Mechanistic investigations of confinement effects on the self-assembly of symmetric amphiphilic copolymers in thin films

2017 ◽  
Vol 19 (33) ◽  
pp. 21938-21945 ◽  
Author(s):  
Dan Mu ◽  
Jian-Quan Li ◽  
Sheng-Yu Feng
Keyword(s):  
Molecular Structure ◽  
Thin Film ◽  
Thin Films ◽  
Self Assembly ◽  
Lamellar Structure ◽  
The Self ◽  
Amphiphilic Copolymers ◽  
Confinement Effects ◽  
Micellar Structure ◽  
Cylindrical Structure

The self-assembly of a copolymer thin film, whose molecular structure is composed of one hydrophobic branch (denoted in green) and two hydrophilic branches (denoted in red), gives (a) cylindrical structure, (b) micellar structure, and (c) lamellar structure.

scholarly journals Synthesis, thin-film self-assembly, and pyrolysis of ruthenium-containing polyferrocenylsilane block copolymers

2018 ◽  
Vol 9 (21) ◽  
pp. 2951-2963 ◽  
Author(s):  
Huda Nasser Al-Kharusi ◽  
Lipeng Wu ◽  
George Whittell ◽  
Robert Harniman ◽  
Ian Manners
Keyword(s):  
Thin Film ◽  
Thin Films ◽  
Block Copolymers ◽  
Self Assembly ◽  
The Self ◽  
Cylindrical Domains ◽  
Catalytic Applications

The self-assembly of a ruthenium-containing polyferrocenylsilane in bulk and thin films yielded spherical or cylindrical domains in a PS matrix; pyrolysis provided a route to bimetallic Fe/Ru NPs for potential catalytic applications.

scholarly journals Solvent Effect on the Self-Assembly of a Thin Film Consisting of Y-Shaped Copolymer

Polymers ◽  
2019 ◽  
Vol 11 (2) ◽  
pp. 261
Author(s):  
Dan Mu ◽  
Jian-Quan Li ◽  
Xing-Shun Cong ◽  
Yu-Wei Mi ◽  
Han Zhang
Keyword(s):  
Thin Film ◽  
Solvent Effect ◽  
Self Assembly ◽  
The Self ◽  
Binary Solvents ◽  
Binary Solvent ◽  
Micellar Structure ◽  
Hydrophilic Solvent ◽  
Average Size ◽  
Hydrophobic Solvent

The self-assembly of an amphiphilic Y-shaped copolymer consisting of two hydrophilic branches and one hydrophobic branch in a thin film is investigated under different conditions by virtue of mesoscopic computer modelling, accompanied by doping with a single solvent, doping with a binary solvent, and those solvent environments together with the introduction of confinement defined by various acting distances and influencing regions. A cylindrical micellar structure is maintained, as it is in the thin film with the doping of either 10% hydrophobic solvent or 10% hydrophilic solvent, whose structure consists of the hydrophobic core and hydrophilic shell. Attributed to the hydrophobicity/hydrophilia nature of the solvents, different solvents play an obvious role on the self-assembled structure, i.e., the hydrophobic solvent presents as a swelling effect, conversely, the hydrophilic solvent presents as a shrinking effect. Further, the synergistic effect of the binary solvents on the self-assembly produces the lowest values in both the average volumetric size and free energy density when the quantity of hydrophobic solvent and hydrophilic solvent is equivalent. Interestingly, the solvent effect becomes more pronounced under the existent of a confinement. When a lateral-oriented confinement is introduced, a periodically fluctuating change in the cylindrical size occurs in two near-wall regions, but the further addition of either hydrophobic or hydrophilic solvent can effectively eliminate such resulting hierarchical-sized cylinders and generate uniform small-sized cylinders. However, with the introduction of a horizontal-orientated confinement, the copolymers self-assemble into the spherical micellar structure. Moreover, the further addition of hydrophobic solvent leads to a decrease in the average size of micelles via coalescence mechanism, in contrast, the further addition of hydrophilic solvent causes an increase in the average size of micelles via splitting mechanism. These findings enrich our knowledge of the potential for the solvent effect on the self-assembly of amphiphilic copolymer system, and then provide theoretical supports on improving and regulating the mesoscopic structure of nanomaterials.

scholarly journals Homochiral Supramolecular Thin Film from Self-Assembly of Achiral Triarylamine Molecules by Circularly Polarized Light

Molecules ◽  
2020 ◽  
Vol 25 (2) ◽  
pp. 402
Author(s):  
Changjun Park ◽  
Jinhee Lee ◽  
Taehyoung Kim ◽  
Jaechang Lim ◽  
Jeyoung Park ◽  
...  
Keyword(s):  
Thin Film ◽  
Thin Films ◽  
Self Assembly ◽  
Polarized Light ◽  
Building Blocks ◽  
The Self ◽  
Assembly Process ◽  
Circularly Polarized Light ◽  
Circularly Polarized ◽  
Self Assembled

Here, we report the formation of homochiral supramolecular thin film from achiral molecules, by using circularly polarized light (CPL) only as a chiral source, on the condition that irradiation of CPL does not induce a photochemical change of the achiral molecules. Thin films of self-assembled structures consisting of chiral supramolecular fibrils was obtained from the triarylamine derivatives through evaporation of the self-assembled triarylamine solution. The homochiral supramolecular helices with the desired handedness was achieved by irradiation of circularly polarized visible light during the self-assembly process, and the chiral stability of supramolecular self-assembled product was achieved by photopolymerization of the diacetylene moieties at side chains of the building blocks, with irradiation of circularly polarized ultraviolet light. This work provides a novel methodology for the generation of homochiral supramolecular thin film from the corresponding achiral molecules.

Bottom-up Evolution from Disks to High-Genus Polymersomes

2018 ◽  
Author(s):  
Claudia Contini ◽  
Russell Pearson ◽  
Linge Wang ◽  
Lea Messager ◽  
Jens Gaitzsch ◽  
...  
Keyword(s):  
Self Assembly ◽  
The Self ◽  
Amphiphilic Copolymers ◽  
Chain Entanglement ◽  
Bottom Up ◽  
New Approach ◽  
High Genus ◽  
Transmission Electron ◽  
Minimal Radius ◽  
Stop Flow

<div><div><div><p>We report the design of polymersomes using a bottom-up approach where the self-assembly of amphiphilic copolymers poly(2-(methacryloyloxy) ethyl phosphorylcholine)–poly(2-(diisopropylamino) ethyl methacrylate) (PMPC-PDPA) into membranes is tuned using pH and temperature. We study this process in detail using transmission electron microscopy (TEM), nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and stop-flow ab- sorbance disclosing the molecular and supramolecular anatomy of each structure observed. We report a clear evolution from disk micelles to vesicle to high-genus vesicles where each passage is controlled by pH switch or temperature. We show that the process can be rationalised adapting membrane physics theories disclosing important scaling principles that allow the estimation of the vesiculation minimal radius as well as chain entanglement and coupling. This allows us to propose a new approach to generate nanoscale vesicles with genus from 0 to 70 which have been very elusive and difficult to control so far.</p></div></div></div>

Bottom-up Evolution from Disks to High-Genus Polymersomes

2018 ◽  
Author(s):  
Claudia Contini ◽  
Russell Pearson ◽  
Linge Wang ◽  
Lea Messager ◽  
Jens Gaitzsch ◽  
...  
Keyword(s):  
Self Assembly ◽  
The Self ◽  
Amphiphilic Copolymers ◽  
Chain Entanglement ◽  
Bottom Up ◽  
New Approach ◽  
High Genus ◽  
Transmission Electron ◽  
Minimal Radius ◽  
Stop Flow

<div><div><div><p>We report the design of polymersomes using a bottom-up approach where the self-assembly of amphiphilic copolymers poly(2-(methacryloyloxy) ethyl phosphorylcholine)–poly(2-(diisopropylamino) ethyl methacrylate) (PMPC-PDPA) into membranes is tuned using pH and temperature. We study this process in detail using transmission electron microscopy (TEM), nuclear magnetic resonance (NMR) spectroscopy, dynamic light scattering (DLS), and stop-flow ab- sorbance disclosing the molecular and supramolecular anatomy of each structure observed. We report a clear evolution from disk micelles to vesicle to high-genus vesicles where each passage is controlled by pH switch or temperature. We show that the process can be rationalised adapting membrane physics theories disclosing important scaling principles that allow the estimation of the vesiculation minimal radius as well as chain entanglement and coupling. This allows us to propose a new approach to generate nanoscale vesicles with genus from 0 to 70 which have been very elusive and difficult to control so far.</p></div></div></div>

scholarly journals Carbon Nano-Onions Reinforced Multilayered Thin Film System for Stimuli-Responsive Drug Release

Pharmaceutics ◽  
2020 ◽  
Vol 12 (12) ◽  
pp. 1208
Author(s):  
Narsimha Mamidi ◽  
Ramiro Velasco Delgadillo ◽  
Aldo Gonzáles Ortiz ◽  
Enrique Barrera
Keyword(s):  
Thin Film ◽  
Thin Films ◽  
Drug Release ◽  
Self Assembly ◽  
Critical Role ◽  
Layer By Layer ◽  
Film System ◽  
Stimuli Responsive ◽  
Ph Responsive ◽  
Thin Film System

Herein, poly (N-(4-aminophenyl) methacrylamide))-carbon nano-onions (PAPMA-CNOs = f-CNOs) and anilinated-poly (ether ether ketone) (AN-PEEK) have synthesized, and AN-PEEK/f-CNOs composite thin films were primed via layer-by-layer (LbL) self-assembly for stimuli-responsive drug release. The obtained thin films exhibited pH-responsive drug release in a controlled manner; pH 4.5 = 99.2% and pH 6.5 = 59.3% of doxorubicin (DOX) release was observed over 15 days. Supramolecular π-π stacking interactions between f-CNOs and DOX played a critical role in controlling drug release from thin films. Cell viability was studied with human osteoblast cells and augmented viability was perceived. Moreover, the thin films presented 891.4 ± 8.2 MPa of the tensile strength (σult), 43.2 ± 1.1 GPa of Young’s modulus (E), and 164.5 ± 1.7 Jg−1 of toughness (K). Quantitative scrutiny revealed that the well-ordered aligned nanofibers provide critical interphase, and this could be responsible for augmented tensile properties. Nonetheless, a pH-responsive and mechanically robust biocompatible thin-film system may show potential applications in the biomedical field.

scholarly journals Self-assembly of amphiphilic copolymers containing polysaccharide: PISA versus nanoprecipitation, and the temperature effect

2020 ◽  
Vol 11 (29) ◽  
pp. 4729-4740 ◽  
Author(s):  
Djallal Ikkene ◽  
Ana Andreea Arteni ◽  
Malika Ouldali ◽  
Jean-Luc Six ◽  
Khalid Ferji
Keyword(s):  
Temperature Effect ◽  
Self Assembly ◽  
The Self ◽  
Amphiphilic Copolymers ◽  
Considerable Impact

The self-assembly methods and the temperature have a considerable impact on the morphology of the resulting nanoobjects in the case of amphiphilic glycopolymers.

Mechanism of Surfactant Removal from Ordered Nanocomposite Silica Thin Films by Deep-UV Light Exposure

2003 ◽  
Vol 788 ◽  
Author(s):  
Andrew M. Dattelbaum ◽  
Meri L. Amweg ◽  
Julia D. Ruiz ◽  
Laurel E. Ecke ◽  
Andrew P. Shreve ◽  
...  
Keyword(s):  
Thin Film ◽  
Thin Films ◽  
Self Assembly ◽  
Uv Light ◽  
Light Exposure ◽  
Complete Removal ◽  
Combined Application ◽  
Silica Thin Films ◽  
Deep Uv ◽  
Surfactant Removal

ABSTRACTIn recent years, methods have been developed for the generation of complex ordered nanocomposite materials through organic templating of inorganic structures. One approach involves preparation of composite materials by an evaporation induced self-assembly process involving organization of organic surfactants and formation of inorganic silica from soluble precursors. Recently, we have shown that deep-UV light (185–254nm) is efficient at removing the surfactant microphase for a routine production of well-ordered mesoporous silica thin films. Here we probe the evolution of surfactant removal from nanocomposite thin film silica mesophases as a function of deep-UV exposure using a combined application of FTIR and single wavelength ellipsometry. Taken together, these data indicate that surfactant removal occurs in a step-wise fashion with the formation of oxidized intermediates prior to complete removal of the surfactant from the thin film.

Polymeric Janus nanoparticles templated by block copolymer thin films

RSC Advances ◽  
2015 ◽  
Vol 5 (55) ◽  
pp. 44218-44221 ◽  
Author(s):  
Elio Poggi ◽  
Jean-Pierre Bourgeois ◽  
Bruno Ernould ◽  
Jean-François Gohy
Keyword(s):  
Thin Films ◽  
Surface Modification ◽  
Block Copolymer ◽  
Block Copolymers ◽  
Self Assembly ◽  
The Self ◽  
Polymer Grafting ◽  
Novel Approach ◽  
Janus Nanoparticles

We report a novel approach to synthesize well-defined polymeric Janus nanoparticles by combining the self-assembly of block copolymers in thin films and surface modification by polymer grafting.

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