Controlled multi-vinyl monomer homopolymerization through vinyl oligomer combination as a universal approach to hyperbranched architectures

Zhao, Tianyu; Zheng, Yu; Poly, Julien; Wang, Wenxian

doi:10.1038/ncomms2887

Cited by 99 publications

(125 citation statements)

References 39 publications

(44 reference statements)

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“…Two vinyl groups exist within the EGDMA monomer that can form a branch point under the right synthetic conditions, thus yielding a dendritic architecture (instead of a crosslinked network) using controlled/living free radical polymerization 47,48 . During copolymerization towards the dendritic polymer, poly(EGDMA-co-DMAEMA-co-HEMA-co-Azo), (H1) was monitored by tetrahydrofuran gel permeation chromatography (THF-GPC) (refractive index detector, Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

Interfacial assembly of dendritic microcapsules with host–guest chemistry

et al. 2014

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The self-assembly of nanoscale materials to form hierarchically ordered structures promises new opportunities in drug delivery, as well as magnetic materials and devices. Herein, we report a simple means to promote the self-assembly of two polymers with functional groups at a water-chloroform interface using microfluidic technology. Two polymeric layers can be assembled and disassembled at the droplet interface using the efficiency of cucurbit[8]uril (CB[8]) host-guest supramolecular chemistry. The microcapsules produced are extremely monodisperse in size and can encapsulate target molecules in a robust, well-defined manner. In addition, we exploit a dendritic copolymer architecture to trap a small hydrophilic molecule in the microcapsule skin as cargo. This demonstrates not only the ability to encapsulate small molecules but also the ability to orthogonally store both hydrophilic and hydrophobic cargos within a single microcapsule. The interfacially assembled supramolecular microcapsules can benefit from the diversity of polymeric materials, allowing for fine control over the microcapsule properties.

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Section: Resultsmentioning

confidence: 99%

Interfacial assembly of dendritic microcapsules with host–guest chemistry

et al. 2014

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“…12) [149]. Recently Wang and co-workers have been able to shift the intermolecular/intramolecular balance to form either utmost hyperbranched polymers, or single chains self-linked by intramolecular crosslinks by in situ deactivation enhanced ATRP [150]. By controlling the monomer to initiator ratio, along with the percentage of the deactivating Cu II species (enhances deactivation depicted in Fig.…”

Section: Branched Polymersmentioning

confidence: 91%

Prospects for polymer therapeutics in Parkinson's disease and other neurodegenerative disorders

Newland

Werner

et al. 2015

Progress in Polymer Science

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a b s t r a c tParkinson's disease (PD) is characterized by a progressive loss of dopaminergic neurons and represents a growing health burden to western societies. Like many neurodegenerative disorders the cause is unknown, however, as the pathogenesis becomes ever more elucidated, it is becoming clear that effective delivery is a key issue for new therapeutics. The versatility of today's polymerization techniques allows the synthesis of a wide range of polymer materials which hold great potential to aid in the delivery of small molecules, proteins, genetic material or cells. In this review, we capture the recent advances in polymer based therapeutics of the central nervous system (CNS). We place the advances in historical context and, furthermore, provide future prospects in line with newly discovered advancements in the understanding of PD and other neurodegenerative disorders. This review provides researchers in the field of polymer chemistry and materials science an up-to-date understanding of the requirements placed upon materials designed for use in the CNS aiding the focus of polymer therapeutic design.

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“…DSC characterization determined that the T g increased with the mole fraction of f Bn in the hyperbranched copolymers from T g = −8.9°C of HB-(EO 3 ) 25 @Bn 25 to T g = 5.1°C of HB-(EO 3 ) 25 @Bn 100 . It is interesting to note that the T g difference between the HB-(EO 3 ) 25 @Bn 100 and HB-Bn 25 was 12.8°C, much larger than the T g difference of 2.3°C between HB-Bn 25 @(EO 3 ) 100 and HB-(EO 3 ) 25 (Table 1), indicating a less effective shielding of the HB-Bn shell on the HB-EO 3 core, probably due to the larger size of AB 2 -EO 3 monomer than AB 2 -Bn.…”

Section: ■ Introductionmentioning

confidence: 95%

“…As a comparison, a hyperbranched random copolymer, HB-(Bn 25 -r-(EO 3 ) 25 Figure S7). The DSC characterization of the HB-(Bn 25 -r-(EO 3 ) 25 ) hyperbranched copolymer showed a T g = −11.1°C, which was between the T g values of segmented hyperbranched copolymers HB-Bn 25 @(EO 3 ) 25 and HB-(EO 3 ) 25 @Bn 25 , although all of these polymers had the same chemical composition and shared similar molecular weights (Figure 2A).…”

Section: ■ Introductionmentioning

confidence: 99%

Investigate the Glass Transition Temperature of Hyperbranched Copolymers with Segmented Monomer Sequence

et al. 2016

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Hyperbranched copolymers with segmented structures were synthesized using a chain-growth coppercatalyzed azide−alkyne cycloaddition (CuAAC) polymerization via sequential monomer addition in one pot. Three AB 2 -type monomers that contained one alkynyl group (A), two azido groups (B), and one dangling group, either benzyl or oligo(ethylene oxide) (EO x , x = 3 and 7.5), were used in these CuAAC reactions. Varying the addition sequences and feed ratios of the monomers produced a variety of hyperbranched copolymers with tunable compositions, molecular weights, segmented structures, and consequently glass transition temperature (T g ). It was found that the T g of hyperbranched copolymers was little affected by the polymer molecular weights when M n ≥ 5000. However, the values of T g were significantly determined by the compositions of the terminal groups and the outermost segment of the hyperbranched copolymers. The last added AB 2 monomer in the polymerization formed an outermost "shell" and shielded the contribution of inner segments to the glass transition of the copolymers, reflecting a chain sequence effect of hyperbranched polymers on the thermal properties. ■ INTRODUCTIONHyperbranched polymers with analogous structure as compared to dendrimers enjoy tremendous interest in both academia and industries because of their one-pot effortless synthesis to produce highly branched nanostructures with a large number of terminal groups. 1−5 In addition to the development of various synthetic methods to produce hyperbranched polymers, 6−31 the physical properties of hyperbranched polymers have also been intensively studies and compared to those of dendrimers. 1,4,32−37 Various structural parameters, including the molecular weights, polymer compositions, terminal end groups, degree of branching (DB), and segmented architectures, have been investigated, and their influence on the glass transition temperature (T g ) was broadly reported.Back in the 1990s, Frećhet, Hawker, and Wooley 34,38,39 studied the polyester and polyether dendrimers and found that the T g was significantly affected by the composition of chainend groups and the dendrimer molecular weights but little affected by the polymer architecture and DBs. When studying hyperbranched polymers from one-pot synthesis, several groups have reported similar dependence of T g on these structural parameters. 40,41 Meanwhile, copolymerization of AB 2 with AB or AB(BP) monomers (BP representing a protected B group that does not react during the polymerization) has been applied to synthesize hyperbranched polymers with tunable DBs, although the reported effects of DB on the T g were not always consistent. 42,43 For instance, Moore and McHugh 44 synthesized polyether hyperbranched polymers by copolymerization of AB 2 and AB monomers. They found that the T g decreased with the increased DB although the compared hyperbranched copolymers also had different numbers of terminal B groups. A similar strategy was applied by Jayakannan et al. for synthesis of polyester hyperbranched p...

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Controlled multi-vinyl monomer homopolymerization through vinyl oligomer combination as a universal approach to hyperbranched architectures

Cited by 99 publications

References 39 publications

Interfacial assembly of dendritic microcapsules with host–guest chemistry

Interfacial assembly of dendritic microcapsules with host–guest chemistry

Prospects for polymer therapeutics in Parkinson's disease and other neurodegenerative disorders

Investigate the Glass Transition Temperature of Hyperbranched Copolymers with Segmented Monomer Sequence

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