A molecular communication channel consisting of a single reversible chain of hydrogen bonds in a conformationally flexible oligomer

David T.J. Morris; Steven M. Wales; David P. Tilly; Elliot H.E. Farrar; Matthew N. Grayson; John W. Ward; Jonathan Clayden

doi:10.1016/j.chempr.2021.06.022

A molecular communication channel consisting of a single reversible chain of hydrogen bonds in a conformationally flexible oligomer

David T.J. Morris, Steven M. Wales, David P. Tilly, Elliot H.E. Farrar, Matthew N. Grayson, John W. Ward, Jonathan Clayden^*

^*Corresponding author for this work

School of Chemistry

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Abstract

Communication of information through the global switching of conformation in synthetic molecules has hitherto entailed the inversion of chirality. Here, we report a class of oligomer through which information may be communicated through a global reversal of polarity. Ethylene-bridged oligoureas are constitutionally symmetrical, conformationally flexible molecules organized by a single chain of hydrogen bonds running the full length of the oligomer. NMR reveals that this hydrogen-bonded chain may undergo a coherent reversal of directionality. The directional uniformity of the hydrogen-bond chain allows it to act as a channel for the spatial communication of information on a molecular scale. A binding site at the terminus of an oligomer detects local information about changes in pH or anion concentration and transmits that information—in the form of a directionality switch in the hydrogen-bond chain—to a remote polarity-sensitive fluorophore. This propagation of polarity-encoded information provides a new mechanism for molecular communication.

Original language	English
Pages (from-to)	2460-2472
Number of pages	13
Journal	Chem
Volume	7
Issue number	9
Early online date	28 Jul 2021
DOIs	https://doi.org/10.1016/j.chempr.2021.06.022
Publication status	Published - 9 Sept 2021

Bibliographical note

Funding Information:
We acknowledge the support of the EPSRC through the Bristol Chemical Synthesis Centre for Doctoral Training (studentship to D.T.J.M.), Programme grant EP/P027067/1 (Molecular Robotics), and DTP funding (studentship to E.H.E.F.); the ERC through advanced grant 883786 (DOGMATRON); the Europen Commission through a Marie Sklodowska Curie fellowship to D.T.; the Leverhulme Trust; and Dr Hazel Sparkes for X-ray crystallographic analysis. This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. J.C. J.W.W. and S.M.W. devised the project. D.T.J.M. S.M.W. D.P.T. and J.W.W. designed and synthesized the molecular structures, carried out the experimental work, and analyzed the data. J.W.W. contributed to the supervision of the project. E.H.E.F. and M.N.G. carried out the computational work. D.T.J.M. S.M.W. E.H.E.F. M.N.G. and J.C. wrote the manuscript. The authors declare no competing interests.

Funding Information:
We acknowledge the support of the EPSRC through the Bristol Chemical Synthesis Centre for Doctoral Training (studentship to D.T.J.M.), Programme grant EP/P027067/1 (Molecular Robotics), and DTP funding (studentship to E.H.E.F.); the ERC through advanced grant 883786 (DOGMATRON); the Europen Commission through a Marie Sklodowska Curie fellowship to D.T.; the Leverhulme Trust; and Dr Hazel Sparkes for X-ray crystallographic analysis. This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath.

Publisher Copyright:
© 2021 The Authors

Research Groups and Themes

BCS and TECS CDTs

Keywords

dynamic foldamer
urea
conformation
hydrogen bonding
NMR
communication
information theory
oligomer
binding
stimulus responsive

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title = "A molecular communication channel consisting of a single reversible chain of hydrogen bonds in a conformationally flexible oligomer",

abstract = "Communication of information through the global switching of conformation in synthetic molecules has hitherto entailed the inversion of chirality. Here, we report a class of oligomer through which information may be communicated through a global reversal of polarity. Ethylene-bridged oligoureas are constitutionally symmetrical, conformationally flexible molecules organized by a single chain of hydrogen bonds running the full length of the oligomer. NMR reveals that this hydrogen-bonded chain may undergo a coherent reversal of directionality. The directional uniformity of the hydrogen-bond chain allows it to act as a channel for the spatial communication of information on a molecular scale. A binding site at the terminus of an oligomer detects local information about changes in pH or anion concentration and transmits that information—in the form of a directionality switch in the hydrogen-bond chain—to a remote polarity-sensitive fluorophore. This propagation of polarity-encoded information provides a new mechanism for molecular communication.",

keywords = "dynamic foldamer, urea, conformation, hydrogen bonding, NMR, communication, information theory, oligomer, binding, stimulus responsive",

author = "Morris, {David T.J.} and Wales, {Steven M.} and Tilly, {David P.} and Farrar, {Elliot H.E.} and Grayson, {Matthew N.} and Ward, {John W.} and Jonathan Clayden",

note = "Funding Information: We acknowledge the support of the EPSRC through the Bristol Chemical Synthesis Centre for Doctoral Training (studentship to D.T.J.M.), Programme grant EP/P027067/1 (Molecular Robotics), and DTP funding (studentship to E.H.E.F.); the ERC through advanced grant 883786 (DOGMATRON); the Europen Commission through a Marie Sklodowska Curie fellowship to D.T.; the Leverhulme Trust; and Dr Hazel Sparkes for X-ray crystallographic analysis. This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. J.C. J.W.W. and S.M.W. devised the project. D.T.J.M. S.M.W. D.P.T. and J.W.W. designed and synthesized the molecular structures, carried out the experimental work, and analyzed the data. J.W.W. contributed to the supervision of the project. E.H.E.F. and M.N.G. carried out the computational work. D.T.J.M. S.M.W. E.H.E.F. M.N.G. and J.C. wrote the manuscript. The authors declare no competing interests. Funding Information: We acknowledge the support of the EPSRC through the Bristol Chemical Synthesis Centre for Doctoral Training (studentship to D.T.J.M.), Programme grant EP/P027067/1 (Molecular Robotics), and DTP funding (studentship to E.H.E.F.); the ERC through advanced grant 883786 (DOGMATRON); the Europen Commission through a Marie Sklodowska Curie fellowship to D.T.; the Leverhulme Trust; and Dr Hazel Sparkes for X-ray crystallographic analysis. This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. Publisher Copyright: {\textcopyright} 2021 The Authors",

year = "2021",

month = sep,

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doi = "10.1016/j.chempr.2021.06.022",

language = "English",

volume = "7",

pages = "2460--2472",

journal = "Chem",

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publisher = "Cell Press",

number = "9",

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T1 - A molecular communication channel consisting of a single reversible chain of hydrogen bonds in a conformationally flexible oligomer

AU - Morris, David T.J.

AU - Wales, Steven M.

AU - Tilly, David P.

AU - Farrar, Elliot H.E.

AU - Grayson, Matthew N.

AU - Ward, John W.

AU - Clayden, Jonathan

N1 - Funding Information: We acknowledge the support of the EPSRC through the Bristol Chemical Synthesis Centre for Doctoral Training (studentship to D.T.J.M.), Programme grant EP/P027067/1 (Molecular Robotics), and DTP funding (studentship to E.H.E.F.); the ERC through advanced grant 883786 (DOGMATRON); the Europen Commission through a Marie Sklodowska Curie fellowship to D.T.; the Leverhulme Trust; and Dr Hazel Sparkes for X-ray crystallographic analysis. This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. J.C. J.W.W. and S.M.W. devised the project. D.T.J.M. S.M.W. D.P.T. and J.W.W. designed and synthesized the molecular structures, carried out the experimental work, and analyzed the data. J.W.W. contributed to the supervision of the project. E.H.E.F. and M.N.G. carried out the computational work. D.T.J.M. S.M.W. E.H.E.F. M.N.G. and J.C. wrote the manuscript. The authors declare no competing interests. Funding Information: We acknowledge the support of the EPSRC through the Bristol Chemical Synthesis Centre for Doctoral Training (studentship to D.T.J.M.), Programme grant EP/P027067/1 (Molecular Robotics), and DTP funding (studentship to E.H.E.F.); the ERC through advanced grant 883786 (DOGMATRON); the Europen Commission through a Marie Sklodowska Curie fellowship to D.T.; the Leverhulme Trust; and Dr Hazel Sparkes for X-ray crystallographic analysis. This research made use of the Balena High Performance Computing (HPC) Service at the University of Bath. Publisher Copyright: © 2021 The Authors

PY - 2021/9/9

Y1 - 2021/9/9

N2 - Communication of information through the global switching of conformation in synthetic molecules has hitherto entailed the inversion of chirality. Here, we report a class of oligomer through which information may be communicated through a global reversal of polarity. Ethylene-bridged oligoureas are constitutionally symmetrical, conformationally flexible molecules organized by a single chain of hydrogen bonds running the full length of the oligomer. NMR reveals that this hydrogen-bonded chain may undergo a coherent reversal of directionality. The directional uniformity of the hydrogen-bond chain allows it to act as a channel for the spatial communication of information on a molecular scale. A binding site at the terminus of an oligomer detects local information about changes in pH or anion concentration and transmits that information—in the form of a directionality switch in the hydrogen-bond chain—to a remote polarity-sensitive fluorophore. This propagation of polarity-encoded information provides a new mechanism for molecular communication.

AB - Communication of information through the global switching of conformation in synthetic molecules has hitherto entailed the inversion of chirality. Here, we report a class of oligomer through which information may be communicated through a global reversal of polarity. Ethylene-bridged oligoureas are constitutionally symmetrical, conformationally flexible molecules organized by a single chain of hydrogen bonds running the full length of the oligomer. NMR reveals that this hydrogen-bonded chain may undergo a coherent reversal of directionality. The directional uniformity of the hydrogen-bond chain allows it to act as a channel for the spatial communication of information on a molecular scale. A binding site at the terminus of an oligomer detects local information about changes in pH or anion concentration and transmits that information—in the form of a directionality switch in the hydrogen-bond chain—to a remote polarity-sensitive fluorophore. This propagation of polarity-encoded information provides a new mechanism for molecular communication.

KW - dynamic foldamer

KW - urea

KW - conformation

KW - hydrogen bonding

KW - NMR

KW - communication

KW - information theory

KW - oligomer

KW - binding

KW - stimulus responsive

U2 - 10.1016/j.chempr.2021.06.022

DO - 10.1016/j.chempr.2021.06.022

M3 - Article (Academic Journal)

C2 - 34553103

SN - 2451-9294

VL - 7

SP - 2460

EP - 2472

JO - Chem

JF - Chem

IS - 9

ER -

A molecular communication channel consisting of a single reversible chain of hydrogen bonds in a conformationally flexible oligomer

Abstract

Bibliographical note

Research Groups and Themes

Keywords

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