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| Home > Publications database > Self-Assembly of Mixtures of Telechelic and Monofunctional Amphiphilic Polymers in Water: From Clusters to Flowerlike Micelles > print |
| 001 | 838841 | ||
| 005 | 20240619091919.0 | ||
| 024 | 7 | _ | |a 10.1021/acs.macromol.7b01501 |2 doi |
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| 100 | 1 | _ | |a Zinn, Thomas |0 P:(DE-Juel1)141611 |b 0 |
| 245 | _ | _ | |a Self-Assembly of Mixtures of Telechelic and Monofunctional Amphiphilic Polymers in Water: From Clusters to Flowerlike Micelles |
| 260 | _ | _ | |a Washington, DC |c 2017 |b Soc. |
| 336 | 7 | _ | |a article |2 DRIVER |
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| 520 | _ | _ | |a We study the self-assembly of mixtures of n-alkyl mono- and difunctionalized poly(ethylene oxide) (PEO) chains in the dilute concentration regime. The monofunctional PEOs were prepared by living anionic polymerization with varying n-alkyl length (n = 14, 16, 22, 28) and constant PEO molecular weight of 5 kg/mol. The difunctional materials were obtained through end-to-end coupling of two of the monofunctionalized PEOs via their terminal hydroxyl groups. The chosen synthetic pathway yields well-defined model compounds with narrow molecular weight distribution and complete end-group functionalization. By using both small-angle neutron scattering (SANS) and dynamic light scattering (DLS) combined with theoretical data modeling, we have systematically investigated both the global and inner structure of the self-assembled micellar structures. For short n-alkyl chain-ends, we find a formation of clustered micelles with a finite size whereas, intriguingly, at longer n-alkyls, we observe a crossover to flowerlike micelles. This was confirmed both by DLS, which is very sensitive to formation of larger clusters, as well as with SANS, which also showed a clear transition from attractive to repulsive intermicellar interactions upon increasing n-alkyl length. We attribute this to the balance between the hydrophobic enthalpic terms that favor anchoring of both chain-ends to the core and the entropic cost associated with the bending of the polymer chains. For short n-alkyls, exposure of the chain-ends in the corona structure leads to net dominance of the attractive interactions while for longer hydrophobic chains it leads to a stabilization of loops and consequently flowerlike micellar morphology. Using contrast-variation SANS, the contribution of mono- and difunctional chains could be separated, confirming the flowerlike micellar structure. |
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| 700 | 1 | _ | |a Willner, Lutz |0 P:(DE-Juel1)131036 |b 1 |e Corresponding author |
| 700 | 1 | _ | |a Knudsen, Kenneth D. |0 P:(DE-HGF)0 |b 2 |
| 700 | 1 | _ | |a Lund, Reidar |0 0000-0001-8017-6396 |b 3 |e Corresponding author |
| 773 | _ | _ | |a 10.1021/acs.macromol.7b01501 |g Vol. 50, no. 18, p. 7321 - 7332 |0 PERI:(DE-600)1491942-4 |n 18 |p 7321 - 7332 |t Macromolecules |v 50 |y 2017 |x 1520-5835 |
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