Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

Ghadban, Ali; Albertin, Luca

doi:10.3390/polym5020431

Cited by 61 publications

(49 citation statements)

References 253 publications

(326 reference statements)

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“…During the last decades, the design of well-tailored polymers molecules with predetermined number average chain length, high end-group functionality (EGF), controlled topology and low dispersity has been the topic of many research activities [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. These advanced macromolecular architectures are typically acquired via controlled radical polymerization (CRP), which is also known as reversible deactivation radical polymerization (RDRP).…”

Section: Introductionmentioning

confidence: 99%

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

et al. 2014

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Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000), optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP). Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr 2 /PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation () polymer property. Careful selection or fed-batch addition of the conventional radical initiator I 2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1) . Fed-batch addition of not only I 2 , but also comonomer and deactivator (50 ppm) under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

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Section: Introductionmentioning

confidence: 99%

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

et al. 2014

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“…the stabilizing effect of the phenyl group on dithiobenzoates is ideal for polymerizing methacrylates and methacrylamides [95]. Numerous RAFT agents of various structures have consequently been reported (see Figure 3.8 C) [71]. The RAFT mechanism also ensures that polymers synthesized by this technique carry thiocarbonyl thio end groups.…”

Section: Raft Polymerizations (Paper Iii)mentioning

confidence: 98%

“…The former three were initially popular, but in the 1990's radical polymerization became the primary polymerization method in glycopolymer synthesis [45,63]. The emergence of various reversible-deactivation radical polymerization (RDRP) (formerly known as living/controlled radical polymerization) techniques around that time enabled precision synthesis of well-defined glycopolymers with complex architectures [71]. Due to this versatility and the wide range of different techniques available, we decided on a radical polymerization approach in the attempt to synthesize type IV FMGs.…”

Section: Polymerization Strategymentioning

confidence: 99%

“…These polymers also readily react upon the addition of more monomers (hence being formerly known as living radical polymerizations). Some RDRP techniques such as nitroxide-mediated radical polymerization (NMP), cyanoxyl-mediated free-radical polymerization (CMRP), atom transfer radical polymerization (ATRP), and reversible addition-fragmentation chain transfer polymerization (RAFT) have been especially prolific in the synthesis of glycopolymers [71]. When planning the synthesis of a suitable sulfated α-L-fucoside monomer for radical polymerization it seemed wise to use already explored fucoside 3.…”

Section: Radical Polymerization Mechanismmentioning

confidence: 99%

“…Therefore, by tailoring both the Z-and the R-group of the RAFT agent, chain end functionalities can be obtained in both chain ends. General structure of a RAFT agent (A), the mechanism of RAFT polymerization (B) [94][95][96][97][98], and various RAFT agents (C) [71].…”

Section: Raft Polymerizations (Paper Iii)mentioning

confidence: 99%

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Fucoidan-Mimetic Glycopolymers : Synthesis and Biomedical Applications

Tengdelius¹

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Cover: 3D models of three different fucoidan-mimetic glycopolymers Linköping Studies in Science and Technology Dissertations No. 1743 Printed by LiU-Tryck, Linköping, Sweden, 2016 Till morfar som inspirerade mig att börja och Lina och Theo som inspirerar mig att fortsätta. Mattias Tengdelius Fucoidan-Mimetic Glycopolymers -Synthesis and Biomedical Applications I AbstractThe marine polysaccharide fucoidan has demonstrated several interesting biological properties, for instance being antiviral, anticoagulant, anti-inflammatory, anticancer, and platelet activating. Many of these properties are desirable for various biomedical applications. Yet, there are few reports on fucoidan being used in such applications. The reasons for this are primarily the heterogeneity and low structural reproducibility of fucoidan.This thesis describes the synthesis of polymers with pendant saccharides bearing the key structural features of fucoidan. These glycopolymers were synthesized via different radical polymerization techniques yielding polymers of different chain lengths and dispersity. These glycopolymers showed antiviral and platelet activating properties similar to those of natural fucoidan, thus making them fucoidan-mimetic glycopolymers. However, compared to fucoidan from natural sources, the fucoidan-mimetic glycopolymers had homogeneous and reproducible structures making them suitable for biomedical applications.Further studies demonstrated that platelet activation, caused by these glycopolymers, showed dose-response curves almost identical to fucoidan. The platelet activation was induced via intracellular signaling and caused platelet surface changes similar to those of fucoidan. Fucoidan-mimetic glycopolymers can therefore be used as unique biomolecular tools for studying the molecular and cellular responses of human platelets.Fucoidan-mimetic glycopolymers generally assert their antiviral activity by blocking viral entry to host cells, thus inhibiting spreading of the viral infection but not acting virucidal, i.e. not killing the viruses. Introduction of hydrophobic groups to the polymer's chain ends improved the antiviral properties significantly and is an important step towards yielding glycopolymers with virucidal properties.The fucoidan-mimetic glycopolymers were also applied as capping agents when synthesizing gold nanoparticles. These fucoidan-mimetic glycopolymer coated gold nanoparticles showed improved colloidal stability compared to uncapped gold nanoparticles. Furthermore, the nanoparticles also demonstrated selective cytotoxicity against a human colon cancer cell line over fibroblast cells. III Populärvetenskaplig SammanfattningSedan urminnes tider har människan vänt sig till naturen för att bota sjukdomar och andra krämpor. Genom extrakt från framförallt växter har bland annat feber, inflammationer och olika infektioner behandlats långt innan läkemedelskonsten utvecklades till vad den är idag. Även när den moderna läkemedelsvetenskapen, farmakologin, började utvecklas var det naturen som var den främst...

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Synthesis and Application of Glycopolymers

Babiuch

Stenzel

2014

Encyclopedia of Polymer Science and Technology

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Multimeric representations of carbohydrates play a pivotal role in many biological processes. Polymer chemists aim at copying these biologically active biopolymers by the design of glycopolymers, synthetic polymers with pendant sugars. This article is focused on the synthetic methods as well as applications of these macromolecules. Since the first description of glycopolymers in the late 1950s, a myriad of glycopolymer structures have been reported. The first glycopolymer was prepared via free radical polymerization, but soon other techniques including ionic chain polymerization, ring‐opening polymerization, and ring‐opening methatesis polymerization followed. The arrival of living radical polymerization techniques caused a surge in publications on glycopolymers. Although most polymerization techniques have been employed to create glycopolymers, atom‐transfer radical polymerization and reversible addition‐fragmentation chain transfer (RAFT) polymerization dominate the literature. Architectures reported range from simple homopolymers to block copolymers, endfunctional glycopolymers, and stars and gels. Immobilization of initiators or RAFT agents led to bioactive surfaces. In recent years, the focus has shifted from the pure interest in the synthesis to the investigation of the biological activity of these glycopolymers. While the direct synthesis using glycomonomers dominated the literature for years, recent times saw the increased use of postmodification procedures. Reactive polymers were conjugated with sugars using an array of reactions including click chemistry and various reactions based on thiol‐ or amino sugars. This article gives a brief historical account on the synthesis of glycopolymers and outline briefly the different techniques—direct synthesis and postmodification—to design glycopolymers. The main focus will be, however, the advancements in applications of glycopolymers since around 2010, which contributed to the existing knowledge on how the structure of the glycopolymer affects the binding with lectin.

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Synthesis of Glycopolymer Architectures by Reversible-Deactivation Radical Polymerization

Cited by 61 publications

References 253 publications

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

Fucoidan-Mimetic Glycopolymers : Synthesis and Biomedical Applications

Synthesis and Application of Glycopolymers

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