Phosphites as alternative coreagents for the one‐pot aminolysis/thiol‐ene synthesis of maleimide‐functionalized RAFT polymers

Ho, Hien The; Levere, Martin E.; Pascual, Sagrario; Montembault, Véronique; Soutif, Jean‐Claude; Fontaine, Laurent

doi:10.1002/pola.25934

Cited by 17 publications

(15 citation statements)

References 33 publications

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“…The RAFTmediated polymerization of vinyl acetate was adapted from a published procedure and gave, after 23 h of bulk polymerization, the desired xanthate end-functionalized polyvinyl acetate (Scheme 1). [15] Gel permeation chromatography in tetrahydrofuran indicated a molecular weight average of 15 kDa and a polydispersity index of 1.3 (see the Supporting Information, SI). The thiolated form was obtained in a onepot aminolysis of the xanthate moiety under inert atmosphere using n-hexylamine.…”

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confidence: 99%

Polyvinyl Alcohol as a Biocompatible Alternative for the Passivation of Gold Nanorods

et al. 2014

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The functionalization of gold nanorods (GNRs) with polymers is essential for both their colloidal stability and biocompatibility. However, a bilayer of the toxic cationic surfactant cetyl trimethylammonium bromide (CTAB) adsorbed on the nanorods complicates this process. Herein, we report on a strategy for the biocompatible functionalization of GNRs with a hydrophobic polymeric precursor, polyvinyl acetate, which is then transformed into its hydrophilic analogue, polyvinyl alcohol. This polymer was chosen due to its well-established biocompatibility, tunable "stealth" properties, tunable hydrophobicity, and high degree of functionality. The biocompatibility of the functionalized GNRs was tested by exposing them to primary human blood monocyte derived macrophages; the advantages of tunable hydrophobicity were demonstrated with the long-term stable encapsulation of a model hydrophobic drug molecule.

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Polyvinyl Alcohol as a Biocompatible Alternative for the Passivation of Gold Nanorods

et al. 2014

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“…19,20 In the latter case alkyl amines act as suitable agents for the aminolysis as well as the thiol-ene reaction. In all literature procedures, reaction solutions were freed from oxygen, and relatively fast reaction on the order of few hours were reported.…”

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Use of a continuous-flow microreactor for thiol–ene functionalization of RAFT-derived poly(butyl acrylate)

Vandenbergh

Junkers

2012

Polym. Chem.

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This study describes the synthesis of functionalized RAFT-derived poly(n-butyl acrylate) polymers via the use of a continuous-flow microreactor, in which aminolysis as well as thiol-ene reactions are executed in reaction times of just 20 minutes. Poly(n-butyl acrylate) (M n ¼ 3800 g mol À1, PDI ¼ 1.10) with a trithiocarbonate end group was prepared via a conventional RAFT process. The polymer was then functionalized via aminolysis/thiol-ene reactions in the micro-flow reactor with isobornyl acrylate, propargyl acrylate, poly(ethylene glycol) methyl ether acrylate and pentaerythritol tetraacrylate. To optimize the reaction time and reaction temperature of the micro-flow reactor, freshly collected samples were studied with soft ionization mass spectrometry. With this technique, efficient and very fast aminolysis and subsequent thiol-ene reactions take place on the RAFT-precursor polymer, yielding quantitative end group conversion within 20 min and functionalized polymers of 3700-4000 g mol À1, depending on the type of acrylate coupled. The use of a continuous-flow microreactor opens the pathway towards upsizing lab scale methods into larger processes without suffering from problems associated with reproducibility and tedious optimization issues.An often less valued key aspect of contemporary polymer synthesis, be it in the realm of controlled polymerization, click-like modifications or polymer analogous reactions, is the ability to upscale existing synthesis protocols. The adaption of procedures from microgram scale to significant production of materials on gram scale or larger is often tedious and accompanied with a loss in reaction efficiency or unreasonable reaction volumes. A convenient solution to this problem is the employment of microreactor technology.1 Miniaturized flow reactors offer the ability to optimize reaction conditions on a small scale while concomitantly allowing for simple upscale of reactions by going from small reactors to massive parallelization in reactor arrays or simply longer runtimes of the individual reactors. Also accelerations of the reactions can often be achieved by the rapid mixing of the components due to short diffusion lengths inside the microreactor, 2 as well as employing unconventional temperature regimes making microreactors in that respect comparable to the use of microwave reactors. The improved heat transfer of microreactors is a distinct advantage of these devices making their use especially interesting for highly exothermic reactions.3 While a wide array of commercial microreactors already exists, only a few studies have been reported so far on applications from the polymer field. Recently, Bally et al. described the synthesis of branched polymers from atom transfer radical polymerization (ATRP), 4 in a tubular microreactor. 5Also, polymerizations following the reversible addition fragmentation transfer (RAFT) 6 protocol have been described lately 7,8 as well as end group modifications 9 . Some earlier work on polymerizations in flow microreactors is summarized in a re...

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“…Die Abmessungen der Stäbchen betrugen nach Analyse von Transmissionselektronenmikroskopie(TEM)‐Bildern 57×12 nm, wobei das Verhältnis von Stäbchen zu kugelförmigen Nanopartikeln 96 % betrug. Ein bereits bestehendes Protokoll zur RAFT‐gesteuerten Polymerisation von Vinylacetat wurde angepasst, und nach einer Reaktionszeit von 23 h konnte die gewünschte Endfunktionalisierung von Polyvinylacetat erreicht werden (Schema ) 15. Gelpermeationschromatographie in Tetrahydrofuran zeigte im Durchschnitt ein Molekulargewicht von 15 kDa mit einem Polydispersitätsindex von 1.3 (siehe Hintergrundinformationen, SI).…”

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Polyvinylalkohol als biokompatibles Polymer zur Passivierung von Goldnanostäbchen

et al. 2014

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Die Oberflächenfunktionalisierung von Goldnanostäbchen mit Polymeren ist aufgrund der daraus resultierenden kolloidalen Stabilität und der Bioverträglichkeit der Nanopartikel von großer Bedeutung. Die normalerweise vorhandene toxische Doppelschicht aus dem kationische Tensid Cetyltrimethylammoniumbromid (CTAB), das an die Oberfläche der Nanostäbchen adsorbiert ist, erschwert diesen Prozess jedoch erheblich. Nachstehend erläutern wir eine Strategie zur biokompatiblen Funktionalisierung der Nanostäbchen mit hydrophoben Polymervorläufern, hier Polyvinylacetat, die anschließend in ihr hydrophiles Gegenstück, Polyvinylalkohol, überführt werden. Dieses Polymer wurde aufgrund seiner hohen Bioverträglichkeit, den veränderbaren hydrophilen und hydrophoben Eigenschaften und dem hohem Funktionalisierungsgrad gewählt. Die Verträglichkeit der oberflächenfunktionalisierten Goldnanostäbchen wurde an primären Makrophagen, die aus Monozyten differenziert wurden, getestet; die Vorteile der veränderlichen hydrophoben Eigenschaften wurden durch die langfristig stabile Einkapselung eines hydrophoben Beispielmedikaments gezeigt.

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Phosphites as alternative coreagents for the one‐pot aminolysis/thiol‐ene synthesis of maleimide‐functionalized RAFT polymers

Cited by 17 publications

References 33 publications

Polyvinyl Alcohol as a Biocompatible Alternative for the Passivation of Gold Nanorods

Polyvinyl Alcohol as a Biocompatible Alternative for the Passivation of Gold Nanorods

Use of a continuous-flow microreactor for thiol–ene functionalization of RAFT-derived poly(butyl acrylate)

Polyvinylalkohol als biokompatibles Polymer zur Passivierung von Goldnanostäbchen

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