The major challenge of the pharmaceutical industry is to find potential solvents for poorly water-soluble drug molecules. Ionic liquids (ILs) have attracted this industry as (co-) solvents due to their unique physicochemical and biological properties. Herein, a straightforward approach for the enhancement of the water solubility of paracetamol and sodium diclofenac is presented, using new biocompatible N-acetyl amino acid N-alkyl cholinium-based ionic liquids as co-solvents (0.2-1mol%). These new ionic liquids were able to increase the water solubility of these drugs up to four times that in pure water or in an inorganic salt solution. In the presence of these ILs, the drugs lipophilicity (log P was not significantly changed for paracetamol, but for sodium diclofenac it was possible to decrease significantly its lipophilicity. Concerning cytotoxicity in human dermal fibroblasts it was observed that ILs did not show a significant toxicity, and were able to improve cell viability compared with the respective precursors.

Artificial olfaction is a fast-growing field aiming to mimic natural olfactory systems. Olfactory systems rely on a first step of molecular recognition in which volatile organic compounds (VOCs) bind to an array of specialized olfactory proteins. This results in electrical signals transduced to the brain where pattern recognition is performed. An efficient approach in artificial olfaction combines gas-sensitive materials with dedicated signal processing and classification tools. In this work, films of gelatin hybrid gels with a single composition that change their optical properties upon binding to VOCs were studied as gas-sensing materials in a custom-built electronic nose. The effect of films thickness was studied by acquiring signals from gelatin hybrid gel films with thicknesses between 15 and 90 μm when exposed to 11 distinct VOCs. Several features were extracted from the signals obtained and then used to implement a dedicated automatic classifier based on support vector machines for data processing. As an optical signature could be associated to each VOC, the developed algorithms classified 11 distinct VOCs with high accuracy and precision (higher than 98%), in particular when using optical signals from a single film composition with 30 μm thickness. This shows an unprecedented example of soft matter in artificial olfaction, in which a single gelatin hybrid gel, and not an array of sensing materials, can provide enough information to accurately classify VOCs with small structural and functional differences.

The composition and architecture of a scaffold determine its supportive role in tissue regeneration. In this work, we demonstrate the feasibility of obtaining a porous electrospun fibrous structure from biodegradable polyurethanes (Pus) synthesized using polycaprolactone-diol as soft segment and, as chain extenders, chitosan (CS) and/or dimethylol propionic acid. Fourier transform infrared spectroscopy and proton nuclear magnetic resonance confirmed the syntheses. Fibre mats' properties were analysed and compared with those of solvent cast films. Scanning electron microscopy images of the electrospun scaffolds revealed fibres with diameters around 1 μm. From tensile tests, we found that Young's modulus increases with CS content and is higher for films (2.5 MPa to 6.5 MPa) than for the corresponding fibre mats (0.8 MPa to 3.2 MPa). The use of CS as the only chain extender improves recovery ratio and resilience. From X-ray diffraction, a higher crystalline degree was identified in fibre mats than in the corresponding films. Films' wettability was enhanced by the presence of CS as shown by the decrease of water contact angle. X-ray photoelectron spectroscopy revealed that while ester groups are predominant at the films' surface, ester and urethanes are present in similar concentrations at fibres' surface, favouring the interaction with water molecules. Both films and fibres undergo hydrolytic degradation. In vitro evaluation was performed with human dermal fibroblasts. No PU sample revealed cytotoxicity. Cells adhered to fibre mats better than to films and proliferation was observed only for samples of CS-containing PUs. Results suggest that electrospun fibres of CS-based polyurethanes are good candidate scaffolds for soft tissue engineering.

Online monitoring of carbon fiber reinforced plastic (CFRP) ropes requires non-destructive testing (NDT) methods capable of detecting multiple damage types at high inspection speeds. Three NDT methods are evaluated on artificial and realistic imperfections in order to assess their suitability for online monitoring of CFRP ropes. To support testing, the microstructure and electrical conductivity of a carbon fiber rope is characterized. The compared methods are thermography via thermoelastic stress analysis, ultrasonic testing with commercial phased array transducers, and eddy current testing, supported by tailor-made probes. While thermoelastic stress analysis and ultrasonics proved to be accurate methods for detecting damage size and the shape of defects, they were found to be unsuitable for high-speed inspection of a CFRP rope. Instead, contactless inspection using eddy currents is a promising solution for real-time online monitoring of CFRP ropes at high inspection speeds.

The aim of the present study is to investigate the effect of the hydrolysis process on the properties of nanocrystalline cellulose (NCC) isolated from different precursors and the subsequent use of the extracted NCC for the reduction of graphene oxide (GO). The raw materials (almond and peanut shells) chosen for the isolation of cellulose were selected on the basis of their abundance and their poorly investigation in the production of NCC. Microcrystalline cellulose (MCC) was firstly extracted by alkali and bleaching treatments, then hydrolyzed under different processes to produce NCC polymorphs with structure I (NCC-I) and NCC structure II (NCC-II). The Fourier transform infrared spectroscopy, the X-ray diffraction (XRD) and the 13C NMR studies of the alkali and bleached products confirmed the formation of cellulose type I with high purity and good crystallinity, while scanning electron microscopy (SEM) showed micrometric fibers with lengths reaching 80 µm. Sulfuric acid treatment of these microfibers results in NCC type I or II, depending on the hydrolysis process. SEM of the NCC samples exhibited nanorods with diameter and aspect ratio in the range of 20–40 and 20–25 nm, respectively. Thermogravimetric analysis (TGA) of the MCC and NCC products indicated stable materials with a degradation temperature reaching 240 and 200 °C for MCC and NCC, respectively. The other part of our work concerns the use of the obtained cellulose nanocrystals (type II) for the preparation of reduced graphene oxide composite (NCC/RGO), to demonstrate the reducing properties of the isolated NCCII.

The aim of the present study is to investigate the effect of the hydrolysis process on the properties of nanocrystalline cellulose (NCC) isolated from different precursors and the subsequent use of the extracted NCC for the reduction of graphene oxide (GO). The raw materials (almond and peanut shells) chosen for the isolation of cellulose were selected on the basis of their abundance and their poorly investigation in the production of NCC. Microcrystalline cellulose (MCC) was firstly extracted by alkali and bleaching treatments, then hydrolyzed under different processes to produce NCC polymorphs with structure I (NCC-I) and NCC structure II (NCC-II). The Fourier transform infrared spectroscopy, the X-ray diffraction (XRD) and the 13C NMR studies of the alkali and bleached products confirmed the formation of cellulose type I with high purity and good crystallinity, while scanning electron microscopy (SEM) showed micrometric fibers with lengths reaching 80 µm. Sulfuric acid treatment of these microfibers results in NCC type I or II, depending on the hydrolysis process. SEM of the NCC samples exhibited nanorods with diameter and aspect ratio in the range of 20–40 and 20–25 nm, respectively. Thermogravimetric analysis (TGA) of the MCC and NCC products indicated stable materials with a degradation temperature reaching 240 and 200 °C for MCC and NCC, respectively. The other part of our work concerns the use of the obtained cellulose nanocrystals (type II) for the preparation of reduced graphene oxide composite (NCC/RGO), to demonstrate the reducing properties of the isolated NCCII.

Twelve biochars from forest and agri-food wastes (pruning of Quercus ilex, Eucalyptus grandis, Pinus pinaster, Quercus suber, Malus pumila, Prunus spinosa, Cydonia oblonga, Eriobotrya japonica, Juglans regia, Actinidia deliciosa, Citrus sinensis and Vitis vinifera) were investigated as potential low-cost and renewable adsorbents for removal of a commonly used pharmaceutical, fluoxetine. Preliminary adsorption experiments allowed to select the most promising adsorbents, Quercus ilex, Cydonia oblonga, Eucalyptus, Juglans regia and Vitis vinifera pruning material. They were characterized by proximate, elemental and mineral analysis, thermogravimetric analysis, Fourier transform infrared spectroscopy, determination of specific surface area and pH at the point of zero charge. Batch and equilibrium studies were performed, and the influence of pH was evaluated. The equilibrium was reached in less than 15 min in all systems. The maximum adsorption capacity obtained was 6.41 mg/g for the Eucalyptus biochar, which also demonstrated a good behavior in continuous mode (packed column).

Silver nanoparticles (AgNPs) were prepared by GREEN chemistry relying on the reduction of AgNO3 by phytochemicals present in black tea extract. AgNPs were fully characterized by transmission electron microscopy (TEM), ultraviolet-visible spectroscopy ((UV-vis)), X-ray diffraction (XRD) and energy dispersive absorption spectroscopy (EDS). The synthesized AgNPs induced a decrease of the cell viability in a dose-dependent manner with a low IC50 (0.5 ± 0.1 μM) for an ovarian carcinoma cell line (A2780) compared to primary human fibroblasts (IC50 5.0 ± 0.1 μM). The DNA binding capability of CT (calf thymus) DNA was investigated using electronic absorption and fluorescence spectroscopies, circular dichroism and viscosity titration methods. Additionally, the AgNPs strongly quench the intrinsic fluorescence of BSA, as determined by synchronous fluorescence spectra.

Two mononuclear NiII and MnII compounds, [Ni(bdtbpza)2(CH3OH)4] (1) and [Mn(bdtbpza)2(CH3OH)2(H2O)2] (2), are afforded by employing a ‘scorpionate’ type precursor [bdtbpza = bis(3,5-di-t-butylpyrazol-1-yl)acetate]. The single crystal X-ray structure reveals that the central metal ion (NiII for 1 and MnII for 2) is surrounded by a pair of Oacetate atoms of two bis(pyrazol-1-yl)acetate units, while four OMeOH donors for 1 and two OMeOH plus two Owater for 2 complete the first coordination sphere. Thus, both compounds exhibit a slightly distorted octahedral geometry possessing an O6 coordination environment. EPR spectra of CuII-doped 1 and of 2 recorded on the polycrystalline solids and in organic solution confirm the octahedral geometry around the metal ions and the binding of six oxygen atoms. The electrochemical study of compounds 1 and 2 shows that one electron reduction of MnII occurs at a more negative potential than NiII, indicating a lower tendency of reduction for Mn than Ni. Both compounds displayed a high cytotoxic activity against A2780 ovarian carcinoma cells and no cytotoxic activity in normal primary human fibroblasts for concentrations up to 55 μM. Notwithstanding, compound 1 is found to be the most cytotoxic towards A2780 cancer cells. The cytotoxic activity of compound 1 is correlated with the induction of apoptosis associated with a higher mitochondria dysfunction and autophagy cell death. In addition, the compounds can induce oxidative damage leading to ROS accumulation. Overall, the data presented here demonstrate that 1 has potential for further in vivo studies aiming at its future application in ovarian cancer therapy.

Silver nanoparticles (AgNPs) were prepared by GREEN chemistry relying on the reduction of AgNO3 by phytochemicals present in black tea extract. AgNPs were fully characterized by transmission electron microscopy (TEM), ultraviolet-visible spectroscopy ((UV-vis)), X-ray diffraction (XRD) and energy dispersive absorption spectroscopy (EDS). The synthesized AgNPs induced a decrease of the cell viability in a dose-dependent manner with a low IC50 (0.5+/-0.1muM) for an ovarian carcinoma cell line (A2780) compared to primary human fibroblasts (IC50 5.0+/-0.1muM). The DNA binding capability of CT (calf thymus) DNA was investigated using electronic absorption and fluorescence spectroscopies, circular dichroism and viscosity titration methods. Additionally, the AgNPs strongly quench the intrinsic fluorescence of BSA, as determined by synchronous fluorescence spectra.

The heterogenization of the highly active monovacant polyoxotungstate ([PW11O39]7 −, abbreviated as PW11) was achieved by preparing the corresponding long chain quaternary ammonium salt (ODA7PW11, ODA = CH3(CH2)17(CH3)3N). The complete cation exchange confers total heterogeneity to the monovacant catalyst while keeping its oxidative catalytic activity. In fact, the heterogeneous catalyst allowed for the complete desulfurization of a multicomponent model diesel (2000 ppm S) after 40 min of reaction, conciliating extraction (using BMIMPF6 solvent) and oxidation (ECODS process using H2O2 oxidant). The heterogeneous catalyst has shown a superior desulfurization performance when compared with the homogeneous quaternary ammonium TBAPW11 catalyst (TBA = (C4H9)4 N). Both hybrid catalysts have been successfully reused in consecutive ECODS cycles. Additionally, the long carbon chain cations provide a protective environment around the polyoxometalate allowing for ODA7PW11 to retain its heterogeneity and structure after the ECODS process.

In the present work composite membranes were produced by combining magnetic nanoparticles (NPs) with cellulose acetate (CA) membranes for magnetic hyperthermia applications. The non-woven CA membranes were produced by electrospinning technique, and magnetic NPs were incorporated by adsorption at fibers surface or by addition to the electrospinning solution. Therefore, different designs of composite membranes were obtained. Superparamagnetic NPs synthesized by chemical precipitation were stabilized either with oleic acid (OA) or dimercaptosuccinic acid (DMSA) to obtain stable suspensions at physiological pH. The incorporation of magnetic NP into CA matrix was confirmed by scanning and transmission electron microscopy. The results showed that adsorption of magnetic NPs at fibers’ surface originates composite membranes with higher heating ability than those produced by incorporation of magnetic NPs inside the fibers. However, adsorption of magnetic NPs at fibers’ surface can cause cytotoxicity depending on the NPs concentration. Tensile tests demonstrated a reinforcement effect caused by the incorporation of magnetic NPs in the non-woven membrane.

This paper studied the alteration of three soda-rich-silicate glass types (Cristallo, façon-de-Venise and soda-lime silicate). Replica samples were exposed to different environments simulating museum-like conditions – room temperature and different relative humidities (RH). Results were analysed by SIMS, μ-FTIR, Optical Microscopy and Optical 3D profilometry. Cristallo appears as the most vulnerable, whilst the soda-lime glass appears as the most resistant to the environmental deterioration. The thickness of the altered layer is proportional to the time of exposure and to the RH of the surrounding atmosphere. From the results obtained, the glass composition and the water available and adsorbed to the surface strongly influence the kinetics of the surface alteration.

Abstract This work reports for the first time a new series of promising porous catalytic carbon materials, functionalized with Lewis and Brønsted acid sites useful in the green synthesis of 2,3-dihydro-1H-1,5-benzodiazepine – nitrogen heterocyclic compounds. Benzodiazepines and derivatives are fine chemicals exhibiting interesting therapeutic properties. Carbon materials have been barely investigated in the synthesis of this type of compounds. Two commercial carbon materials were selected exhibiting different textural properties: i) Norit RX3 (N) as microporous sample and ii) mesoporous xerogel (X), both used as supports of ZrO2 (Zr) and ZrO2/SO42− (SZr). The supported SZr led to higher conversion values and selectivities to the target benzodiazepine. Both chemical and textural properties influenced significantly the catalytic performance. Particularly relevant are the results concerning the non-sulfated samples, NZr and XZr, that were able to catalyze the reaction leading to the target benzodiazepine with high selectivity (up to 80 %; 2 h). These results indicated an important role of the carbon own surface functional groups, avoiding the use of H2SO4. Even very low amounts of SZr supported on carbon reveal high activity and selectivity. Therefore, the carbon materials herein reported can be considered an efficient and sustainable alternative bifunctional catalysts for the benzodiazepine synthesis.