Glucose-Responsive Hybrid Nanoassemblies in Aqueous Solutions: Ordered Phenylboronic Acid within Intermixed Poly(4-hydroxystyrene)-block-poly(ethylene oxide) Block Copolymer.
Coassembly behavior of the double hydrophilic block copolymer poly(4-hydroxystyrene)-block-poly(ethylene oxide) (PHOS-PEO) with three amphiphilic phenylboronic acids (PBA) differing in hydrophobicity, 4-dodecyloxyphenylboronic acid (C12), 4-octyloxyphenylboronic acid (C8), and 4-isobutoxyphenylboronic acid (i-Bu) was studied in alkaline aqueous solutions and in mixtures of NaOHaq/THF by spin-echo (1)H NMR spectroscopy, dynamic and electrophoretic light scattering, and SAXS. The study reveals that only the coassembly of C12 with PHOS-PEO provides spherical nanoparticles with intermixed PHOS and PEO blocks, containing densely packed C12 micelles. NMR measurements have shown that spatial proximity of PHOS-PEO and C12 leads to the formation of ester bonds between -OH of PHOS block and hydroxyl groups of -B(OH)2. Due to the presence of PBA moieties, the release of compounds with 1,2- or 1,3-dihydroxy groups loaded in the coassembled PHOS-PEO/PBA nanoparticles by covalent binding to PBA can be triggered by addition of a surplus of glucose that bind to PBA competitively. The latter feature has been confirmed by fluorescence measurements using Alizarin Red as a model compound. Nanoparticles were proved to exhibit swelling in response to glucose as detected by light scattering.
Department of Physical and Macromolecular Chemistry Faculty of Science, Charles University in Prague , Hlavova 2030, 128 40 Prague 2, Czech Republic.|Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology , Noakowskiego 3, 00664 Warsaw, Poland.
Alicja
A
Matuszewska
Department of Physical and Macromolecular Chemistry Faculty of Science, Charles University in Prague , Hlavova 2030, 128 40 Prague 2, Czech Republic.
Mariusz
M
Uchman
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology , Noakowskiego 3, 00664 Warsaw, Poland.
Agnieszka
A
Adamczyk-Woźniak
Department of Physical Chemistry, Faculty of Chemistry, Warsaw University of Technology , Noakowskiego 3, 00664 Warsaw, Poland.
Andrzej
A
Sporzyński
Theoretical & Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vassileos Constantinou Avenue, 11635 Athens, Greece.
Stergios
S
Pispas
Institute of Cellular Biology and Pathology, First Faculty of Medicine, Charles University in Prague , Albertov 4, 128 01 Prague 2, Czech Republic.
Lubomír
L
Kováčik
Department of Physical and Macromolecular Chemistry Faculty of Science, Charles University in Prague , Hlavova 2030, 128 40 Prague 2, Czech Republic.
Miroslav
M
Štěpánek
D000880:Anthraquinones / Q000737:chemistry; D001897:Boronic Acids / Q000737:chemistry*; D003692:Delayed-Action Preparations; D065546:Drug Liberation; D005947:Glucose / Q000737:chemistry*; D007328:Insulin / Q000737:chemistry*; D007700:Kinetics; D008823:Micelles; D053758:Nanoparticles / Q000737:chemistry* / Q000648:ultrastructure; D010636:Phenols / Q000737:chemistry*; D011092:Polyethylene Glycols / Q000737:chemistry*; D058105:Polymerization; D012996:Solutions; D014867:Water
D000880:Anthraquinones; D001897:Boronic Acids; D003692:Delayed-Action Preparations; D007328:Insulin; D008823:Micelles; D010636:Phenols; D012996:Solutions; D014867:Water; D011092:Polyethylene Glycols; C010078:alizarin; D005947:Glucose; C010686:benzeneboronic acid; C030626:4-vinylphenol