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FIGURE 8 Scanning electron micrographs of Porous PS-PEO: (a) parallel and (b) perpendicular to the cylinder axes.
Ungar, G. J. Chem. Soc. Perkin Trans. 1 1993, 2799–2811; (j)
Percec, V.; Heck, J. A.; Tomazos, D.; Ungar, G. J. Chem. Soc.
Perkin Trans. 2 1993, 2381–2388; (k) Percec, V.; Topmazos, D.;
Heck, J.; Blackwell, H.; Ungar, G. J. Chem. Soc. Perkin Trans. 2
1994, 31–44; (l) Johansson, G.; Percec, V.; Ungar, G.; Abramic,
D. J. Chem. Soc. Perkin Trans. 1 1994, 447–459; (m) Percec, V.;
Heck, J.; Johansson, G.; Tomazos, D.; Kawasumi, M.; Ungar, G.
J. Macromol. Sci. Pure Appl. Chem. 1994, 31, 1031–1070; (n)
Percec, V.; Heck, J.; Johansson, G.; Tomazos, D.; Ungar, G.
Macromol. Symp. 1994, 77, 237–265; (o) Percec, V.; Heck, J.;
Johansson, G.; Tomazos, D.; Kawasumi, M.; Chu, P.; Ungar, G.
J. Macromol. Sci. Pure Appl. Chem. 1994, 31, 1719–1758.
Several porous PS materials having sparse hydroxyl groups
on the walls were known to be floating on the water because
the whole wall properties were not hydrophilic enough for
water uptake.20 In contrast, Porous PS-PEO could sink to
the bottom in water. This behavior must be due to enhanced
water wettability of the pore wall composed of hydrophilic
PEO chains.21
CONCLUSIONS
A dendritic terpolymer was successfully prepared via step-
wise click reactions of individually prepared PEO, PS (by an
ATRP), and PLA (by a ROP) blocks. The terpolymer self-
assembled into a hexagonal columnar morphology consisting
of PEO/PLA cylindrical cores and a PS matrix while a three-
phase lamellar morphology was induced on doping lithium
salt. This morphological transformation could be explained by
(i) microphase separation between PEO and PLA blocks and
(ii) alleviation of the conformational energy of the longest
PLA chain. A nanoporous PS-PEO could be obtained by chemi-
cally etching the hexagonal columnar terpolymer using NaOH.
The presence of PEO chain on the wall rendered the porous
PS-PEO to be water compatible. The nanoporous material pre-
pared via the terpolymer assembly could be used as a chro-
matographic substance for various nanosized analytes.
3 (a) Chung, Y.-W.; Lee, J.-K.; Zin, W.-C.; Cho, B.-K. J. Am.
Chem. Soc. 2008, 130, 7139–7147; (b) Lee, E.; Lee, B.-I.; Kim,
S.-H.; Lee, J.-K.; Zin, W.-C.; Cho, B.-K. Macromolecules 2009,
42, 4134–4140; (c) Choi, J.-W.; Cho, B.-K. J. Polym. Sci. Part A:
Polym. Chem. 2011, 49, 2468–2473.
4 (a) Liu, H.; Li, C.; Liu, H.; Liu, S. Langmuir 2009, 25,
4724–4734; (b) Li, C.; Ge, Z.; Liu, H.; Liu, S. J. Polym. Sci. Part
A: Polym. Chem. 2009, 47, 4001–4013; (c) Erdogan, T.; Gungor,
E.; Durmaz, H.; Hizal, G.; Tunca, U. J. Polym. Sci. Part A:
Polym. Chem. 2006, 44, 1396–1403; (d) Liu, C.; Hillmyer, M. A.;
Lodge, T. P. Langmuir 2008, 24, 12001–12009.
5 (a) Percec, V.; Barboiu, B.; Grigoras, C.; Bera, T. K. J. Am.
Chem. Soc. 2003, 125, 6503–6516; (b) Percec, V.; Grigoras, C.;
Kim, H.-J. J. Polym. Sci. Part A: Polym. Chem. 2004, 42,
505–513; (c) Percec, V.; Grigoras, C.; Bera, T. K.; Barboiu, B.;
Bissel, P. J. Polym. Sci. Part A: Polym. Chem. 2005, 43,
4894–4906; (d) Rosen, B. M.; Percec, V. Chem. Rev. 2009, 109,
5069–5119.
REFERENCES AND NOTES
6 (a) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K.
B. Angew. Chem. Int. Ed. Engl. 2002, 41, 2596–2599; (b) Franc,
G.; Kakkar, A. Chem. Commun. 2008, 5267–5276; (c) Rosen, B.
M.; Lligadas, G.; Hahn, C.; Percec, V. J. Polym. Sci. Part A:
Polym. Chem. 2009, 47, 3940–3948; (d) Rosen, B. M.; Lligadas,
G.; Hahn, C.; Percec, V. J. Polym. Sci. Part A: Polym. Chem.
2009, 47, 3931–3939; (e) Tasdelen, M. A. Polym. Chem. 2011, 2,
2133–2145.
1 Bosman, A. W.; Janssen, H. M.; Meijer, E. W. Chem. Rev.
1999, 99, 1665–1688.
2 (a) Rosen, B.; Wilson, C. J.; Wilson, D. A.; Peterca, M.; Imam,
M. R.; Percec, V. Chem. Rev. 2009, 109, 6275–6540; (b) Khanna,
K.; Varshney, S.; Kakkar, A. Polym. Chem. 2010, 1, 1171–1185;
(c) Cho, B.-K.; Jain, A.; Gruner, S. M.; Wiesner, U. Science
2004, 305, 1598–1601; (d) Rangou, S.; Avgeropoulos, A. J.
Polym. Sci. Part A: Polym. Chem. 2009, 47, 1567–1574; (e)
Johnson, M. A.; Iyer, J.; Hammond, P. T. Macromolecules
7 (a) Ryu, M.-H.; Choi, J.-W.; Cho, B.-K. J. Mater. Chem. 2010,
20, 1806–1810; (b) Ryu, M.-H.; Choi, J.-W.; Kim, H.-J.; Park, N.;
Cho, B.-K. Angew. Chem. Int. Ed. Engl. 2011, 50, 5737–5740; (c)
Choi, J.-W.; Ryu, M.-H.; Lee, E.; Cho, B.-K. Chem. Eur. J. 2010,
16, 9006–9009; (d) Choi, J.-W.; Cho, B.-K. Soft Matter 2011, 7,
4045–4049; (e) Xia, Y.; Verduzco, R.; Grubbs, R. H.; Kornfield, J.
A. J. Am. Chem. Soc. 2008, 130, 1735–1740; (f) Gallardo, H.;
Ely, F.; Bortoluzzi, A. J.; Conte.G. Liq. Cryst. 2005, 32, 667–671.
ꢀ
2004, 37, 2490–2501; (f) Roman, C.; Fischer, H. R.; Meijer, E. W.
Macromolecules 1999, 32, 5525–5531; (g) Leduc, M. R.; Hawker,
ꢀ
C. J.; Dao, J.; Frechet, J. M. J. J. Am. Chem. Soc. 1996, 118,
11111–11118; (h) Percec, V.; Johansson, G.; Heck, J.; Ungar, G.;
Batty, S. V. J. Chem. Soc. Perkin Trans 1 1993, 1411–1420; (i)
Percec, V.; Heck, J.; Tomazos, D.; Falkenberg, F.; Blackwell, H.;
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