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Thefabrication of micrometer-sized core–shell particles for ultrasound-triggereddelivery offers a variety of applications in medical research. Inthis work, we report the design and development of a glass capillarymicrofluidic system containing three concentric glass capillary tubesfor the development of core–shell particles. The setup enablesthe preparation of perfluorocarbon-alginate core–shell microspheresin a single process, avoiding the requirement for further extensivepurification steps. Core–shell microspheres in the range of110–130 μm are prepared and are demonstrated to be stableup to 21 days upon immersion in calcium chloride solution or water.The mechanical stability of the particles is tested by injecting themthrough a 23 gauge needle into a polyacrylamide gel to mimic the tissuematrix. The integrity of the particles is maintained after the injectionprocess and is disrupted after ultrasound exposure for 15 min. Theresults suggest that the perfluorcarbon-alginate microparticles couldbe a promising system for the delivery of compounds, such as proteins,peptides, and small-molecule drugs in ultrasound-based therapies. [ABSTRACT FROM AUTHOR]

Engineeringmetabolically demanding tissues requires the supplyof nutrients, oxygen, and removal of metabolic byproducts, as wellas adequate mechanical properties. In this work, we propose the developmentof chitosan (CHIT)/alginate (ALG) freestanding membranes fabricatedby layer-by-layer (LbL) assembly. CHIT/ALG membranes were cross-linkedwith genipin at a concentration of 1 mg·mL–1or 5 mg·mL–1. Mass transport properties ofglucose and oxygen were evaluated on the freestanding membranes. Thediffusion of glucose and oxygen decreases with increasing cross-linkingconcentration. Mechanical properties were also evaluated in physiological-simulatedconditions. Increasing cross-linking density leads to an increaseof storage modulus, Young modulus, and ultimate tensile strength,but to a decrease in the maximum hydrostatic pressure. The in vitrobiological performance demonstrates that cross-linked films are morefavorable for cell adhesion. This work demonstrates the versatilityand feasibility of LbL assembly to generate nanostructured constructswith tunable permeability, mechanical, and biological properties. [ABSTRACT FROM AUTHOR]

Wild thyme (Thymus serpyllum L.) herbal dust has been recognized as a potential underutilized resource for the recovery of antioxidants. The aim of this paper was to optimize natural deep eutectic solvent (NADES) extraction of polyphenols to obtain improved antioxidant activity of extracts determined by selected in vitro assays (DPPH, FRAP, and ABTS). Twenty different NADES systems were investigated in the first step of the screening of the extraction solvent and l-proline (Pro)–glycerine (Gly) based solvents provided the best results. Preliminary experiments organized by 25−1 fractional factorial design narrowed down the number of extraction factors from five (temperature, extraction time, NADES type, water content and L/S ratio) to three and determined their experimental domain for the final step. A face-centered central composite design with temperature (40–55–70 °C), extraction time (60–120–180 min) and L/S ratio (10–20–30 g NADES/g sample) was applied for influence analysis and process optimization. Multi-response optimization suggested a temperature of 65 °C, time of extraction of 180 min and L/S ratio of 28 g NADES/g DW as optimal extraction parameters. Experimental validation confirmed good agreement between experimental and predicted results in the extract obtained at optimal conditions and the interactions in the most suitable NADES (N16; Pro–Gly–H2O; 1:2:1) were confirmed by the 1H-NMR. [ABSTRACT FROM AUTHOR]

Nowadays, producing energy from solar thermal power plants based on organic Rankine cycles coupled with phase change material has attracted the attention of researchers. Obviously, in such solar plants, the physical properties of the utilized phase change material (PCM) play important roles in the amounts of generated power and the efficiencies of the plant. Therefore, to choose the best PCM, various factors must be taken into account. In addition, considering the physical properties of the candidate PCM, the issue of environmental sustainability should also be considered when making the selection. Deep eutectic solvents (DESs) are novel green solvents, which, in addition to having various favorable characteristics, are environmentally sustainable. Accordingly, in this work, the feasibility of using seven different deep eutectic solvents as the PCMs of solar thermal power plants with organic Rankine cycles was investigated. By applying exergy and energy analyses, the performances of each were compared to paraffin, which is a conventional PCM. According to the achieved results, most of the investigated "DES cycles" produce more power than the conventional cycle using paraffin as its PCM. Furthermore, lower amounts of the PCM are required when paraffin is replaced by a DES at the same operational conditions. [ABSTRACT FROM AUTHOR]

In this study, the aqueous mixture viscosities of two phenolic DESs, consisting of (1 ChCl: 3 phenol) and (1 ChCl: 4 phenol), were measured at atmospheric pressure over the temperature range of 293.15–333.15 K. According to the measured data, the values of viscosity deviations for the investigated aqueous systems were calculated to indicate deviating viscosity behavior with respect to ideality. Both aqueous systems showed negative viscosity deviations over the entire composition range and at all of the investigated temperatures. The Redlich-Kister model was applied to estimate the viscosity deviations of both aqueous systems at different compositions and temperatures, while the viscosity behavior, itself, was modeled by different literature models, consisting of the Grunberg-Nissan, Jouyban-Acree, McAllister, Preferential Solvation, and an Arrhenius-like viscosity model. All of the models presented satisfactory agreement, however the Preferential Solvation and the Jouyban-Acree models succeeded to achieve more reliable results as compared to the others. In addition to the mixture viscosity estimation models, the Jones-Dole viscosity model was applied to both of the aqueous systems to suggest the interactions in the mixture. By calculating and analyzing the values of the B -coefficients of this model, possibly stronger interactions among the DESs and water molecules in the mixture were suggested, as compared to the self-species interactions. [ABSTRACT FROM AUTHOR]

Defatted raspberry seeds were used as an alternative source of antioxidants and ellagic acid (EA) extracted using Natural deep eutectic solvents (NADES). In the preliminary study, the best NADES combination (citric acid-betaine) and the most influential variables (temperature, time, and NADES/plant ratio) were selected for the further optimization process. All samples were analyzed in terms of total polyphenol, EA content, and antioxidant activity. Two sets of optimal conditions were generated by response surface methodology. The first set (Opt1) was designed for higher conversion of ellagitannins to EA while the latter set (Opt2) for higher EA content/100 g extract. Opt1 and Opt2 had higher values for all investigated responses compared to 80% ethanolic extract but had a lower conversion rate of ellagitannins to EA compared to acidified methanol extract. The third set of parameters (Opt3) selected beyond the initial experimental domain was used to obtain a sample with the highest EA content/100 g extract. Due to their nature, NADES extracts are ready to use and could have various technological roles in products since they are antioxidants, acidifiers, and colorants. NADES raspberry extracts exhibited higher anti-proliferative activity compared to ethanolic extracts in terms of EC50 values. However, the main contributor of anti-cancer activity in NADES raspberry extracts were individual NADES compounds and/or their newly formed NADES structure. [ABSTRACT FROM AUTHOR]

Abstract: One of the major scientific challenges that tissue engineering and regenerative medicine (TERM) faces to move from benchtop to bedside regards biomaterials development, despite the latest advances in polymer processing technologies. A variety of scaffolds processing techniques have been developed and include solvent casting and particles leaching, compression molding and particle leaching, thermally induced phase separation, rapid prototyping, among others. Supercritical fluids appear as an interesting alternative to the conventional methods for processing biopolymers as they do not require the use of large amounts of organic solvents and the processes can be conducted at mild temperatures. However, this processing technique has only recently started to receive more attention from researchers. Different processing methods based on the use of supercritical carbon dioxide have been proposed for the creation of novel architectures based on natural and synthetic polymers and these will be unleashed in this paper. [Copyright &y& Elsevier]

Abstract: The aim of this study was to evaluate the possibility of preparing chitosan porous matrixes using supercritical fluid technology. Supercritical immersion precipitation technique was used to prepare scaffolds of a natural biocompatible polymer, chitosan for tissue engineering purposes. The physicochemical and biological properties of chitosan make it an excellent material for the preparation of drug delivery systems and for the development of new biomedical applications in many fields from skin to bone or cartilage. Supercritical assisted phase inversion experiments were carried out and the effect of different organic solvents on the morphology of the scaffolds was assessed. Chitosan scaffold morphology, porosity and pore size were evaluated by SEM and micro-CT. A thermodynamic analysis of the process was carried out and insights on the solubility parameter and Flory–Huggins interaction parameters are given. The preparation of a highly porous and interconnected structure of a natural material, chitosan, using a clean and environmentally friendly technology constitutes a new processing technology for the preparation of scaffolds for tissue engineering using these materials. [Copyright &y& Elsevier]

Abstract: A new generation of scaffolds capable of acting not only as support for cells but also as a source of biological cues to promote tissue regeneration is currently a hot topic of in bone Tissue Engineering (TE) research. The inclusion of growth factor (GF) controlled release functionalities in the scaffolds is a possible strategy to achieve such goal. Platelet Lysate (PL) is an autologous source of GFs, providing several bioactive agents known to act on bone regeneration. In this study, chitosan-chondroitin sulfate nanoparticles loaded with PL were included in a poly(d,l-lactic acid) foam produced by supercritical fluid foaming. The tridimensional (3D) structures were then seeded with human adipose-derived stem cells (hASCs) and cultured in vitro under osteogenic stimulus. The osteogenic differentiation of the seeded hASCs was observed earlier for the PL-loaded constructs, as shown by the earlier alkaline phosphatase peak and calcium detection and stronger Runx2 expression at day 7 of culture, in comparison with the control scaffolds. Osteocalcin gene expression was upregulated in presence of PL during all culture period, which indicates an enhanced osteogenic induction. These results suggest the synergistic effect of PL and hASCs in combinatory TE strategies and support the potential of PL to increase the multifunctionality of the 3D hybrid construct for bone TE applications. [Copyright &y& Elsevier]

Abstract: A marine derived polysaccharide, ulvan, extracted from green algae, was combined with poly-d, l-lactic acid (PDLLA) in order to produce a novel scaffold for bone tissue engineering applications. Three dimensional (3D) scaffolds of PDLLA loaded with ulvan particles were originally prepared by subcritical fluid sintering with carbon dioxide at 40°C and 50bar. Prepared matrixes were characterized in order to validate their suitability to be used as scaffolds for bone tissue regeneration. Characterization included micro-computed tomography, mechanical compression testing, water uptake and degradation testing, and cytotoxicity assays. In addition, ulvan particles loaded with dexamethasone, were also dispersed within the PDLLA matrix and the respective release profile from the samples was evaluated. Prepared PDLLA scaffolds enriched with ulvan particles demonstrated appropriate physicochemical and cytocompatible features to be used for the envisaged applications. On the other hand, the release of dexamethasone from ulvan particles embedded within the PDLLA matrix revealed that the designed systems can be potentially suitable for localized drug delivery. These results further contribute to the establishment of ulvan as a potential novel biomaterial. [Copyright &y& Elsevier]

Abstract: The application of green chemistry principles in the processing of materials for advanced technologies is a steadily increasing field of research. In this work porous chitin-based materials were developed by combining the processing of chitin using ionic liquids (ILs) as a green solvent together with the use of supercritical fluid technology (SCF) as clean technology. Chitin was dissolved in 1-butyl-3-imidazolium acetate, followed by regeneration of the polymer in ethanol in specific moulds. The IL was removed using Soxhlet extraction and successive steps of extraction with SCF using carbon dioxide/ethanol ratios of 50/50 and 70/30. The developed porous chitin-based structures (ChIL) can be classified as mesoporous materials, with very low density and high porosity. The cytotoxicity of ChIL extracts was investigated using L929 fibroblast-like cells, and the results demonstrated that the produced materials have extremely low cytotoxicity levels. Therefore, the findings suggest that the porous chitin structures may be potential candidates for a number of biomedical applications, including tissue engineering. [Copyright &y& Elsevier]

Abstract: Starch-based polymers have been proposed for different tissue engineering applications due to their inherent properties. In this work, a polymeric blend of starch-poly-(ɛ-caprolactone) (SPCL) was processed using supercritical fluid technology, namely, by supercritical assisted phase inversion. As SPCL is a biodegradable polymer, the matrices produced are susceptible of undergoing enzymatic degradation upon implantation in the human body. In vitro assessment of the enzymatic degradation of SPCL was carried out in different buffer solutions containing α-amylase and/or lipase. The effect of the presence of these enzymes was studied by monitoring different parameters in order to characterise both bulk and the surface of the scaffolds. As regards to bulk analysis, weight loss of the samples incubated for 1, 3, 7, 14 and 21 days was determined, further differential scanning calorimetry was carried out. The morphology of the scaffolds after these periods was analysed by micro-computed tomography (μ-CT) and surface chemistry was characterised by infra-red spectroscopy and contact angle measurements. Results suggest that SPLC scaffolds undergo bulk degradation, which is typically characterised by hydrolysis of chemical bonds in the polymer chain at the centre of the matrix, resulting in a highly porous material. [Copyright &y& Elsevier]

Abstract: This work addresses the preparation of 3D porous scaffolds of blends of chitosan and poly(l-lactic acid), CHT and PLLA, using supercritical fluid technology. Supercritical assisted phase-inversion was used to prepare scaffolds for tissue engineering purposes. The physicochemical and biological properties of chitosan make it an excellent material for the preparation of drug delivery systems and for the development of new biomedical applications in many fields from skin to bone or cartilage regeneration. On the other hand, PLLA is a synthetic biodegradable polymer widely used for biomedical applications. Supercritical assisted phase-inversion experiments were carried out in samples with different polymer ratios and different polymer solution concentrations. The effect of CHT:PLLA ratio and polymer concentration and on the morphology and topography of the scaffolds was assessed by SEM and Micro-CT. Infra-red spectroscopic imaging analysis of the scaffolds allowed a better understanding on the distribution of the two polymers within the matrix. This work demonstrates that supercritical fluid technology constitutes a new processing technology, clean and environmentally friendly for the preparation of scaffolds for tissue engineering using these materials. [Copyright &y& Elsevier]

Abstract: A laboratory-scale reactor system is built and operated to measure the kinetic of formation for single and mixed carbon dioxide–tetrahydrofuran hydrates. The T-cycle method, which is used to collect the kinetic data, is briefly discussed. For single carbon dioxide hydrate, the induction time decreases with the increase of the initial carbon dioxide pressure up to 2.96MPa. Beyond this pressure, the induction time is becoming relatively constant with the increase of initial carbon dioxide pressure indicating that the liquid phase is completely supersaturated with carbon dioxide. Experimental results show that the inclusion of tetrahydrofuran reduces the induction time required for hydrate formation. These observations indicate hydrate nucleation process and onset growth are more readily to occur in the presence of tetrahydrofuran. In contrast, the presence of sodium chloride prolongs the induction time due to clustering of water molecules with the ions and the salting-out effects. It is also shown that the degree of subcooling required for hydrate formation is affected by the presence of tetrahydrofuran and sodium chloride in the hydrate forming system. The presence of tetrahydrofuran in the hydrate system significantly reduces the amount of carbon dioxide uptake. The apparent rate constant, k, for those systems are reported. [ABSTRACT FROM AUTHOR]

Abstract: Electrospun structures were proposed as scaffolds owing to their morphological and structural similarities with the extracellular matrix found in many native tissues. These fibrous structures were also proposed as drug release systems by exploiting the direct dependence of the release rate of a drug on the surface area. An osteogenic differentiation factor, dexamethasone (DEX), was incorporated into electrospun polycaprolactone (PCL) nanofibers at different concentrations (5, 10, 15 and 20 wt.% polymer), in a single-step process. The DEX incorporated into the polymeric carrier is in amorphous state, as determined by DSC, and does not influence the typical nanofibers morphology. In vitro drug release studies demonstrated that the dexamethasone release was sustained over a period of 15 days. The bioactivity of the released dexamethasone was assessed by cultivating human bone marrow mesenchymal stem cells (hBMSCs) on 15 wt.% DEX-loaded PCL NFMs, under dexamethasone-absent osteogenic differentiation medium formulation. An increased concentration of alkaline phosphatase and deposition of a mineralized matrix was observed. Phenotypic and genotypic expression of osteoblastic-specific markers corroborates the osteogenic activity of the loaded growth/differentiation factor. Overall data suggests that the electrospun biodegradable nanofibers can be used as carriers for the sustained release of growth/differentiation factors relevant for bone tissue engineering strategies. [Copyright &y& Elsevier]

In this work, a starch-based polymer, namely a blend of starch-poly(ε-caprolactone) was processed by supercritical assisted phase inversion process. This processing technique has been proposed for the development of 3D structures with potential applications in tissue engineering applications, as scaffolds. The use of carbon dioxide as non-solvent in the phase inversion process leads to the formation of a porous and interconnected structure, dry and free of any residual solvent. Different processing conditions such as pressure (from 80 up to 150 bar) and temperature (45 and 55°C) were studied and the effect on the morphological features of the scaffolds was evaluated by scanning electron microscopy and micro-computed tomography. The mechanical properties of the SPCL scaffolds prepared were also studied. Additionally, in this work, the in vitro biological performance of the scaffolds was studied. Cell adhesion and morphology, viability and proliferation was assessed and the results suggest that the materials prepared are allow cell attachment and promote cell proliferation having thus potential to be used in some for biomedical applications. [ABSTRACT FROM AUTHOR]

Abstract: The aim of this study was to evaluate the possibility of preparing dexamethasone-loaded starch-based porous matrices in a one-step process. Supercritical phase inversion technique was used to prepare composite scaffolds of dexamethasone and a polymeric blend of starch and poly(l-lactic acid) (SPLA) for tissue engineering purposes. Dexamethasone is used in osteogenic media to direct the differentiation of stem cells towards the osteogenic lineage. Samples with different drug concentrations (5–15 wt.% polymer) were prepared at 200bar and 55°C. The presence of dexamethasone did not affect the porosity or interconnectivity of the polymeric matrices. Water uptake and degradation studies were also performed on SPLA scaffolds. We conclude that SPLA matrices prepared by supercritical phase inversion have a swelling degree of nearly 90% and the material presents a weight loss of ∼25% after 21days in solution. Furthermore, in vitro drug release studies were carried out and the results show that a sustained release of dexamethasone was achieved over 21days. The fitting of the power law to the experimental data demonstrated that drug release is governed by an anomalous transport, i.e., both the drug diffusion and the swelling of the matrix influence the release of dexamethasone out of the scaffold. The kinetic constant was also determined. This study reports the feasibility of using supercritical fluid technology to process in one step a porous matrix loaded with a pharmaceutical agent for tissue engineering purposes. [Copyright &y& Elsevier]

Abstract: The aim of this study was to evaluate the possibility of preparing starch-based porous matrixes using supercritical fluid technology. Supercritical immersion precipitation technique was used to prepare scaffolds of a polymeric blend of starch and poly(l-lactic acid) for tissue engineering purposes.Immersion precipitation experiments were carried out at different operational conditions and highly porous and interconnected scaffolds were obtained. Two organic solvents, dichloromethane and chloroform were tested, and from the results obtained chloroform was the more favourable for the process. The effect of polymer solution concentration (5 up to 20wt%), temperature (35 up to 55°C) and pressure (100 up to 200bar) in the SPLA (50:50wt%) membrane morphology, porosity and interconnectivity was evaluated. All the conditions tested were in the region of total miscibility between the organic solvent and carbon dioxide. Additionally, a blend with a different starch-poly(l-lactic acid) ratio (30:70wt%) was tested. Bicontinuous structures were formed indicating that the L–L demixing process that governs the phase inversion is the spinodal decomposition. [Copyright &y& Elsevier]

The goal of the study was to establish a procedure for improving the efficiency of supercritical carbon dioxide (scCO2) extraction of Origanum vulgare L. spp. hirtum (Greek oregano) and enhancing the quality of obtained extracts. Microwave and enzymatic pretreatments of the plant material were applied prior to the scCO2 extraction. It was determined that the microwave pretreatment with irradiation power 360 W during 2 min accelerated the extraction of lipophilic compounds and provided a twofold higher extraction yield compared to the control. Moreover, this pretreatment also led to an increase in oxygenated monoterpenes content and the most dominant component carvacrol, as well as the extracts' antioxidant activity. The enzymatic pretreatment caused a significant increase in the extraction yield and the attainment of the extract with the most potent antioxidant properties. Coupling the pretreatments with scCO2 extraction improves the process of obtaining high value lipophilic products of oregano in terms of utilization of the plant material, acceleration of the extraction with the possibility to adjust its selectivity and quality of extracts, and enhancement of biological activity. [ABSTRACT FROM AUTHOR]

Abstract: Supercritical fluid impregnation was tested to prepare a new scaffold loaded with a bioactive compound. Dexamethasone is used in osteogenic media to direct the differentiation of stem cells towards the osteogenic lineage. Dexamethasone was impregnated in chitosan scaffolds at different operating conditions, in order to optimize the impregnation process. Pressure and temperature affect the carbon dioxide density and influence the swelling of the polymer and the drug solubility in the fluid phase, therefore these are two important parameters that were studied in this work. Chitosan sponges prepared by freeze drying were impregnated with the active compound at pressures from 8.0 up to 14.0MPa and temperatures from 35 up to 55°C. The effect of the impregnation contact time (3h and 6h) was also evaluated. From the experiments performed we can conclude that the yield of impregnation is lower when increasing pressure and temperature. The contact time will mainly influence the amount of drug impregnated in the scaffold and for higher contact times the impregnation yield is also higher. Scanning electron microscopy shows particles of dexamethasone in the bulk of the scaffold, which confirms the feasibility of the supercritical fluid impregnation technology for the preparation of delivery devices. The loading capacity of the scaffolds was determined by spectroscopic analysis and the highest loading was achieved for the experiments performed at 8.0MPa and 35°C. Furthermore, in vitro drug release studies were carried out and the results show that dexamethasone was sustainably released. Supercritical fluid impregnation proved to be feasible for the preparation of a drug delivery system for bone tissue engineering purposes. [Copyright &y& Elsevier]

What if a new technology based on therapeutic deep eutectic systems would disrupt the current treatment of major economic and socially burden diseases? The classical definition of eutectic systems is that they are the combination of two or more compounds that interact via hydrogen bonds, from which results a melting temperature depression in comparison with that of its individual components. Therapeutic deep eutectic systems are defined as eutectic systems in which at least one of the individual components is an active pharmaceutical ingredient, or a eutectic system in which the active pharmaceutical ingredient is dissolved. Current literature reports on tuberculosis have been mostly based on the most common anti-tuberculosis drugs prescribed. Using eutectic systems based on naturally occurring molecules known for their anti-microbial activity may also present a promising therapeutic strategy able to cope with the prevalence of Mycobacterium tuberculosis and prevent the appearance of multidrug resistance strains. With regards to colorectal cancer, literature has been unravelling combinations of terpenes with anti-inflammatory drugs that are selectively cytotoxic towards colorectal cancer cells and do not compromise the viability of normal intestinal cells. This technology could contribute to preventing tumor growth and metastasis while providing a patient compliance therapeutics, which will be crucial to the success of overcoming the challenges presented by cancers. [ABSTRACT FROM AUTHOR]

Abstract: Supercritical fluid impregnation was tested to prepare a new ophthalmic drug delivery device. Poly(methylmethacrylate-co-ethylhexylacrylate-co-ethyleneglycoldimethacrylate), P(MMA-EHA-EGDMA) has been proposed by Mariz [M. Mariz, Preparação de uma lente intra-ocular dotada de um sistema de libertação controlada de fármaco, Master Thesis, Universidade de Coimbra, 1999] as a promising matrix to be used for intraocular delivery of anti-inflammatory drugs used in eye surgery. This matrix was successfully impregnated with flurbiprofen, a non-steroidal anti-inflammatory agent. The success of the impregnation was evaluated by scanning electron microscopy (SEM) analysis and also by in vitro drug release studies. The effect of some operating parameters was evaluated, namely, pressure and contact time. The operating pressure will influence both the solubility of the drug in the supercritical fluid but also the sorption degree of the polymeric matrix in the presence of carbon dioxide. The solubility of the drug in carbon dioxide and the sorption degree are reported in previous studies. A comparison between the batch and the semi-continuous impregnation process is also presented. The supercritical fluid impregnation proved to be feasible for the preparation of a new ophthalmic drug delivery system. The drug release profiles suggest that the drug can be released up to three months, which is a major advantage for the prevention of the inflammatory response after ophthalmic surgery. [Copyright &y& Elsevier]

Abstract: Carbon dioxide solubility in a natural biodegradable polymer, namely poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and the diffusion coefficients are reported. Equilibrium solubility of dense carbon dioxide in PHBV was studied by a gravimetric method in a temperature range from 308 to 313K and a pressure range from 10.0 to 15.0MPa. The copolymer presented Fickian behavior and Fick''s diffusion model was applied to determine the amount of carbon dioxide present in the samples after a predermined exposure time as well as the diffusion coefficients. Diffusion coefficients for the sorption under supercritical (sc) conditions and desorption at ambient conditions were determined and compared. To evaluate the influence of the HV content in the amount of maximum sorption degree of the polymer, different samples of PHBV copolymers were tested and the sorption curves are here presented. [Copyright &y& Elsevier]

Abstract: In situ ATR-IR spectroscopy was used to simultaneously measure the sorption and swelling of carbon dioxide at high pressures in a biocompatible acrylate copolymer poly(methylmethacrylate-co-ethylhexylacrylate-co-ethyleneglycoldimethacrylate), P(MMA–EHA–EGDMA). The ν 3 band of CO2 dissolved in the polymer (at 2335cm−1) was used to calculate the sorption data and the polymer swelling was determined by analyzing the changes in the absorbance of the ν(Cat 1730cm−1) of the polymer. Transmission spectroscopy in the near-IR region was also used to study the sorption of CO2 in the polymer using combinational and overtone bands. The experiments were carried out in a pressure range of 2.0–12.0MPa and in a temperature range of 27–40°C. The data for CO2 sorption in this polymer obtained by in situ spectroscopic methods have been compared to the data obtained by the gravimetric technique. [Copyright &y& Elsevier]

Deep eutectic solvents (DES) are often regarded as greener sustainable alternative solvents and are currently employed in many industrial applications on a large scale. Bearing in mind the industrial importance of DES—and because the vast majority of DES has yet to be synthesized—the development of cheminformatic models and tools efficiently profiling their density becomes essential. In this work, after rigorous validation, quantitative structure-property relationship (QSPR) models were proposed for use in estimating the density of a wide variety of DES. These models were based on a modelling dataset previously employed for constructing thermodynamic models for the same endpoint. The best QSPR models were robust and sound, performing well on an external validation set (set up with recently reported experimental density data of DES). Furthermore, the results revealed structural features that could play crucial roles in ruling DES density. Then, intelligent consensus prediction was employed to develop a consensus model with improved predictive accuracy. All models were derived using publicly available tools to facilitate easy reproducibility of the proposed methodology. Future work may involve setting up reliable, interpretable cheminformatic models for other thermodynamic properties of DES and guiding the design of these solvents for applications. [ABSTRACT FROM AUTHOR]

Most nonsteroidal anti-inflammatory drugs (NSAIDs) present poor aqueous solubility, impairing their efficiency in physiological media. In this context, Low Transition Temperature Mixtures (LTTMs) are a promising platform to overcome drugs' poor solubility, forming therapeutic liquid formulations. In this work, the LTTMs of citric acid:L-arginine:water (C:A:W) and glycerol:sorbitol (G:S) were studied in terms of their features and assessed in terms of their ability to increase the solubility of six NSAIDs in physiological media. The physicochemical properties of LTTMs were characterized by state-of-art techniques commonly used for these systems. The cytotoxicity of G:S was also evaluated in L929 mouse fibroblasts and the viscosity, polarity, and pH properties of the studied mixtures were related to the solubility of NSAIDs. The pH and polarity were the parameters that most influenced the drugs' solubility. Ibuprofen, naproxen, ketoprofen, indomethacin, and flurbiprofen did not present any solubility improvement in the formulations tested. However, concentrated mixtures of C:A:W or G:S in the physiologic-mimicked media (PBS) rendered a celecoxib solubility 4 and 5 times higher than PBS, respectively. These therapeutic liquid formulations of celecoxib in C:A:W or G:S can be a promising tool to increase celecoxib's therapeutic efficiency in local applications. [ABSTRACT FROM AUTHOR]

In this study, the viscosity behavior of two mixtures of Ethaline (1 ChCl:2 ethylene glycol) with either methanol or ethanol were investigated over the temperature range of 283.15–333.15 K at atmospheric pressure. The measured viscosities of neat Ethaline, methanol, and ethanol showed reliable agreement with the corresponding reported literature values. The mixture viscosities were modeled by an Arrhenius-like model to determine the behavior of viscosity with respect to temperature. The data were also modeled by the four well-known mixture viscosity models of Grunberg–Nissan, Jouyban–Acree, McAllister, and Preferential Solvation. All of the model results were reliable, with the Jouyban–Acree and Preferential Solvation models showing the most accurate agreement with the experimental measurements. The Jones–Dole viscosity model was also investigated for the measured viscosities, and by analyzing the results of this model, strong interactions among Ethaline and the alcohol molecules were proposed for both systems. As a final analysis, viscosity deviations of the investigated systems were calculated to study the deviations of the viscosity behaviors with respect to ideal behavior. Both systems showed negative viscosity deviations at all of the investigated temperatures, with the negative values tending towards zero, and hence more ideal behavior, with increasing temperatures. Moreover, in order to correlate the calculated viscosity deviations, the Redlich–Kister model was successfully used for both systems and at each investigated temperature. [ABSTRACT FROM AUTHOR]

• Densities of aqueous solutions of 1 ChCl + 4 Phenol were measured from 20 to 50 °C. • A comprehensive volumetric investigation was carried out on the investigated mixtures. • All of the investigated mixtures showed negative excess molar volumes. In this study, the densities of the pseudo-binary systems of water and the deep eutectic solvent, 1 choline chloride + 4 phenol were measured and reported for the first time in literature, and a comprehensive investigation on the various volumetric properties was carried out. Nine mixtures, with different compositions of water, were prepared. The densities of the prepared mixtures, as well as pure water and pure deep eutectic solvent (DES) were measured within a temperature range of 293.15–333.15 K at atmospheric pressure. Various volumetric properties, such as excess molar volumes and isobaric volume expansions, partial molar volumes and excess partial molar volumes were calculated for the investigated compositions. Furthermore, partial molar volumes and excess partial molar volumes at infinite dilution were estimated for water and the DES. By analysing the calculated properties, the interstitial accommodation effect was suggested for the investigated mixtures. The stronger tendency of water to be solvated in the mixture, as compared to the DES, was observed for all investigated temperatures. This suggests that, most probably, hydrogen bonds in the investigated mixtures are established in a manner in which water molecules are located at central positions, surrounded by the DES pseudo-molecules. [ABSTRACT FROM AUTHOR]

Tuberculosis is an highly contagious disease still considered by the WHO as one of most infectious diseases worldwide. The therapeutic approach, used to prevent and treat tuberculosis targets the Mycobacterium tuberculosis complex, comprises a combination of drugs administrated for long periods of time, which, in many cases, could cause several adverse effects and, consequently, low compliance of the patient to the treatment and drug-resistance. Therefore, therapeutic liquid mixtures formulated with anti-tuberculosis drugs and/or adjuvants in tuberculosis therapy are an interesting approach to prevent toxic effects and resistance to anti-tuberculosis drugs. The herein formulated therapeutic liquid mixtures, including ethambutol, arginine, citric acid and water under different molar ratios, were studied through a molecular dynamics approach to understand how ethambutol and arginine could be stabilized by the presence of citric acid and/or water in the mixture. To gain insights on how the uptake of these mixtures into the mycobacteria cell may occur and how a mycobacterial ABC transporter could contribute to this transport, multiple simultaneous ligand docking was performed. Interactions between citric acid and ethambutol involving the carboxyl and hydroxyl groups of citric acid with the amines of ethambutol were identified as the most critical ones. Water molecules present in the mixture provides the necessary network of hydrogen bonds that stabilize the mixture. Molecular docking additionally provided an interesting hypothesis on how the different mixture components may favor binding of ethambutol to an ABC importer. The data presented in this work helps to better understand these mixtures as well as to provide cues on the mechanisms that allow them to cross the mycobacterial cell membrane. [ABSTRACT FROM AUTHOR]

In this study, the integrated application of supercritical CO2 and natural deep eutectic solvents (NADES) was investigated in order to establish a green procedure that enables obtaining and stabilizing the aroma volatile constituents of Rosmarinus officinalis L. Supercritical CO2 was used to obtain rosemary extracts that possessed an abundance of terpenes, particularly monoterpenes 68.97–88.08% and sesquiterpenes 5.38–21.22%. The obtained extracts were further dispersed in different NADES (betaine/glycerol (Bet/Gly), betaine/ethylene glycol (Bet/EG), and betaine/glycerol/sucrose/water (Bet/Gly/Suc/W) and their stability was assessed at room temperature. The headspace profile of the samples and their antioxidant activity were monitored for 6 months. Changes in the chemical profile of the extract were detected, which corresponded to terpene transformation reactions. In the control (CO2 extract), the development of non-terpene components such as acetic acid was detected, which make the product unsuitable for use. Conversely, the accumulation of acetic acid was not observed in the NADES samples. The antioxidant activity of the control was the most significantly decreased during 6 months, while among the NADES samples, the reduction of activity occurred only in Bet/Gly sample. In Bet/EG and Bet/Gly/Suc/W samples, activity remained the same during the same period. The results suggest that the NADES could serve as stabilization media for CO2-extracted rosemary volatile components. Furthermore, this represents a simple, green process of obtaining readily applicable products with extended stability at room temperature. [ABSTRACT FROM AUTHOR]

This work aimed at evaluating the potential of using natural deep eutectic systems (NADES) as cryoprotectant agents (CPAs). Several combinations between natural primary metabolites that have been identified in animals that live in extreme cold climates were prepared. All systems showed very little cytoxicity towards L929 cells at concentrations high as 1–2 M. Moreover, this cell line was highly tolerant to 10% (w/v) of NADES when compared to Me 2 SO. To test NADES as CPAs, two cell lines were used, L929 and HacaT cells. After freeze/thawing cycle, it was possible to observe that for L929 cells, NADES presented similar behaviour to Me 2 SO. For Hacat cell line a significant improvement on post-thawing recovery was observed. Moreover, the results presented herein showed that NADES do not need to be removed from the freezing media after thawing the cells, which is a great advantage of these materials. Additionally, we have shown that NADES can act as CPA when cells are frozen at −20 °C. In overall, the results demonstrate the high potential of NADES to be used in cryobiology as alternative CPAs. [ABSTRACT FROM AUTHOR]

The green and versatile character of deep eutectic solvents (DES) has turned them into significant tools in the development of green and sustainable technologies. For this purpose, their use in polymeric applications has been growing and expanding to new areas of development. The present review aims to summarize the progress in the field of DES applied to polymer science and engineering. It comprises fundamentals studies involving DES and polymers, recent applications of DES in polymer synthesis, extraction and modification, and the early developments on the formulation of DES–polymer products. The combination of DES and polymers is highly promising in the development of new and 'greener' materials. Still, there is plenty of room for future research in this field. [ABSTRACT FROM AUTHOR]