The side chain dynamics of poly(quinoxaline-2,3-diyl)s (PQXs) are expected to influence their conformation. To investigate these dynamics experimentally, quasielastic neutron scattering (QENS) was performed for PQXs in deuterated tetrahydrofuran (THF-d8) and deuterated 1,1,2-trichloroethane/THF (1,1,2-TCE-d3/THF-d8), in which they formed right-handed and left-handed helical structures, respectively. The mean-square displacement of the PQX side chains in 1,1,2-TCE-d3/THF-d8 was lower than that in THF-d8. Furthermore, QENS complementary studies and molecular dynamics simulations unraveled a coupling between the main-chain and side chain dynamics of PQXs, suggesting the possibility of controlling the main-chain helical chirality through the dynamics of chiral side chains. These insights present a novel strategy for the design of synthetic helical macromolecules with precise chirality control.

Topics
Molecular dynamics, Neutron scattering, Macromolecules
1.
E.
Yashima
,
K.
Maeda
,
H.
Iida
,
Y.
Furusho
, and
K.
Nagai
,
Chem. Rev.
109
,
6102
–
6211
(
2009
).
https://doi.org/10.1021/cr900162q
Google Scholar
Crossref
Search ADS
PubMed
 
2.
E.
Yashima
,
N.
Ousaka
,
D.
Taura
,
K.
Shimomura
,
T.
Ikai
, and
K.
Maeda
,
Chem. Rev.
116
,
13752
–
13990
(
2016
).
https://doi.org/10.1021/acs.chemrev.6b00354
Google Scholar
Crossref
Search ADS
PubMed
 
3.
K.
Maeda
 and
E.
Yashima
,
Top. Curr. Chem.
375
,
72
(
2017
).
https://doi.org/10.1007/s41061-017-0161-4
Google Scholar
Crossref
Search ADS
 
4.
Y.
Nagata
,
T.
Nishikawa
, and
M.
Suginome
,
J. Am. Chem. Soc.
136
,
15901
–
15904
(
2014
).
https://doi.org/10.1021/ja509531t
Google Scholar
Crossref
Search ADS
 
5.
Y.
Nagata
,
T.
Yamada
,
T.
Adachi
,
Y.
Akai
,
T.
Yamamoto
, and
M.
Suginome
,
J. Am. Chem. Soc.
135
,
10104
–
10113
(
2013
).
https://doi.org/10.1021/ja403391m
Google Scholar
Crossref
Search ADS
 
6.
T.
Yamada
,
Y.
Nagata
, and
M.
Suginome
,
Chem. Commun.
46
,
4914
–
4916
(
2010
).
https://doi.org/10.1039/c001564d
Google Scholar
Crossref
Search ADS
 
7.
Y.
Nagata
,
T.
Nishikawa
,
M.
Suginome
,
S.
Sato
,
M.
Sugiyama
,
L.
Porcar
,
A.
Martel
,
R.
Inoue
, and
N.
Sato
,
J. Am. Chem. Soc.
140
,
2722
–
2726
(
2018
).
https://doi.org/10.1021/jacs.7b11626
Google Scholar
Crossref
Search ADS
 
8.
T.
Imae
,
T.
Kanaya
,
M.
Furusaka
, and
N.
Torikai
,
Neutrons in Soft Matter
(
John Wiley and Sons
,
Hoboken, NJ
,
2011
).
Google Scholar
Crossref
Search ADS
 
9.
D.
Richter
,
M.
Monkenbusch
,
A.
Arbe
, and
J.
Colmenero
,
Adv. Polym. Sci.
174
,
1
–
221
(
2005
).
https://doi.org/10.1007/b99835
Google Scholar
Crossref
Search ADS
 
10.
B.
Farago
,
I. D.
Nicholl
,
S.
Wang
,
X.
Cheng
,
D. J. E.
Callaway
, and
Z.
Bu
,
Proc. Natl. Acad. Sci. U. S. A.
118
,
e2025012118
(
2021
).
https://doi.org/10.1073/pnas.2025012118
Google Scholar
Crossref
Search ADS
PubMed
 
11.
R.
Inoue
,
T.
Oda
,
H.
Nakagawa
,
T.
Tominaga
,
T.
Saio
,
Y.
Kawakita
,
M.
Shimizu
,
A.
Okuda
,
K.
Morishima
,
N.
Sato
,
R.
Urade
 et al,
Sci. Rep.
10
,
21678
(
2020
).
https://doi.org/10.1038/s41598-020-78311-4
Google Scholar
Crossref
Search ADS
PubMed
 
12.
K.
Shibata
,
N.
Takahashi
,
Y.
Kawakita
,
M.
Matsuura
,
T.
Yamada
,
T.
Tominaga
,
W.
Kambara
,
M.
Kobayashi
,
Y.
Inamura
,
T.
Nakatani
,
K.
Nakajima
, and
M.
Arai
,
JPS Conf. Proc.
8
,
036022
(
2015
).
https://doi.org/10.7566/JPSCP.8.036022
Google Scholar
Crossref
Search ADS
 
13.
S. W.
Provencher
,
Comput. Phys. Commun.
27
,
229
–
242
(
1982
).
https://doi.org/10.1016/0010-4655(82)90174-6
Google Scholar
Crossref
Search ADS
 
14.
Materials Studio 2020 with Forcite Module, Dassault Systèmes BIOVIA, https://www.3ds.com/ja/products-services/biovia/products/molecular-modeling-simulation/biovia-materials-studio/,
2020
.
15.
M.
Monkenbusch
,
A.
Stadler
,
R.
Biehl
,
J.
Ollivier
,
M.
Zamponi
, and
D.
Richter
,
J. Chem. Phys.
143
,
075101
(
2015
).
https://doi.org/10.1063/1.4928512
Google Scholar
Crossref
Search ADS
 
16.
M.
Sarter
,
D.
Niether
,
B. W.
Koenig
,
W.
Lohstroh
,
M.
Zamponi
,
N. H.
Jalarvo
,
S.
Wiegand
,
J.
Fitter
, and
A. M.
Stadler
,
J. Phys. Chem. B
124
,
324
–
335
(
2020
).
https://doi.org/10.1021/acs.jpcb.9b08467
Google Scholar
Crossref
Search ADS
 
17.
A.
Ortega
,
D.
Amorós
, and
J.
García de la Torre
,
Biophys. J.
101
,
892
–
898
(
2011
).
https://doi.org/10.1016/j.bpj.2011.06.046
Google Scholar
Crossref
Search ADS
PubMed
 
18.
S.
Dellerue
,
A. J.
Petrescu
,
J. C.
Smith
, and
M. C.
Bellissent-Funel
,
Biophys. J.
81
,
1666
–
1676
(
2001
).
https://doi.org/10.1016/s0006-3495(01)75820-1
Google Scholar
Crossref
Search ADS
PubMed
 
19.
R.
Inoue
,
T.
Kanaya
,
T.
Masuda
,
K.
Nishida
, and
O.
Yamamuro
,
Macromolecules
45
,
6008
–
6014
(
2012
).
https://doi.org/10.1021/ma301225y
Google Scholar
Crossref
Search ADS
 
20.
M. D.
Kemple
,
P.
Buckley
,
P.
Yuan
, and
F. G.
Prendergast
,
Biochemistry
36
,
1678
–
1688
(
1997
).
https://doi.org/10.1021/bi962146+
Google Scholar
Crossref
Search ADS
PubMed
 
21.
F.
Volino
,
J. C.
Perrin
, and
S.
Lyonnard
,
J. Phys. Chem. B
110
,
11217
–
11223
(
2006
).
https://doi.org/10.1021/jp061103s
Google Scholar
Crossref
Search ADS
 
22.
R.
Inoue
,
T.
Oroguchi
,
T.
Oda
,
B.
Farago
,
A.
Martel
,
L.
Porcar
,
M.
Sato
, and
M.
Sugiyama
,
Phys. Rev. Res.
5
,
043154
(
2023
).
https://doi.org/10.1103/physrevresearch.5.043154
Google Scholar
Crossref
Search ADS
 
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