Salt and Temperature Effects on Xanthan Gum Polysaccharide in Aqueous Solutions.

Xanthan gum (XG) is a carbohydrate polymer with anionic properties that is widely used as a rheology modifier in various applications, including foods and petroleum extraction. The aim was to investigate the effect of Na+, K+, and Ca2+ on the physicochemical properties of XG in an aqueous solution as a function of temperature. Huggins, Kraemer, and Rao models were applied to determine intrinsic viscosity, [η], by fitting the relative viscosity (ηrel) or specific viscosity (ηsp) of XG/water and XG/salt/water solutions. With increasing temperature in water, Rao 1 gave [η] the closest to the Huggins and Kraemer values. In water, [η] was more sensitive to temperature increase (~30% increase in [η], 20-50 °C) compared to salt solutions (~15-25% increase). At a constant temperature, salt counterions screened the XG side-chain-charged groups and decreased [η] by up to 60% over 0.05-100 mM salt. Overall, Ca2+ was much more effective than the monovalent cations in screening charge. As the salt valency and concentration increased, the XG coil radius decreased, making evident the effect of shielding the intramolecular and intermolecular XG anionic charge. The reduction in repulsive forces caused XG structural contraction. Further, higher temperatures led to chain expansion that facilitated increased intermolecular interactions, which worked against the salt effect.

Ionic Liquid-Controlled Shape Transformation of Spherical to Nonspherical Polymersomes via Hierarchical Self-Assembly of a Diblock Copolymer.

Here, we report the self-assembly of poly(ethylene glycol) methyl ether-block-poly(ε-caprolactone) (PEG-b-PCL) copolymer in three ionic liquids (ILs) possessing different cations with common bis(trifluoromethylsulfonyl)imide anion. The observed polymeric nanostructures in ILs were directly visualized by room temperature conventional transmission and field emission scanning electron microscopy and were further examined for their size and shape by dynamic light scattering technique. The results show that through changes in the concentration of PEG-b-PCL and/or changing the solvent by using a different IL, we can effectively induce shape transformation of self-assembled PEG-b-PCL nanostructures in order to generate nonspherical polymersomes, such as worm-like aggregates, stomatocytes, nanotubes, large hexagonal and tubular-shaped polymersomes. These findings provide a promising platform for the design of biodegradable soft dynamic systems in the micro-/nano-motor field for cancer-targeted delivery, diagnosis and imaging-guided therapy, and controlled release of therapeutic drugs for treatment of many diseases. Non-spherical polymersome-based vaccines may be taken up more efficiently, especially against viruses for pulmonary drug delivery than the spherical polymersomes-based.

Assessing rotation and solvation dynamics in ethaline deep eutectic solvent and its solutions with methanol.

Steady-state and time-resolved fluorescence were used to investigate the solvation of coumarin 153 (C153) and coumarin 343 (C343) in methanol + ethaline binary solutions, a deep eutectic solvent composed of a 1:2 molar ratio choline chloride + ethylene glycol. In addition, time-resolved anisotropy decays were used to determine the solute's rotational reorientation time as a function of viscosity. Measurements were made in solutions covering the entire range of mole fraction. Viscosity measurements were used to characterize the bulk solvent properties, and as expected, addition of methanol resulted in an decreased viscosity, showing an exponential decrease with mole fraction, up to ∼50-fold at xMeOH = 1.0. Probe rotational reorientation times were found to be biexponential at xMeOH < 0.3 for C153 and xMeOH < 0.5 for C343 and monoexponential at richer methanol content. In proportion to viscosity, C153 and C343 average rotation times decreased ∼30-fold from xMeOH = 0 to 0.9 and showed a power law dependence of ∼η0.85. Rotation times approached the stick boundary limit on dilution with methanol. Time-resolved Stokes shifts quantified the solvation dynamics and were nearly single exponential for C153 but were clearly biexponential for C343. Solvation times also tracked with viscosity according to a power law dependence, with exponents of 0.3 and 0.4 for C153 and C343, respectively. The dilution effect of methanol was not linear in proportion to the viscosity change and alone cannot account for the change in solvation. Dilution also showed a different correlation to solvation than did temperature variations to govern the viscosity change.

Interactions between a dsDNA Oligonucleotide and Imidazolium Chloride Ionic Liquids: Effect of Alkyl Chain Length, Part I.

Ionic liquids (ILs) have become nearly ubiquitous solvents and their interactions with biomolecules has been a focus of study. Here, we used the fluorescence emission of DAPI, a groove binding fluorophore, coupled with molecular dynamics (MD) simulations to report on interactions between imidazolium chloride ([Imn,1]+) ionic liquids and a synthetic DNA oligonucleotide composed entirely of T/A bases (7(TA)) to elucidate the effects ILs on a model DNA duplex. Spectral shifts on the order of 500-1000 cm-1, spectral broadening (~1000 cm-1), and excitation and emission intensity ratio changes combine to give evidence of an increased DAPI environment heterogeneity on added IL. Fluorescence lifetimes for DAPI/IL solutions yielded two time constants 0.15 ns (~80% to 60% contribution) and 2.36-2.71 ns for IL up to 250 mM. With DNA, three time constants were required that varied with added IL (0.33-0.15 ns (1-58% contribution), ~1.7-1.0 ns (~5% contribution), and 3.8-3.6 ns (94-39% contribution)). MD radial distribution functions revealed that π-π stacking interactions between the imidazolium ring were dominant at lower IL concentration and that electrostatic and hydrophobic interactions become more prominent as IL concentration increased. Alkyl chain alignment with DNA and IL-IL interactions also varied with IL. Collectively, our data showed that, at low IL concentration, IL was primarily bound to the DNA minor groove and with increased IL concentration the phosphate regions and major groove binding sites were also important contributors to the complete set of IL-DNA duplex interactions.

NMR relaxometric probing of ionic liquid dynamics and diffusion under mesoscopic confinement within bacterial cellulose ionogels.

Bacterial cellulose ionogels (BCIGs) represent a new class of material comprising a significant content of entrapped ionic liquid (IL) within a porous network formed from crystalline cellulose microfibrils. BCIGs suggest unique opportunities in separations, optically active materials, solid electrolytes, and drug delivery due to the fact that they can contain as much as 99% of an IL phase by weight, coupled with an inherent flexibility, high optical transparency, and the ability to control ionogel cross-sectional shape and size. To allow for the tailoring of BCIGs for a multitude of applications, it is necessary to better understand the underlying principles of the mesoscopic confinement within these ionogels. Toward this, we present a study of the structural, relaxation, and diffusional properties of the ILs, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([bmpy][Tf2N]), using 1H and 19F NMR T1 relaxation times, rotational correlation times, and diffusion ordered spectroscopy (DOSY) diffusion coefficients, accompanied by molecular dynamics (MD) simulations. We observed that the cation methyl groups in both ILs were primary points of interaction with the cellulose chains and, while the pore size in cellulose is rather large, [emim]+ diffusion was slowed by ∼2-fold, whereas [Tf2N]- diffusion was unencumbered by incorporation in the ionogel. While MD simulations of [bmpy][Tf2N] confinement at the interface showed a diffusion coefficient decrease roughly 3-fold compared to the bulk liquid, DOSY measurements did not reveal any significant changes in diffusion. This suggests that the [bmpy][Tf2N] alkyl chains dominate diffusion through formation of apolar domains. This is in contrast to [emim][Tf2N] where delocalized charge appears to preclude apolar domain formation, allowing interfacial effects to be manifested at a longer range in [emim][Tf2N].

Carboxymethyl hydroxypropyl guar gum physicochemical properties in dilute aqueous media.

We investigate carboxymethyl hydroxypropyl guar gum (CMHPG) solution properties in water and NaCl, KCl, and CaCl2 aqueous solutions. The Huggins, Kraemer, and Rao models were applied by fitting specific and relative viscosity of CMHPG/water and CMHPG/salt/water to determine the intrinsic viscosity [η]. The Rao models yielded better results (R2 = 0.779-0.999) than Huggins and Kraemer equations. [η] decreased up to 84% in salt solution over the range 0.9-100 mM compared to water. Salt effects screened the CMHPG charged side groups chains leading to a compacted structure. In 0.9 mM NaCl(aq), the hydrodynamic coil radius (Rcoil) was 28% smaller and 45% smaller in 100 mM NaCl solution relative to water. Similar decreases were seen in KCl and CaCl2 solutions. KCl and CaCl2 were more effective than NaCl. CMHPG is salt-tolerant and shows comparatively less viscosity change than native guar gum, with modest reduced viscosity increases with CMHPG dilution at all salt concentrations. The electrostatic interactions were effective up to 100 mM salt. The activation energy of viscous flow for CMHPG solutions was computed and compared to measured xanthan gum and several literature values. These data show that the barrier to CMHPG flow is higher than for xanthan gum.

Determining mushroom tyrosinase inhibition by imidazolium ionic liquids: A spectroscopic and molecular docking study.

The inhibition effects of imidazolium ionic liquids (ILs) on the enzyme kinetics of mushroom tyrosinase is reported. A simple UV-VIS spectrophotometric assay was used to measure the reaction kinetics of the reaction between mushroom tyrosinase and L-dopa. Seven different imidazolium ILs, comprised of 1-alkyl-3-methylimidazolium ([Imn1+], n=2, 4, 6) cations paired with several anions that included Cl-, [NO3-], methanesulfonate ([MeSO3-]), trifluoromethanesulfonate (or triflate, [TFMS-]), and bis(trifluoromethylsulfonyl)imide ([Tf2N-]). Lineweaver-Burk plots were generated from the recovered kcat and Km parameters using four to six substrate concentrations per measurement. The results show that mushroom tyrosinase activity was consistently inhibited by all of the ILs and that the type of inhibition was non-competitive in nearly all cases. Only the data for [Im21+][Tf2N-] suggested that the inhibition mechanism was competitive with the substrate. Molecular docking simulations were performed using AutoDock4.2 and AutoDock Vina and revealed that all cations docked in the L-dopa active site. Anions showed varied results that included locations both within and outside of the active site.

Solvation and rotation dynamics in the trihexyl(tetradecyl)phosphonium chloride ionic liquid/methanol cosolvent system.

The interactions and solvent structure in trihexyl(tetradecyl)phosphonium chloride ionic liquid ([P(14,6,6,6)(+)][Cl(-)], "PIL-Cl")/methanol (MeOH) solutions across the entire range of mole fraction PIL-Cl (x(IL) = 0-1) are discussed. Viscosity and conductivity measurements are used to characterize the bulk solvent properties. At x(IL) < 0.1, the log(η) data show a nonlinear dependence on mole fraction in contrast to the data for x(IL) > 0.1 where the data vary linearly with mole fraction. Conductivity data show a maximum at x(IL) = 0.03 in good agreement with conductivity measurements in imidazolium ILs. Steady-state and time-resolved fluorescence spectroscopies were used to measure the equilibrium, lifetime, and rotational response of coumarin 153 (C153) in neat and MeOH cosolvent modified PIL-Cl. The collective set of data depicts the formation of an increasingly aggregated solvent structure that changes in proportion to the amount of PIL-Cl present in MeOH. Average solvation and rotation times are found to scale with solution viscosity. At x(IL) values of 0.02-0.2, the rotation times are at or near the hydrodynamic stick limit, whereas for x(IL) > 0.2 rotation times drop to between 40 and 70% of the stick limit, consistent with the IL literature. In this cosolvent system, the most dramatic changes in solution behavior occur between 0 and 10% PIL-Cl.