title: Porous Gold Nanoparticle-Decorated Nanoreactors Prepared from Smartly Designed Functional Polystyrene-block-Poly(d,l-Lactide) Diblock Copolymers: Toward Efficient Systems for Catalytic Cascade Reaction Processes.
abstract: Original porous catalytic supports can be engineered via an effective and straightforward synthetic route to polystyrene-block-poly(d,l-lactide) diblock copolymer precursors displaying an acid-cleavable acetal junction between both blocks. To this purpose, we synthesized an acetal-containing heterodifunctional initiator, thus enabling to combine two different polymerization methods, i.e., first atom transfer radical polymerization (ATRP) of styrene, and then ring-opening polymerization (ROP) of d,l-lactide. Thanks to the labile nature of the acetal junction, oriented porous frameworks could be obtained upon trifluoroacetic acid-mediated cleavage of the latter, after orientation of the block copolymer nanodomains by solvent vapor annealing. The resulting porous materials bearing a reactive aldehyde function at the pore surface allowed for further chemical modification via reductive amination with amino-containing compounds, such as tetraethylenepentamine, thus leading to amine-functionalized porous polystyrene. In situ generated gold nanoparticles could then be immobilized within such functionalized porous nanoreactors, and these hybrid materials could find interesting applications in heterogeneous supported catalysis. In this regard, model catalytic reactions, including C-C homocoupling of benzeneboronic acid derivatives, hydride-mediated reduction of nitroaromatic compounds, and especially unprecedented "one-pot" cascade reactions consisting of the latter consecutive reactions from 3-nitrobenzeneboronic acid, were successfully monitored by different chromatographic and spectroscopic techniques.
authors.affiliation: Université Paris-Est , Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182 CNRS-UPEC, 2 rue Henri Dunant, 94320 Thiais, France.
authors.forename: Romain
authors.identifier: http://orcid.org/0000-0001-8311-2101
authors.initials: R
authors.lastname: Poupart
authors.affiliation: Université Paris-Est , Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182 CNRS-UPEC, 2 rue Henri Dunant, 94320 Thiais, France.
authors.forename: Antoine
authors.initials: A
authors.lastname: Benlahoues
authors.affiliation: Université Paris-Est , Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182 CNRS-UPEC, 2 rue Henri Dunant, 94320 Thiais, France.
authors.forename: Benjamin
authors.identifier: http://orcid.org/0000-0002-5757-3606
authors.initials: B
authors.lastname: Le Droumaguet
authors.affiliation: Université Paris-Est , Institut de Chimie et des Matériaux Paris-Est (ICMPE), UMR 7182 CNRS-UPEC, 2 rue Henri Dunant, 94320 Thiais, France.
authors.forename: Daniel
authors.initials: D
authors.lastname: Grande
keywords: acetal; boronic acid C−C homocoupling; cascade reactions; diblock copolymers; functionalization; gold nanoparticles; nitroaromatic reduction; porous catalytic supports