scholarly journals Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs

2020 ◽  
Vol 117 (50) ◽  
pp. 31639-31647
Author(s):  
Jing Sun ◽  
Zhiwei Wang ◽  
Chenhui Zhu ◽  
Meiyao Wang ◽  
Zhekun Shi ◽  
...  
Keyword(s):  
Diblock Copolymer ◽  
Self Assembly ◽  
Elevated Temperatures ◽  
Protein Crystallization ◽  
Supramolecular Assembly ◽  
Molecular Packing ◽  
One Pot ◽  
Precise Control ◽  
Assembly Mechanism ◽  
Copolymer Poly

Hierarchical nanomaterials have received increasing interest for many applications. Here, we report a facile programmable strategy based on an embedded segmental crystallinity design to prepare unprecedented supramolecular planar nanobrush-like structures composed of two distinct molecular packing motifs, by the self-assembly of one particular diblock copolymer poly(ethylene glycol)-block-poly(N-octylglycine) in a one-pot preparation. We demonstrate that the superstructures result from the temperature-controlled hierarchical self-assembly of preformed spherical micelles by optimizing the crystallization−solvophobicity balance. Particularly remarkable is that these micelles first assemble into linear arrays at elevated temperatures, which, upon cooling, subsequently template further lateral, crystallization-driven assembly in a living manner. Addition of the diblock copolymer chains to the growing nanostructure occurs via a loosely organized micellar intermediate state, which undergoes an unfolding transition to the final crystalline state in the nanobrush. This assembly mechanism is distinct from previous crystallization-driven approaches which occur via unimer addition, and is more akin to protein crystallization. Interestingly, nanobrush formation is conserved over a variety of preparation pathways. The precise control ability over the superstructure, combined with the excellent biocompatibility of polypeptoids, offers great potential for nanomaterials inaccessible previously for a broad range of advanced applications.

Synthesis of poly(methyl methacrylate)-b-poly(acrylic acid) by DPE method

e-Polymers ◽  
2008 ◽  
Vol 8 (1) ◽  
Author(s):  
Dong Chen ◽  
Ruixue Liu ◽  
Zhifeng Fu ◽  
Yan Shi
Keyword(s):  
Molecular Weight ◽  
Acrylic Acid ◽  
Methyl Methacrylate ◽  
Diblock Copolymer ◽  
Self Assembly ◽  
Gel Permeation Chromatography ◽  
Amphiphilic Diblock Copolymer ◽  
Poly Methyl Methacrylate ◽  
Copolymer Poly ◽  
Poly Acrylic Acid

AbstractAmphiphilic diblock copolymer poly(methyl methacrylate)-b-poly(acrylic acid) (PMMA-b-PAA) was prepared by 1,1-diphenylethene (DPE) method. Firstly, free radical polymerization of methyl methacrylate was carried out with AIBN as initiator in the presence of DPE, giving a DPE-containing PMMA precursor with controlled molecular weight. tert-Butyl acrylate (tBA) was then polymerized in the presence of the PMMA precursor, and PMMA-b-PtBA diblock copolymer with controlled molecular weight was prepared. Finally, amphiphilic diblock copolymer PMMA-b-PAA was obtained by hydrolysis of PMMA-b-PtBA. The formation of PMMA-b-PAA was confirmed by 1H NMR spectrum and gel permeation chromatography. Transmission electron microscopy and dynamic light scattering were used to detect the self-assembly behavior of the amphiphilic diblock polymers in methanol.

Nanoparticles as template for porphyrin nanostructure growth

2019 ◽  
Vol 23 (04n05) ◽  
pp. 526-533 ◽  
Author(s):  
Mariana Hamer ◽  
Rolando M. Caraballo ◽  
Peter J. Eaton ◽  
Craig Medforth
Keyword(s):  
Self Assembly ◽  
Soret Band ◽  
Surface Interactions ◽  
Water Soluble ◽  
The Self ◽  
Stacking Interactions ◽  
Aromatic System ◽  
One Pot ◽  
Assembly Mechanism ◽  
Scattering Measurements

Porphyrins and metalloporphyrins are one of the most widely studied platforms for the construction of supramolecular structures. These compounds have an extended aromatic system that allows [Formula: see text]–[Formula: see text] stacking interactions which, together with hydrogen bonds, electrostatic forces and the formation of inter-metallic complexes arising from peripheral groups, offer a versatile platform to control the self-assembly mechanism. In this work, we present the study of nanostructures formed by self-assembly of the water-soluble porphyrins meso-tetra([Formula: see text]-methyl-4-pyridyl)porphyrin (TMPyP) and meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) in the presence of hard nanotemplates. Different nanoparticles (silica, gold, and polystyrene), concentrations and synthetic procedures were explored. The obtained materials were characterized by SEM and AFM microscopies, UV-vis absorption spectroscopy and dynamic light scattering measurements. A clear modification of the SiO2 NP surface roughness using one-pot synthesis was observed. The results were variable depending on the porphyrin–surface interactions and concentrations used. At lower porphyrin concentrations, a shift of the Soret band was observed, while at higher concentrations, free NS were formed. This reflects a competition between surface and solution directed self-assembly.

A biocompatible cobaltporphyrin-based complex micelle constructed via supramolecular assembly for oxygen transfer

2016 ◽  
Vol 4 (5) ◽  
pp. 857-862 ◽  
Author(s):  
Liangliang Shen ◽  
Rui Qu ◽  
Hejin Shi ◽  
Fan Huang ◽  
Yingli An ◽  
...  
Keyword(s):  
Ethylene Glycol ◽  
Diblock Copolymer ◽  
Oxygen Transfer ◽  
Supramolecular Assembly ◽  
Poly Ethylene Glycol ◽  
Hierarchical Assembly ◽  
Poly Ethylene ◽  
Copolymer Poly

Herein, a complex micelle as an oxygen nano-carrier is constructed through the hierarchical assembly of the diblock copolymer poly(ethylene glycol)-block-poly(l-lysine) (PEG-b-PLys), tetrakis(4-sulfonatophenyl)porphinato cobalt(ii) (Co(ii)TPPS), a heptapeptide (Cys-His-His-His-His-His-His) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TM-β-CD).

Supramolecular assembly in metal complexes: Two structural cases

2013 ◽  
Vol 85 (2) ◽  
pp. 397-404 ◽  
Author(s):  
Mohamed Ghazzali
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Theoretical Calculations ◽  
Supramolecular Assembly ◽  
Halogen Bonding ◽  
One Pot ◽  
Iron Coordination ◽  
Structural Database ◽  
Molecular Components ◽  
Theoretical Analyses

With the current advances in our understanding of molecular components in the solid-state world, the relation between energy and geometry remains controversial. In this study, we deliver a concise account for supramolecular chemistry, and in order to illustrate some of its concepts we describe some structural and theoretical analyses for two unique cases of our work. We elaborate on a supramolecular model of controlled “one-pot” host–guest metal-mediated self-assembly reaction inside iron coordination polymer grid architecture, and we review halogen bonding by specifically observing M–Cl···Cl–M intermolecular interactions using Cambridge Structural Database (CSD) hit analyses with theoretical calculations.

scholarly journals Synthesis and Self-Assembly of Multistimulus-Responsive Azobenzene-Containing Diblock Copolymer through RAFT Polymerization

Polymers ◽  
2019 ◽  
Vol 11 (12) ◽  
pp. 2028
Author(s):  
Po-Chih Yang ◽  
Yueh-Han Chien ◽  
Shih-Hsuan Tseng ◽  
Chia-Chung Lin ◽  
Kai-Yu Huang
Keyword(s):  
Uv Irradiation ◽  
Diblock Copolymer ◽  
Self Assembly ◽  
Raft Polymerization ◽  
Solution Temperature ◽  
Micellar Aggregates ◽  
Before And After ◽  
Assembly Behavior ◽  
Copolymer Poly ◽  
Polymer Aqueous Solution

This paper gathered studies on multistimulus-responsive sensing and self-assembly behavior of a novel amphiphilic diblock copolymer through a two-step reverse addition-fragmentation transfer (RAFT) polymerization technique. N-Isopropylacrylamide (NIPAM) macromolecular chain transfer agent and diblock copolymer (poly(NIPAM-b-Azo)) were discovered to have moderate thermal decomposition temperatures of 351.8 and 370.8 °C, respectively, indicating that their thermal stability was enhanced because of the azobenzene segments incorporated into the block copolymer. The diblock copolymer was determined to exhibit a lower critical solution temperature of 34.4 °C. Poly(NIPAM-b-Azo) demonstrated a higher photoisomerization rate constant (kt = 0.1295 s−1) than the Azo monomer did (kt = 0.088 s−1). When ultraviolet (UV) irradiation was applied, the intensity of fluorescence gradually increased, suggesting that UV irradiation enhanced the fluorescence of self-assembled cis-isomers of azobenzene. Morphological aggregates before and after UV irradiation are shown in scanning electron microscopy (SEM) and dynamic light scattering (DLS) analyses of the diblock copolymer. We employed photoluminescence titrations to reveal that the diblock copolymer was highly sensitive toward Ru3+ and Ba2+, as was indicated by the crown ether acting as a recognition moiety between azobenzene units. Micellar aggregates were formed in the polymer aqueous solution through dissolution; their mean diameters were approximately 205.8 and 364.6 nm at temperatures of 25.0 and 40.0 °C, respectively. Our findings contribute to research on photoresponsive and chemosensory polymer material developments.

scholarly journals Industrially-relevant polymerization-induced self-assembly formulations in non-polar solvents: RAFT dispersion polymerization of benzyl methacrylate

2015 ◽  
Vol 6 (16) ◽  
pp. 3054-3062 ◽  
Author(s):  
Matthew J. Derry ◽  
Lee A. Fielding ◽  
Steven P. Armes
Keyword(s):  
Diblock Copolymer ◽  
Self Assembly ◽  
Dispersion Polymerization ◽  
Mineral Oil ◽  
Polar Solvents ◽  
One Pot

Diblock copolymer spheres, worms and vesicles are prepared via RAFT dispersion polymerization of benzyl methacrylate in either mineral oil or a poly(α-olefin) using polymerization-induced self-assembly; an efficient ‘one-pot’ protocol is reported for spheres at 30% solids in mineral oil.

scholarly journals Structural and Nanotribological Properties of a BODIPY Self-Assembly

2021 ◽  
Vol 9 ◽  
Author(s):  
Shanchao Tan ◽  
Wendi Luo ◽  
Yongjie Zhang ◽  
Xiang-Kui Ren ◽  
Yuhong Liu ◽  
...  
Keyword(s):  
Self Assembly ◽  
Density Functional ◽  
Supramolecular Assembly ◽  
Dft Method ◽  
The Self ◽  
Scanning Tunneling ◽  
Tunneling Microscopy ◽  
Force Microscopy ◽  
Atomic Force ◽  
Assembly Mechanism

Boron-dipyrromethenes (BODIPY) are promising functional dyes, whose exceptional optical properties are closely related to their supramolecular assembly. Herein, the self-assembly of a BODIPY derivative functionalized with uracil groups is explicitly and thoroughly investigated by using scanning tunneling microscopy (STM). Based on the simulation and calculation by density functional theory (DFT) method, it can be concluded that the construction of ordered self-assembly structure is attributed to the formation of hydrogen bonds between uracil groups. Moreover, the nanotribological property of the self-assembly on HOPG surface is measured by using atomic force microscopy (AFM). The effort on self-assembly of the BODIPY derivative could enhance the understanding of surface assembly mechanism.

scholarly journals Simulation Study of Process-Controlled Supramolecular Block Copolymer Phase Separation with Reversible Reaction Algorithm

Polymers ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 528
Author(s):  
Jian-Bo Wu ◽  
Hong Liu ◽  
Zhong-Yuan Lu
Keyword(s):  
Diblock Copolymer ◽  
Self Assembly ◽  
Microphase Separation ◽  
Dynamic Properties ◽  
Dissipative Particle Dynamics ◽  
Reversible Reaction ◽  
Stimuli Responsive ◽  
Assembly Mechanism ◽  
Copolymer Melts ◽  
Non Equilibrium

A supramolecular diblock copolymer formed by reversible bonds between the two blocks shows a rich microphase separation behavior and has great application potential in stimuli-responsive materials. We propose a novel method to describe supramolecular reactions in dissipative particle dynamics, which includes a reversible reaction to accurately reproduce the strength, saturation, and dynamic properties of the reversible bonds in the simulations. The thermodynamic properties and dynamic processes of the supramolecular diblock copolymer melts in both equilibrium and non-equilibrium states were studied using this method. The simulation results show that the method can faithfully characterize phase behaviors and dynamic properties of supramolecular diblock copolymer melts, especially in a non-equilibrium state, which provides a novel tool to unveil self-assembly mechanism and describe the properties of supramolecular block copolymers.

A polymerization-induced self-assembly process for all-styrenic nano-objects using the living anionic polymerization mechanism

2020 ◽  
Vol 11 (15) ◽  
pp. 2635-2639 ◽  
Author(s):  
Chengcheng Zhou ◽  
Jian Wang ◽  
Peng Zhou ◽  
Guowei Wang
Keyword(s):  
Diblock Copolymer ◽  
Anionic Polymerization ◽  
Self Assembly ◽  
Assembly Process ◽  
Living Anionic Polymerization ◽  
Polymerization Mechanism ◽  
Copolymer Poly

By combination of the living anionic polymerization (LAP) mechanism with the polymerization-induced self-assembly (PISA) technique, the all-styrenic diblock copolymer poly(p-tert-butylstyrene)-b-polystyrene (PtBS-b-PS) based LAP PISA was successfully developed.

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