A cysteine selenosulfide redox switch for protein chemical synthesis

Diemer, Vincent; Ollivier, Nathalie; Leclercq, B.; Drobecq, Hervé; Vicogne, Jérôme; Agouridas, Vangelis; Melnyk, Oleg

doi:10.1038/s41467-020-16359-6

Cited by 24 publications

(30 citation statements)

References 54 publications

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“…We successfully coupled the diffusion-controlled light-harvesting thiyl radical chemistry with the molecular recognition processes occurring in a complex foldameric network. Disulphide linkage has a long history, and its nucleophilic exchange mechanism is currently popular in systems chemistry applications 31,32 . The performance of the UV light-induced homolytic cleavage and recombination cycle of the disulphide bond to drive dissipative processes extended its applicability beyond the thiolate-mediated dynamics.…”

Section: Discussionmentioning

confidence: 99%

Light-Fuelled Dissipative Replication and Selection in Adaptive Biomimetic Chemical Networks

Bartus¹,

Mag²,

Bajcsi³

et al. 2021

Preprint

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<p>Evolvability of the chemical replicator systems requires non-equilibrium energy dissipation, effective death pathways and transfer of structural information in the autocatalytic cycles. We engineered a chemical network with peptidic foldamer components, where UV light fuelled dissipative sequence-dependent exponential replication and replicator decomposition. The light-harvesting formation-recombination cycle of the thiyl radicals was coupled with the molecular recognition steps in the replication cycles. Thiyl radical-mediated chain reaction was responsible for the replicator death. The competing and kinetically asymmetric replication and decomposition processes led to light intensity-dependent selection and competitive exclusion. Dynamic adaptation to the energy input and the selection factor maximised the dissipation rate in the regime of exponential growth. The results contribute to the development of chemically evolvable replicator systems.</p>

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Section: Discussionmentioning

confidence: 99%

Light-Fuelled Dissipative Replication and Selection in Adaptive Biomimetic Chemical Networks

Bartus¹,

Mag²,

Bajcsi³

et al. 2021

Preprint

View full text Add to dashboard Cite

show abstract

“…We successfully coupled light-harvesting thiyl radical chemistry with the molecular recognition processes occurring in a foldameric network. Disulfide linkage has a long history and its nucleophilic exchange mechanism is currently popular in systems chemistry applications 29,30 . The photocatalytic rearrangement reaction of disulfides has also been known for decades.…”

Section: Discussionmentioning

confidence: 99%

Light-Fuelled Dissipative Replication and Selection in Adaptive Biomimetic Chemical Networks

Bartus¹,

Mag²,

Bajcsi³

et al. 2021

Preprint

View full text Add to dashboard Cite

Evolvability of chemical replicator systems requires non-equilibrium energy dissipation, effective decomposition pathways and transfer of structural information in the autocatalytic cycles. We engineered a chemical network with peptidic foldamer components, which displays dissipative sequence-dependent replication and replicator decomposition fuelled by UV light. The light-harvesting formation-recombination cycle of thiyl radicals was coupled with the molecular recognition steps in the replication cycles. Thiyl radical-mediated chain reaction was responsible for the replicator breakdown. The competing and kinetically asymmetric replication and decomposition processes led to light intensity-dependent selection, which differs from the equilibrium composition. The results contribute to the development of chemically evolvable dissipative replicator systems.

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“…Protein was dissolved in a solution of 25 mM NH 4 HCO 3 (1 mg/ml, 100 µL). Trypsin (0.5 mg/ml, 10 µL) was firstly added to the mixture to digest the protein ( Diemer et al, 2020 ). The reaction was carried out at 37°C for 2 h. Then, the enzymatic reaction was analyzed by LC-MS directly.…”

Section: Methodsmentioning

confidence: 99%

Chemical Synthesis of the Sec-To-Cys Homologue of Human Selenoprotein F and Elucidation of Its Disulfide-pairing Mode

Liao

2021

Front. Chem.

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Herein, we document a highly optimized synthesis of the Sec-to-Cys homologue of the human selenoprotein F (SelF) through a three-segment two-ligation semisynthesis strategy. Highlighted in this synthetic route are two one-pot manipulations, i.e. the first ligation followed by a desulfurization and the second ligation followed by the protein refolding. This way multi-milligrams of the folded synthetic protein was obtained, which set the stage for the synthesis of the natural selenoprotein. Moreover, the disulfide pairing mode of the SelF was elucidated through a combination of site-directed mutagenesis and LC-MS study. It provides not only a criterion to judge the viability of the synthetic protein, and more importantly, useful structural insights into the previously unresolved UGGT-binding domain of SelF.

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A cysteine selenosulfide redox switch for protein chemical synthesis

Cited by 24 publications

References 54 publications

Light-Fuelled Dissipative Replication and Selection in Adaptive Biomimetic Chemical Networks

Light-Fuelled Dissipative Replication and Selection in Adaptive Biomimetic Chemical Networks

Light-Fuelled Dissipative Replication and Selection in Adaptive Biomimetic Chemical Networks

Chemical Synthesis of the Sec-To-Cys Homologue of Human Selenoprotein F and Elucidation of Its Disulfide-pairing Mode

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