Green technology actively seeks new solvents to replace common organic solvents that present inherent toxicity and have high volatility, leading to evaporation of volatile organic compounds to the atmosphere. Over the past two decades, ionic liquids (ILs) have gained enormous attention from the scientific community, and the number of reported articles in the literature has grown exponentially. Nevertheless, IL "greenness" is often challenged, mainly due to their poor biodegradability, biocompatibility, and sustainability. An alternative to ILs are deep eutectic solvents (DES). Deep eutectic solvents are defined as a mixture of two or more components, which may be solid or liquid and that at a particular composition present a high melting point depression becoming liquids at room temperature. When the compounds that constitute the DES are primary metabolites, namely, aminoacids, organic acids, sugars, or choline derivatives, the DES are so called natural deep eutectic solvents (NADES). NADES fully represent green chemistry principles. Can natural deep eutectic solvents be foreseen as the next generation solvents and can a similar path to ionic liquids be outlined? The current state of the art concerning the advances made on these solvents in the past few years is reviewed in this paper, which is more than an overview on the different applications for which they have been suggested, particularly, biocatalysis, electrochemistry, and extraction of new data. Citotoxicity of different NADES was evaluated and compared to conventional imidazolium-based ionic liquids, and hints at the extraction of phenolic compounds from green coffee beans and on the foaming effect of NADES are revealed. Future perspectives on the major directions toward which the research on NADES is envisaged are here discussed, and these comprised undoubtedly a wide range of chemically related subjects.

a b s t r a c tThis paper presents a novel approach toward the production of hybrid alginate-lignin aerogels. The key idea of the approach is to employ pressurized carbon dioxide for gelation. Exposure of alginate and lignin aqueous alkali solution containing calcium carbonate to CO 2 at 4.5 MPa resulted in a hydrogel formation. Various lignin and CaCO 3 concentrations were studied. Stable hydrogels could be formed up to 2:1 (w/w) alginate-to-lignin ratio (1.5 wt% overall biopolymer concentration). Upon substitution of water with ethanol, gels were dried in supercritical CO 2 to produce aerogels. Aerogels with bulk density in the range 0.03-0.07 g/cm 3 , surface area up to 564 m 2 /g and pore volume up to 7.2 cm 3 /g were obtained. To introduce macroporosity, the CO 2 induced gelation was supplemented with rapid depressurization (foaming process). Macroporosity up to 31.3 ± 1.9% with interconnectivity up to 33.2 ± 8.3% could be achieved at depressurization rate of 3 MPa/min as assessed by micro-CT. Young's modulus of alginate-lignin aerogels was measured in both dry and wet states. Cell studies revealed that alginate-lignin aerogels are non-cytotoxic and feature good cell adhesion making them attractive candidates for a wide range of applications including tissue engineering and regenerative medicine.

Low voltage actuators based on poly(vinylidene fluoride) (PVDF) with 10, 25 and 40 % 1-hexyl-3-methylimidazolium chloride ([C6mim][Cl]) and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C6mim][NTf2]) are prepared by solvent casting in order to evaluate the effect of anion size in the bending properties. Independently of the ionic liquid type and content, its presence leads to the crystallization of PVDF in the phase. The addition of ionic liquid into the polymer matrix decreases significantly its degree of crystallinity and the elastic modulus. It is also confirmed the good miscibility between PVDF and IL, determined by the interaction of the CF2 groups from the PVDF chains with the imidazolium ring in the ionic liquid (IL). The AC conductivity of the composites depends both on the amount of ionic liquid content and anion size. The bending movement of the IL/PVDF composites is correlated to their degree of crystallinity, mechanical properties and ionic conductivity value and the best value of bending response (0.53 %) being found for IL/PVDF composite with 40 wt% of [C6mim][Cl] at an applied voltage of 10 volts square signal.

Highlights • alginate-starch Ca-crosslinked aerogels by CO 2 induced gelation and sc-drying; • macroporosity due to CO 2 expansion and intrinsically high mesoporosity; • alginate-starch aerogels are bioactive and non-cytotoxic. ABSTRACT Aerogels are a special class of ultra-light porous materials with growing interest in biomedical applications due to their open pore structure and high surface area. However, they usually lack macroporosity, while mesoporosity is typically high. In this work, carbon dioxide induced gelation followed by expansion of the dissolved CO 2 was performed to produce hybrid calcium-crosslinked alginate-starch hydrogels with dual meso-and macroporosity. The hydrogels were subjected to solvent exchange and supercritical drying to obtain aerogels. Significant increase in macroporosity from 2 to 25 % was achieved by increasing expansion rate from 0.1 to 30 bar/min with retaining mesoporosity (BET surface and BJH pore volume in the range 183-544 m 2 /g and 2.0-6.8 cm 3 /g, respectively). In vitro bioactivity studies showed that the alginate-starch aerogels are bioactive, i.e. they form hydroxyapatite crystals when immersed in a simulated body fluid solution. Bioactivity is attributed to the presence of calcium in the matrix. The assessment of the biological performance showed that the aerogels do not present a cytotoxic effect and the cells are able to colonize and grow on their surface. Results presented in this work provide a good indication of the potential of the alginate-starch aerogels in biomedical applications, particularly for bone regeneration. KEYWORDS aerogels, alginate, starch, tissue engineering, supercritical fluids, CO 2 induced gelation INTRODUCTION An ideal scaffold for tissue engineering must meet particular requirements to achieve the desired biological response: the scaffold should possess interconnecting pores of appropriate size to favor tissue integration and vascularization, be made from material with controlled biodegradability, have appropriate surface chemistry to favor cellular attachment, differentiation and proliferation, possess adequate mechanical properties to match the intended site of implantation and handling, should not induce any adverse response and be easily fabricated into a variety of shapes and sizes [1]. Some attempts have recently been made to address tissue engineering and regenerative medicine (TERM) problems using aerogels as scaffolds. Aerogels are well known ultra-light highly porous materials with an open structure, large specific surface area and pore volume. High mesoporosity comparable to the native extracellular matrix (ca. 80% porosity) is favorable condition for cell growth, making aerogels an ideal candidate for a number of biomedical applications, including tissue engineering. Nevertheless, macroporosity of these structures should be improved to promote cell migration into the matrices and enhance mass transfer between the scaffold and the bulk phase. The fact that biopolymers can be used for aerogel production was recognized by Samuel...

The action of sinapic acid and its alkyl esters as potential antioxidants has been investigated. For this purpose, a series of sinapic acid ester derivatives was synthesized and their antioxidant activities were evaluated using distinctive analytical methods, namely, 2,2-diphenyl-1-picrylhydrazyl (DPPH) and FRAP UV-vis methods and differential scanning calorimetry. The electron-donating activity and lipophilicity of these phenolic compounds were also evaluated. From the overall results it was concluded that alkyl ester sinapates (linear alkyl esters) present almost the same antioxidant activity, albeit slightly lower, exhibited by the parent compound (sinapic acid). Furthermore, the addition of an alkyl ester side chain has a positive effect on the partition coefficient of sinapic acid, improving its utility as an antioxidant in a more lipophilic medium. The data on the antioxidant activity obtained by different analytical methods correlated well with each other and have revealed interesting antioxidant data of alkyl esters of sinapic acid.