Conference Paper

19F Labelled Polyion Micelles as Diffusional Nanoprobes

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We designed complex coacervate micelles, internally labeled with 4 wt% 19F and functionalized with a PEO corona, for diffusional probing of heterogeneous biopolymer gels. The particles are spherical and monodisperse with a hydrodynamic diameter of 31 nm and can be used for NMR diffusion experiments with observation times of order 10-500 ms. We assessed the performance of these particles for diffusometry experiments in heterogeneous kappa-carrageenan gels of different densities. Although 19F sensitivity is lower than 1H, 19F diffusometry allows for background-free observations of the particles, which will become a significant advantage for diffusometry experiments in compositionally complex systems.

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A set of functionalized nanoparticles (PEGylated dendrimers, d = 2.8 - 9 nm) was used to probe the structural heterogeneity in Na+/K+ induced κ-carrageenan gels. The self-diffusion behavior of these nanoparticles as observed by 1H PFG NMR, FRAP and RICS revealed a fast and a slow compo nent, pointing towards microstructural heterogeneity in the gel network. The self-diffusion behavior of the faster nanoparticles could be modelled with obstruction by a coarse network (average mesh size <100 nm), while the slower diffusing nanoparticles are trapped in a dense network (lower mesh size limit of 4.6 nm). Overhauser DNP-enhanced NMR relaxometry revealed a reduced local solvent water diffusivity near TEMPO-labelled nanoparticles trapped in the dense network, showing that heterogeneity in the physical network is also reflected in heterogeneous self-diffusivity of water. The observed heterogeneity in mesh sizes and in water self-diffusivity is of interest for understanding and modelling of transport through and release of solutes from heterogeneous biopolymer gels.
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 (kappa-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 kappa-carrageenan gels, bi-modal nanoparticle diffusion was observed, which is a signpost of microstructural heterogeneity of the network.
A derivation is given of the effect of a time-dependent magnetic field gradient on the spin-echo experiment, particularly in the presence of spin diffusion. There are several reasons for preferring certain kinds of time-dependent magnetic field gradients to the more usual steady gradient. If the gradient is reduced during the rf pulses, H1 need not be particularly large; if the gradient is small at the time of the echo, the echo will be broad and its amplitude easy to measure. Both of these relaxations of restrictions on the measurement of diffusion coefficients by the spin-echo technique serve to extend its range of applicability. Furthermore, a pulsed gradient can be recommended when it is critical to define the precise time period over which diffusion is being measured. The theoretical expression derived has been verified experimentally for several choices of time dependent magnetic field gradient. An apparatus is described suitable for the production of pulsed gradients with amplitudes as large as 100 G cm−1. The diffusion coefficient of dry glycerol at 26°±1°C has been found to be (2.5±0.2)×10−8 cm2 sec−1, a value smaller than can ordinarily be measured by the steady gradient method.
Diffusion in polymer solutions and gels has been studied by various techniques such as gravimetry, membrane permeation, fluorescence and radioactive labeling. These studies have led to a better knowledge on polymer morphology, transport phenomena, polymer melt and controlled release of drugs from polymer carriers. Various theoretical descriptions of the diffusion processes have been proposed. The theoretical models are based on different physical concepts such as obstruction effects, free volume effects and hydrodynamic interactions. With the availability of pulsed field gradient NMR techniques and other modern experimental methods, the study of diffusion has become much easier and data on diffusion in polymers have become more available. This review article summarizes the different physical models and theories of diffusion and their uses in describing the diffusion in polymer solutions, gels and even solids. Comparisons of the models and theories are made in an attempt to illustrate the applicability of the physical concepts. Examples in the literature are used to illustrate the application and applicability of the models in the treatment of diffusion data in various systems.
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