Single‐Chain Polymeric Nanoparticles by Stepwise Folding

Mes, Tristan; Weegen, Rob van der; Palmans, Anja R. A.; Meijer, E. W.

doi:10.1002/anie.201100104

Cited by 211 publications

(189 citation statements)

References 56 publications

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“…31,[34][35][36][37][38] These results suggest that the controlled topology of the polymer chains allows the selfassembly motifs, that is, BTA units and Ru(II)-SDP units, to act in an orthogonal way. 27,34 Dynamic light scattering (DLS) experiments were performed to elucidate the single chain folding of the prepared copolymers. When linear polymers fold into SCPNs, hydrodynamic diameters (D H ) of around 10 nm are expected.…”

Section: CD Dls and Fluorescence Characterization Of P1-p5 In Solutionmentioning

confidence: 91%

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

Artar

Terashima

Sawamoto

et al. 2013

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

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110

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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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Section: CD Dls and Fluorescence Characterization Of P1-p5 In Solutionmentioning

confidence: 91%

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

Artar

Terashima

Sawamoto

et al. 2013

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

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110

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“…For the systems in which folding is governed by BTA self-assembly, CD spectroscopy is a powerfull technique as shown by Mes et al (28). When the BTAs are non-racemic, helical aggregates of one helicity are biased and this assembly process gives rise to a signature Cotton effect.…”

Section: Characterization Of Dynamic Scpnsmentioning

confidence: 96%

“…The size of the SCPNs could be tuned via varying the molecular weight of the polymer (37). Foillowing these first experiments, Mes et al showed that benzene-1,3,5-tricarboxamides (BTAs) can also be utilized as a supramolecular unit to form SCPNs (28). In this example, a prepolymer was synthesized via activators regenerated by electron transfer atom transfer radical polymerization (ARGET-ATRP), using isobornyl methacrylate and silyl-protected propargyl methacrylate as the monomers.…”

Section: Synthetic Access To Dynamic Scpnsmentioning

confidence: 98%

“…In non-dynamic SCPNs, many different types of covalent bond formation have been applied successfully for the intramolecular crosslinking of the polymers (16)(17)(18)(19)(20)(21)(22)(23). In dynamic SCPNs, reversible covalent bonds such as disulfides (24) or acyl hydrazones (25) have been utilized as well as non-covalent bonds such as diamides (26), 2-ureido-pyrimidinones (UPys) (27), benzene-1,3,5-tricarboxamides (BTAs) (28), a combination of BTAs and UPys (29), BTA-bipyridines (30), cucurbit [8]uril (31), thymine-diaminopyridine (32), six-point cyanuric acid-Hamilton wedge interactions (33) and a combination of the last two (34).…”

Section: Synthetic Access To Dynamic Scpnsmentioning

confidence: 99%

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Dynamic Single Chain Polymeric Nanoparticles: From Structure to Function

Artar

Martinez

Meijer

et al. 2014

ACS Symposium Series

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Achieving the perfection of Nature in forming ordered structures in three dimensions is one of the great challenges for supramolecular chemists.Recently, the merger of supramolecular and polymer chemistry resulted in the preparation of polymers with pendant supramolecular motifs that intramolecularly self-assemble in solution into structures of defined size and shape. This review summarizes the recent progress made in preparing and characterizing such compartmentalized structures in solution in which the internal structure arises from non-covalent bond formation, making the obtained particles dynamic and adaptable. In addition, the potential of these so-called dynamic single-chain polymeric nanoparticles (SCPNs) is explored. We highlight the potential of SCPNs for catalysis in water and sensing, functions that all arise as a result of the well-defined conformations that are attained by directional non-covalent interactions

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“…Due to these advances that stem from a thorough understanding of the polymerization mechanisms involved, more and more complex polymeric structures have been synthesized, such as brush polymers, 10,11 dendrimers, [12][13][14] micrometer-sized toroids, 15 and polymers that fold and unfold in a controlled fashion. [16][17][18][19] Concomitant to the development of polymeric structures formed by covalent bonds, supramolecular polymers have been introduced. [20][21][22][23] In these structures, the building blocks of the polymer are connected by noncovalent interactions like hydrophobic interactions, hydrogen-bonding, and metal-ligand bonding.…”

mentioning

confidence: 99%

Toward model‐driven engineering of supramolecular copolymers

Korevaar

Grenier

Meijer

2014

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

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The coassembly of two oligo-(p-phenylene vinylene) (OPV) derivatives with different sizes and opposite chirality is studied. Short R-chiral ROPV 3 molecules experience a high energetic mismatch penalty when incorporated in helices formed by long S-chiral SOPV 4 molecules. In contrast, SOPV 4 easily coassembles into helices dominated by ROPV 3 . As a result, the coassembly behavior (i.e., mixing or phase separation of ROPV 3 and SOPV 4 within the assemblies) highly depends on the ratio between both molecular building blocks. By a combination of experiments and models, the assembly pathways are analyzed. Furthermore, the model allows identifying key parameters in the coassembly behavior, such as the cooperativity and the mismatch penalties. The model-driven approach is anticipated to be generally applicable in the engineering of functional supramolecular copolymers. This article is dedicated to the 70th birthday of Jean Fr echet and we thank him for being a continuous source of inspiration for our group.

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Single‐Chain Polymeric Nanoparticles by Stepwise Folding

Cited by 211 publications

References 56 publications

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

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

Dynamic Single Chain Polymeric Nanoparticles: From Structure to Function

Toward model‐driven engineering of supramolecular copolymers

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