scholarly journals Amphiphilic Nucleobase-Containing Polypeptide Copolymers—Synthesis and Self-Assembly

Polymers ◽  
2020 ◽  
Vol 12 (6) ◽  
pp. 1357
Author(s):  
Michel Nguyen ◽  
Khalid Ferji ◽  
Sébastien Lecommandoux ◽  
Colin Bonduelle
Keyword(s):  
Self Assembly ◽  
Ring Opening ◽  
Building Blocks ◽  
Ring Opening Polymerization ◽  
The Self ◽  
Amphiphilic Copolymers ◽  
Transmission Electron ◽  
Scattering Measurements ◽  
Thymidine Monophosphate ◽  
The Impact

Nucleobase-containing polymers are an emerging class of building blocks for the self-assembly of nanoobjects with promising applications in nanomedicine and biology. Here we present a macromolecular engineering approach to design nucleobase-containing polypeptide polymers incorporating thymine that further self-assemble in nanomaterials. Diblock and triblock copolypeptide polymers were prepared using sequential ring-opening polymerization of γ-Benzyl-l-glutamate N-carboxyanhydride (BLG-NCA) and γ-Propargyl-l-glutamate N-carboxyanhydride (PLG-NCA), followed by an efficient copper(I)-catalyzed azide alkyne cycloaddition (CuAAc) functionalization with thymidine monophosphate. Resulting amphiphilic copolymers were able to spontaneously form nanoobjects in aqueous solutions avoiding a pre-solubilization step with an organic solvent. Upon self-assembly, light scattering measurements and transmission electron microscopy (TEM) revealed the impact of the architecture (diblock versus triblock) on the morphology of the resulted nanoassemblies. Interestingly, the nucleobase-containing nanoobjects displayed free thymine units in the shell that were found available for further DNA-binding.

Preparation and characterization of stereocomplex aggregates based on PLA–P188–PLA

RSC Advances ◽  
2016 ◽  
Vol 6 (56) ◽  
pp. 50543-50552 ◽  
Author(s):  
Weiwei Zhang ◽  
Delong Zhang ◽  
Xiaoshan Fan ◽  
Guangyue Bai ◽  
Yuqin Jiang ◽  
...  
Keyword(s):  
Click Chemistry ◽  
Self Assembly ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Release Profile ◽  
The Self ◽  
Amphiphilic Copolymers ◽  
Assembly Behavior

Novel dumbbell-shaped amphiphilic copolymers based on P188 and PLA were synthesized by click chemistry and ring opening polymerization. The self-assembly behavior of the stereocomplexes and the DOX release profile from the aggregates were studied.

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 Thermo-Responsive Graphene Oxide/Poly(Ethyl Ethylene Phosphate) Nanocomposite via Ring Opening Polymerization

Nanomaterials ◽  
2019 ◽  
Vol 9 (2) ◽  
pp. 207 ◽  
Author(s):  
Xue Jiang ◽  
Guolin Lu ◽  
Xiaoyu Huang ◽  
Yu Li ◽  
Fangqi Cao ◽  
...  
Keyword(s):  
Graphene Oxide ◽  
Photoelectron Spectroscopy ◽  
Self Assembly ◽  
Ring Opening ◽  
Aqueous Dispersion ◽  
Ring Opening Polymerization ◽  
Nucleophilic Attack ◽  
Force Microscopy ◽  
Transmission Electron ◽  
Epoxy Groups

An efficient strategy for growing thermo-sensitive polymers from the surface of exfoliated graphene oxide (GO) is reported in this article. GO sheets with hydroxyls and epoxy groups on the surface were first prepared by modified Hummer’s method. Epoxy groups on GO sheets can be easily modified through ring-opening reactions, involving nucleophilic attack by tris(hydroxymethyl) aminomethane (TRIS). The resulting GO-TRIS sheets became a more versatile precursor for next ring opening polymerization (ROP) of ethyl ethylene phosphate (EEP), leading to GO-TRIS/poly(ethyl ethylene phosphate) (GO-TRIS-PEEP) nanocomposite. The nanocomposite was characterized by 1H NMR, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), differential thermal gravity (DTG), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Since hydrophilic PEEP chains make the composite separate into single layers through hydrogen bonding interaction, the dispersity of the functionalized GO sheets in water is significantly improved. Meanwhile, the aqueous dispersion of GO-TRIS-PEEP nanocomposite shows reversible temperature switching self-assembly and disassembly behavior. Such a smart graphene oxide-based hybrid material is promising for applications in the biomedical field.

scholarly journals Nucleation of protein mesocrystals via oriented attachment

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Alexander E. S. Van Driessche ◽  
Nani Van Gerven ◽  
Rick R. M. Joosten ◽  
Wai Li Ling ◽  
Maria Bacia ◽  
...  
Keyword(s):  
Self Assembly ◽  
Building Blocks ◽  
Oriented Attachment ◽  
Great Promise ◽  
Inorganic Systems ◽  
Transmission Electron ◽  
Designer Proteins ◽  
Rate Limit ◽  
The Impact

AbstractSelf-assembly of proteins holds great promise for the bottom-up design and production of synthetic biomaterials. In conventional approaches, designer proteins are pre-programmed with specific recognition sites that drive the association process towards a desired organized state. Although proven effective, this approach poses restrictions on the complexity and material properties of the end-state. An alternative, hierarchical approach that has found wide adoption for inorganic systems, relies on the production of crystalline nanoparticles that become the building blocks of a next-level assembly process driven by oriented attachment (OA). As it stands, OA has not yet been observed for protein systems. Here we employ cryo-transmission electron microscopy (cryoEM) in the high nucleation rate limit of protein crystals and map the self-assembly route at molecular resolution. We observe the initial formation of facetted nanocrystals that merge lattices by means of OA alignment well before contact is made, satisfying non-trivial symmetry rules in the process. As these nanocrystalline assemblies grow larger we witness imperfect docking events leading to oriented aggregation into mesocrystalline assemblies. These observations highlight the underappreciated role of the interaction between crystalline nuclei, and the impact of OA on the crystallization process of proteins.

Poly(Ethylene Oxide)-B-Poly(ε-Caprolactone) Amphiphilic Block Copolymers: Synthesis and Self-Assembly

2011 ◽  
Vol 284-286 ◽  
pp. 1877-1885
Author(s):  
Ke Xin Kang ◽  
Min Ying Liu ◽  
Qing Xiang Zhao ◽  
Peng Fu ◽  
Xiao Bing Wang
Keyword(s):  
Molecular Weight ◽  
Block Copolymers ◽  
Self Assembly ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
Amphiphilic Block Copolymers ◽  
H Nmr ◽  
Transmission Electron ◽  
Particle Size Analyzer ◽  
Anionic Ring

A series of amphiphilic block copolymers mPEO-b-PCL with different PCL molecular weight were successfully prepared by combination of anionic ring-opening polymerization with coordination-insertion ring-opening polymerization. Firstly, the linear mPEO was prepared by anionic ring-opening copolymerization of EO with 2-(2-methoxyethoxy) ethoxide potassium as the small molecule initiators, then the mPEO as the macroinitiator was used to initiate the ring-opening polymerization of CL, in the absence of Sn(Oct)2 as the catalyst, and amphiphilic block copolymers mPEO-b-PCL were obtained. By changing the ratio of monomer and macroinitiator, prepared a series of different molecular weight mPEO-b-PCL. The structure of intermediates and final products were characterized by 1H NMR and GPC. The critical micelle concentration (cmc) of the final copolymer was measured. In addition, the sizes and morphologies of the obtained micelles at different PCL chains were studied with Laser nano-particle size analyzer and transmission electron microscopy (TEM).

scholarly journals Ring-opening polymerization-induced crystallization-driven self-assembly of poly-L-lactide-block-polyethylene glycol block copolymers (ROPI-CDSA)

2020 ◽  
Vol 11 (1) ◽  
Author(s):  
Paul J. Hurst ◽  
Alexander M. Rakowski ◽  
Joseph P. Patterson
Keyword(s):  
Molecular Structure ◽  
Polyethylene Glycol ◽  
Block Copolymers ◽  
Self Assembly ◽  
Ring Opening ◽  
Ring Opening Polymerization ◽  
The Self ◽  
Assembly Mechanism ◽  
2D And 3D ◽  
Induced Crystallization

Abstract The self-assembly of block copolymers into 1D, 2D and 3D nano- and microstructures is of great interest for a wide range of applications. A key challenge in this field is obtaining independent control over molecular structure and hierarchical structure in all dimensions using scalable one-pot chemistry. Here we report on the ring opening polymerization-induced crystallization-driven self-assembly (ROPI-CDSA) of poly-L-lactide-block-polyethylene glycol block copolymers into 1D, 2D and 3D nanostructures. A key feature of ROPI-CDSA is that the polymerization time is much shorter than the self-assembly relaxation time, resulting in a non-equilibrium self-assembly process. The self-assembly mechanism is analyzed by cryo-transmission electron microscopy, wide-angle x-ray scattering, Fourier transform infrared spectroscopy, and turbidity studies. The analysis revealed that the self-assembly mechanism is dependent on both the polymer molecular structure and concentration. Knowledge of the self-assembly mechanism enabled the kinetic trapping of multiple hierarchical structures from a single block copolymer.

Efficient synthesis and self-assembly of hetero-grafted amphiphilic polypepide bottlebrushes

2012 ◽  
Vol 84 (12) ◽  
pp. 2569-2578 ◽  
Author(s):  
Chunhui Luo ◽  
Chongyi Chen ◽  
Zhibo Li
Keyword(s):  
Self Assembly ◽  
Ring Opening ◽  
Click Reaction ◽  
Ring Opening Polymerization ◽  
The Self ◽  
Molar Ratio ◽  
Efficient Synthesis ◽  
Poly Ethylene Glycol ◽  
New Type ◽  
Poly Ethylene

A new type of hetero-grafted molecular bottlebrush with polypeptide as backbone was synthesized using graft-onto strategy. Poly(γ-propargyl-L-glutamate) (PPLG) as backbone was firstly synthesized via ring-opening polymerization (ROP) of γ-propargyl-L-glutamate (PLG) N-carboxyanhydride (NCA). Next, polystyrene-N3 (PS-N3) and monomethoxy poly(ethylene glycol)-N3 (mPEG-N3) as side chains were grafted onto the PPLG backbone using copper-catalyzed click reaction, which afforded good grafting density and efficiency. Two polypeptide bottlebrushes with PS-to-mPEG molar ratio at 70/30 and 30/70 were prepared. The self-assembly behaviors of these two polypeptide bottlebrushes were investigated using the cosolvent method, and their supramolecular structures were characterized using light scattering (LS) and electron microscopy.

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