Journal of the American Chemical Society
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erated at the Heinz MaierꢀLeibnitz (MLZ), Garching, Gerꢀ
many.
sized semiꢀrigid (and generally amphipathic) ice binding
faces of AFPs,14,39 and the flexible hydrophilic ‘glycan
face’ of AFGPs, providing evidence that facial amꢀ
phipathy is a key motif for introducing IRI activity into a
diverse range of polymers.
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Fig 5 SANS data for poly(FulvoꢀcoꢀDiol)ꢀ11 (100%, red) and
poly(FulvoꢀcoꢀDiol)ꢀ17 (100%, blue) in D2O at 25 °C. Straight
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To conclude, we have designed and synthesized facially
amphipathic glycopolymers to mimic the solution conꢀ
firmation and selective functions of antifreeze glycoproꢀ
teins. It was found that the addition of hydrophobic facꢀ
es, opposing the glycan units, introduced potent IRI acꢀ
tivity, but that substitution with a more hydrophilic ether
unit removed activity. These results support a mechaꢀ
nism for IRI activity which is dependent upon local waꢀ
ter ordering rather than an essential ice binding unit, and
there was no evidence of dynamic ice shaping; with
small angle neutron scattering supporting a locally rigid
confirmation, as seen for AF(G)Ps, supporting the hyꢀ
pothesis of amphipathy as the driver for activity.
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Gibson, M. I. Polym. Chem. 2010, 1 (8), 1141.
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ASSOCIATED CONTENT
Supporting Information.
Full
experimental
details,
including
syntheꢀ
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Capicciotti, C. J.; Kurach, J. D. R.; Turner, T. R.;
Mancini, R. S.; Acker, J. P.; Ben, R. N. Sci. Rep.
2015, 5, 9692.
sis/characterization, additional IRI data and SANS analysis
is in the Supporting Information. This material is available
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Mochizuki, K.; Molinero, V. J. Am. Chem. Soc.
2018, 10.1021/jacs.7b13630.
Mitchell, D. E.; Clarkson, G.; Fox, D. J.; Vipond,
R. A.; Scott, P.; Gibson, M. I. J. Am. Chem. Soc.
2017, 139 (29), 9835.
AUTHOR INFORMATION
Corresponding Author
Prof. Matthew I. Gibson, m.i.gibson@warwick.ac.uk.
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Geng, H.; Liu, X.; Shi, G.; Bai, G.; Ma, J.; Chen,
J.; Wu, Z.; Song, Y.; Fang, H.; Wang, J. Angew.
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Liu, K.; Wang, C.; Ma, J.; Shi, G.; Yao, X.; Fang,
H.; Song, Y.; Wang, J. Proc. Natl. Acad. Sci. 2016,
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Notes
No competing financial interests have been declared.
ACKNOWLEDGMENT
MIG holds an ERC Starter Grant (CRYOMAT 638661).
Thanks to A. L. DeVries for supplying the antifreeze glyꢀ
coprotein AFGPꢀ8. The SANS portion of this work is based
upon experiments performed at the KWSꢀ2 instrument opꢀ
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Leclère, M.; Kwok, B. K.; Wu, L. K.; Allan, D. S.;
Ben, R. N. Bioconjug. Chem. 2011, 22 (9), 1804.
Mai, Y.; Eisenberg, A. Chem. Soc. Rev. 2012, 41
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