Cyclodextrins: Properties and Applications.

Cyclodextrins (CDs) are cyclic oligosaccharides that contain at least six d-(+)-glucopyranose units linked by α-(1, 4) glucosidic bonds [...].

Interactions between Sodium Hyaluronate and ß-Cyclodextrin as Seen by Transport Properties.

Knowledge of mass transport parameters, diffusion, and viscosity of hyaluronic acid (HA) in the presence of cyclodextrins is of considerable importance for areas such as food packaging and drug delivery, among others. Despite a number of studies investigating the functionalization of HA or the corresponding sodium salt by cyclodextrins, only a few studies have reported the effect of cyclodextrins on the mass transport of HA in the presence of these oligosaccharides. Here, we report the tracer binary and ternary interdiffusion coefficients of sodium hyaluronate (NaHy) in water and aqueous ß-cyclodextrin solutions. The diffusion behavior of sodium hyaluronate was dependent on the reduced viscosity of NaHy, which, in turn, presented a concave dependence on concentration, with a minimum at approximately 2.5 g dm-3. The significant decrease in the limiting diffusion coefficient of NaHy (at most 45%) at NaHy concentrations below 1 g dm-3 in the presence of ß-cyclodextrin, taking water as the reference, allowed us to conclude that NaHy strongly interacted with the cyclodextrin.

Interactions of Sodium Salicylate with ß-Cyclodextrin and an Anionic Resorcin[4]arene: Mutual Diffusion Coefficients and Computational Study.

The interaction between sodium salicylate (NaSal) and the two macrocycles 5,11,17,23-tetrakissulfonatomethylene-2,8,14,20-tetra(ethyl)resorcinarene (Na4EtRA) and ß-cyclodextrin (ß-CD) has been studied by the determination of ternary mutual diffusion coefficients, and spectroscopic and computational techniques. The results obtained by the Job method suggest that the complex formation is given in a 1:1 ratio for all systems. The mutual diffusion coefficients and the computational experiments have shown that the ß-CD-NaSal system presents an inclusion process, whereas the Na4EtRA-NaSal system forms an outer-side complex. This fact is also in line with the results obtained from the computational experiments, where the calculated solvation free energy has been found to be more negative for the Na4EtRA-NaSal complex because of the partial entry of the drug inside the Na4EtRA cavity.

Effect of 1,2-propanediol on the Critical Micelle Concentration of Decyltrimethylammonium Bromide at Temperatures from 293.15 K to 308.15 K.

It is well known that polar organic compounds, such as alcohols and polyols, exert an appreciable influence on water structure and thus have important effects on surfactant micellization. These substances are often used to modify the properties of surfactants in aqueous solutions, increasing the practical applications they have in diverse industries. In this work, the critical micelle concentration (CMC) of decyltrimethylammonium bromide (C10TAB) in water and in 1,2-propanediol aqueous solutions was determined from both sound velocity and surface tension measurements as a function of surfactant concentration in the temperature range of (293.15 to 308.15) K. The critical micelle concentration of the surfactant increases as the concentration of 1,2-propanediol becomes higher, while the effect on temperature does not show important changes within the range considered. At the selected temperatures, the standard thermodynamic parameters of micellization suggests that the addition of 1,2-propanediol makes the micellization process less favorable. Thermodynamic analysis suggests that the micelle formation of C10TAB is an entropy-driven process at the temperatures considered in this study.

Effect of Hofmeister Ions on Transport Properties of Aqueous Solutions of Sodium Hyaluronate.

Tracer diffusion coefficients obtained from the Taylor dispersion technique at 25.0 °C were measured to study the influence of sodium, ammonium and magnesium salts at 0.01 and 0.1 mol dm-3 on the transport behavior of sodium hyaluronate (NaHy, 0.1%). The selection of these salts was based on their position in Hofmeister series, which describe the specific influence of different ions (cations and anions) on some physicochemical properties of a system that can be interpreted as a salting-in or salting-out effect. In our case, in general, an increase in the ionic strength (i.e., concentrations at 0.01 mol dm-3) led to a significant decrease in the limiting diffusion coefficient of the NaHy 0.1%, indicating, in those circumstances, the presence of salting-in effects. However, the opposite effect (salting-out) was verified with the increase in concentration of some salts, mainly for NH4SCN at 0.1 mol dm-3. In this particular salt, the cation is weakly hydrated and, consequently, its presence does not favor interactions between NaHy and water molecules, promoting, in those circumstances, less resistance to the movement of NaHy and thus to the increase of its diffusion (19%). These data, complemented by viscosity measurements, permit us to have a better understanding about the effect of these salts on the transport behaviour of NaHy.

Effect of Cobalt and Chromium Ions on the Chlorhexidine Digluconate as Seen by Intermolecular Diffusion.

Metal ions such as cobalt (II) and chromium (III) might be present in the oral cavity, as a consequence of the corrosion of Co-Cr dental alloys. The diffusion of such metal ions into the organism, carried by saliva, can cause health problems as a consequence of their toxicity, enhanced by a cumulative effect in the body. The effect of the chlorhexidine digluconate, which is commonly used in mouthwash formulations, on the transport of these salts is evaluated in this paper by using the Taylor dispersion technique, which will allow an assessment of how the presence of chlorhexidine digluconate (either in aqueous solution or in a commercial formulation) may affect the diffusion of metal ions. The ternary mutual diffusion coefficients of metal ions (Co and Cr) in the presence of chlorhexidine digluconate, in an artificial saliva media, were measured. Significant coupled diffusion of CoCl2 (and CrCl3) and chlorhexidine digluconate is observed by analysis of the non-zero values of the cross-diffusion coefficients, D12 and D21. The observed interactions between metal ions and chlorhexidine digluconate suggest that the latter might be considered as an advantageous therapeutic agent, once they contribute to the reduction of the concentration of those ions inside the mouth.

Limiting diffusion coefficients of [Formula: see text],[Formula: see text]-amino acids in water and in sodium chloride aqueous solutions at 298.15 K.

Transport properties of model compounds in aqueous solutions such as amino acids can provide valuable information in order to understand the complex interactions in aqueous solutions as well as the protein stability in water and the relevant factors involved. Informations about the diffusion of amino acids in water and in aqueous solutions of sodium chloride are very scarce, especially for the 5-aminopentanoic acid and 6-aminohexanoic acid. In this study, limiting binary mutual diffusion coefficients at 298.15 K of 5-aminopentanoic and 6-aminohexanoic acids in aqueous solutions of NaCl 0.15 mol kg-1, using the Taylor dispersion technique, were determined and the results compared with the limiting binary mutual diffusion coefficients for 2-aminopentanoic acid, and 2-aminohexanoic acid, obtained in the same experimental conditions. The discussion of the properties of the selected amino acids is centered on the positions of the ionic groups in the hydrocarbon chain and, in addition, we have discussed the effects of NaCl on their structures and properties. The data on diffusion properties are supported by 1H, 13C and 23Na NMR experiments, which we have obtained for 5-aminopentanoic and 6-aminohexanoic acids, in aqueous solution, also in the presence of NaCl.

Limiting values of diffusion coefficients of glycine, alanine, α-amino butyric acid, norvaline and norleucine in a relevant physiological aqueous medium.

The side chain effect on transport in ionic aqueous salt solutions was investigated for [Formula: see text]-amino acids glycine, alanine, [Formula: see text]-amino butyric acid, norvaline, and norleucine --that together define a chemical homologous series based on the length of the characteristic side chain which increases from zero to four carbons, respectively. Binary mutual diffusion coefficients at infinitesimal concentration in aqueous solutions of NaCl (0.15 mol kg -1) are measured by means of Taylor dispersion technique for this series and significant differences were found against previous published results for identical systems in pure water. In this way, NaCl effect on the transport of each amino acid is thus assessed and discussed in terms of salting-out effects. Also, solvated Stokes hydrodynamic radii were computed for the series showing comparable results in water and NaCl solution. The new information should prove useful in the design and characterization of transport-controlled systems in physiological and pharmacological studies.

On Interactions of Sulfamerazine with Cyclodextrins from Coupled Diffusometry and Toxicity Tests.

This scientific study employs the Taylor dispersion technique for diffusion measurements to investigate the interaction between sulfamerazine (NaSMR) and macromolecular cyclodextrins (ß-CD and HP-ß-CD). The results reveal that the presence of ß-CD influences the diffusion of the solution component, NaSMR, indicating a counterflow of this drug due to solute interaction. However, diffusion data indicate no inclusion of NaSMR within the sterically hindered HP-ß-CD cavity. Additionally, toxicity tests were conducted, including pollen germination (Actinidia deliciosa) and growth curve assays in BY-2 cells. The pollen germination tests demonstrate a reduction in sulfamerazine toxicity, suggesting potential applications for this antimicrobial agent with diminished adverse effects. This comprehensive investigation contributes to a deeper understanding of sulfamerazine-cyclodextrin interactions and their implications for pharmaceutical and biological systems.

Cyclodextrins as Drug Release Modulators and Toxic Compound Removal Agents.

This Special Issue shows new strategies for the controlled release of drugs using cyclodextrins as carriers [...].

Calculations of Diffusion Coefficients of Iron Salts in Aqueous Solutions at 298.15 K: A Useful Tool for the Knowledge of the Structure of these Systems.

Diffusion coefficients, thermodynamic and mobility factors of iron salts in aqueous solutions are estimated from Onsager-Fuoss model. The influence of the ion size parameter a, "mean distance of closest approach of ions", determined from different approaches, on the variation of diffusion coefficients with concentration, is also discussed. The aim of this work is to have a better understanding of the structure of these systems and of the thermodynamic behaviour of iron salts in aqueous media.

Advanced Studies on Toxic Chemicals: Properties and Characteristics.

Examining the toxic scope of substances used in daily life (referred to as Contaminants of Emerging Concern (CEC)) in food, medicines, utensils, work and other industries, provides us with interesting information that will help us to prevent and recover from the dangerous organic unbalances that these substances can cause [...].

Removal of Toxic Metal Ions Using Poly(BuMA-co-EDMA) Modified with C-Tetra(nonyl)calix[4]resorcinarene.

A copolymer of poly(BuMA-co-EDMA) modified with C-tetra(nonyl)calix[4]resorcinarene was obtained via the impregnation method. The formation of the modified copolymer was confirmed and investigated using various techniques; in this way, the presence of calix[4]resorcinarene was confirmed by FT-IR spectroscopy and by high resolution transmission electron microscopy. The modified copolymer was used for the removal of highly toxic cations (Pb2+, Hg2+, and Cd2+) from aqueous solutions. To perform the removal, we used the batch sorption technique and the effects of time of contact, pH, and volume of sample on the effective sorption were determined. The best results were observed for Pb2+ extraction, which was comparatively more efficient. Adsorption-desorption experiments revealed that the modified copolymer could be used for several cycles without significant loss of adsorption capacity. Finally, the results showed that the modified copolymer application is highly efficient for the removal of lead ions from aqueous solutions.

Recognition of Heavy Metals by Using Resorcin[4]arenes Soluble in Water.

The complexing properties of two water-soluble resorcin[4]arenes (tetrasodium 5,11,17,23-tetrakissulfonatemethylen 2,8,14,20-tetra(butyl)resorcin[4]arene, Na4BRA, and tetrasodium 5,11,17,23-tetrakissulfonatemethylen-2,8,14,20-tetra(2-(methylthio)ethyl)resorcin[4]arene, Na4SRA) with polluting heavy metals such as Cu2+, Pb2+, Cd2+ and Hg2+ were studied by conductivity, and the findings were confirmed by using other techniques to try to apply this knowledge to removing them. The results indicate that Na4BRA is able to complex Cu2+ in a 1:1 ratio and Pb2+ in a 1:2 ratio, while Na4SRA complexes Hg2+ in a 1:1 ratio. On the contrary, no indications have been observed that either of the resorcin[4]arenes studied complexes the Cd2+ ions. The results suggest that the bonds established between the sulfur atoms located at the lower edge of the SRA4- and the solvent hydrogens could prevent the entry of the guest into the host cavity. However, in the case of Hg2+ ions, the entry is favoured by the interactions between the sulfur donor atoms present on the lower edge of Na4SRA and the Hg2+ ions. Therefore, it can be said that Na4BRA is selective for Cu2+ and Pb2+ ions and Na4SRA is selective for Hg2+ ions.

Photocatalytic Degradation of Dielectric Mineral Oil with PCBs Content Coupled with Algae Treatment.

Insulating oil contaminated with polychlorinated biphenyls (PCBs) is an environmentally important pollutant. This research focused on the establishment of the optimum conditions under which photocatalytic oxidation can be used together with biotreatment using the Nostoc sp. microorganism to degrade PCBs present in used dielectric oils. Among the optimal conditions studied were PCB concentration, initial pH, and titanium dioxide (TiO2) concentration for the photocatalytic step, and PCB concentration and photoperiod for the biotreatment step. The results indicate that the optimal conditions necessary for photocatalytic degradation were a pH of 6.10, 113 mg/L TiO2, and 765 mg/L PCBs, achieving close to 90% removal. For the biotreatment step, the results showed that PCBs progressively inhibited the microbiological growth, with the lowest cellular growth observed in the medium with the highest PCB concentration.

Diffusion of Vanadium Ions in Artificial Saliva and Its Elimination from the Oral Cavity by Pharmacological Compounds Present in Mouthwashes.

In this study, diffusion coefficients of ammonium vanadate at tracer concentrations in artificial saliva with and without sodium fluoride, at different pH values, were measured using an experimental model based on the Taylor dispersion technique. Ternary mutual diffusion coefficients (D11, D22, D12, and D21) for four aqueous systems {NH4VO3 (component 1) + ß-cyclodextrin (ß-CD) (component 2),} {NH4VO3 (component 1) + ß-cyclodextrin (HP-ß-CD) (component 2)}, {NH4VO3 (component 1) + sodium dodecyl sulphate (SDS) (component 2)} and {NH4VO3 (component 1) + sodium hyaluronate (NaHy) (component 2)} at 25.00 °C were also measured by using the same technique. These data showed that diffusion of ammonium vanadate was strongly affected in all aqueous media studied. Furthermore, a significant coupled diffusion of this salt and ß-CD was observed through the non-zero values of the cross-diffusion coefficients, D12, allowing us to conclude that there is a strong interaction between these two components. This finding is very promising considering the removal, from the oral cavity, of vanadium resulting from tribocorrosion of Ti-6Al-4V prosthetic devices.

Complexation of 5-Fluorouracil with ß-Cyclodextrin and Sodium Dodecyl Sulfate: A Useful Tool for Encapsulating and Removing This Polluting Drug.

The formation of complexes of the drug 5-fluorouracil (5-FU) with ß-cyclodextrin (ß-CD) and sodium dodecyl sulphate (SDS) was studied through experimental measurements of the ternary mutual diffusion coefficients (D11, D22, D12, and D21) for the systems {5-FU (component 1) + ß-CD (component 2) + water} and {5-FU (component 1) + SDS (component 2) + water} at 298.15 K and at concentrations up to 0.05 mol dm-3 by using the Taylor dispersion method, with the objective of removing this polluting drug from the residual systems in which it was present. The results found showed that a coupled diffusion of 5-FU occurred with both ß-CD and SDS, as indicated by the nonzero values of the cross-diffusion coefficients, D12 and D21, as a consequence of the complex formation between 5-FU and the ß-CD or SDS species. That is, 5-FU was solubilized (encapsulated) by both carriers, although to a greater extent with SDS (K = 20.0 (±0.5) mol-1 dm3) than with ß-CD (K = 10.0 (±0.5) mol-1 dm3). Values of 0.107 and 0.190 were determined for the maximum fraction of 5-FU solubilized with ß-CD and SDS (at concentrations above its CMC), respectively. This meant that SDS was more efficient at encapsulating and thus removing the 5-FU drug.

Estimation of the mean distance of closest approach of actinides and lanthanides ions in aqueous solutions: some experimental and theoretical calculations.

The estimation of numerical values of the mean distance of closest approach of ions, a, of lanthanides and actinides ion salts in aqueous solutions, determined from activity coefficients, as well as from different theoretical approaches, is presented and discussed.

Diffusion coefficients of sodium fluoride in aqueous solutions at 298.15 k and 310.15 k.

Mutual diffusion coefficients (interdiffusion coefficients) have been measured for sodium fluoride in water at 298.15 K and 310.15 K at concentrations between 0.003 mol dm-3 and 0.05 mol dm-3. The diffusion coefficients were measured using a conductimetric cell. The experimental mutual diffusion coefficients are discussed on the basis of the Onsager-Fuoss model. The limiting molar conductivity of the fluoride ion in these solutions at 310.15 K has been estimated using these results.

Drug Delivery Systems: Study of Inclusion Complex Formation between Methylxanthines and Cyclodextrins and Their Thermodynamic and Transport Properties.

This paper presents an analysis of the molecular mechanisms involved in the formation of inclusion complexes together with some structural interpretation of drug-carrier molecule interactions in aqueous multicomponent systems comprising methylxanthines and cyclodextrins. The determination of apparent partial molar volumes (Φv) from experimental density measurements, both for binary and ternary aqueous solutions of cyclodextrins and methylxanthines, was performed at low concentration range to be consistent with their therapeutic uses in the drug-releasing field. The estimation of the equilibrium constant for inclusion complexes of 1:1 stoichiometry was done through the mathematical modelling of this apparent molar property. The examination of the volume changes offered information about the driving forces for the insertion of the xanthine into the cyclodextrin molecule. The analysis on the volumes of transfer, Δ, Φv,c and the viscosity B-coefficients of transfer, ΔB, for the xanthine from water to the different aqueous solutions of cyclodextrin allowed evaluating the possible interactions between aqueous solutes and/or solute-solvent interactions occurring in the solution. Mutual diffusion coefficients for binary, and ternary mixtures composed by xanthine, cyclodextrin, and water were measured with the Taylor dispersion technique. The behavior diffusion of these multicomponent systems and the coupled flows occurring in the solution were analyzed in order to understand the probable interactions between cyclodextrin-xanthine by estimating their association constants and leading to clearer insight of these systems structure. The measurements were performed at the standard (298.15 ± 0.01) K and physiological (310.15 ± 0.01) K temperatures.