Molecular Insights into the Wettability and Adsorption of Acid Gas-Water Mixture.

Sequestration of acid gas in geological formations is a disposal method with potential economic and environmental benefits. The process is governed by variables such as gas-water interfacial tension, wetting transition, and gas adsorption into water, among other things. However, the influence of the pressure and temperature on these parameters is poorly understood. This study investigates these parameters using coarse-grained molecular dynamics (CG-MD) simulations and density gradient theory (DGT). Simulations were carried out at 313.15 K and a pressure range of 0-15 MPa. A comparison was made against H2S-water systems to clarify the effects of adsorption on interfacial tension due to vapor-liquid-liquid equilibrium. The predicted H2S-water interfacial tension and phase densities by CG-MD and DGT matched the experimental values well. The adsorption can be quantified via the Gibbs Adsorption function Γ12, which correlated well with the three-phase transition. On the one hand, pressure increments below the three-phase transition revealed a significant adsorption of H2S. On the other hand, above the three-phase transition, the Gibbs Adsorption capacity remained constant, which indicated a saturation of H2S at the water surface due to liquid-liquid equilibrium. Finally, H2S behaves markedly differently in wetting transition, rather than the involved for CO2 to different molecular layers beneath the surface of aqueous solutions. In this respect, H2S is represented by a first-order wetting transition while CO2 presents a critical wetting. Finally, it has also been found that the preferential adsorption of H2S over the H2O interface is greater if compared to that of CO2, due to its strong interaction with water. In fact, we have also demonstrated that CO2 under triphasic conditions strongly influences the wetting of the ternary system.

Ionogels Derived from Fluorinated Ionic Liquids to Enhance Aqueous Drug Solubility for Local Drug Administration.

Gelatin is a popular biopolymer for biomedical applications due to its harmless impact with a negligible inflammatory response in the host organism. Gelatin interacts with soluble molecules in aqueous media as ionic counterparts such as ionic liquids (ILs) to be used as cosolvents to generate the so-called Ionogels. The perfluorinated IL (FIL), 1-ethyl-3-methylpyridinium perfluorobutanesulfonate, has been selected as co-hydrosolvent for fish gelatin due to its low cytotoxicity and hydrophobicity aprotic polar structure to improve the drug aqueous solubility. A series of FIL/water emulsions with different FIL content and their corresponding shark gelatin/FIL Ionogel has been designed to enhance the drug solubility whilst retaining the mechanical structure and their nanostructure was probed by simultaneous SAXS/WAXS, FTIR and Raman spectroscopy, DSC and rheological experiments. Likewise, the FIL assisted the solubility of the antitumoural Doxorubicin whilst retaining the performing mechanical properties of the drug delivery system network for the drug storage as well as the local administration by a syringe. In addition, the different controlled release mechanisms of two different antitumoral such as Doxorubicin and Mithramycin from two different Ionogels formulations were compared to previous gelatin hydrogels which proved the key structure correlation required to attain specific therapeutic dosages.

Multifunctional PLA/Gelatin Bionanocomposites for Tailored Drug Delivery Systems.

A series of bionanocomposites composed of shark gelatin hydrogels and PLA nanoparticles featuring different nanostructures were designed to generate multifunctional drug delivery systems with tailored release rates required for personalized treatment approaches. The global conception of the systems was considered from the desired customization of the drug release while featuring the viscoelastic properties needed for their ease of storage and posterior local administration as well as their biocompatibility and cell growth capability for the successful administration at the biomolecular level. The hydrogel matrix offers the support to develop a direct thermal method to convert the typical kinetic trapped nanostructures afforded by the formulation method whilst avoiding the detrimental nanoparticle agglomeration that diminishes their therapeutic effect. The nanoparticles generated were successfully formulated with two different antitumoral compounds (doxorubicin and dasatinib) possessing different structures to prove the loading versatility of the drug delivery system. The bionanocomposites were characterized by several techniques (SEM, DLS, RAMAN, DSC, SAXS/WAXS and rheology) as well as their reversible sol-gel transition upon thermal treatment that occurs during the drug delivery system preparation and the thermal annealing step. In addition, the local applicability of the drug delivery system was assessed by the so-called "syringe test" to validate both the storage capability and its flow properties at simulated physiological conditions. Finally, the drug release profiles of the doxorubicin from both the PLA nanoparticles or the bionanocomposites were analyzed and correlated to the nanostructure of the drug delivery system.

Characterization of Tuna Gelatin-Based Hydrogels as a Matrix for Drug Delivery.

The skin of yellowfin tuna is one of the fishery industry solid residues with the greatest potential to add extra value to its circular economy that remains yet unexploited. Particularly, the high collagen content of fish skin allows generating gelatin by hydrolysis, which is ideal for forming hydrogels due to its biocompatibility and gelling capability. Hydrogels have been used as drug carriers for local administration due to their mechanical properties and drug loading capacity. Herein, novel tuna gelatin hydrogels were designed as drug vehicles with two structurally different antitumoral model compounds such as Doxorubicin and Crocin to be administrated locally in tissues with complex human anatomies after surgical resection. The characterization by gel permeation chromatography (GPC) of purified gelatin confirmed their heterogeneity composition, exhibiting three major bands that correspond to the ß and α chains along with high molecular weight species. In addition, the Fourier Transform Infrared (FT-IR) spectra of gelatin probed the secondary structure of the gelatin showing the simultaneous existence of α helix, ß sheet, and random coil structures. Morphological studies at different length scales were performed by a multi-technique approach using SAXS/WAXS, AFM and cryo-SEM that revealed the porous network formed by the interaction of gelatin planar aggregates. In addition, the sol-gel transition, as well as the gelation point and the hydrogel strength, were studied using dynamic rheology and differential scanning calorimetry. Likewise, the loading and release profiles followed by UV-visible spectroscopy indicated that the novel gelatin hydrogels improve the drug release of Doxorubicin and Crocin in a sustained fashion, indicating the structure-function importance in the material composition.

Integration of Stable Ionic Liquid-Based Nanofluids into Polymer Membranes. Part II: Gas Separation Properties toward Fluorinated Greenhouse Gases.

Membrane technology can play a very influential role in the separation of the constituents of HFC refrigerant gas mixtures, which usually exhibit azeotropic or near-azeotropic behavior, with the goal of promoting the reuse of value-added compounds in the manufacture of new low-global warming potential (GWP) refrigerant mixtures that abide by the current F-gases regulations. In this context, the selective recovery of difluorometane (R32, GWP = 677) from the commercial blend R410A (GWP = 1924), an equimass mixture of R32 and pentafluoroethane (R125, GWP = 3170), is sought. To that end, this work explores for the first time the separation performance of novel mixed-matrix membranes (MMMs) functionalized with ioNanofluids (IoNFs) consisting in a stable suspension of exfoliated graphene nanoplatelets (xGnP) into a fluorinated ionic liquid (FIL), 1-ethyl-3-methylpyridinium perfluorobutanesulfonate ([C2C1py][C4F9SO3]). The results show that the presence of IoNF in the MMMs significantly enhances gas permeation, yet at the expense of slightly decreasing the selectivity of the base polymer. The best results were obtained with the MMM containing 40 wt% IoNF, which led to an improved permeability of the gas of interest (PR32 = 496 barrer) with respect to that of the neat polymer (PR32= 279 barrer) with a mixed-gas separation factor of 3.0 at the highest feed R410A pressure tested. Overall, the newly fabricated IoNF-MMMs allowed the separation of the near-azeotropic R410A mixture to recover the low-GWP R32 gas, which is of great interest for the circular economy of the refrigeration sector.

Rheological and volumetric properties of TiO2-ethylene glycol nanofluids.

Homogeneous stable suspensions obtained by dispersing dry TiO2 nanoparticles in pure ethylene glycol were prepared and studied. Two types of nanocrystalline structure were analyzed, namely anatase and rutile phases, which have been characterized by scanning electron microscopy. The rheological behavior was determined for both nanofluids at nanoparticle mass concentrations up to 25%, including flow curves and frequency-dependent storage and loss moduli, using a cone-plate rotational rheometer. The effect of temperature over these flow curve tests at the highest concentration was also analyzed from 283.15 to 323.15 K. Furthermore, the influence of temperature, pressure, nanocrystalline structure, and concentration on the volumetric properties, including densities and isobaric thermal expansivities, were also analyzed.

Rheological non-Newtonian behaviour of ethylene glycol-based Fe2O3 nanofluids.

The rheological behaviour of ethylene glycol-based nanofluids containing hexagonal scalenohedral-shaped α-Fe2O3 (hematite) nanoparticles at 303.15 K and particle weight concentrations up to 25% has been carried out using a cone-plate Physica MCR rheometer. The tests performed show that the studied nanofluids present non-Newtonian shear-thinning behaviour. In addition, the viscosity at a given shear rate is time dependent, i.e. the fluid is thixotropic. Finally, using strain sweep and frequency sweep tests, the storage modulus G', loss modulus G″ and damping factor were determined as a function of the frequency showing viscoelastic behaviour for all samples.

Thermal conductivity and viscosity measurements of ethylene glycol-based Al2O3 nanofluids.

The dispersion and stability of nanofluids obtained by dispersing Al2O3 nanoparticles in ethylene glycol have been analyzed at several concentrations up to 25% in mass fraction. The thermal conductivity and viscosity were experimentally determined at temperatures ranging from 283.15 K to 323.15 K using an apparatus based on the hot-wire method and a rotational viscometer, respectively. It has been found that both thermal conductivity and viscosity increase with the concentration of nanoparticles, whereas when the temperature increases the viscosity diminishes and the thermal conductivity rises. Measured enhancements on thermal conductivity (up to 19%) compare well with literature values when available. New viscosity experimental data yield values more than twice larger than the base fluid. The influence of particle size on viscosity has been also studied, finding large differences that must be taken into account for any practical application. These experimental results were compared with some theoretical models, as those of Maxwell-Hamilton and Crosser for thermal conductivity and Krieger and Dougherty for viscosity.