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Two synthetic replicators compete to process a dynamic reagent pool

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Two synthetic replicators compete to process a dynamic reagent pool. / Kosikova, Tamara; Philp, Douglas.

In: Journal of the American Chemical Society, Vol. 141, No. 7, 20.02.2019, p. 3059-3072.

Research output: Contribution to journalArticlepeer-review

Harvard

Kosikova, T & Philp, D 2019, 'Two synthetic replicators compete to process a dynamic reagent pool', Journal of the American Chemical Society, vol. 141, no. 7, pp. 3059-3072. https://doi.org/10.1021/jacs.8b12077

APA

Kosikova, T., & Philp, D. (2019). Two synthetic replicators compete to process a dynamic reagent pool. Journal of the American Chemical Society, 141(7), 3059-3072. https://doi.org/10.1021/jacs.8b12077

Vancouver

Kosikova T, Philp D. Two synthetic replicators compete to process a dynamic reagent pool. Journal of the American Chemical Society. 2019 Feb 20;141(7):3059-3072. https://doi.org/10.1021/jacs.8b12077

Author

Kosikova, Tamara ; Philp, Douglas. / Two synthetic replicators compete to process a dynamic reagent pool. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 7. pp. 3059-3072.

Bibtex - Download

@article{362e1e4c6ad340ada3e5985827b466fb,
title = "Two synthetic replicators compete to process a dynamic reagent pool",
abstract = "Complementary building blocks, comprising a set of four aromatic aldehydes and a set of four nucleophiles—three anilines and one hydroxylamine—combine through condensation reactions to afford a dynamic covalent library (DCL) consisting of the eight starting materials and 16 condensation products. One of the aldehydes and, consequently, all of the DCL members derived from this compound bear an amidopyridine recognition site. Exposure of this DCL to two maleimides, Mp and Mm, each equipped with a carboxylic acid recognition site, results in the formation of a series of products through irreversible 1,3-dipolar cycloaddition reactions with the four nitrones present in the DCL. However, only the two cycloadducts in the product pool that incorporate both recognition sites, Tp and Tm, are self-replicators that can harness the DCL as feedstock for their own formation, facilitating their own synthesis via autocatalytic and cross-catalytic pathways. The ability of these replicators to direct their own formation from the components present in the dynamic reagent pool in response to the input of instructions in the form of preformed replicators is demonstrated through a series of quantitative 19F{1H} NMR spectroscopy experiments. Simulations establish the critical relationships between the kinetic and thermodynamic parameters of the replicators, the initial reagent concentrations, and the presence or absence of the DCL and their influence on the competition between Tp and Tm. Thus, we establish the rules that govern the behavior of the competing replicators under conditions where their formation is coupled tightly to the processing of a DCL.",
author = "Tamara Kosikova and Douglas Philp",
note = "This work was supported by the award of a Postgraduate Studentship from Engineering and Physical Sciences Research Council (EP/K503162/1) to TK and by the University of St Andrews.",
year = "2019",
month = feb,
day = "20",
doi = "10.1021/jacs.8b12077",
language = "English",
volume = "141",
pages = "3059--3072",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "AMER CHEMICAL SOC",
number = "7",

}

RIS (suitable for import to EndNote) - Download

TY - JOUR

T1 - Two synthetic replicators compete to process a dynamic reagent pool

AU - Kosikova, Tamara

AU - Philp, Douglas

N1 - This work was supported by the award of a Postgraduate Studentship from Engineering and Physical Sciences Research Council (EP/K503162/1) to TK and by the University of St Andrews.

PY - 2019/2/20

Y1 - 2019/2/20

N2 - Complementary building blocks, comprising a set of four aromatic aldehydes and a set of four nucleophiles—three anilines and one hydroxylamine—combine through condensation reactions to afford a dynamic covalent library (DCL) consisting of the eight starting materials and 16 condensation products. One of the aldehydes and, consequently, all of the DCL members derived from this compound bear an amidopyridine recognition site. Exposure of this DCL to two maleimides, Mp and Mm, each equipped with a carboxylic acid recognition site, results in the formation of a series of products through irreversible 1,3-dipolar cycloaddition reactions with the four nitrones present in the DCL. However, only the two cycloadducts in the product pool that incorporate both recognition sites, Tp and Tm, are self-replicators that can harness the DCL as feedstock for their own formation, facilitating their own synthesis via autocatalytic and cross-catalytic pathways. The ability of these replicators to direct their own formation from the components present in the dynamic reagent pool in response to the input of instructions in the form of preformed replicators is demonstrated through a series of quantitative 19F{1H} NMR spectroscopy experiments. Simulations establish the critical relationships between the kinetic and thermodynamic parameters of the replicators, the initial reagent concentrations, and the presence or absence of the DCL and their influence on the competition between Tp and Tm. Thus, we establish the rules that govern the behavior of the competing replicators under conditions where their formation is coupled tightly to the processing of a DCL.

AB - Complementary building blocks, comprising a set of four aromatic aldehydes and a set of four nucleophiles—three anilines and one hydroxylamine—combine through condensation reactions to afford a dynamic covalent library (DCL) consisting of the eight starting materials and 16 condensation products. One of the aldehydes and, consequently, all of the DCL members derived from this compound bear an amidopyridine recognition site. Exposure of this DCL to two maleimides, Mp and Mm, each equipped with a carboxylic acid recognition site, results in the formation of a series of products through irreversible 1,3-dipolar cycloaddition reactions with the four nitrones present in the DCL. However, only the two cycloadducts in the product pool that incorporate both recognition sites, Tp and Tm, are self-replicators that can harness the DCL as feedstock for their own formation, facilitating their own synthesis via autocatalytic and cross-catalytic pathways. The ability of these replicators to direct their own formation from the components present in the dynamic reagent pool in response to the input of instructions in the form of preformed replicators is demonstrated through a series of quantitative 19F{1H} NMR spectroscopy experiments. Simulations establish the critical relationships between the kinetic and thermodynamic parameters of the replicators, the initial reagent concentrations, and the presence or absence of the DCL and their influence on the competition between Tp and Tm. Thus, we establish the rules that govern the behavior of the competing replicators under conditions where their formation is coupled tightly to the processing of a DCL.

U2 - 10.1021/jacs.8b12077

DO - 10.1021/jacs.8b12077

M3 - Article

VL - 141

SP - 3059

EP - 3072

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 7

ER -

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