Complex Coacervate Core Micelles with Spectroscopic Labels for Diffusometric Probing of Biopolymer Networks

Nadia Bourouina, D.W. De Kort*, F.J.M. Hoeben, H.M. Janssen, Henk Van As, Johannes Hohlbein, J.P.M. Van Duynhoven, J.M. Kleijn

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

6 Citations (Scopus)

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 19F-labeled micelle, for which we used PAH and a 19F-labeled diblock copolymer tailor-made from poly(ethylene oxide)-poly(acrylic acid) (mPEO79-b-PAA14). These micelles contain approximately 4 wt % of 19F and can be detected by 19F NMR. The 19F labels are placed at the end of a small spacer to allow for the necessary rotational mobility. We used these ATTO- and 19F-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.

Original languageEnglish
Pages (from-to)12635-12643
JournalLangmuir
Volume31
Issue number46
DOIs
Publication statusPublished - 2015

Fingerprint

Biopolymers
biopolymers
Micelles
Labels
micelles
Polyethylene oxides
Gels
gels
carbopol 940
Carrageenan
polycyclic aromatic hydrocarbons
Polycyclic aromatic hydrocarbons
ethylene oxide
probes
Dyes
dyes
Xanthan gum
Nanoparticles
Photobleaching
fluorescence

Cite this

Bourouina, Nadia ; De Kort, D.W. ; Hoeben, F.J.M. ; Janssen, H.M. ; Van As, Henk ; Hohlbein, Johannes ; Van Duynhoven, J.P.M. ; Kleijn, J.M. / Complex Coacervate Core Micelles with Spectroscopic Labels for Diffusometric Probing of Biopolymer Networks. In: Langmuir. 2015 ; Vol. 31, No. 46. pp. 12635-12643.
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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 19F-labeled micelle, for which we used PAH and a 19F-labeled diblock copolymer tailor-made from poly(ethylene oxide)-poly(acrylic acid) (mPEO79-b-PAA14). These micelles contain approximately 4 wt {\%} of 19F and can be detected by 19F NMR. The 19F labels are placed at the end of a small spacer to allow for the necessary rotational mobility. We used these ATTO- and 19F-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.",
author = "Nadia Bourouina and {De Kort}, D.W. and F.J.M. Hoeben and H.M. Janssen and {Van As}, Henk and Johannes Hohlbein and {Van Duynhoven}, J.P.M. and J.M. Kleijn",
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doi = "10.1021/acs.langmuir.5b03496",
language = "English",
volume = "31",
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Complex Coacervate Core Micelles with Spectroscopic Labels for Diffusometric Probing of Biopolymer Networks. / Bourouina, Nadia; De Kort, D.W.; Hoeben, F.J.M.; Janssen, H.M.; Van As, Henk; Hohlbein, Johannes; Van Duynhoven, J.P.M.; Kleijn, J.M.

In: Langmuir, Vol. 31, No. 46, 2015, p. 12635-12643.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Complex Coacervate Core Micelles with Spectroscopic Labels for Diffusometric Probing of Biopolymer Networks

AU - Bourouina, Nadia

AU - De Kort, D.W.

AU - Hoeben, F.J.M.

AU - Janssen, H.M.

AU - Van As, Henk

AU - Hohlbein, Johannes

AU - Van Duynhoven, J.P.M.

AU - Kleijn, J.M.

PY - 2015

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N2 - 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 19F-labeled micelle, for which we used PAH and a 19F-labeled diblock copolymer tailor-made from poly(ethylene oxide)-poly(acrylic acid) (mPEO79-b-PAA14). These micelles contain approximately 4 wt % of 19F and can be detected by 19F NMR. The 19F labels are placed at the end of a small spacer to allow for the necessary rotational mobility. We used these ATTO- and 19F-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.

AB - 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 19F-labeled micelle, for which we used PAH and a 19F-labeled diblock copolymer tailor-made from poly(ethylene oxide)-poly(acrylic acid) (mPEO79-b-PAA14). These micelles contain approximately 4 wt % of 19F and can be detected by 19F NMR. The 19F labels are placed at the end of a small spacer to allow for the necessary rotational mobility. We used these ATTO- and 19F-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.

U2 - 10.1021/acs.langmuir.5b03496

DO - 10.1021/acs.langmuir.5b03496

M3 - Article

VL - 31

SP - 12635

EP - 12643

JO - Langmuir

JF - Langmuir

SN - 0743-7463

IS - 46

ER -