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ChemComm
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DOI: 10.1039/C6CC10046E
COMMUNICATION
Journal Name
packing. Mixing scaffold
1 in similar fibres as 2 was previously we anticipate that the studies described here are useful for the
shown to improve the stiffness at the macroscopic level design of biomaterials.
significantly. This was proposed to be due to a difference in
This work was supported by the European Research
exchange rates at the molecular scale.18 Here we confirm that Council (Grant Agreement 246829), The Royal Netherlands
the exchange rates of the dye-labelled monomers are Academy of Science, the Netherlands Organization of Sciences
dominated by the scaffold type, and to a lesser extent by the (NWO-Newpol), and the Dutch Ministry of Education, Culture
multivalency of the dye-labelled monomer. Moreover, the and Science (Gravity program 024.001.035).
hydrophobic nature of the dyes might result in a preference to
reside in the hydrophobic pocket of the fibre. Although no
Notes and references
clear differences in fibre formation were observed with cryo-
TEM and UV-vis (ESI, Fig. S7), changes in the exchange kinetics
are likely to occur.22
1
2
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Fig. 5 STORM images of scaffolds formed by monovalent 1 (top and middle row) and
bivalent 2 (bottom row) with 2 mol% of incorporated mDye 3a+3b (cTotal=12.5 µM).
Left; merged channel, middle; Cy5 excited channel, and right; Cy3 excited channel.
Directly after mixing mDye 3a and 3b incorporated in monovalent scaffold 1, negligible
exchange was observed (top, t=1 min), after 20 hours a small degree of exchange was
observed (middle, t=20 hours). When the dyes were incorporated in bivalent scaffold 2,
instant exchange was observed (bottom, t=1 min). The scale bars represent 2 µm.
17 P. Y. W. Dankers, T. M. Hermans, T. W. Baughman, Y.
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Despite that it remains a challenge to unravel the exact
molecular structure and kinetics of supramolecular systems,
cryo-TEM, FRET and STORM proved to be
a powerful
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combination of techniques to study supramolecular fibres into
great detail. The results indicate that both the structure and
dynamics of these fibres heavily depend on the design of the
UPy monomers, and we showed that it is possible to control
their properties by mixing the different monomer variants.
These are important findings for the design of functional
monomers such as bioactive peptides and proteins introduced
in supramolecular fibres, since they might change the packing
within the fibres, and as a consequence, the macroscopic
properties. Because there is a delicate balance between
dynamic spatiotemporal presentation and the ability of the cell
to locally remodel the surrounding microscopic environment,
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