Co-initiated hyperbranched-polydendron building blocks for the direct nanoprecipitation of dendron-directed patchy particles with heterogeneous surface functionality

Hern, Faye Y.; Hill, Alexander P.; Owen, Andrew; Rannard, Steve P.

doi:10.1039/c8py00291f

Cited by 10 publications

(10 citation statements)

References 23 publications

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“…Well-defined nanoparticles have also been formed using branched polymers encapsulated within A-B linear copolymers, and their self-assembly and colloidal properties have been extensively studied previously. 45,46 We therefore selected polymers P2 and P5 as the model PEGylated copolymers (one linear and one branched) to encapsulate HB2 through a conanoprecipitation step. DLS analysis of the individual NPs/ HBs in aqueous solution showed a single population, and the control mixed solution of P2 + HB2 and P5 + HB2 showed two populations corresponding to the individual components as expected.…”

Section: Nanoparticle Formation and Dye Encapsulationmentioning

confidence: 99%

Amphiphilic tri- and tetra-block co-polymers combining versatile functionality with facile assembly into cytocompatible nanoparticles

et al. 2019

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Section: Nanoparticle Formation and Dye Encapsulationmentioning

confidence: 99%

Amphiphilic tri- and tetra-block co-polymers combining versatile functionality with facile assembly into cytocompatible nanoparticles

et al. 2019

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“…80 This technique has been used to generate various p(nBMA) architectures including: linear homopolymers, AB block copolymers, ABA triblock copolymers, branched statistical copolymers, branched statistical block copolymers and hyperbranched polydendrons. 81,82 Herein, we present our most recent work which expands the scope of hydrophobic monomers that can be polymerised via Cu-catalysed RDRP in anhydrous alcohol solvents. Pyrene fluorescence emission spectroscopy has been utilised to assess the relative polarity of homogeneous alcohol polymerisation mixtures across a range of methacrylate monomers and related to the controlled nature of Cu-catalysed RDRP in anhydrous methanol or isopropyl alcohol (IPA) during the formation of numerous polymer architectures including linear homopolymers and branched statistical copolymers.…”

Section: Introductionmentioning

confidence: 99%

Expanding the monomer scope of linear and branched vinyl polymerisations via copper-catalysed reversible-deactivation radical polymerisation of hydrophobic methacrylates using anhydrous alcohol solvents

et al. 2019

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Cu-Catalysed reversible-deactivation radical polymerisation of hydrophobic methacrylate monomers in anhydrous alcohols has been expanded to explore the scope of this unusual choice of solvent. A range of linear methacrylic homopolymers with well-targeted molecular weight and low dispersity (Đ = 1.12-1.53) have been generated in anhydrous methanol and isopropanol with relative ease. These solvents are normally considered antisolvents and employed to precipitate such polymers; therefore, our studies have assessed the polymerisation reaction mixture homogeneity and extent of reaction control. Statistical copolymerisations with the bi-functional monomer, ethylene glycol di-methacrlylate (EGDMA), has led to branched statistical copolymers with weight average molecular weights up to M w = 1.76 × 10 6 g mol −1 ; subsequent triple-detection size exclusion chromatography studies have provided insight into the impact of monomer structure on the extent of branching within the final isolated polymers. The ability to control branched copolymer molecular weights under these conditions through variation of EGDMA concentrations was seen to be highly dependent on methacrylate monomer chemistry. A number of factors which are likely to effect branching reactions during the polymerisation of hydrophobic methacrylates in anhydrous alcohols are discussed. † Electronic supplementary information (ESI) available: Experimental details, NMR spectra, TD-SEC analyses, additional figures and calculations. See

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“…This potentially new class of dendritic molecules can be viewed as dendronized dendritic polymers featured by the structure of multiple dendrimers/dendrons on a dendrimer-like skeleton with relatively narrow distribution of molecular weights. It is different from the previously reported classes of dendritic polymers, such as hyperbranched polydendrons − and dendron functionalized core cross-linked star polymers; in both systems, dendron initiators are being synthesized and used to initiate, in the former, the copolymerization of vinyl/divinyl monomers to form broad distribution products, while in the latter, the homopolymerization of vinyl monomers followed by end-linking using divinyl monomers. In this paper, we report, as a proof of concept, the first synthesis of such a hierarchically branched dendritic structure with multiple carbonate-based dendrons on a dendrimer-like polystyrene trunk.…”

Section: Introductionmentioning

confidence: 77%

Synthesis of a Hierarchically Branched Dendritic Polymer Possessing Multiple Dendrons on a Dendrimer-like Backbone

Zou

2021

Macromolecules

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We hereby report the synthesis of a novel type of dendritic structure, a hierarchically branched dendritic polymer, in which discrete dendrons are built at the branch points of a dendrimer-like skeleton. The synthesis consists of two stages, i.e., the preparation of dendrimer-like polystyrene through anionic polymerization and a chlorosilane coupling reaction as well as the formation of carbonate-containing dendrons from the primary hydroxy groups at the branch points of dendrimer-like polystyrene through highly selective reactions between imidazole carboxylic esters and primary hydroxyls. The hydroxy group is introduced by monoaddition of a 1,1-diphenylethylene derivative possessing −OSiBuMe 2 during anionic polymerization followed by deprotection. A hierarchically branched dendritic polymer, G3-g3, containing 21 carbonate-derived dendrons and 167 (theoretically 232) hydroxyl groups (subsequently transformed into acetoxy groups for better solubility), in a single dendrimer-like polystyrene, is prepared and characterized by NMR monitoring the synthetic process. The ultimate product shows higher multiplicity of functional groups owing to the high-level dendritic or multiple dendrons on dendrimer-like structure.

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Co-initiated hyperbranched-polydendron building blocks for the direct nanoprecipitation of dendron-directed patchy particles with heterogeneous surface functionality

Abstract: A synthetic strategy branched polymer building blocks that allow the rapid construction of patchy nanoparticles is presented. Hyperbranched polydendrons with mixtures of PEG and thiol-functional dendrons nanoprecipitate to form isolated zones that are imaged with gold nanoparticles.

Cited by 10 publications

References 23 publications

Amphiphilic tri- and tetra-block co-polymers combining versatile functionality with facile assembly into cytocompatible nanoparticles

Amphiphilic tri- and tetra-block co-polymers combining versatile functionality with facile assembly into cytocompatible nanoparticles

Expanding the monomer scope of linear and branched vinyl polymerisations via copper-catalysed reversible-deactivation radical polymerisation of hydrophobic methacrylates using anhydrous alcohol solvents

Synthesis of a Hierarchically Branched Dendritic Polymer Possessing Multiple Dendrons on a Dendrimer-like Backbone

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