The development of new materials for the controlled release of molecules represents a topic of primary importance in medicine, as well as in food science. In recent years, eutectic solvents have been applied as releasing media due to their improved capacity to interact with specific molecules, offering a broad range of tunability. Nevertheless, their application in essential oil dissolution are rare and more data are needed to develop new generations of effective systems.
View Article and Find Full Text PDFIt is a common belief that memories, over time, become progressively independent of the hippocampus and are gradually stored in cortical areas. This view is mainly based on evidence showing that prefrontal cortex (PFC) manipulations impair the retrieval of remote memories, while hippocampal inhibition does not. More controversial is whether activity in the medial PFC is required immediately after learning to initiate consolidation.
View Article and Find Full Text PDFAluminum-sulfur (Al-S) batteries are promising energy storage devices due to their high theoretical capacity, low cost, and high safety. However, the high viscosity and inferior ion transport of conventionally used ionic liquid electrolytes (ILEs) limit the kinetics of Al-S batteries, especially at sub-zero temperatures. Herein, locally concentrated ionic liquid electrolytes (LCILE) formed via diluting the ILEs with non-solvating 1,2-difluorobenzene (dFBn) co-solvent are proposed for wide-temperature-range Al-S batteries.
View Article and Find Full Text PDFThe possibility of using deep eutectic solvents (DESs) as co-solvents for stabilizing and preserving the native structure of DNA provides an attractive opportunity in the field of DNA biotechnology. The rationale of this work is a systematic investigation of the effect of hydrated choline-based DES on the structural stability of a 30-base-pair double-stranded DNA model via a combination of spectroscopic experiments and MD simulations. UV absorption and CD experiments provide evidence of a significant contribution of DESs to the stabilization of the double-stranded canonical (B-form) DNA structure.
View Article and Find Full Text PDFLithium metal batteries (LMBs) with nickel-rich cathodes are promising candidates for next-generation high-energy-density batteries, but the lack of sufficiently protective electrode/electrolyte interphases (EEIs) limits their cyclability. Herein, trifluoromethoxybenzene is proposed as a cosolvent for locally concentrated ionic liquid electrolytes (LCILEs) to reinforce the EEIs. With a comparative study of a neat ionic liquid electrolyte (ILE) and three LCILEs employing fluorobenzene, trifluoromethylbenzene, or trifluoromethoxybenzene as cosolvents, it is revealed that the fluorinated groups tethered to the benzene ring of the cosolvents not only affect the electrolytes' ionic conductivity and fluidity, but also the EEIs' composition via adjusting the contribution of the 1-ethyl-3-methylimidazolium cation (Emim ) and bis(fluorosulfonyl)imide anion.
View Article and Find Full Text PDFTraining with long inter-session intervals, termed distributed training, has long been known to be superior to training with short intervals, termed massed training. In the present study we compared c-Fos expression after massed and distributed training protocols in the Morris water maze to outline possible differences in the learning-induced pattern of neural activation in the dorsal CA1 in the two training conditions. The results demonstrate that training and time lags between learning opportunities had an impact on the pattern of neuronal activity in the dorsal CA1.
View Article and Find Full Text PDFBijels (bicontinuous interfacially jammed emulsion gels) raised an increasing interest as biomaterials for controlled drug delivery due to their biphasic nature organized in mesoscopic tortuous domains. Two bijel formulations were prepared and explored as delivery systems for both hydrophilic and lipophilic drugs, ethosuximide and dimethyl fumarate. The two bijel-like structures, based on polymerized ε-caprolactone/water, differ in the stabilizing nanoparticle hydroxyapatite (inorganic) and nanogel-based nanoparticles (organic).
View Article and Find Full Text PDFHydrogels based on hyaluronic acid (HA) and agarose-carbomer (AC) raised an increasing interest as drug delivery systems. The complex architecture of the polymer network, such as mesh size, HA molecular weight and drug-polymer non covalent interactions across the 3D polymer matrix strongly influence the release capability/profile of these materials. In this study, AC-HA hydrogels with different mesh sizes have been prepared and characterised.
View Article and Find Full Text PDFThe treatment of used vegetable oil (UVO) with seven different adsorbents and through two different procedures (stirring and gravity filtration) was explored. Important differences in terms of density, turbidity, electrical resistance, free fatty acids (FFAs) content and relative fatty acid distribution were observed. Different outcomes were shown depending both on the adsorbent and on the procedure.
View Article and Find Full Text PDFCholine-based deep eutectic solvents (DESs) are potential candidates to replace flammable organic solvent electrolytes in lithium-ion batteries (LIBs). The effect of the addition of a lithium salt on the structure and dynamics of the material needs to be clarified before it enters the battery. Here, the archetypical DES choline chloride:urea at 1:2 mole fraction has been added with lithium chloride at two different concentrations and the effect of the additional cation has been evaluated with respect to the non-doped system via multinuclear NMR techniques.
View Article and Find Full Text PDFThe challenging issue of spent nuclear fuel (SNF) management is being tackled by developing advanced technologies that point to reduce environmental footprint, long-term radiotoxicity, volumes and residual heat of the final waste, and to increase the proliferation resistance. The advanced recycling strategy provides several promising processes for a safer reprocessing of SNF. Advanced hydrometallurgical processes can extract minor actinides directly from Plutonium and Uranium Reduction Extraction raffinate by using selective hydrophilic and lipophilic ligands.
View Article and Find Full Text PDFThe development of Li/sulfurized polyacrylonitrile (SPAN) batteries requires electrolytes that can form stable electrolyte/electrode interphases simultaneously on lithium-metal anodes (LMAs) and SPAN cathodes. Herein, a low-flammability locally concentrated ionic liquid electrolyte (LCILE) employing monofluorobenzene (mFBn) as the diluent is proposed for Li/SPAN cells. Unlike non-solvating diluents in other LCILEs, mFBn partially solvates Li , decreasing the coordination between Li and bis(fluorosulfonyl)imide (FSI ).
View Article and Find Full Text PDFEnviron Sci Pollut Res Int
February 2023
The traditional use of organic solvents in various branches of industry is being rethought as these compounds very often display high volatility, toxicity and lipophilicity (related to the ability to interact with biological membranes). More recently, developments in the field of Green Chemistry are focusing on the design of more sustainable and cost-effective solvent alternatives like Ionic Liquids (ILs), bio-based solvents and natural deep eutectic solvents (NADESs). The present study aimed at performing an ecotoxicological screening of 15 NADESs using an extensive set of marine and freshwater bioassays, based on different endpoints as the following: immobilization of the crustacean Daphnia magna, growth inhibition of Raphidocelis subcapitata and of Phaeodactylum tricornutum, larval development alterations on the serpulid Ficopomatus enigmaticus and bioluminescence inhibition of Aliivibrio fischeri.
View Article and Find Full Text PDFProtic ionic liquids (PILs) are potential candidates as electrolyte components in energy storage devices. When replacing flammable and volatile organic solvents, PILs are expected to improve the safety and performance of electrochemical devices. Considering their technical application, a challenging task is the understanding of the key factors governing their intermolecular interactions and physicochemical properties.
View Article and Find Full Text PDFThe behaviour of triazolylidene ligands coordinated at a {Fe(CO)(µ-dithiolate)} core related to the active site of [FeFe]-hydrogenases have been considered to determine whether such carbenes may act as redox electron-reservoirs, with innocent or non-innocent properties. A novel complex featuring a mesoionic carbene (MIC) [Fe(CO)(Pmpt)(µ-pdt)] (; Pmpt = 1-phenyl-3-methyl-4-phenyl-1,2,3-triazol-5-ylidene; pdt = propanedithiolate) was synthesized and characterized by IR, H, C{H} NMR spectroscopies, elemental analyses, X-ray diffraction ,and cyclic voltammetry. Comparison with the spectroscopic characteristics of its analogue [Fe(CO)(Pmbt)(µ-pdt)] (; Pmbt = 1-phenyl-3-methyl-4-butyl-1,2,3-triazol-5-ylidene) showed the effect of the replacement of a n-butyl by a phenyl group in the 1,2,3-triazole heterocycle.
View Article and Find Full Text PDFIn this work, aqueous solutions of two prototypical ionic liquids (ILs), [BMIM][BF] and [BMIM][TfO], were investigated by UV Raman spectroscopy and small-angle neutron scattering (SANS) in the water-rich domain, where strong heterogeneities at mesoscopic length scales (microheterogeneity) were expected. Analyzing Raman data by a differential method, the solute-correlated (SC) spectrum was extracted from the OH stretching profiles, emphasizing specific hydration features of the anions. SC-UV Raman spectra pointed out the molecular structuring of the interfacial water in these microheterogeneous IL/water mixtures, in which IL aggregates coexist with bulk water domains.
View Article and Find Full Text PDFWithin a spent nuclear fuel recycling strategy, in the past few years, the pyridine-bis-triazole unit was found to be rather effective and selective in minor actinide (MA) separation from synthetic high active raffinate (HAR). In this research work, the main features of the recently studied ligand were investigated in order to evaluate its potentialities in SANEX-like processes. Its applicability in advanced separation processes was demonstrated, even at process temperatures.
View Article and Find Full Text PDFSignificanceDistributed training has long been known to lead to more robust memory formation as compared to massed training. Using the water maze, a well-established task for assessing memory in laboratory rodents, we found that distributed and massed training differentially engage the dorsolateral and dorsomedial striatum, and optogenetic priming of dorsolateral striatum can artificially increase the robustness of massed training to the level of distributed training. Overall, our findings demonstrate that spatial memory consolidation engages different neural substrates depending on the training regimen, identifying a therapeutic avenue for memory enhancement.
View Article and Find Full Text PDFThe nuclear Overhauser effect (NOE) is a powerful tool in molecular structure elucidation, combining the subtle chemical shift of NMR and three-dimensional information independent of chemical connectivity. Its usage for intermolecular studies, however, is fundamentally limited by an unspecific long-ranged interaction behavior. This joint experimental and computational work shows that proper selection of interacting isotopes can overcome these limitations: Isotopes with strongly differing gyromagnetic ratios give rise to short-ranged intermolecular NOEs.
View Article and Find Full Text PDFThe utility of ionic liquids (ILs) as alternative solvents for stabilizing and preserving the native structure of DNA over the long term may be envisaged for biotechnological and biomedical applications in the near future. The delicate balance between the stabilizing and destabilizing effects of IL-mediated interactions with the structure of DNA is complex and is still not well understood. This work reports a fundamental study dealing with the effect exerted by cations and anions in imidazolium-based ILs on the thermal structural stability of large nucleic acid molecules.
View Article and Find Full Text PDFThe dynamics of xenon gas, loaded in a series of 1-alkyl-3-methylimidazolium based ionic liquids, probes the formation of increasingly blurred polar/apolar nanodomains as a function of the anion type and the cation chain length. Exploiting Xe NMR spectroscopy techniques, like Pulse Gradient Spin Echo (PGSE) and inversion recovery (IR), the diffusion motion and relaxation times are determined for 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C C im][TFSI]. A correlation between the ILs nano-structure and both xenon diffusivity and relaxation times, as well as chemical shifts, is outlined.
View Article and Find Full Text PDFWe report on the thermodynamic, structural, and dynamic properties of a recently proposed deep eutectic solvent, formed by choline acetate (ChAc) and urea (U) at the stoichiometric ratio 1:2, hereinafter indicated as ChAc:U. Although the crystalline phase melts at 36-38 °C depending on the heating rate, ChAc:U can be easily supercooled at sub-ambient conditions, thus maintaining at the liquid state, with a glass-liquid transition at about -50 °C. Synchrotron high energy x-ray scattering experiments provide the experimental data for supporting a reverse Monte Carlo analysis to extract structural information at the atomistic level.
View Article and Find Full Text PDFIn this communication, we report on the use of deep eutectic solvents (DESs) for processing nuclear waste, with a view to selectively recovering minor actinides (MA) from highly active raffinate solutions. DESs are an interesting new class of green and eco-sustainable solvents. Herein, a representative family of DES was tested as a co-solvent for MA/lanthanides partitioning based on Selective ActiNide EXtraction (SANEX)-like hydrometallurgical processes.
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