Abstract
In this work, we demonstrate the formation of various 3D structures formed by a structural reorganization; a process not governed by self-assembly. First, we packaged well-defined diblocks, thermoresponsive poly(N-isopropylacrylamide- b-styrene) or P(NIPAM-b-STY), into spherical particles made in situ using a reversible addition-fragmentation chain transfer (RAFT) nanoreactor technique in water to obtain high polymer solids. The resultant spheres reorganized through a temperature stimulus to form equilibrium and kinetically trapped structures; we denote this process as temperature directed morphology transformation (TDMT). Cylinder and vesicle structures, other more unusual loop, buckled sphere and cauliflower (via ultrasound) structures were observed below the lower critical solution temperature (LCST) of PNIPAM. These structures were produced efficiently, rapidly, reproducibly at high polymer solids and can be stored for years in solution or be freeze-dried and rehydrated without a change in structure, which becomes important in biological applications. We generated the first phase diagram for the TDMT changes of thermoresponsive diblock micelles in concentrated solutions (> 7% polymer solids) produced from narrow molecular weight diblock copolymers (PDI ∼ 1.1). The sphere/cylinder and cylinder/vesicle transition in the phase diagram were surprisingly found to be predominantly dictated by the length of the hydrophilic block, poly(N-isopropylacrylamide).
| Original language | English |
|---|---|
| Pages (from-to) | 4879-4887 |
| Number of pages | 9 |
| Journal | Journal of Polymer Science, Part A: Polymer Chemistry |
| Volume | 50 |
| Issue number | 23 |
| DOIs | |
| Publication status | Published - 1 Dec 2012 |
| Externally published | Yes |
Keywords
- 3D nanostructures
- block polymers
- living radical polymerization
- nanoreactors
- reversible addition-fragmentation chain transfer (RAFT)
- self-organization
- thermoresponsive polymers
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Aqueous reversible addition-fragmentation chain transfer dispersion polymerization of thermoresponsive diblock copolymer assemblies : Temperature directed morphology transformations. / Kessel, Stefanie; Truong Phuoc, Nghia; Jia, Zhongfan; Monteiro, Michael J.
In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 50, No. 23, 01.12.2012, p. 4879-4887.Research output: Contribution to journal › Article › Research › peer-review
TY - JOUR
T1 - Aqueous reversible addition-fragmentation chain transfer dispersion polymerization of thermoresponsive diblock copolymer assemblies
T2 - Temperature directed morphology transformations
AU - Kessel, Stefanie
AU - Truong Phuoc, Nghia
AU - Jia, Zhongfan
AU - Monteiro, Michael J
N1 - Cited By :24 Export Date: 25 July 2016 CODEN: JPACE Correspondence Address: Monteiro, M.J.; Australian Institute for Bioengineering and Nanotechnology, University of Queensland, Brisbane, QLD 4072, Australia; email: m.monteiro@uq.edu.au References: Won, Y.-Y., Davis, H.T., Bates, F.S., (1999) Science, 283, pp. 960-963; Pochan, D.J., Chen, Z., Cui, H., Hales, K., Qi, K., Wooley, K.L., (2004) Science, 306, pp. 94-97; Zhang, L., Eisenberg, A., (1995) Science, 268, pp. 1728-1731; Whittaker, M.R., Monteiro, M.J., (2006) Langmuir, 22, pp. 9746-9752; Wang, X., Guerin, G., Wang, H., Wang, Y., Manners, I., Winnik, M.A., (2007) Science, 317, pp. 644-647; Discher, D.E., Eisenberg, A., (2002) Science, 297, pp. 967-973; Lonsdale, D.E., Whittaker, M.R., Monteiro, M.J., (2009) J. Polym. Sci. Part A: Polym. Chem., 47, pp. 6292-6303; Hillmyer, M.A., Bates, F.S., Almdal, K., Mortensen, K., Ryan, A.J., Fairclough, J.P.A., (1996) Science, 271, pp. 976-978; Lonsdale, D.E., Monteiro, M.J., (2011) J. Polym. Sci. Part A: Polym. Chem., 49, pp. 4603-4612; Stover, T.C., Kim, Y.S., Lowe, T.L., Kester, M., (2007) Biomaterials, 29, pp. 359-369; Skwarczynski, M., Zaman, M., Urbani, C.N., Lin, I.C., Jia, Z., Batzloff, M.R., Good, M.F., Toth, I., (2010) Angew. Chem. Int. Ed., 49, pp. 5742-5745. , S5742/1- S5742/14; Lee, K.Y., Mooney, D., (2001) J. Chem. Rev., 101, pp. 1869-1879; Monteiro, M., (2010) J. Macromolecules, 43, pp. 1159-1168; Urbani, C.N., Monteiro, M., (2009) J. Macromolecules, 42, pp. 3884-3886; Sebakhy, K.O., Kessel, S., Monteiro, M.J., (2010) Macromolecules, 43, pp. 9598-9600; Halperin, A., (1987) Macromolecules, 20, pp. 2943-2946; Izzo, D., Marques, C.M., (1993) Macromolecules, 26, pp. 7189-7194; Izzo, D., Marques, C.M., (1997) Macromolecules, 30, pp. 6544-6549; Termonia, Y., (2002) J. Polym. Sci. Part B: Polym. Phys., 40, pp. 890-895; Zhulina, E.B., Adam, M., Larue, I., Sheiko, S.S., Rubinstein, M., (2005) Macromolecules, 38, pp. 5330-5351; Larue, I., Adam, M., Da Silva, M., Sheiko, S.S., Rubinstein, M., (2004) Macromolecules, 37, pp. 5002-5005; Cai, Y., Aubrecht, K.B., Grubbs, R.B., (2011) J. Am. Chem. Soc., 133, pp. 1058-1065; Jiang, Y., Chen, T., Ye, F., Liang, H., Shi, A.-C., (2005) Macromolecules, 38, pp. 6710-6717; Smith, A.E., Xu, X., Kirkland-York, S.E., Savin, D.A., McCormick, C.L., (2010) Macromolecules, 43, pp. 1210-1217; Li, Y., Lokitz, B.S., Armes, S.P., McCormick, C.L., (2006) Macromolecules, 39, pp. 2726-2728; Li, Y., Lokitz, B.S., McCormick, C.L., (2006) Angew. Chem. Int. Ed., 45, pp. 5792-5795; Boisse, S., Rieger, J., Belal, K., Di-Cicco, A., Beaunier, P., Li, M.-H., Charleux, B., (2010) Chem. Commun., 46, pp. 1950-1952; Delaittre, G., Dire, C., Rieger, J., Putaux, J.-L., Charleux, B., (2009) Chem. Commun., pp. 2887-2889; Li, Y., Armes, S.P., (2010) Angew. Chem. Int. Ed., 49, pp. 4042-4046; Sugihara, S., Blanazs, A., Armes, S.P., Ryan, A.J., Lewis, A.L., (2011) J. Am. Chem. Soc., 133 (1), pp. 5707-1571. , 3; Kessel, S., Urbani, C.N., Monteiro, M.J., (2011) Angew. Chem. Int. Ed., 50, pp. 8082-8085; Ganachaud, F., Monteiro, M.J., Gilbert, R.G., Dourges, M.-A., Thang, S.H., Rizzardo, E., (2000) Macromolecules, 33, pp. 6738-6745; Monteiro, M.J., De Brouwer, H., (2001) Macromolecules, 34, pp. 349-352; Barner-Kowollik, C., Charleux, B., Buback, M., Coote, M.L., Drache, M., Fukuda, T., Goto, A., Vana, P., (2006) J. Polym. Sci. Part A: Polym. Chem., 44, pp. 5809-5831; Larue, I., Adam, M., Pitsikalis, M., Hadjichristidis, N., Rubinstein, M., Sheiko, S.S., (2006) Macromolecules, 39, pp. 309-314; Sacanna, S., Irvine, W.T.M., Chaikin, P.M., Pine, D., (2010) J. Nature, 464, pp. 575-578; Caruso, M.M., Davis, D.A., Shen, Q., Odom, S.A., Sottos, N.R., White, S.R., Moore, J.S., (2009) Chem. Rev., 109, pp. 5755-5798
PY - 2012/12/1
Y1 - 2012/12/1
N2 - In this work, we demonstrate the formation of various 3D structures formed by a structural reorganization; a process not governed by self-assembly. First, we packaged well-defined diblocks, thermoresponsive poly(N-isopropylacrylamide- b-styrene) or P(NIPAM-b-STY), into spherical particles made in situ using a reversible addition-fragmentation chain transfer (RAFT) nanoreactor technique in water to obtain high polymer solids. The resultant spheres reorganized through a temperature stimulus to form equilibrium and kinetically trapped structures; we denote this process as temperature directed morphology transformation (TDMT). Cylinder and vesicle structures, other more unusual loop, buckled sphere and cauliflower (via ultrasound) structures were observed below the lower critical solution temperature (LCST) of PNIPAM. These structures were produced efficiently, rapidly, reproducibly at high polymer solids and can be stored for years in solution or be freeze-dried and rehydrated without a change in structure, which becomes important in biological applications. We generated the first phase diagram for the TDMT changes of thermoresponsive diblock micelles in concentrated solutions (> 7% polymer solids) produced from narrow molecular weight diblock copolymers (PDI ∼ 1.1). The sphere/cylinder and cylinder/vesicle transition in the phase diagram were surprisingly found to be predominantly dictated by the length of the hydrophilic block, poly(N-isopropylacrylamide).
AB - In this work, we demonstrate the formation of various 3D structures formed by a structural reorganization; a process not governed by self-assembly. First, we packaged well-defined diblocks, thermoresponsive poly(N-isopropylacrylamide- b-styrene) or P(NIPAM-b-STY), into spherical particles made in situ using a reversible addition-fragmentation chain transfer (RAFT) nanoreactor technique in water to obtain high polymer solids. The resultant spheres reorganized through a temperature stimulus to form equilibrium and kinetically trapped structures; we denote this process as temperature directed morphology transformation (TDMT). Cylinder and vesicle structures, other more unusual loop, buckled sphere and cauliflower (via ultrasound) structures were observed below the lower critical solution temperature (LCST) of PNIPAM. These structures were produced efficiently, rapidly, reproducibly at high polymer solids and can be stored for years in solution or be freeze-dried and rehydrated without a change in structure, which becomes important in biological applications. We generated the first phase diagram for the TDMT changes of thermoresponsive diblock micelles in concentrated solutions (> 7% polymer solids) produced from narrow molecular weight diblock copolymers (PDI ∼ 1.1). The sphere/cylinder and cylinder/vesicle transition in the phase diagram were surprisingly found to be predominantly dictated by the length of the hydrophilic block, poly(N-isopropylacrylamide).
KW - 3D nanostructures
KW - block polymers
KW - living radical polymerization
KW - nanoreactors
KW - reversible addition-fragmentation chain transfer (RAFT)
KW - self-organization
KW - thermoresponsive polymers
UR - http://www.scopus.com/inward/record.url?scp=84868142112&partnerID=8YFLogxK
U2 - 10.1002/pola.26313
DO - 10.1002/pola.26313
M3 - Article
AN - SCOPUS:84868142112
VL - 50
SP - 4879
EP - 4887
JO - Journal of Polymer Science, Part A: Polymer Chemistry
JF - Journal of Polymer Science, Part A: Polymer Chemistry
SN - 0887-624X
IS - 23
ER -