Facile synthesis of comb, star, and graft polymers via reversible addition–fragmentation chain transfer (RAFT) polymerization

Quinn, John F.; Chaplin, R.P.; Davis, Thomas P.

doi:10.1002/pola.10369

Cited by 142 publications

(137 citation statements)

References 33 publications

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“…[23,24] RAFT has enabled the synthesis of complex architectures, including block copolymers, dendrimers, and star structures of targeted molecular weights and low polydispersities. [25][26][27][28] An important feature of RAFT polymerization is that the chain transfer agent is the chain-end functionality, and allows for the subsequent polymerization of other monomers to form block copolymers. Moreover, the unprecedented flexibility of RAFT allows the polymerization of a diverse range of monomers, including (meth)acrylates, styrenes, and acrylamides, under relatively mild polymerization conditions.…”

Section: Introductionmentioning

confidence: 99%

Fluorogenic 1,3‐Dipolar Cycloaddition within the Hydrophobic Core of a Shell Cross‐Linked Nanoparticle

O’Reilly

Joralemon

Hawker

et al. 2006

Chemistry A European J

146

102

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Using either nitroxide mediated polymerization (NMP) or reversible addition fragmentation transfer (RAFT) techniques, novel block copolymers that present terminal acetylenes, in the side chain of the styrenic block, were obtained with narrow polydispersities and targeted molecular weights. For the conversion of these acetylene-functionalized polymers to amphiphilic block copolymers, RAFT techniques were preferred. Mild protection/deprotection chemistries were employed which were compatible with the incorporation of the acetylene functionality in the hydrophobic segment. These acetylene-functionalized, Click-readied amphiphilic block copolymers were then self-assembled and cross-linked to afford shell cross-linked knedel-like (SCK) nanoparticles that contained acetylene groups in the core domain. The hydrodynamic diameters (D(h)) of the block copolymer micelles and nanoparticles were determined by dynamic light scattering (DLS), and the dimensions of the nanoparticles were characterized using tapping-mode atomic force microscopy (AFM) and transmission electron microscopy (TEM). The chemical availability of the Click functionality within the core domain of the SCKs was investigated using the copper(I)-catalyzed 1,3-dipolar fluorogenic cycloaddition with a non-fluorescent 3-azidocoumarin profluorophore to afford intensely fluorescent nanoparticles.

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Section: Introductionmentioning

confidence: 99%

Fluorogenic 1,3‐Dipolar Cycloaddition within the Hydrophobic Core of a Shell Cross‐Linked Nanoparticle

O’Reilly

Joralemon

Hawker

et al. 2006

Chemistry A European J

146

102

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“…It is a key step that the immobilization of RAFT agent on the surfaces of PVBCS nanospheres for this work. Generally, the reaction of benzyl chloride group with carbazole and carbon sulfide is very active and the substitution efficiency of chlorine atoms was reported to be close to 100% [37,38]. However, the chloride signal can still be discernible in the XPS wide scan spectrum, indicating that there are chlorine atoms in the range of the XPS probing.…”

Section: Characterizationsmentioning

confidence: 93%

Synthesis and property of polymer nanospheres with Pd/P4VP shells via surface RAFT polymerization

Shi¹,

Zhang²,

Zhu³

et al. 2009

Express Polym. Lett.

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Abstract.A reversible addition-fragmentation chain transfer (RAFT) agent with carbazole as Z-group was immobilized on the surfaces of the cross-linked poly (4-vinylbenzyl chloride-co-styrene) (PVBCS) nanospheres with a diameter of about 70 nm by the reaction of benzyl chloride groups in the PVBCS between carbazole and carbon sulfide. Then surface RAFT polymerization of 4-vinylpyridine (4VP) was used to modify the nanospheres to produce a well-defined and covalently tethered P4VP shell. By surface activation in a PdCl2 solution and then reduction by hydrazine hydrate (N2H4·H2O), the P4VP composite shells were obtained containing densely palladium metal nanoparticles. The chemical composition of the nanosphere surfaces at various stages of the surface modification was characterized by X-ray photoelectron spectroscopy (XPS). Transmission electron microscopy (TEM) was used to characterize the morphology of the hybrid nanospheres. The Pd/P4VP shell nanospheres were also applied to the catalytic reaction and proved to be efficient and reusable for the Heck reaction.

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“…The pioneering work using multivalent RAFT agents to synthesize star polymers was performed by the CSIRO group. [15] Subsequently, we have prepared a variety of star polymers using multifunctional RAFT agents based on hexakis(thiobenzoylthiomethyl)benzene, [16] b-cyclodextrin (b-CD), [17] pentaerythritol [18] or 1,1,1-tris(hydroxymethyl)propane, [18,19] (co)polymers of vinyl benzyl dithiobenzoate, [20] and dendrimers. [21,22] Although the multifunctional transfer agents mentioned above enable the synthesis of a wide variety of polymers, these particular agents yield materials built using carbon-carbon bonds.…”

Section: Core-first Approachmentioning

confidence: 99%

Synthesis of Star Polymers by RAFT Polymerization as Versatile Nanoparticles for Biomedical Applications

Qiao

Whittaker

et al. 2017

Aust. J. Chem.

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The precise control of polymer chain architecture has been made possible by developments in polymer synthesis and conjugation chemistry. In particular, the synthesis of polymers in which at least three linear polymeric chains (or arms) are tethered to a central core has yielded a useful category of branched architecture, so-called star polymers. Fabrication of star polymers has traditionally been achieved using either a core-first technique or an arm-first approach. Recently, the ability to couple polymeric chain precursors onto a functionalized core via highly efficient coupling chemistry has provided a powerful new methodology for star synthesis. Star syntheses can be implemented using any of the living polymerization techniques using ionic or living radical intermediates. Consequently, there are innumerable routes to fabricate star polymers with varying chemical composition and arm numbers. In comparison with their linear counterparts, star polymers have unique characteristics such as low viscosity in solution, prolonged blood circulation, and high accumulation in tumour regions. These advantages mean that, far beyond their traditional application as rheology control agents, star polymers may also be useful in the medical and pharmaceutical sciences. In this account, we discuss recent advances made in our laboratory focused on star polymer research ranging from improvements in synthesis through to novel applications of the product materials. Specifically, we examine the core-first and arm-first preparation of stars using reversible addition-fragmentation chain transfer (RAFT) polymerization. Further, we also discuss several biomedical applications of the resulting star polymers, particularly those made by the arm-first protocol. Emphasis is given to applications in the emerging area of nanomedicine, in particular to the use of star polymers for controlled delivery of chemotherapeutic agents, protein inhibitors, signalling molecules, and siRNA. Finally, we examine possible future developments for the technology and suggest the further work required to enable clinical applications of these interesting materials.

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Facile synthesis of comb, star, and graft polymers via reversible addition–fragmentation chain transfer (RAFT) polymerization

Cited by 142 publications

References 33 publications

Fluorogenic 1,3‐Dipolar Cycloaddition within the Hydrophobic Core of a Shell Cross‐Linked Nanoparticle

Fluorogenic 1,3‐Dipolar Cycloaddition within the Hydrophobic Core of a Shell Cross‐Linked Nanoparticle

Synthesis and property of polymer nanospheres with Pd/P4VP shells via surface RAFT polymerization

Synthesis of Star Polymers by RAFT Polymerization as Versatile Nanoparticles for Biomedical Applications

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