title: Complex Coacervate Core Micelles with Spectroscopic Labels for Diffusometric Probing of Biopolymer Networks.
abstract: We present the design, preparation, and characterization of two types of complex coacervate core micelles (C3Ms) with cross-linked cores and spectroscopic labels and demonstrate their use as diffusional probes to investigate the microstructure of percolating biopolymer networks. The first type consists of poly(allylamine hydrochloride) (PAH) and poly(ethylene oxide)-poly(methacrylic acid) (PEO-b-PMAA), labeled with ATTO 488 fluorescent dyes. We show that the size of these probes can be tuned by choosing the length of the PEO-PMAA chains. ATTO 488-labeled PEO113-PMAA15 micelles are very bright with 18 dye molecules incorporated into their cores. The second type is a (19)F-labeled micelle, for which we used PAH and a (19)F-labeled diblock copolymer tailor-made from poly(ethylene oxide)-poly(acrylic acid) (mPEO79-b-PAA14). These micelles contain approximately 4 wt % of (19)F and can be detected by (19)F NMR. The (19)F labels are placed at the end of a small spacer to allow for the necessary rotational mobility. We used these ATTO- and (19)F-labeled micelles to probe the microstructures of a transient gel (xanthan gum) and a cross-linked, heterogeneous gel (κ-carrageenan). For the transient gel, sensitive optical diffusometry methods, including fluorescence correlation spectroscopy, fluorescence recovery after photobleaching, and super-resolution single nanoparticle tracking, allowed us to measure the diffusion coefficient in networks with increasing density. From these measurements, we determined the diameters of the constituent xanthan fibers. In the heterogeneous κ-carrageenan gels, bimodal nanoparticle diffusion was observed, which is a signpost of microstructural heterogeneity of the network.
authors.affiliation: Physical Chemistry and Soft Matter, Wageningen University , P.O. Box 8038, 6700 EK Wageningen, The Netherlands.|TI-COAST, Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: Nadia
authors.initials: N
authors.lastname: Bourouina
authors.affiliation: Laboratory of Biophysics, Wageningen University , P.O. Box 8128, 6700 ET Wageningen, The Netherlands.|TI-COAST, Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: Daan W
authors.initials: DW
authors.lastname: de Kort
authors.affiliation: SyMO-Chem B.V., Het Kraneveld 4, 5612 AZ Eindhoven, The Netherlands.|TI-COAST, Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: Freek J M
authors.initials: FJ
authors.lastname: Hoeben
authors.affiliation: SyMO-Chem B.V., Het Kraneveld 4, 5612 AZ Eindhoven, The Netherlands.|TI-COAST, Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: Henk M
authors.initials: HM
authors.lastname: Janssen
authors.affiliation: Laboratory of Biophysics, Wageningen University , P.O. Box 8128, 6700 ET Wageningen, The Netherlands.|TI-COAST, Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: Henk
authors.initials: H
authors.lastname: Van As
authors.affiliation: Laboratory of Biophysics, Wageningen University , P.O. Box 8128, 6700 ET Wageningen, The Netherlands.
authors.forename: Johannes
authors.initials: J
authors.lastname: Hohlbein
authors.affiliation: Laboratory of Biophysics, Wageningen University , P.O. Box 8128, 6700 ET Wageningen, The Netherlands.|Unilever R&D, Olivier van Noortlaan 120, 3133 AT Vlaardingen, The Netherlands.|TI-COAST, Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: John P M
authors.initials: JP
authors.lastname: van Duynhoven
authors.affiliation: Physical Chemistry and Soft Matter, Wageningen University , P.O. Box 8038, 6700 EK Wageningen, The Netherlands.|TI-COAST, Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: J Mieke
authors.initials: JM
authors.lastname: Kleijn
mesh_terms: D002351:Carrageenan / Q000737:chemistry*; D004058:Diffusion; D015195:Drug Design; D005452:Fluoresceins / Q000737:chemistry; D005456:Fluorescent Dyes / Q000737:chemistry*; D008823:Micelles; D008958:Models, Molecular; D008968:Molecular Conformation; D011092:Polyethylene Glycols / Q000737:chemistry*; D011109:Polymethacrylic Acids / Q000737:chemistry*; D011135:Polysaccharides, Bacterial / Q000737:chemistry*; D013057:Spectrum Analysis
chemical_list: C585059:Atto 488 maleimide; D005452:Fluoresceins; D005456:Fluorescent Dyes; D008823:Micelles; D011109:Polymethacrylic Acids; D011135:Polysaccharides, Bacterial; C547781:poly(ethylene oxide)-b-poly(methacrylic acid); D011092:Polyethylene Glycols; D002351:Carrageenan; C002563:xanthan gum