PDMAEMA-b-PLMA-b-POEGMA triblock terpolymers via RAFT polymerization and their self-assembly in aqueous solutions

2017 ◽  
Vol 8 (31) ◽  
pp. 4538-4547 ◽  
Author(s):  
Athanasios Skandalis ◽  
Stergios Pispas

Novel PDMAEMA-b-PLMA-b-POEGMA triblock terpolymers were synthesized by RAFT polymerization. Triblock polyelectrolytes were obtained by quaternization. PDMAEMA-b-PLMA-b-POEGMA and QPDMAEMA-b-PLMA-b-POEGMA terpolymers self-assemble into spherical micelles with a mixed corona in aqueous media.

Polymers ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 1382 ◽  
Author(s):  
Despoina Giaouzi ◽  
Stergios Pispas

In this work, the synthesis, selective chemical modifications, and self-assembly behavior in aqueous media of a novel poly(2-(dimethylamino)ethyl acrylate)20-b-poly(N-isopropylacrylamide)11-b-poly(oligo ethylene glycol methyl ether acrylate)18 (PDMAEA20-b-PNIPAM11-b-POEGA18) dual-responsive (pH and temperature) and triply hydrophilic amino-based triblock terpolymer are reported. The amine functional triblock terpolymer was synthesized by sequential reversible addition fragmentation chain transfer polymerization (RAFT) polymerization and molecularly characterized by size exclusion chromatography (SEC) and 1H-NMR spectroscopy that evidenced the success of the three-step polymerization scheme. The tertiary amine pendant groups of the PDMAEA block were chemically modified in order to produce the Q1PDMAEA20-b-PNIPAM11-b-POEGA18 as well as the Q6PDMAEA20-b-PNIPAM11-b-POEGA18 quaternized triblock terpolymers (Q1 and Q6 prefixes show the number of carbon atoms (C1 and C6) attached on the PDMAEA groups) using methyl iodide (CH3I) and 1-iodohexane (C6H13I) as the quaternizing agents and the SPDMAEA20-b-PNIPAM11-b-POEGA18 sulfobetainized triblock terpolymer using 1,3 propanesultone (C3H6O3S) as the sulfobetainization agent. The self-assembly properties of the triblock terpolymers in aqueous solutions upon varying temperature and solution pH were studied by light scattering and fluorescence spectroscopy experiments. The novel triblock terpolymers self-assemble into nanosized aggregates upon solution temperature rise above the nominal lower critical solution temperature (LCST) of the temperature-responsive PNIPAM block. The remarkable stimuli-responsive self-assembly behavior of the novel triblock terpolymers in aqueous media make them interesting candidates for biomedical applications in the fields of drug and gene delivery.


RSC Advances ◽  
2017 ◽  
Vol 7 (39) ◽  
pp. 24522-24536 ◽  
Author(s):  
N. S. Serkhacheva ◽  
O. I. Smirnov ◽  
A. V. Tolkachev ◽  
N. I. Prokopov ◽  
A. V. Plutalova ◽  
...  

Hydrophilic and amphiphilic polymeric trithiocarbonates based on polyacrylic acid are able to provide polymerization-induced self-assembly in copolymerization of butyl and fluoroalkyl acrylates.


2015 ◽  
Vol 36 (15) ◽  
pp. 1402-1408 ◽  
Author(s):  
Rui Qi ◽  
Yong Jin ◽  
Xinfeng Cheng ◽  
Baozhu Fan ◽  
Tongbing Sun ◽  
...  

2015 ◽  
Vol 7 (6) ◽  
pp. 2738-2746 ◽  
Author(s):  
Zhao Wang ◽  
Zhongkui Yang ◽  
Tao Gao ◽  
Jingwen He ◽  
Laijiang Gong ◽  
...  

An amphiphilic block copolymer-based colorimetric and fluorescent chemosensor for Hg2+was prepared, which was synthesized by sequential RAFT polymerization of NIPAM and R6GDM (a novel Hg2+-sensitive rhodamine monomer).


RSC Advances ◽  
2015 ◽  
Vol 5 (80) ◽  
pp. 65583-65590 ◽  
Author(s):  
Huiyong Wang ◽  
Bo Tan ◽  
Hucheng Zhang ◽  
Jianji Wang

The pH responsive fluids consisting of single-chain ionic liquid surfactants [Cnmim]Br (n = 12, 14) and hydrotropes can reversibly transform from spherical micelles to vesicles then to spherical micelles again with the change of the solution pH value.


2019 ◽  
Author(s):  
Xin Wu ◽  
Patrick Wang ◽  
Peter Turner ◽  
William Lewis ◽  
Osman Catal ◽  
...  

<p>Artificial receptors that recognise anionic species <i>via</i>noncovalent interactions have a wide range of biomedical, industrial and environmental applications. A major challenge in this area of research is to achieve high affinity and selective anion binding in aqueous media. So far, only a few examples of receptors capable of strong (> 10<sup>5</sup>M<sup>-1</sup>) anion binding in solutions containing > 50% water are available and none show selectivity for chloride. We report here the discovery of a <i>D</i><sub>4h</sub>-symmetric fluorinated tetraurea macrocycle that fulfils this function owing to its unique self-assembly properties. The macrocycle has a strong tendency to self-associate into columnar aggregates <i>via</i>intermolecular hydrogen bonds and aromatic stacking. In aqueous solutions, macrocycle aggregation generates hydrophobic and size-selective binding pockets favourable for hydrogen bonding with chloride. As a result, micromolar affinity and highly selective chloride binding has been achieved with this simple small molecule (MW < 700) in <a>60 vol% water/</a>acetonitrile.</p>


Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1698
Author(s):  
Athanasios Skandalis ◽  
Theodore Sentoukas ◽  
Despoina Giaouzi ◽  
Martha Kafetzi ◽  
Stergios Pispas

This review article aims to cover the most recent advances regarding the synthesis of linear ABC-type triblock terpolymers and star-shaped polymers by RAFT polymerization, as well as their self-assembly properties in aqueous solutions. RAFT polymerization has received extensive attention, as it is a versatile technique, compatible with a great variety of functional monomers and reaction conditions, while providing exceptional and precise control over the final structure, with well-defined side-groups and post-polymerization engineering potential. Linear triblock terpolymers synthesis can lead to very interesting novel ideas, since there are countless combinations of stimuli/non-stimuli and hydrophilic/hydrophobic monomers that someone can use. One of their most interesting features is their ubiquitous ability to self-assemble in different nanostructures depending on their degree of polymerization (DP), block composition, solubilization protocol, internal and external stimuli. On the other hand, star-shaped polymers exhibit a more stable nanostructure, with a distinct crosslinked core and arm blocks that can also incorporate stimuli-responsive blocks for “smart” applications.


2017 ◽  
Vol 8 (46) ◽  
pp. 7217-7228 ◽  
Author(s):  
Povilas Radzevicius ◽  
Medeina Steponaviciute ◽  
Tatjana Krivorotova ◽  
Ricardas Makuska

Pentablock copolymers synthesized by one-pot successive RAFT polymerization are double thermoresponsive and exhibit block sequence dependent aggregation in aqueous solutions.


2018 ◽  
Author(s):  
Xin Wu ◽  
Patrick Wang ◽  
Peter Turner ◽  
William Lewis ◽  
Osman Catal ◽  
...  

<p>Artificial receptors that recognise anionic species via noncovalent</p> <p>interactions have a wide range of biomedical, industrial and environmental applications. A major challenge in this area of research is to achieve high affinity and selective anion binding in aqueous media. So far, only a few rare examples of receptors capable of strong (>105 M-1) anion binding in solutions containing > 50% water are available and none show selectivity for the highly biologically relevant anion chloride. We report here the discovery of a D4-symmetric fluorinated tetraurea macrocycle that fulfils this function owing to its unique self-assembly properties. The</p> <p>macrocycle has a strong tendency to self-associate into columnar aggregates via intermolecular hydrogen bonds and aromatic stacking interactions. In aqueous solutions, macrocycle aggregation generates size-selective and hydrophobic binding</p> <p>pockets favourable for interactions with chloride via urea hydrogen bond donors. As a result, micromolar affinity and highly selective chloride binding has been achieved with this simple small molecule (MV < 700) in 60 vol% water/acetonitrile.</p>


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