Star-Shaped Copolymers Based on Poly(N-vinylcaprolactam) and their Use as Nanocarriers of Methotrexate

2017 ◽  
Vol 70 (12) ◽  
pp. 1291 ◽  
Author(s):  
Norma A. Cortez-Lemus ◽  
Angel Licea-Claverie
Keyword(s):  
Polyethylene Glycol ◽  
Block Copolymers ◽  
Diblock Copolymers ◽  
Raft Polymerization ◽  
Drug Loading ◽  
Gel Permeation Chromatography ◽  
Solution Temperature ◽  
Star Copolymers ◽  
Vis Spectroscopy ◽  
Star Block Copolymers

Star-shaped poly(N-vinylcaprolactam)-block-poly(ethylhexylacrylate)-block-polyethylene glycol (PNVCL-b-PEHA-b-PEG) triblock copolymers and star-shaped poly(N-vinylcaprolactam)-block-polyethylene glycol (PNVCL-b-PEG) diblock copolymers were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. The resulting star block copolymers were characterized using 1H NMR and UV-vis spectroscopy, gel permeation chromatography, and dynamic light scattering. The star-shaped PNVCL-b-PEG and PNVCL-b-PEHA-b-PEG block copolymers self-assemble spontaneously into aggregates in water. The aggregates formed ranged from ~17 to 135 nm in diameter and were used to encapsulate methotrexate (MTX). It was observed that the aggregates from PNVCL-b-PEHA-b-PEG copolymers exhibited a higher drug loading and a lower release of MTX (19 wt-% and 54 %) as compared with star copolymers without PEHA (5 wt-% and 81 %) after 24 h at a temperature below their lower critical solution temperature values.

scholarly journals Preparation of Doxorubicin-Loaded Amphiphilic Poly(D,L-Lactide-Co-Glycolide)-b-Poly(N-Acryloylmorpholine) AB2 Miktoarm Star Block Copolymers for Anticancer Drug Delivery

Materials ◽  
2020 ◽  
Vol 13 (17) ◽  
pp. 3713
Author(s):  
Kalyan Ramesh ◽  
Avnish Kumar Mishra ◽  
Jin Kon Kim ◽  
Yeon Tae Jeong ◽  
Yeong-Soon Gal ◽  
...  
Keyword(s):  
Drug Delivery ◽  
Block Copolymers ◽  
Anticancer Drug ◽  
Polymeric Micelles ◽  
Drug Loading ◽  
Gel Permeation Chromatography ◽  
Critical Micellar Concentration ◽  
Anticancer Drug Delivery ◽  
Miktoarm Star ◽  
Star Block Copolymers

Owing to their unique topology and physical properties, micelles based on miktoarm amphiphilic star block copolymers play an important role in the biomedical field for drug delivery. Herein, we developed a series of AB2-type poly(D,L-lactide-co-glycolide)-b-poly(N-acryloyl morpholine) (PLGA-b-PNAM2) miktoarm star block copolymers by reversible addition–fragmentation chain–transfer polymerization and ring-opening copolymerization. The resulting miktoarm star polymers were investigated by 1H NMR spectroscopy and gel permeation chromatography. The critical micellar concentration value of the micelles increases with an increase in PNAM block length. As revealed by transmission electron microscopy and dynamic light scattering, the amphiphilic miktoarm star block copolymers can self-assemble to form spherical micellar aggregates in water. The anticancer drug doxorubicin (DOX) was encapsulated by polymeric micelles; the drug-loading efficiency and drug-loading content of the DOX-loaded micelles were 81.7% and 9.1%, respectively. Acidic environments triggered the dissociation of the polymeric micelles, which led to the more release of DOX in pH 6.4 than pH 7.4. The amphiphilic PLGA-b-PNAM2 miktoarm star block copolymers may have broad application as nanocarriers for controlled drug delivery.

scholarly journals Synthesis and characteristics of novel azo-based diblock copolymers and their self-assembly behavior via solvents and thermal annealing

e-Polymers ◽  
2017 ◽  
Vol 17 (6) ◽  
pp. 523-535 ◽  
Author(s):  
Athmen Zenati ◽  
Yang-Kyoo Han
Keyword(s):  
Self Assembly ◽  
Nematic Phase ◽  
Weight Control ◽  
Liquid Crystalline ◽  
Diblock Copolymers ◽  
Raft Polymerization ◽  
Gel Permeation Chromatography ◽  
Kinetic Studies ◽  
Morphological Properties ◽  
Scanning Calorimetry

AbstractA series of azo-based diblock copolymers (DBCs) with various compositions were successfully synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization in anisole with PCAEMA-CTA (macro-CTA), DOPAM (new acrylamide monomer) and AIBN (initiator). Kinetic studies on diblock copolymerization manifested a controlled/living manner with good molecular weight control. Structures and properties of monomers and DBCs were determined by 1H nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). Liquid crystalline (LC) phases and morphological properties were investigated using optical polarizing microscope (OPM), atomic force microscopy (AFM), scanning electron microscopy (SEM) and small-angle X-ray scattering (SAXS). Experimental results demonstrated that the prepared PCAEMA-CTA and DBCs possessed low polydispersity index (≤1.37). All DBCs revealed sharp endothermic transition peaks corresponding to the smectic-to-nematic phase. DBCs with high azo contents showed batonnet textures of the smectic phase whereas DBCs of low azo segments displayed threaded textures of the nematic phase. DBC with 49 wt% of azo side-chains generated a lamellar compared to DBCs with low azo block (≤41 wt%) or non-azo block (≤38 wt%) which produced hexagonal-type nanostructures. In addition, all DBCs exhibited reversible trans-cis photoisomerization behavior under UV irradiation and dark storage at different intervals of time.

Preparation of miktoarm star-block copolymers PSn-b-PVAc4-n via combination of ATRP and RAFT polymerization

2010 ◽  
Vol 48 (22) ◽  
pp. 5180-5188 ◽  
Author(s):  
Yansheng Qiu ◽  
Wei Zhang ◽  
Yuefang Yan ◽  
Jian Zhu ◽  
Zhengbiao Zhang ◽  
...  
Keyword(s):  
Block Copolymers ◽  
Raft Polymerization ◽  
Miktoarm Star ◽  
Star Block Copolymers

scholarly journals RAFT synthesis of well-defined PVDF-b-PVAc block copolymers

2016 ◽  
Vol 7 (45) ◽  
pp. 6918-6933 ◽  
Author(s):  
Marc Guerre ◽  
S. M. Wahidur Rahaman ◽  
Bruno Améduri ◽  
Rinaldo Poli ◽  
Vincent Ladmiral
Keyword(s):  
Block Copolymers ◽  
Dft Calculations ◽  
Diblock Copolymers ◽  
Raft Polymerization

This article reports that PVDF-b-PVAc diblock copolymers can be synthesized by RAFT polymerization from PVDF macroCTAs and rationalizes this discovery using DFT calculations.

scholarly journals Rotation Dynamics of Star Block Copolymers under Shear Flow

2018 ◽  
Author(s):  
Diego Jaramillo-Cano ◽  
Christos N. Likos ◽  
Manuel Camargo
Keyword(s):  
Block Copolymers ◽  
Diblock Copolymers ◽  
Building Blocks ◽  
Laboratory Frame ◽  
Rotational Frequency ◽  
Geometrical Approach ◽  
Soft Systems ◽  
Self Assembling ◽  
Star Block Copolymers ◽  
Physical And Chemical

Star block-copolymers (SBCs) are macromolecules formed by a number of diblock copolymers anchored to a common central core, being the internal monomers solvophilic and the end monomers solvophobic. Recent studies have demonstrated that SBCs constitute a self-assembling building blocks with specific softness, functionalization, shape, and flexibility. Depending on different physical and chemical parameters the SBCs can behave as flexible patchy particles. In this paper, we study the rotational dynamics of isolated SBCs using a hybrid mesoscale simulation technique. We compare three different approaches to analyse the dynamics: the laboratory frame, the non-inertial Eckart's frame, and a geometrical approximation relating the conformation of the SBC to the velocity profile of the solvent. We find that the geometrical approach is adequate when dealing with very soft systems while in the opposite extreme, the dynamics is best explained using the laboratory frame. On the other hand, the Eckart frame is found to be very general and to reproduced well both extreme cases. We also compare the rotational frequency and the kinetic energy with the definitions of the angular momentum and inertia tensor different from recent publications.

scholarly journals Novel Complex Polymers with Carbazole Functionality by Controlled Radical Polymerization

2012 ◽  
Vol 2012 ◽  
pp. 1-18 ◽  
Author(s):  
Kazuhiro Nakabayashi ◽  
Hideharu Mori
Keyword(s):  
Block Copolymers ◽  
Radical Polymerization ◽  
Three Dimensional ◽  
Controlled Radical Polymerization ◽  
Controlled Synthesis ◽  
Design And Synthesis ◽  
Star Copolymers ◽  
Novel Complex ◽  
Star Block Copolymers ◽  
Complex Polymers

This review summarizes recent advances in the design and synthesis of novel complex polymers with carbazole moieties using controlled radical polymerization techniques. We focus on the polymeric architectures of block copolymers, star polymers, including star block copolymers and miktoarm star copolymers, comb-shaped copolymers, and hybrids. Controlled radical polymerization ofN-vinylcarbazole (NVC) and styrene and (meth)acrylate derivatives having carbazole moieties is well advanced, leading to the well-controlled synthesis of complex macromolecules. Characteristic optoelectronic properties, assembled structures, and three-dimensional architectures are briefly introduced.

Synthesis and Solution-state Assembly or Bulk State Thiol-ene Crosslinking of Pyrrolidinone- and Alkene-functionalized Amphiphilic Block Fluorocopolymers: From Functional Nanoparticles to Anti-fouling Coatings

2010 ◽  
Vol 63 (8) ◽  
pp. 1159 ◽  
Author(s):  
Jun Ma ◽  
Jeremy W. Bartels ◽  
Zhou Li ◽  
Ke Zhang ◽  
Chong Cheng ◽  
...  
Keyword(s):  
Block Copolymers ◽  
Diblock Copolymers ◽  
Raft Polymerization ◽  
Building Blocks ◽  
Ene Reactions ◽  
Reversible Addition ◽  
Complex Building ◽  
Crosslinked Networks ◽  
Amphiphilic Diblock Copolymers ◽  
Synthetic Methodologies

With an ever increasing interest in the combined functionality and versatility of materials, increasing demands are placed on synthetic methodologies by which to produce such materials. This work demonstrates the preparation of block copolymers having fluorocarbon content, pyrrolidinone units, and alkene groups as complex building blocks for the assembly of discrete nanoparticles in solution and, alternatively, transformation into sophisticated crosslinked networks. Reversible addition–fragmentation chain transfer (RAFT) polymerization is a facile tool for the synthesis of well-defined polymers containing imbedded side-chain functionalities. In this work, the synthesis of well-defined multifunctional fluorinated polymers bearing pendant pyrrolidinone groups, and block copolymers bearing both pyrrolidinone and alkenyl groups on different segments was achieved, by using RAFT polymerizations of unique bifunctional monomers. Upon micellization, the amphiphilic diblock copolymers were transformed into regioselectively-functionalized nanoparticles. Further transformations of pyrrolidinone- and alkene-dual functionalized-block copolymers into complex amphiphilic networks were accomplished by highly efficient UV-induced thiol-ene reactions. Whether as discrete nanoparticles or nanoscopically-segregated crosslinked networks, these materials have great potential for several diverse technologies, including as anti-fouling materials.

scholarly journals Synthesis of Terpyridine-Terminated Amphiphilic Block Copolymers and Their Self-Assembly into Metallo-Polymer Nanovesicles

Materials ◽  
2019 ◽  
Vol 12 (4) ◽  
pp. 601 ◽  
Author(s):  
Tatyana Elkin ◽  
Stacy Copp ◽  
Ryan Hamblin ◽  
Jennifer Martinez ◽  
Gabriel Montaño ◽  
...  
Keyword(s):  
Polyethylene Glycol ◽  
Block Copolymers ◽  
Self Assembly ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Amphiphilic Block Copolymers ◽  
Transmission Electron ◽  
Reversible Addition ◽  
Efficient Route ◽  
High Yields

Polystyrene-b-polyethylene glycol (PS-b-PEG) amphiphilic block copolymers featuring a terminal tridentate N,N,N-ligand (terpyridine) were synthesized for the first time through an efficient route. In this approach, telechelic chain-end modified polystyrenes were produced via reversible addition-fragmentation chain-transfer (RAFT) polymerization by using terpyridine trithiocarbonate as the chain-transfer agent, after which the hydrophilic polyethylene glycol (PEG) block was incorporated into the hydrophobic polystyrene (PS) block in high yields via a thiol-ene process. Following metal-coordination with Mn2+, Fe2+, Ni2+, and Zn2+, the resulting metallo-polymers were self-assembled into spherical, vesicular nanostructures, as characterized by dynamic light scattering and transmission electron microscopy (TEM) imaging.

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