Thermo-responsive metallo-supramolecular gels based on terpyridine end-functionalized amphiphilic diblock copolymers

2013 ◽  
Vol 1499 ◽  
Author(s):  
Jérémy Brassinne ◽  
Charles-André Fustin ◽  
Jean-François Gohy

ABSTRACTA thermo-responsive hydrogel was prepared on the basis of terpyridine endfunctionalized polystyrene-block-poly(N-isopropylacrylamide) diblock copolymer. As a first level of assembly, the copolymer was dissolved in a selective solvent to yield micelles bearing terpyridine ligands at the extremity of the coronal chains. The second level of self-assembly was triggered upon addition of metal ions to the micellar solution. Mechanical properties of the accordingly obtained micellar gel were finally characterized by rotational rheometry, below and above the lower critical solution temperature.

Soft Matter ◽  
2020 ◽  
Vol 16 (26) ◽  
pp. 6056-6062 ◽  
Author(s):  
Xianggui Ye ◽  
Bamin Khomami

Large-scale dissipative particle dynamics (DPD) simulations have been performed to investigate the self-assembly of over 20 000 linear diblock copolymer chains in a selective solvent.


Soft Matter ◽  
2015 ◽  
Vol 11 (26) ◽  
pp. 5204-5213 ◽  
Author(s):  
Ami Fujihara ◽  
Naohiko Shimada ◽  
Atsushi Maruyama ◽  
Kazuhiko Ishihara ◽  
Keita Nakai ◽  
...  

Ureido group-bearing methacrylate-type polymers show an upper critical solution temperature in water. We prepared a thermo-responsive diblock copolymer composed of a ureido group-bearing block.


2015 ◽  
Vol 6 (16) ◽  
pp. 3009-3013 ◽  
Author(s):  
Beibei Chen ◽  
Zhao Wang ◽  
Jinjie Lu ◽  
Xian Yang ◽  
Yong Wang ◽  
...  

A novel amphiphilic diblock copolymer containing cyclic-azobenzene has been synthesized and self-assembled into spherical micelles which show unusual photo-responsive behaviors.


Polymers ◽  
2021 ◽  
Vol 13 (24) ◽  
pp. 4424
Author(s):  
Nicolas Audureau ◽  
Fanny Coumes ◽  
Clémence Veith ◽  
Clément Guibert ◽  
Jean-Michel Guigner ◽  
...  

We have previously demonstrated that poly(N-cyanomethylacrylamide) (PCMAm) exhibits a typical upper-critical solution temperature (UCST)-type transition, as long as the molar mass of the polymer is limited, which was made possible through the use of reversible addition-fragmentation chain transfer (RAFT) radical polymerization. In this research article, we use for the first time N-cyanomethylacrylamide (CMAm) in a typical aqueous dispersion polymerization conducted in the presence of poly(N,N-dimethylacrylamide) (PDMAm) macroRAFT agents. After assessing that well-defined PDMAm-b-PCMAm diblock copolymers were formed through this aqueous synthesis pathway, we characterized in depth the colloidal stability, morphology and temperature-responsiveness of the dispersions, notably using cryo-transmission electron microscopy (cryo-TEM), dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and turbidimetry. The combined analyses revealed that stable nanometric spheres, worms and vesicles could be prepared when the PDMAm block was sufficiently long. Concerning the thermoresponsiveness, only diblocks with a PCMAm block of a low degree of polymerization (DPn,PCMAm < 100) exhibited a UCST-type dissolution upon heating at low concentration. In contrast, for higher DPn,PCMAm, the diblock copolymer nano-objects did not disassemble. At sufficiently high temperatures, they rather exhibited a temperature-induced secondary aggregation of primary particles. In summary, we demonstrated that various morphologies of nano-objects could be obtained via a typical polymerization-induced self-assembly (PISA) process using PCMAm as the hydrophobic block. We believe that the development of this aqueous synthesis pathway of novel PCMAm-based thermoresponsive polymers will pave the way towards various applications, notably as thermoresponsive coatings and in the biomedical field.


Author(s):  
Sophia Pavlenko ◽  
Daniil E Larin ◽  
Elena Nikolaevna Govorun

Abstract Thermoresponsive polymers are usually characterized by a locally amphiphilic chain structure and their self-assembly in solution is controlled, in particular, by the surface activity of the monomer units or side chains. We theoretically study the condensed state of a single diblock copolymer molecule consisting of a hydrophobic block and amphiphilic block with hydrophobic groups in the backbone and pendant polar groups. The equilibrium parameters of the polymer globules of different shapes are determined using the mean-field approach to determine the most favorable structure. Morphological diagrams of condensed macromolecules are presented depending on the chain length, amphiphilic block fraction, interaction parameters, and pendant volume and length. The diagrams are compared with those of a copolymer molecule with the same fraction of amphiphilic monomer units which are regularly distributed along the chain. The diblock copolymer molecule is found to form a single spherical or flattened particle, with the core from the hydrophobic block, or a granular micelle consisting of spherical or nearly spherical particles, in agreement with the experimental data in the literature. The optimal chain parameters for self-assembly into a stable single core-shell particle are predicted.


1994 ◽  
Vol 67 (2) ◽  
pp. 342-347
Author(s):  
Moira Marx Nir ◽  
Robert E. Cohen

Abstract Tensile failure properties of syndiotactic 1,2 polybutadiene/trans 1,4 polybutadiene crystalline blends are improved by addition of 5–10% amorphous 1,2 polybutadiene/1,4 polybutadiene diblock copolymer. The effect of block molecular weight and microphase behavior of the diblock copolymer was investigated. Heterogeneous diblocks enhance blend properties to a greater extent than homogeneous diblocks. In blends with enhanced properties, percent coverage of interfacial surface area by diblock is on the order of 10%.


2011 ◽  
Vol 295-297 ◽  
pp. 11-15
Author(s):  
Hao Zhou ◽  
Qing Hong Liang ◽  
Xiang Ke Shi ◽  
Li Hua Lu ◽  
Li Qun Zhang ◽  
...  

Amphiphilic diblock copolymers based on methoxy polyethylene glycol (MePEG), 1, 6-hexanediol and maleic anhydride with different molar composition were synthesized by solution polycondensation. Self-assemble behavior of amphiphilic diblock copolymer in different solvents by dialyzing technique was discussed. The micelle morphologhy was observed by TEM. It was found that well core-shell MePEG1900/Polyester 2162 copolymer nanoparticles can be formed by self-assemble in acetone solution. In addition, the size of nanospheres measured using dynamic light scattering exhibited a narrow monodisphere size distribution and an average diameter in the ranger of less than 200nm.


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