Organic & Biomolecular Chemistry
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This also affects the glycosidic bond geometry with a high
population at negative degrees (-172˚) for Ψ1, Ψ4 ((AgA)2 red
boxes). The opposite trend is observed when position 6 is
substituted with COO- (d). Due to sterics, the gg conformation
is preferred, with a small percentage of tg stabilised by a COO-
∙∙∙ OH(2) interaction (Figure 1). This interaction also affects the
dihedrals of the adjacent glycosidic bond ((AdA)2 blue boxes).
The substitutions in position 3 influence predominantly the
9.
10.
11.
12.
+
glycosidic bond geometry. The interaction between the NH3 (3)
and the O(5) of the previous residue (R-1) preserved a cellulose-
like character ((AGA)2 red boxes). In contrast, the carboxylate at 13.
position 3 can engage in additional H-bonds, as observed
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Seeberger, H. S. Overkleeft, G. A. van der Marel and J. D.
Codée, Angew. Chem. Int. Ed., 2012, 51, 4393-4396.
S. Eller, M. Collot, J. Yin, H. S. Hahm and P. H. Seeberger,
Angew. Chem. Int. Ed., 2013, 52, 5858-5861.
H. S. Hahm, F. Broecker, F. Kawasaki, M. Mietzsch, R.
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M. W. Weishaupt, S. Matthies, M. Hurevich, C. L. Pereira,
H. S. Hahm and P. H. Seeberger, Beilstein J. Org. Chem.,
2016, 12, 1440-1446.
between COO- and OH(2) of the same residue as well as the
OH(6) of the previous sugar (R-1), resulting in remarkable
changes of the Φ and Ψ dihedrals ((ADA)2 blue boxes).
14.
15.
16.
17.
Conclusions
Four monosaccharide BBs bearing masked carboxylic acid or 18.
amino groups are synthesised. Their good reactivity and
19.
stability make them useful BBs for creation of ionic
oligosaccharides. Twelve well-defined ionic cellulose analogues
were prepared by AGA. Multiply charged oligosaccharides as
well as zwitterionic compounds are accessible. MD simulations
demonstrate how the nature and the position of the
modification (3 vs 6) plays a major role for the flexibility and
conformation of such oligosaccharides. These differences could
play a major role in the formation of supramolecular assembly
based on charged polysaccharides.
20.
21.
22.
23.
Conflicts of interest
There are no conflicts to declare.
24.
25.
26.
27.
28.
29.
A. Pardo-Vargas, M. Delbianco and P. H. Seeberger, Curr.
Opin. Chem. Biol., 2018, 46, 48-55.
M. Guberman, M. Bräutigam and P. H. Seeberger, Chem.
Sci., 2019, 10, 5634-5640.
Acknowledgements
We thank the Max-Planck Society, the Minerva Fast Track Pro-
gram, and the MPG-FhG Cooperation Project Glyco3Dysplay, for
generous financial support.
R. S. Loka, E. T. Sletten, U. Barash, I. Vlodavsky and H. M.
Nguyen, ACS Appl. Mater. Interfaces., 2018, 11, 244-254.
B. Thomas, M. C. Raj, J. Joy, A. Moores, G. L. Drisko and C.
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Singhal, R. J. Fair, A. Grafmüller, P. H. Seeberger and M.
Delbianco, Angew. Chem. Int. Ed., 2019, 58, 13127-13132.
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Schuhmacher, P. H. Seeberger and F. Pfrengle, Chem. Eur.
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G. Veeneman, S. Van Leeuwen and J. Van Boom,
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