Bifunctionalized Redox-Responsive Layers Prepared from a Thiolactone Copolymer

Abstract

The development of multifunctional surfaces is of general interest for the fabrication of biomedical, catalytic, microfluidic or biosensing devices. Herein, we report on the preparation of copolymer layers immobilized on gold surface and showing both free thiol and amino groups. These layers are produced by aminolysis of a thiolactone-based copolymer in the presence of a diamine, according to a one-step procedure. The free thiol and amino groups present in the modified copolymer layers can be successfully functionalized with respectively thiolated and carboxylic derivatives, in order to produce bifunctionalized surfaces. In addition, we show that the grafted thiolated derivative can be released by cleavage of the disulfide bond under mild reducing conditions. On the other hand, a side cross-linking reaction occurring during the grafting process and resulting in the formation of copolymer aggregates on the metal surface is evidenced. The methodology developed for the preparation of these bifunctionalized redox-responsive layers should be advantageously used to produce bioactive surfaces with drug loading/release properties.

Spatioselective functionalization of gold nanopillar arrays

“…As described in our previous studies, 24,25 a P(DMA-co-TlAm) copolymer layer can be efficiently graed on a gold surface in Scheme 2 Grafting of the P(DMA-co-TlAm) copolymer on gold nanopillars in presence of ethanolamine (step 1) and immobilization of gold NPs bearing maleimide groups on their surface, on the thiol groups of the resulting layer (step 2). presence of an amine derivative such as ethanolamine (Scheme 2, step 1).…”

“…Second, aer a partial etching of the sacricial polymer layer to reveal the upper surface of the nanopillars, a polythiolactone-based copolymer was graed on the top of the nanopillars, according to a procedure that we recently reported. 24,25 The further dissolution of the sacricial polymer layer in water exposes the non-functionalized lower part of the gold nanopillars and the background surface, which were then differently modied through the formation of a self-assembled monolayer (SAM) of alkylthiol molecules. To prove the successful spatio-selective chemical surface modication of the Au nanopillar surfaces, the presence of the thiolactone-based copolymer was revealed through coupling of free thiol moieties with maleimide gold nanoparticles.…”

Thiolated cationic poly(aspartamides) with side group dependent gelation properties for the delivery of anionic polyelectrolytes

“…31 Despite many synthetic protocols reported about the synthesis of thiolactone-based polymers for various applications, their use in drug delivery applications is limited. [32][33][34][35] For instance, bifunctionalized redox-responsive layers were developed, which can be used to produce bioactive surfaces with drug loading and release properties. 32 Polymer prodrugs with tumour acidity-promoted cellular internalization and intracellular drug release 34 can be achieved through the modification of drug molecules with thiolactone moiety.…”

Sequential and one-pot post-polymerization modification reactions of thiolactone-containing polymer brushes

“…In exploration of alternative routes to multifunctional homopolymer brush surfaces, we turned our attention to the efficient double modification strategy using γ-thiolactone reported by Du Prez et al [25][26][27][28][29][30][31] Thiolactones undergo a nucleophilic ring-opening reaction with primary amines forming an amide between the carbonyl of the thiolactone, liberating a thiol that can undergo sequential thiol-coupling reactions with alkenes, alkynes, maleimides, or acrylates. Thiolactone double modification reactions exhibit 100 % atom-efficiency and can be performed in an efficient one-pot reaction.…”

“…While Du Prez and others have demonstrated thiolactone chemistry for the versatile design of polymeric architectures, the chemistry has received surprising little attention in the context of surface modification. 29,31,32 To our knowledge, the thiolactone double modification strategy has yet to be exploited for synthesis of multifunctional homopolymer brush surfaces.…”