scholarly journals Phase Diagram for Ideal Diblock-Copolymer Micelles Compared to Polymerization-Induced Self Assembly

Polymers ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 2599
Author(s):  
Alexey A. Gavrilov ◽  
Ruslan M. Shupanov ◽  
Alexander V. Chertovich
Keyword(s):  
Phase Diagram ◽  
Transition Region ◽  
Diblock Copolymer ◽  
Self Assembly ◽  
Diblock Copolymers ◽  
Dynamic Equilibrium ◽  
Polymer Concentration ◽  
Quantitative Agreement ◽  
Wide Range ◽  
Polymer Volume

In this work we constructed a detailed phase diagram for the solutions of ideal diblock-copolymers and compared such diagram with that obtained during polymerization-induced self-assembly (PISA); a wide range of polymer concentrations as well as chain compositions was studied. As the length of the solvophobic block nB increases (the length of the solvophilic block nA was fixed), the transition from spherical micelles to cylinders and further to vesicles (lamellae) occurs. We observed a rather wide transition region between the spherical and cylindrical morphology in which the system contains a mixture of spheres and short cylinders, which appear to be in dynamic equilibrium; the transition between the cylinders and vesicles was found to be rather sharp. Next, upon increasing the polymer concentration in the system, the transition region between the spheres and cylinders shifts towards lower nB/nA values; a similar shift but with less magnitude was observed for the transition between the cylinders and vesicles. Such behavior was attributed to the increased number of contacts between the micelles at higher polymer volume concentrations. We also found that the width of the stability region of the cylindrical micelles for small polymer volume concentrations is in good quantitative agreement with the predictions of analytical theory. The obtained phase diagram for PISA was similar to the case of presynthesized diblock copolymer; however, the positions of the transition lines for PISA are slightly shifted towards higher nB/nA values in comparison to the presynthesized diblock copolymers, which is more pronounced for the case of the cylinders-to-vesicles transition. We believe that the reason for such behavior is the polydispersity of the core-forming blocks: The presence of the short and long blocks being located at the micelle interface and in its center, respectively, helps to reduce the entropy losses due to the insoluble block stretching, which leads to the increased stability of more curved micelles.

Self-assembly of linear diblock copolymers in selective solvents: from single micelles to particles with tri-continuous inner structures

Soft Matter ◽  
2020 ◽  
Vol 16 (26) ◽  
pp. 6056-6062 ◽  
Author(s):  
Xianggui Ye ◽  
Bamin Khomami
Keyword(s):  
Diblock Copolymer ◽  
Self Assembly ◽  
Large Scale ◽  
Diblock Copolymers ◽  
Dissipative Particle Dynamics ◽  
Particle Dynamics ◽  
The Self ◽  
Selective Solvent ◽  
Selective Solvents

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.

Simulation study on the assembly of rod-coil diblock copolymers within coil-selective nanoslits

e-Polymers ◽  
2016 ◽  
Vol 16 (4) ◽  
pp. 343-349 ◽  
Author(s):  
Ya-Juan Su ◽  
Ze-Xin Ma ◽  
Jian-Hua Huang
Keyword(s):  
Phase Diagram ◽  
Self Assembly ◽  
Diblock Copolymers ◽  
Dissipative Particle Dynamics ◽  
Orientational Order ◽  
Particle Dynamics ◽  
The Self ◽  
Ordered Structures ◽  
Assembly Structure ◽  
Dynamics Simulations

AbstractDissipative particle dynamics simulations are performed to study the self-assembly of rod-coil (RC) diblock copolymers confined in a slit with two coil-selective surfaces. The effect of rod length and slit thickness on the assembly structure is investigated. A morphological phase diagram as a function of slit thickness and rod length is presented. We observe several ordered structures, such as perpendicular cylinders, parallel cylinders, and puck-shaped structure. In the assembly structures, long-range rod-rod orientational order is observed when the rod length exceeds a critical rod length. Our results show that the coil-selective slit influences the assembly structure as well as the rod orientation of RC diblock copolymers.

Prediction of solvent-induced morphological changes of polyelectrolyte diblock copolymer micelles

Soft Matter ◽  
2015 ◽  
Vol 11 (42) ◽  
pp. 8236-8245 ◽  
Author(s):  
Nan K. Li ◽  
William H. Fuss ◽  
Lei Tang ◽  
Renpeng Gu ◽  
Ashutosh Chilkoti ◽  
...  
Keyword(s):  
Phase Diagram ◽  
Aqueous Solution ◽  
Diblock Copolymer ◽  
Diblock Copolymers ◽  
Morphological Changes ◽  
Copolymer Micelles

A comprehensive set of data is obtained with the utilization of ISIS DPD model to construct the phase diagram of amphiphilic polyelectrolyte diblock copolymers in aqueous solution.

MONTE CARLO SIMULATION OF SELF-ASSEMBLED AMPHIPHILIC DIBLOCK COPOLYMER IN SOLUTION

2003 ◽  
Vol 17 (01n02) ◽  
pp. 241-244 ◽  
Author(s):  
PINGCHUAN SUN ◽  
YUHUA YIN ◽  
BAOHUI LI ◽  
QINGHUA JIN ◽  
DATONG DING
Keyword(s):  
Monte Carlo Simulation ◽  
Monte Carlo ◽  
Diblock Copolymer ◽  
Self Assembly ◽  
Diblock Copolymers ◽  
The Self ◽  
Amphiphilic Diblock Copolymer ◽  
The Core ◽  
Spherical Micelles ◽  
The Given

In this paper, Monte Carlo method is applied to simulate the process of the self-assembly of amphiphilic diblock copolymer with a series of block lengths of the insoluble and soluble blocks. Under the given simulation conditions, the diblock copolymers form spherical micelles in solution. The dependence of the core radii of spherical micelles on both block lengths is obtained and compared with experimental results of Eisenberg and coworkers.

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
Keyword(s):  
Mechanical Properties ◽  
Diblock Copolymer ◽  
Self Assembly ◽  
Micellar Solution ◽  
Diblock Copolymers ◽  
Solution Temperature ◽  
Selective Solvent ◽  
Critical Solution Temperature ◽  
Terpyridine Ligands ◽  
Amphiphilic Diblock Copolymers

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.

Morphology Transition of Diblock Copolymer with Nanoparticles Confined in Cylindrical Nanopores

2013 ◽  
Vol 275-277 ◽  
pp. 1781-1784 ◽  
Author(s):  
Ying Yu ◽  
Yu Xin Zuo ◽  
Zhao Zhang ◽  
Chun Cheng Zuo
Keyword(s):  
Phase Diagram ◽  
Self Assembly ◽  
Diblock Copolymers ◽  
Coarse Grained ◽  
Morphology Transition ◽  
Polymer Interactions ◽  
Simulation Results ◽  
Assembly Behavior ◽  
Dynamics Simulations ◽  
Polymer Interaction

Coarse-grained molecular dynamics simulations on self-assembly behavior of diblock copolymers (DCP) with nanoparticles confined in cylindrical nanopores are perfomed to study the morphology transition of DCP affected by the confined ratio of the cylindrical confinement diameter to the block copolymer domain spacing, the wall-polymer interactions, the particle-polymer interaction potential and the component concentration. The simulation results show that nanoparticles have a pronounced effect on the morphology transition of DCP and can therefore be considered as an important aspect in controlling the confined self-assembly in cylindrical confinement. Besides, the phase diagram indicates the process of morphology transition.

Cyclic azobenzene-containing amphiphilic diblock copolymers: solution self-assembly and unusual photo-responsive behaviors

2015 ◽  
Vol 6 (16) ◽  
pp. 3009-3013 ◽  
Author(s):  
Beibei Chen ◽  
Zhao Wang ◽  
Jinjie Lu ◽  
Xian Yang ◽  
Yong Wang ◽  
...  
Keyword(s):  
Diblock Copolymer ◽  
Self Assembly ◽  
Diblock Copolymers ◽  
Amphiphilic Diblock Copolymer ◽  
Spherical Micelles ◽  
Self Assembled ◽  
Amphiphilic Diblock Copolymers

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

scholarly journals Segregation of Maghemite Nanoparticles within Symmetric Diblock Copolymer and Triblock Terpolymer Patterns under Solvent Vapor Annealing

Materials ◽  
2020 ◽  
Vol 13 (6) ◽  
pp. 1286
Author(s):  
George Zapsas ◽  
Dimitrios Moschovas ◽  
Konstantinos Ntetsikas ◽  
Andreas Karydis-Messinis ◽  
Nikolaos Chalmpes ◽  
...  
Keyword(s):  
Thin Films ◽  
Diblock Copolymer ◽  
Self Assembly ◽  
Diblock Copolymers ◽  
Maghemite Nanoparticles ◽  
Solvent Vapor ◽  
Vapor Annealing ◽  
The Matrix ◽  
Solvent Vapor Annealing ◽  
Selective Placement

Block copolymers (BCPs), through their self-assembly, provide an excellent guiding platform for precise controlled localization of maghemite nanoparticles (MNPs). Diblock copolymers (di/BCP) represent the most applied matrix to host filler components due to their morphological simplicity. A series of nanocomposites based on diblock copolymer or triblock terpolymer matrices and magnetic nanoparticles were prepared to study and compare the influence of an additional block into the BCP matrix. MNPs were grafted with low molecular weight polystyrene (PS) chains in order to be segregated in a specific phase of the matrix to induce selective localization. After the mixing of the BCPs with 10% w/v PS-g-MNPs, nanocomposite thin films were formed by spin coating. Solvent vapor annealing (SVA) enabled the PS-g-MNPs selective placement within the PS domains of the BCPs, as revealed by atomic force microscopy (AFM). The recorded images have proven that high amounts of functionalized MNPs can be controllably localized within the same block (PS), despite the architecture of the BCPs (AB vs. ABC). The adopted lamellar structure of the “neat” BCP thin films was maintained for MNPs loading approximately up to 10% w/v, while, for higher content, the BCP adopted lamellar morphology is partially disrupted, or even disappears for both AB and ABC architectures.

scholarly journals Synthesis and Characterization of Temperature-Responsive N-Cyanomethylacrylamide-Containing Diblock Copolymer Assemblies in Water

Polymers ◽  
2021 ◽  
Vol 13 (24) ◽  
pp. 4424
Author(s):  
Nicolas Audureau ◽  
Fanny Coumes ◽  
Clémence Veith ◽  
Clément Guibert ◽  
Jean-Michel Guigner ◽  
...  
Keyword(s):  
Diblock Copolymer ◽  
Self Assembly ◽  
Diblock Copolymers ◽  
Colloidal Stability ◽  
Aqueous Dispersion ◽  
Degree Of Polymerization ◽  
Solution Temperature ◽  
Thermoresponsive Polymers ◽  
Aqueous Synthesis ◽  
Reversible Addition

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.

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