General Synthetic Route to Cell-Permeable Block Copolymers via ROMP

Kolonko, Erin M.; Pontrello, Jason K.; Mangold, Shane L.; Kiessling, Laura L.

doi:10.1021/ja809284s

Cited by 110 publications

(108 citation statements)

References 64 publications

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“…in solution. In related work, a number of studies with polynorbornenes prepared via ROMP have shown promise for the development of multivalent ligands that can interact with cell surface proteins and be internalized by cells 120,121 , but here we only discuss work with polynorbornenes with polymeric side-chains and other related bottlebrushes.…”

Section: Non-associating Bottlebrushes For Encapsulation and Deliverymentioning

confidence: 99%

Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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Bottlebrush polymers are a type of branched or graft polymer with polymeric side-chains attached to a linear backbone, and the unusual architecture of bottlebrushes provides a number of unique and potentially useful properties. These include a high entanglement molecular weight, enabling rapid self-assembly of bottlebrush block copolymers into large domain structures, the self-assembly of bottlebrush block copolymer micelles in a selective solvent even at very low dilutions, and the functionalization of bottlebrush side-chains for recognition, imaging, or drug 2 delivery in aqueous environments. This review article focuses on recent developments in the field of bottlebrush polymers with an emphasis on applications of bottlebrush copolymers.Bottlebrush copolymers contain two (or more) different types of polymeric side-chains. Recent work has explored the diverse properties and functions of bottlebrush polymers and copolymers in solutions, films, and melts, and applications explored include photonic materials, bottlebrush films for lithographic patterning, drug delivery, and tumor detection and imaging. We provide a brief introduction to bottlebrush synthesis and physical properties and then discuss work related to: i) bottlebrush self-assembly in melts and bulk thin films, ii) bottlebrushes for photonics and lithography, iii) bottlebrushes for small molecule encapsulation and delivery in solution, and iv) bottlebrush micelles and assemblies in solution. We briefly discuss three potential areas for future research, including developing a more quantitative model of bottlebrush self-assembly in the bulk, studying the properties of bottlebrushes at interfaces, and investigating the solution assembly of bottlebrush copolymers.

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Section: Non-associating Bottlebrushes For Encapsulation and Deliverymentioning

confidence: 99%

Structure, function, self-assembly, and applications of bottlebrush copolymers

et al. 2015

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“…While functional group placement is limited to one unit at the end of each polymer chain, this approach is complementary to the initiator route so that both ends can be labeled if desired. Alternatively, a reactive group such as activated esters, ketones, or azides can be introduced via the above-mentioned methods which can be then further used to attach dye molecules, an approach which has been quite frequently pursued [3,[76][77][78][79].…”

Section: Functionalization Via the Termination Reagentmentioning

confidence: 99%

“…While activated esters [10,77,81,82] and maleimide functionalities can be straightforwardly (co)polymerized via ROMP, terminal alkynes would participate in a metathesis reaction and therefore need to be protected, typically by a trimethylsilyl group which can be conveniently cleaved after polymerization using tetrabutylammonium fluoride. Azides are also not compatible with ROMP but can be introduced after polymerization by nucleophilic substitution of pendant alkyl halogenide chains [83][84][85].…”

Section: Post-polymerization Modificationmentioning

confidence: 99%

Dye-functionalized polymers via ring opening metathesis polymerization: principal routes and applications

2015

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Herein, highlights from the recent literature regarding functional dye-polymer conjugates obtained by ring opening metathesis polymerization (ROMP) are presented and the different approaches to incorporate dyes during the initiation, propagation, and termination step in ROMP are discussed. Applications in the field of chemical sensors, bioimaging, electroactive materials, self-assembly, photochromic and photoreactive materials are used to illustrate the versatility of ROMP as a technique to prepare complex functional materials. Graphical abstract

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“…The most common method to achieve this aim uses substituted vinyl ethers that already carry the desired end group functionality. [6][7][8][9] Reaction with the propagating ruthenium carbene complex yields a Fischer carbene complex and an end functionalized polymer. Nonetheless, the observed degrees of endfunctionality vary substantially depending on the organic moiety transferred and the E/Z ratio of the vinyl ether substrate.…”

Section: Introductionmentioning

confidence: 99%

Branched Polymers via ROMP of Termimers

Hanik

Kilbinger

2016

Macromol. Rapid Commun.

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the desired chemical moiety. In the living ring-opening metathesis polymerization employing Grubbs' ruthenium carbene complexes the reactive site is the propagating catalyst species, i.e., the ruthenium alkylidene complex. However, when utilizing ruthenium carbene complexes, their high tolerance towards oxygen, water and many polar functional groups impede the desired transformation into a functional end group since the number of potential reactants other than olefi ns is limited. Thus, what is generally considered one of the great advantages of ruthenium catalyzed olefi n metathesis is a slight disadvantage in this particular case.Nonetheless, several methods have been recently reported by our group that allow the mono end-functionalization of ROMP polymers with specifi c functional groups such as alcohols, [ 10,11 ] aldehydes and carboxylic acids, [ 12 ] thiols, [ 13 ] and amines. [ 14 ] By end-functionalizing living ROMP polymers using a cyclohexene derivative, a catalytic living ring opening metathesis process could even be achieved. [ 15 ] Synthesizing these end-functional polymers becomes especially useful when using them as macroinitiators for multiblock copolymer syntheses, building blocks for model networks or as macromonomers or prepolymers to reach very high molecular weights in subsequent polymerizations.Here, we describe the synthesis of a functionalizable cis -vinyl ether end-capping reagent that allows the Today's olefi n metathesis catalysts show high reactivity, selectivity, and functional group tolerance and allow the design of new syntheses of precisely functionalized polymers. Here the synthesis of a new end-capping reagent is investigated allowing the introduction of a highly reactive activated ester end-group at the polymer chain end as well as its prefunctionalization to directly introduce functional moieties. The versatility of this new end-capping reagent is demonstrated by utilizing it to synthesize a so-called termimer (a monomer with termination capabilities). Copolymerization of a norbornene derivative with the termimer leads to hyperbranched ring-opening metathesis polymerization polymers as proven by gel permeation chromatography and MALDI-ToF-(matrix-assisted laser desorption/ ionization time of fl ight) mass spectrometry.

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General Synthetic Route to Cell-Permeable Block Copolymers via ROMP

Cited by 110 publications

References 64 publications

Structure, function, self-assembly, and applications of bottlebrush copolymers

Structure, function, self-assembly, and applications of bottlebrush copolymers

Dye-functionalized polymers via ring opening metathesis polymerization: principal routes and applications

Branched Polymers via ROMP of Termimers

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