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Polygalacturonic acid (PGA), being the backbone of pectins, governs their aggregation that is widely applied in industry. The PGA aggregation was studied by dynamic and static light scattering within a limited space of sodium polygalacturonate nanoparticles obtained by nanoprecipitation (drop-wise addition of alkaline solution of PGA to an ethanol bath). With increasing buffer's pH from 4.0 to 9.1, the colloids changed their form from elongated to spherical one, as indicated by decreasing the structure-sensitive ratio Rg/Rh from 1.7 to 1.1. Molecular mass-per-unit-length determined in Holtzer coordinates decreased from 5000 to 1600 Da nm-1 with increasing pH, suggesting partial disintegration of helical bundles due to electrostatic repulsion. Kratky plots also pointed out partial disintegration of the PGA junctions with increasing pH. Nonmonotonic dependence of the colloidal radius of gyration Rg on [NaCl] characterized the osmotic regime characteristic of annealed polyelectrolytes and thus confirmed the star-like structure of junctions.

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We study colloids of nanobiocomposites (NBC) containing Au nanoparticles (NP) obtained by reduction of gold precursor with functional groups of κCAR. The AuNPs content was changed from 2.0 to 5.6 w/w %. Hydrolysis of κCAR during reduction of gold ions produced carboxylate groups supporting nanobioconjugation (FT-IR data) and electrostatic stabilization through increased negative ζ-potential. The self-assembly of AuNPs took place after storing NBC, as shown by UV/vis. extinction and transmission electron microscopy. Analysis of the structure-sensitive Rg/Rh ratios obtained by dynamic and static light scattering showed that the colloids have core-shell structure. The macromolecules in the shell exhibited polyelectrolyte expansion at [NaCl] and [KCl] < 0.02 M. Above 0.02 M, the difference between non-specific sodium and specific potassium ions on the shell thickness was registered. The temperature hysteresis of the hydrodynamic radius Rh was similar to that of the pristine κCAR observed previously by optical rotation. Monitoring the equilibration of light scattering intensity at each mini-quenching step of the cooling run allowed further insight into the hysteresis origin. These colloids are interesting for sensing applications because of enhanced scattering of plasmonically coupled AuNPE. Their thermo- and ion-sensitivity can be useful in drug delivery.

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κ-carrageenan is a linear sulfated anionic gelling polysaccharide obtained from red seaweed algae by an alkaline hydrolysis. We applied static and dynamic light scattering (DLS), capillary viscometry, FT-IR, and electrophoretic DLS to gain insight into the effect of deep alkaline hydrolysis (95 °C, pH = 10 during Th = 60, 75, and 90 min) on κ-carrageenan macromolecules in a coil conformation. As DLS of coil-like κ-carrageenans is usually complicated by spurious permanent aggregates, the alkaline hydrolysis of κ-carrageenans has not been studied by DLS. By applying a double-dialysis procedure (first against water, then against 0.1 M NaCl), we succeeded in obtaining dilute solutions of coil-like κ-carrageenans with unimodal DLS distributions. Association that started with increasing concentration was attributed to attractive dipole-dipole interactions between ion-pairs formed by condensed counter-ions in the vicinity of carboxyl groups of the reducing ends. The second type of stickers resulted from the compositional heterogeneity of κ-carrageenan, namely, from the traces of ι-carrageenan blocks which amount increased with hydrolysis. With increasing Th we observed both the progressive decrease of molecular mass and the growth of association. Lowering the temperature and increasing concentration during lyophilization strengthened the intermolecular junctions, leading to the formation of permanent aggregates.

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Novel water-soluble chiroplasmonic nanobiocomposites with directly varied gold content were synthesized by a one-step redox method in water using a biocompatible polysaccharide κ-carrageenan (industrial product from algae) as both reducing and stabilizing matrix. The influence of the reactants ratio, temperature, and pH on the reaction was studied and the optimal reaction parameters were found. The structure and the properties of composite nanomaterials were examined in solid state and aqueous solutions by using complementary physical-chemical methods X-ray diffraction analysis, transmission electron microscopy, spectroscopy of electron paramagnetic resonance, atomic absorption and optical spectroscopy, polarimetry including optical rotatory dispersion with registration of interphase-crossbred Cotton effect of a chiral polysaccharide matrix on plasmonic chromophore of gold nanoparticles, dynamic and static light scattering. The new perspective multi-purpose nanocomposites demonstrate a complex of chiroplasmonic and magnetic properties, imparted by both nanoparticles and radicals enriched chiral polysaccharide matrix.

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Palladium nanoparticles (PdNPs) are used in catalysis, hydrogen storage, biomedicine, and so on. Arranging the self-assembly of PdNPs within colloidal aggregates is desirable for improving their consumer properties. Stable widely dispersed colloidal aggregates of larch arabinogalactan (LARB) containing nanosized (5-nm) PdNPs were obtained by reducing Pd ions in alkaline solutions of LARB. Centrifugation resulted in a set of LARB-PdNP colloids ranging from 60 to 240 nm. The colloids were studied by static light scattering (SLS) and dynamic light scattering (DLS). The SLS data presented as Kratki plots correspond to a particle scattering factor of linear rather than branched chains. The fractal dimension of the LARB-PdNP colloids was found by SLS to be d = 1.96, which is between the values for diffusion- and reaction-limited aggregation. This result is ascribed to the aggregate's internal motion, which is evident from the power-law exponent of the dependence of the DLS relaxation rate on the scattering vector, <Γ> ~ q(α) with α = 2.24. The structure-sensitive ratio of the radius of gyration to the hydrodynamic radius was found to vary within the interval of 0.8 ≤ R(g)/R(h) ≤ 1.2 corresponding, to the spherical form of LARB-PdNP colloids. A spiderweblike PdNP distribution pattern was observed by transmission electron microscopy. Insertion of PdNPs did not affect the fractal dimension, the power-law exponent α, or the architecture of the pristine LARB aggregates in water. The red shift of the surface plasmon extinction observed with increasing LARB-PdNP colloidal size indicates the collective optical response of the PdNP ensemble in the colloid.

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Colloids of metal nanoparticles (NPs) of Au, Ag, Pd, and Pt protected by natural polymer arabinogalactan (ARB) extracted from Larix sibirica were studied. The nanocomposites were prepared by reduction of metal salts in the water solutions of ARB. We carried out dynamic (DLS) and static light scattering resonantly enhanced by the NP plasmons. The translational diffusion was examined via DLS and a polarized interferometer. The virgin ARB was shown to form aggregates in dilute aqueous solutions. The introduction of NPs reduced the size of the virgin ARB aggregates. The aggregate forms as viewed by the scanning electron microscopy support the light scattering results.

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