong visible absorption ( ε ≈ 2 × 10 6 M −1 cm −1 , 570 nm). 69 Mimicking energy transfer pathways in photosynthesis, protein emission was strongly quenched (85%) by the conjugated metal complex, whilst transient absorption spectroscopy confirmed an energy transfer pathway. The biohybrid photocatalyst powered the desulfurisation of glutathione in aqueous buffers (Fig.…”

Section: Low Energy Irradiationmentioning

confidence: 99%

The forgotten reagent of photoredox catalysis

Connell

2022

Dalton Trans.

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Section: Low Energy Irradiationmentioning

confidence: 99%

The forgotten reagent of photoredox catalysis

Connell

2022

Dalton Trans.

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“…38,46 We designed, investigated, and demonstrated two unique light-harvesting strategies: energy transfer from a dedicated light-harvesting protein to a tethered Ru photocatalyst and triplet−triplet annihilation for direct initiation of freeradical polymerization, in the context of photocatalytic reactions (Figure 6A and C). 3,47 Schlau-Cohen, MacMillan, Doyle, Castellano, and co-workers utilized a low-energy absorbing photosynthetic light-harvesting protein to excite a photocatalyst through energy transfer and catalyze two radical initiation reactions. 3 Natural organisms partition the light-harvesting and reactive processes of photosynthesis into distinct structural components.…”

Section: Low-energy Light-harvesting Strategiesmentioning

confidence: 99%

“…3,47 Schlau-Cohen, MacMillan, Doyle, Castellano, and co-workers utilized a low-energy absorbing photosynthetic light-harvesting protein to excite a photocatalyst through energy transfer and catalyze two radical initiation reactions. 3 Natural organisms partition the light-harvesting and reactive processes of photosynthesis into distinct structural components. 48 This modulation occurs because these processes are contradictory, one requiring harnessing and storing vast amounts of energy and the other quickly dispersing energy toward chemical reactivity.…”

Section: Low-energy Light-harvesting Strategiesmentioning

confidence: 99%

Bioinspired Supercharging of Photoredox Catalysis for Applications in Energy and Chemical Manufacturing

et al. 2022

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Metrics & MoreArticle Recommendations CONSPECTUS: For more than a decade, photoredox catalysis has been demonstrating that when photoactive catalysts are irradiated with visible light, reactions occur under milder, cheaper, and environmentally friendlier conditions. Furthermore, this methodology allows for the activation of abundant chemicals into valuable products through novel mechanisms that are otherwise inaccessible. The photoredox approach, however, has been primarily used for pharmaceutical applications, where its implementation has been highly effective, but typically with a more rudimentary understanding of the mechanisms involved in these transformations.From a global perspective, the manufacture of everyday chemicals by the chemical industry as a whole currently accounts for 10% of total global energy consumption and generates 7% of the world's greenhouse gases annually. In this context, the Bio-Inspired Light-Escalated Chemistry (BioLEC) Energy Frontier Research Center (EFRC) was founded to supercharge the photoredox approach for applications in chemical manufacturing aimed at reducing its energy consumption and emissions burden, by using bioinspired schemes to harvest multiple electrons to drive endothermically uphill chemical reactions. The Center comprises a diverse group of researchers with expertise that includes synthetic chemistry, biophysics, physical chemistry, and engineering. The team works together to gain a deeper understanding of the mechanistic details of photoredox reactions while amplifying the applications of these light-driven methodologies.In this Account, we review some of the major advances in understanding, approach, and applicability made possible by this collaborative Center. Combining sophisticated spectroscopic tools and photophysics tactics with enhanced photoredox reactions has led to the development of novel techniques and reactivities that greatly expand the field and its capabilities. The Account is intended to highlight how the interplay between disciplines can have a major impact and facilitate the advance of the field. For example, techniques such as time-resolved dielectric loss (TRDL) and pulse radiolysis are providing mechanistic insights not previously available. Hypothesis-driven photocatalyst design thus led to broadening of the scope of several existing transformations. Moreover, bioconjugation approaches and the implementation of triplet−triplet annihilation mechanisms created new avenues for the exploration of reactivities. Lastly, our multidisciplinary approach to tackling real-world problems has inspired the development of efficient methods for the depolymerization of lignin and artificial polymers.

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“…Using light to drive photochemical synthesis is a very attractive method owing to its directional, cheap, clean, and tunable characteristics [ 79 , 80 , 81 , 82 , 83 ]. Regarding the organic chemical reactions triggered by TTA-UC systems, the biggest challenge might be molecular oxygen because it quickly quenches the triplet species.…”

Section: Photochemistry Of Porphyrin-based Tta-uc For Chemical Transf...mentioning

confidence: 99%

Recent Advances in the Photoreactions Triggered by Porphyrin-Based Triplet–Triplet Annihilation Upconversion Systems: Molecular Innovations and Nanoarchitectonics

Yao¹,

Sun²,

He³

et al. 2022

IJMS

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Triplet–triplet annihilation upconversion (TTA-UC) is a very promising technology that could be used to convert low-energy photons to high-energy ones and has been proven to be of great value in various areas. Porphyrins have the characteristics of high molar absorbance, can form a complex with different metal ions and a high proportion of triplet states as well as tunable structures, and thus they are important sensitizers for TTA-UC. Porphyrin-based TTA-UC plays a pivotal role in the TTA-UC systems and has been widely used in many fields such as solar cells, sensing and circularly polarized luminescence. In recent years, applications of porphyrin-based TTA-UC systems for photoinduced reactions have emerged, but have been paid little attention. As a consequence, this review paid close attention to the recent advances in the photoreactions triggered by porphyrin-based TTA-UC systems. First of all, the photochemistry of porphyrin-based TTA-UC for chemical transformations, such as photoisomerization, photocatalytic synthesis, photopolymerization, photodegradation and photochemical/photoelectrochemical water splitting, was discussed in detail, which revealed the different mechanisms of TTA-UC and methods with which to carry out reasonable molecular innovations and nanoarchitectonics to solve the existing problems in practical application. Subsequently, photoreactions driven by porphyrin-based TTA-UC for biomedical applications were demonstrated. Finally, the future developments of porphyrin-based TTA-UC systems for photoreactions were briefly discussed.

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A biohybrid strategy for enabling photoredox catalysis with low-energy light

Cited by 32 publications

References 80 publications

The forgotten reagent of photoredox catalysis

The forgotten reagent of photoredox catalysis

Bioinspired Supercharging of Photoredox Catalysis for Applications in Energy and Chemical Manufacturing

Recent Advances in the Photoreactions Triggered by Porphyrin-Based Triplet–Triplet Annihilation Upconversion Systems: Molecular Innovations and Nanoarchitectonics

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