Intramolecular Cross-Linking Methodologies for the Synthesis of Polymer Nanoparticles

Mavila, Sudheendran; Eivgi, Or; Berkovich, Inbal; Lemcoff, N. Gabriel

doi:10.1021/acs.chemrev.5b00290

Cited by 353 publications

(340 citation statements)

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“…[8][9][10][11][12][13][14] Although the design and synthesis of single chain objects has recently received great attention, 15 the development in this field is still in its initial phase. So far, several types of strategies to mediate the single chain collapse to form SCNPs have been explored, [16][17][18][19][20][21][22] ranging from hydrogen bonding, 23-27, 10, 28-31 covalent bonding, [32][33][34][35][36] to dynamic covalent bonding. [37][38][39][40] All these recent advances have provided versatile approaches to induce the folding of a single polymer chain.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding–Chain Extension–Folding Process

et al. 2016

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Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:"This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work http://pubs.acs.org/page/policy/articlesonrequest/index.html ." A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL above for details on accessing the published version and note that access may require a subscription. ABSTRACTThe specific activity of proteins can be traced back to their highly defined tertiary structure, which is a result of a perfectly controlled intra-chain folding process. In the herein presented work the folding of different distinct domains within a single macromolecule is demonstrated. RAFT polymerization was used to produce multi-block copolymers, which are decorated with pendant hydroxyl groups in foldable sections, separated by non-functional spacer blocks in between. OH-bearing blocks were folded using an isocyanate cross linker prior to chain extension to form single chain nanoparticles (SCNP). After addition of a spacer block and a further OH decorated block, folding was repeated to generate individual SCNP within a polymer chain. Control experiments were performed indicating the absence of inter block cross linking. SCNP were found to be condensed by a combination of covalent and supra molecular (hydrogen bonds) linkage. The approach was used to create a highly complex penta-block copolymer having three individually folded subdomains with an overall dispersity of 1.21. The successful formation of SCNP was confirmed by size exclusion chromatography (SEC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and atomic force microscopy (AFM).

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Section: Introductionmentioning

confidence: 99%

Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding–Chain Extension–Folding Process

et al. 2016

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“…In order to engineering functional soft nanomaterials that closely mimic biomolecules in structure and behaviour, a paradigm in polymer synthesis involves handling single polymer chains 1 . Among the various techniques employed to these ends, the collapse of single polymer chains (precursors) via purely intramolecular cross-linking, into single-chain nanoparticles (SCNPs), has gained increasing interest over recent years [2][3][4][5] . Significant effort is being devoted to endow SCNPs with useful functions for multiple applications in, e.g., nanomedicine, biosensing, bioimaging or catalysis [6][7][8][9][10] .…”

Section: Introductionmentioning

confidence: 99%

Tunable slow dynamics in a new class of soft colloids

et al. 2016

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By means of extensive simulations, we investigate concentrated solutions of globular single-chain nanoparticles (SCNPs), an emergent class of synthetic soft nano-objects. By increasing the concentration, the SCNPs show a reentrant behaviour in their structural and dynamical correlations, as well as a soft caging regime and weak dynamic heterogeneity. The latter is confirmed by validation of the Stokes-Einstein relation up to concentrations far beyond the overlap density. Therefore SCNPs arise as a new class of soft colloids, exhibiting slow dynamics and actualizing in a real system structural and dynamical anomalies proposed by models of ultrasoft particles. Quantitative differences in the dynamical behaviour depend on the SCNP deformability, which can be tuned through the degree of internal cross-linking.

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“…The calculation of C ∞ for the investigated semiflexible chains by simulating the corresponding melts is computationally expensive since convergence to the long-N limit is much slower than for k = 0. However, an accurate estimation [38] can be obtained as C ∞ = (1 + cos θ )/(1 − cos θ ), with cos θ = 1 + e 2βk (βk − 1) + βk (e 2βk − 1)βk (4) and β = (k B T ) −1 . By using the former equations we find C ∞ ≈ 5, 9 and 15 for k = 3, 5 and 8, respectively.…”

Section: Model and Simulation Detailsmentioning

confidence: 99%

“…A growing interest is being devoted in recent years to the synthesis of polymeric singlechain nanoparticles (SCNPs) [1,2,3,4,5,6] with potential applications in, e.g., nanomedicine [7,8], bioimaging [9,10], biosensing [11], catalysis [12,13,14,15], or rheology [16,17,18]. SCNPs are obtained, generally at highly diluted conditions, through purely intramolecular cross-linking of single polymer precursors.…”

Section: Introductionmentioning

confidence: 99%

Effect of chain stiffness on the structure of single-chain polymer nanoparticles

Moreno

Bačová

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et al. 2017

J. Phys.: Condens. Matter

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Abstract.Polymeric single-chain nanoparticles (SCNPs) are soft nano-objects synthesized by purely intramolecular cross-linking of single polymer chains. By means of computer simulations, we investigate the conformational properties of SCNPs as a function of the bending stiffness of their linear polymer precursors. We investigate a broad range of characteristic ratios from the fully flexible case to those typical of bulky synthetic polymers. Increasing stiffness hinders bonding of groups separated by short contour distances and increases looping over longer distances, leading to more compact nanoparticles with a structure of highly interconnected loops. This feature is reflected in a crossover in the scaling behaviour of several structural observables. The scaling exponents change from those characteristic for Gaussian chains or rings in θ-solvents in the fully flexible limit, to values resembling fractal or 'crumpled' globular behaviour for very stiff SCNPs. We characterize domains in the SCNPs. These are weakly deformable regions that can be seen as disordered analogues of domains in disordered proteins. Increasing stiffness leads to bigger and less deformable domains. Surprisingly, the scaling behaviour of the domains is in all cases similar to that of Gaussian chains or rings, irrespective of the stiffness and degree of cross-linking. It is the spatial arrangement of the domains which determines the global structure of the SCNP (sparse Gaussian-like object or crumpled globule). Since intramolecular stiffness can be varied through the specific chemistry of the precursor or by introducing bulky side groups in its backbone, our results propose a new strategy to tune the global structure of SCNPs.

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Intramolecular Cross-Linking Methodologies for the Synthesis of Polymer Nanoparticles

Cited by 353 publications

References 273 publications

Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding–Chain Extension–Folding Process

Synthesis of Sequence-Controlled Multiblock Single Chain Nanoparticles by a Stepwise Folding–Chain Extension–Folding Process

Tunable slow dynamics in a new class of soft colloids

Effect of chain stiffness on the structure of single-chain polymer nanoparticles

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