A Modular Approach toward Functionalized Three-Dimensional Macromolecules:  From Synthetic Concepts to Practical Applications

Bosman, Anton W.; Vestberg, Robert; Heumann, Andi; Fréchet, Jean M. J.; Hawker, Craig J.

doi:10.1021/ja028392s

Cited by 324 publications

(294 citation statements)

References 128 publications

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“…[14][15][16] Polydispersities obtained for CRPs can approach the values typically obtained for living procedures (ca. 1.1) [17] and are often tolerant to trace impurities in the reaction medium.…”

Section: Well-defined Polymeric Nanostructuresmentioning

confidence: 99%

Catalytic polymeric nanoreactors: more than a solid supported catalyst

2012

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Polymeric nanostructures can be synthesized where the catalytic motif is covalently attached within the core domain and protected from the environment by a polymeric shell. Such nanoreactors can be easily recycled, and have shown unique properties when catalyzing reactions under pseudohomogeneous conditions. Many examples of how these catalytic nanostructures can act as nanosized reaction vessels have been reported in the literature. This prospective will focus on the exclusive features observed for these catalytic systems and highlight their potential as enzyme mimics, as well as the importance of further studies to unveil their full potential.

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Section: Well-defined Polymeric Nanostructuresmentioning

confidence: 99%

Catalytic polymeric nanoreactors: more than a solid supported catalyst

2012

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“…On the other hand, creating sufficiently hydrophobic domains around the catalytic sites to ensure compatibility of the homogeneous organo-or metal-based catalysts with aqueous environments has remained a major challenge. [1][2][3] For this reason, artificial metalloenzymes, [4][5][6] DNA-based catalysts, 7 amphiphilic copolymers, [8][9][10] star polymers, [11][12][13][14][15] micellar systems, [16][17][18][19][20] molecularly imprinted nano and microgels, [21][22][23] and dendrimers [24][25][26][27][28] were designed to achieve the necessary compartmentalization for efficient catalysis in water. Supramolecular folding of polymer chains into single chain polymeric nanoparticles (SCPNs) is an attractive alternative to prepare compartmentalized, water-soluble, nanometersized particles with a hydrophobic interior.…”

Section: Introductionmentioning

confidence: 99%

Understanding the catalytic activity of single‐chain polymeric nanoparticles in water

Artar

Terashima

Sawamoto

et al. 2013

J. Polym. Sci. Part A: Polym. Chem.

105

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ABSTRACT:The structuring role of benzene-1,3,5-tricarboxamide (BTA) groups for the catalytic activity of single chain polymeric nanoparticles in water was investigated in the transfer hydrogenation of ketones. To this end, a set of segmented, amphiphilic copolymers was prepared, which comprised oligo (ethylene glycol) side chains to impart water solubility, BTA and/or lauryl side chains to induce hydrophobicity and diphenylphosphinostyrene (SDP) units in the middle part as a ligand to bind a ruthenium catalyst. All copolymers were obtained by reversible addition-fragmentation chain transfer (RAFT) polymerization and showed low dispersities (M w /M n 5 1.23-1.38) and controlled molecular weights (M n 5 44-28 kDa). A combination of circular dichroism (CD) spectroscopy and dynamic light scattering (DLS) showed that all copolymers fold into a single chain polymeric nanoparticles (SCPNs) as a result of the helical selfassembly of the pendant BTA units and/or hydrophilic-hydrophobic phase separation. To create catalytic sites, RuCl 2 (PPh 3 ) 3 was incorporated into the copolymers. The Cotton effects of the copolymers before and after Ru(II) loading were identical, indicating that the helical self-assembly of the BTA units and the complexation of SDP ligands and Ru(II) occurs in an orthogonal manner. DLS revealed that after Ru(II) loading, SDP-bearing copolymers retained their single chain character in water, while copolymers lacking SDP units clustered into larger aggregates. The Ru(II) loaded SCPNs were tested in the transfer hydrogenation of cyclohexanone. This study reveals that BTA induced stack formation is not crucial for SCPN formation and catalytic activity; SDP-bearing copolymers folded by Ru(II) complexation and hydrophobic pendants suffice to provide hydrophobic, isolated reaction pockets around Ru(II) complexes. V C 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52,[12][13][14][15][16][17][18][19][20]

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“…2,3 A significant amount of effort has been devoted to developing efficient methods for accurately controlling polymer topology and architecture with the aim of preparing polymeric materials with new properties. 4 Many concepts and synthetic approaches have been developed to prepare macromolecules with various architectures and topologies, including dendrimers [5][6][7][8] and hyperbranched polymers, 9 -15 supramolecular polymers, 16 -21 cylindrical and spherical polymers, [22][23][24] polymers having folded structures, [25][26][27] molecular wires, 28 -30 metal-core polymers, 31,32 and polymeric nanostructures. [33][34][35] Vinyl polymers are an important category of synthetic materials, with millions of tons produced every year for broad applications such as fibers, plastics, and elastomers.…”

Section: Introductionmentioning

confidence: 99%

Z. Guan, Control of polymer topology through late‐transition‐metal catalysis, J Polym Sci Part A: Polym Chem (2003), 41(22), 3680–3692

Guan

2003

J. Polym. Sci. A Polym. Chem.

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ABSTRACT:In this article, recent examples are reviewed of late-transition-metal catalysis applied to polymer topology control. By the judicious selection or design of latetransition-metal catalysts, polymers with a broad range of topologies, including linear, short-chain-branched, hyperbranched, dendritic, and cyclic topologies, have been successfully synthesized. A distinctive advantage of the catalyst approach is that polymers with complex topologies can be prepared in one pot from simple commercial monomers. A fundamental difference of the catalyst approach with respect to other approaches is that the polymer topology is controlled by the catalysts instead of the monomer structure. In our own laboratory, we have successfully used two strategies to control the polymer topology with late-transition-metal catalysts. In the first strategy, hyperbranched polymers are prepared by the direct free-radical polymerization of divinyl monomers through control of the competition between propagation and chain transfer with a cobalt chain-transfer catalyst. In the second strategy, polyethylene topology is successfully controlled by the regulation of the competition between propagation and chain walking with the Brookhart Pd II -␣-bisimine catalyst.

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A Modular Approach toward Functionalized Three-Dimensional Macromolecules: From Synthetic Concepts to Practical Applications

Cited by 324 publications

References 128 publications

Catalytic polymeric nanoreactors: more than a solid supported catalyst

Catalytic polymeric nanoreactors: more than a solid supported catalyst

Understanding the catalytic activity of single‐chain polymeric nanoparticles in water

Z. Guan, Control of polymer topology through late‐transition‐metal catalysis, J Polym Sci Part A: Polym Chem (2003), 41(22), 3680–3692

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