TY  - JOUR
A1  - Adelsberger, Joseph
A1  - Grillo, Isabelle
A1  - Kulkarni, Amit
A1  - Sharp, Melissa
A1  - Bivigou Koumba, Achille Mayelle
A1  - Laschewsky, André
A1  - Müller-Buschbaum, Peter
A1  - Papadakis, Christine M.
T1  - Kinetics of aggregation in micellar solutions of thermoresponsive triblock copolymers - influence of concentration, start and target temperatures
JF  - Soft matter
N2  - In aqueous solution, symmetric triblock copolymers with a thermoresponsive middle block and hydrophobic end blocks form flower-like core-shell micelles which collapse and aggregate upon heating through the cloud point (CP). The collapse of the micellar shell and the intermicellar aggregation are followed in situ and in real-time using time-resolved small-angle neutron scattering (SANS), while heating micellar solutions of a poly((styrene-d(8))-b-(N-isopropyl acrylamide)-b-(styrene-d(8))) triblock copolymer in D2O rapidly through their CP. The influence of polymer concentration as well as of the start and target temperatures is addressed. In all cases, the micellar collapse is very fast. The collapsed micelles immediately form small clusters which contain voids. They densify which slows down or even stops their growth. For low concentrations and target temperatures just above the CP, i.e. shallow temperature jumps, the subsequent growth of the clusters is described by diffusion-limited aggregation. In contrast, for higher concentrations and/or higher target temperatures, i.e. deep temperature jumps, intermicellar bridges dominate the growth. Eventually, in all cases, the clusters coagulate which results in macroscopic phase separation. For shallow temperature jumps, the cluster surfaces stay rough; whereas for deep temperature jumps, a concentration gradient develops at late stages. These results are important for the development of conditions for thermal switching in applications, e.g. for the use of thermoresponsive micellar systems for transport and delivery purposes.
Y1  - 2013
U6  - https://doi.org/10.1039/c2sm27152d
SN  - 1744-683X
VL  - 9
IS  - 5
SP  - 1685
EP  - 1699
PB  - Royal Society of Chemistry
CY  - Cambridge
ER  - 
TY  - JOUR
A1  - Adelsberger, Joseph
A1  - Kulkarni, Amit
A1  - Jain, Abhinav
A1  - Wang, Weinan
A1  - Bivigou Koumba, Achille Mayelle
A1  - Busch, Peter
A1  - Pipich, Vitaliy
A1  - Holderer, Olaf
A1  - Hellweg, Thomas
A1  - Laschewsky, André
A1  - Müller-Buschbaum, Peter
A1  - Papadakis, Christine M.
T1  - Thermoresponsive PS-b-PNIPAM-b-PS micelles : aggregation behavior, segmental dynamics, and thermal response
N2  - We have studied I lie thermal behavior of amphiphilic, symmetric triblock copolymers having short, deuterated polystyrene (PS) end blocks and a large poly(N-isopropylacrylarnicle) (PNIPAM) middle block exhibiting a lower critical solution temperature (LCST) in aqueous solution. A wide range of concentrations (0.1-300 mg/mL) is investigated using it number of analytical methods such as fluorescence correlation spectroscopy (FCS), turbidimetry, dynamic light scattering (DLS), small-angle neutron scattering (SANS), and neutron spin-echo spectroscopy (NSE). The critical micelle concentration is determined using FCS to be 1 mu M or less. The collapse of the micelles at the LCST is investigated using turbidimetry and DLS and shows a weak dependence on the degree of polymerization of the PNIPAM block. SANS with contrast matching allows its to reveal the core-shell Structure of the micelles as well as their correlation as a function of temperature. The segmental dynamics of the PNIPAM shell are studied as a function of temperature and arc found to be faster in the collapsed state than in the swollen state. The mode detected has a linear dispersion in q(2) and is found to be faster in the collapsed state as compared to the swollen state. We attribute this result to the averaging over mobile and immobilized segments.
Y1  - 2010
UR  - http://pubs.acs.org/journal/mamobx
U6  - https://doi.org/10.1021/Ma902714p
SN  - 0024-9297
ER  -