Macromolecules
Article
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re-formation of these nanoparticles by looking at the samples
for TEM at different time points during the cooling step
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(
1
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7
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(
Figure S25). It is clear that the nanoparticles are small initially,
finally reaching the particle size similar to that observed before
heat−cool cycle. These results show that these nanoparticles
are thermally reversible and that the formation of the
nanoparticles is likely due to equilibrium self-assembly.
(
CONCLUSIONS
■
(
1
(
In summary, we report on a supramolecular nanoparticle that is
autonomously self-assembled by conjugated polymers based on
boronate ester. We have shown that (i) the polymers inducing
nucleation for the formation of the particle involves a N-E
polymerization step, (ii) dative bond between the nitrogen in
the imine building blocks and the boron in the boronate ester is
regarded as the necessary secondary interaction for the specific
reaction, (iii) their particle size could be easily adjusted by
controlling the mixing concentration, (iv) imine density and
solvent can affect the particle formation, and (v) these boronate
nanoparticles exhibit thermally responsive disassembly behavior
due to the relatively weak dative covalent B−N bond. To our
knowledge, this is the first time for a cooperative polymer-
ization to use covalent dative bond as the driving force. We
believe that this will open new doors for autonomous self-
assembly strategies to achieve not only monodisperse but also
functionally diverse nanoassemblies.
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ASSOCIATED CONTENT
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*
S
Supporting Information
(
2192−2200.
(25) Cruz-Huerta, J.; Salazar-Mendoza, D.; Hernandez-Paredes, J.;
Hernandez Ahuactzi, I. F.; Hopfl, H. Chem. Commun. 2012, 48, 4241−
4
243.
AUTHOR INFORMATION
■
(
26) Sheepwash, E.; Krampl, V.; Scopelliti, R.; Sereda, O.; Neels, A.;
Severin, K. Angew. Chem., Int. Ed. 2011, 50, 3034−3037.
27) Zhang, Y.; Li, M.; Chandrasekaran, S.; Gao, X.; Fang, X.; Lee, H.
W.; Hardcastle, K.; Yang, J.; Wang, B. Tetrahedron 2007, 63, 3287−
292.
28) Kiviranta, P. H.; Leppan
Lahtela-Kakkonen, M.; Tervo, A. J.; Wittekindt, C.; Suuronen, T.;
Kuusisto, E.; Jar
*
(
Notes
3
The authors declare no competing financial interest.
(
̈
en, J.; Kyrylenko, S.; Salo, H. S.;
ACKNOWLEDGMENTS
■
1
̈
vinen, T. J. Med. Chem. 2006, 49, 7907−7911.
We thank NSF for supporting this work through CHE-
307118. We also thank the NSF- Center for Hierarchical
(29) Spitler, E. L.; Dichtel, W. R. Nat. Chem. 2010, 2, 672−677.
(30) Spitler, E. L.; Giovino, M. R.; White, S. L.; Dichtel, W. R. Chem.
Sci. 2011, 2, 1588−1593.
Manufacturing for partial support. Mass spectra data were
obtained at the University of Massachusetts Mass Spectrometry
Center. Thanks to Dr. Rinat Abzalimov for his help with
analysis on mass spectra.
(31) Brewer, S. H.; Allen, A. M.; Lappi, S. E.; Chasse, T. L.;
Briggman, K. A.; Gorman, C. B.; Franzen, S. Langmuir 2004, 20,
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33) Jak
5
(
(
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le, F. Angew. Chem., Int. Ed. 2009, 48, 2313−2316.
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le, F. Coord. Chem. Rev. 2006, 250, 1107−1121.
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dx.doi.org/10.1021/ma5015808 | Macromolecules XXXX, XXX, XXX−XXX