Search Results (14)

Dopamine (DA) is a neurotransmitter responsible for important functions in mammals’ bodies, including mood, movement and motivation. High or low dopamine levels are associated mainly with mental illnesses such as schizophrenia and depression. Therefore, contributing to the development of electrochemical devices to precisely determine the DA levels in urine samples, a simple and low-cost sensor is proposed in this work. The proposed sensor design is based on crosslinked chitosan films combining carbon black (CB) and deep eutectic solvents (DESs), incorporated onto the surface of a glassy carbon electrode (GCE). Fourier Transform Infrared Spectroscopy (FT-IR) was applied to characterize the produced DESs and their precursors, while the films were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The sensor modified with CB and DES–ethaline (DES (ETHA)-CB/GCE) showed a significantly enhanced analytical signal for DA using differential pulse voltammetry under the optimized working conditions. Moreover, a better heterogeneous electron transfer rate constant (k⁰) was obtained, about 45 times higher than that of the bare GCE. The proposed sensor achieved a linear response range of 0.498 to 26.8 µmol L⁻¹ and limits of detection and quantification of 80.7 and 269 nmol L⁻¹, respectively. Moreover, the sensor was successfully applied in the quantification of DA in the synthetic urine samples, with recovery results close to 100%. Furthermore, the sensor presented good precision, as shown from the repeatability tests. The presented method to electrochemically detect DA has proven to be efficient and simple compared to the conventional methods commonly reported. Full article

The development of metallic coatings as Ni-Co alloys, with particular emphasis on their homogeneity, processability, and sustainability, is of the utmost significance. To address these challenges, the utilization of phenylsalicylimines (PSIs) as additives within deep eutectic solvents (DES) was investigated, assessing their influence on the electrodeposition process of these metals at an intermediate temperature of 60 °C, while circumventing aqueous reaction conditions. The findings demonstrated that the incorporation of PSIs markedly enhances coating uniformity, resulting in an optimal cobalt content of 37% and an average thickness of 24 µm. Electrochemical evaluations revealed improvements in charge and mass transfer, thereby optimizing process efficiency. Moreover, computational studies confirmed that PSIs form stable complexes with Co (II), modulating the electrochemical characteristics of the system through the introduction of the diethylamino electron-donating group, which significantly stabilizes the coordinated forms with both components of the DES. Additionally, the coatings displayed exceptional corrosion resistance, with a rate of 0.781 µm per year, and achieved an optimal hardness of 38 N HRC, conforming to ASTM B994 standards. This research contributes to the development of electroplating bath designs for metallic coating deposition and lays the groundwork for the advancement of sophisticated technologies in functional coatings that augment corrosion resistance and mechanical properties. Full article

Deep eutectic solvents (DESs) are environmentally friendly solvents formed by combining hydrogen bond donors and acceptors, resulting in a eutectic mixture with a lower melting point than the individual components. While there is extensive research on the electrochemical synthesis of platinum nanoparticles in DESs, to the best of our knowledge, there are no studies on the chemical reactivity of platinum(II) complexes in these systems. This study investigates the simple model reaction between K₂PtCl₄ and ethylenediamine (en), exploring the behaviour in DES environment, to optimize the synthesis of simple cisplatin-like platinum compounds with the potential objective of improving the traditional methods, decreasing the number of steps required for obtaining target compounds and reducing chemical waste. The reactions were performed in two hydrophilic DESs: choline chloride:glycerol 1:2 (glyceline, GL) and choline chloride:ethylene glycol 1:2 (ethaline, EG). The experiments, conducted in a 70% (v/v) DES and 30% 1:1 H₂O/D₂O mixture to allow for direct NMR analysis, revealed that en quickly formed [PtCl₂(en)], which further reacted to produce [Pt(en)₂]Cl₂. Reaction products were characterised by 1D (¹H and ¹⁹⁵Pt{¹H}) and 2D ([¹H,¹³C]-HSQC and [¹H,¹⁵N]-HSQC) NMR experiments. The discolouration of solutions, due to the consumption of K₂PtCl₄, and the precipitation of the purple Magnus salt [Pt(en)₂][PtCl₄] occurred over time. The main observed difference between the two solvent mixtures was the slower reactivity in glyceline, due to the much higher viscosity of the solution. Diffusion-ordered spectroscopy (DOSY) indicated lower water mobility in DES mixtures than pure water, with the reaction products closely associated with DES molecules. Full article

This study investigates the structural and transport properties of SDS, CTAB, and SB3-12 micelles in three deep eutectic solvents (DESs), Ethaline, Glyceline, and Reline, using molecular dynamics (MD) simulations. The influence of solvent composition on micelle morphology, interactions, and dynamics was explored, revealing key differences driven by the DES environment. Structural analyses, including eccentricity and radius of gyration, demonstrated that micelle shape and compactness vary significantly depending on the solvent. In Ethaline and Reline, larger micelles showed significant deviations from spherical shapes, while micelles in Glyceline became more spherical and compact, particularly those formed by SB3-12. Radial distribution functions highlighted different levels of micelle–solvent interactions, with SDS showing strong interactions with HBD components and SB3-12 exhibiting prominent self-interaction. According to hydrogen bonding analysis, micelles slightly disrupt the DES hydrogen bond network, with SB3-12 establishing the most significant hydrogen bond connections. The transport property analysis revealed that larger micelles have lower diffusion coefficients, whereas smaller micelles enhance DESs’ component mobility. These findings advance the understanding of micelle behavior in DESs and also help in the optimization of DES–surfactant systems for applications such as electrodeposition, nanomaterial templating, and drug delivery. Future research will focus on surfactant interactions with surfaces to further improve these applications. Full article

For over a century, cyanidation has been a highly effective method for extracting gold from gold-bearing sources. However, due to environmental, health, and safety concerns associated with this process, considerable efforts have been devoted to exploring the use of alternative, less toxic, and environmentally friendly reagents. In this study, a comparative cyanide and ethaline deep eutectic solvent (DES) leaching study of gold from the Witwatersrand gold tailings was undertaken. A Statistical Design of Experiments (DOE) was used for the screening and optimization of significant process factors to achieve optimal gold extraction. The factors investigated include the reagent concentration, leaching time, pulp density, and solution temperature. The subsequent gold recovery from leach solutions was undertaken using activated carbon (AC). Mineralogical analysis by X–ray diffraction (XRD) showed that the tailings consisted of quartz (72.13%), muscovite (7.49%), chlorite (2.65%), pyrophyllite (1.50%), clinochlore (1.30%), and other trace minerals. Mineral liberation analysis (MLA) employing the Sparse Liberation–Dual Zoom (SPL-DZ) method showed that gold was associated with iron oxides (Fe₂O₃, Fe₃O₄). Fire assay analysis (FAA) showed that the bulk tailings had a grade of 0.32 g/t Au. Ethaline was found to be the most efficient reagent, achieving up to 71.9% gold extraction, thereby exceeding the 46.9% gold extraction obtained via the cyanidation process. Moreover, gold recovery using AC from ethaline leach solution was 75%. The high gold extraction from tailings using ethaline suggests a potentially feasible alternative to the traditional cyanidation process, particularly for the processing of gold locked in iron oxide phases, offering the advantages of low toxicity, cost-effectiveness, and ease of preparation. Full article

Nowadays, deep eutectic solvents (DESs) are seen as environmentally friendly alternatives with the potential to replace traditional solvents used in hydrometallurgical processes. Although DESs have been successfully applied in the recovery of metals from secondary sources, there is still innovative potential regarding DESs as green leaching agents applied in the recovery of metals from primary sources like polysulfide ores. This study aimed to evaluate the characteristics of DESs as solvents for some of the main metals present in typical polymetallic concentrates, like Cu, Fe, Pb, and Zn. Thus, three DESs based on choline chloride (ChCl) were prepared: 1:2 ChCl-urea (also known as reline), 1:2 ChCl-ethylene glycol (also known as ethaline), and 1:2 ChCl-glycerol (also known as glyceline). Then, dissolution tests at 30 °C were carried out with these DESs and different metal- (Cu, Fe, Pb, and Zn) bearing compounds (sulfates, oxides, and sulfides). According to the dissolution tests, it was found that the solubility of the studied metals (expressed as g of metal per Kg of DES) was dictated by the bearing species, reaching the dissolution of the metals from sulfates with values as high as two orders of magnitude higher than the metal solubility values for metal oxides and sulfides. Full article

Carbon materials derived from marine waste have been drawing attention for supercapacitor applications. In this work, chitins from squid and prawn marine wastes were used as carbon precursors for further application as electrodes for energy storage devices. Chitins were obtained through a deproteinization method based on enzymatic hydrolysis as an alternative to chemical hydrolysis as commonly presented in the literature. The obtained porous carbons were characterized using a BET surface area analyzer to determine the specific surface area and pore size, as well as scanning electron microscopy (SEM) with energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), Raman spectroscopy, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), to characterize their morphology, composition, and structure. The electrochemical characterization was performed using a glassy carbon (GC) electrode modified with marine waste-based porous carbons as the working electrode through cyclic voltammetry and galvanostatic charge/discharge using ethaline, a choline chloride-based deep eutectic solvent (DES), as an eco-friendly and sustainable electrolyte. Squid and prawn chitin-based carbons presented a surface area of 149.3 m² g⁻¹ and 85.0 m² g⁻¹, pore volume of 0.053 cm³ g⁻¹ and 0.029 cm³ g⁻¹, and an associated specific capacitance of 20 and 15 F g⁻¹ at 1 A g⁻¹, respectively. Preliminary studies were performed to understand the effect of -OH groups on the chitin-based carbon surface with DES as an electrolyte, as well as the effect of aqueous electrolytes (1 mol L⁻¹ sulphuric acid (H₂SO₄) and 1 mol L⁻¹ potassium hydroxide (KOH)) on the capacitance and retention of the half-cell set up. It is provided, for the first time, the use of chitin-based carbon materials obtained through a one-step carbonization process combined with an eco-friendly DES electrolyte for potential application in energy storage devices. Full article

Traditional coupling of ligands for gold wet etching makes large-scale applications problematic. Deep eutectic solvents (DESs) are a new class of environment-friendly solvents, which could possibly overcome the shortcomings. In this work, the effect of water content on the Au anodic process in DES ethaline was investigated by combining linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Meanwhile, we employed atomic force microscopy (AFM) to image the evolution of the surface morphology of the Au electrode during its dissolution and passivation process. The obtained AFM data help to explain the observations about the effect of water content on the Au anodic process from the microscopic perspective. High water contents make the occurrence of anodic dissolution of gold at higher potential, but enhances the rate of the electron transfer and gold dissolution. AFM results reveal the occurrence of massive exfoliation, which confirms that the gold dissolution reaction is more violent in ethaline with higher water contents. In addition, AFM results illustrate that the passive film and its average roughness could be tailored by changing the water content of ethaline. Full article

Edaravone, acting as a cerebral protective agent, is administered to treat acute brain infarction. Its poor solubility is addressed here by means of optimizing the composition of the aqueous choline chloride (ChCl)-based eutectic solvents prepared with ethylene glycol (EG) or glycerol (GL) in the three different designed solvents compositions. The slurry method was used for spectroscopic solubility determination in temperatures between 298.15 K and 313.15 K. Measurements confirmed that ethaline (ETA = ChCl:EG = 1:2) and glyceline (GLE = ChCl:GL = 1:2) are very effective solvents for edaravone. The solubility at 298.15 K in the optimal compositions was found to be equal x_E = 0.158 (c_E = 302.96 mg/mL) and x_E = 0.105 (c_E = 191.06 mg/mL) for glyceline and ethaline, respectively. In addition, it was documented that wetting of neat eutectic mixtures increases edaravone solubility which is a fortunate circumstance not only from the perspective of a solubility advantage but also addresses high hygroscopicity of eutectic mixtures. The aqueous mixture with 0.6 mole fraction of the optimal composition yielded solubility values at 298.15 K equal to x_E = 0.193 (c_E = 459.69 mg/mL) and x_E = 0.145 (c_E = 344.22 mg/mL) for glyceline and ethaline, respectively. Since GLE is a pharmaceutically acceptable solvent, it is possible to consider this as a potential new liquid form of this drug with a tunable dosage. In fact, the recommended amount of edaravone administered to patients can be easily achieved using the studied systems. The observed high solubility is interpreted in terms of intermolecular interactions computed using the Conductor-like Screening Model for Real Solvents (COSMO-RS) approach and corrected for accounting of electron correlation, zero-point vibrational energy and basis set superposition errors. Extensive conformational search allowed for identifying the most probable contacts, the thermodynamic and geometric features of which were collected and discussed. It was documented that edaravone can form stable dimers stabilized via stacking interactions between five-membered heterocyclic rings. In addition, edaravone can act as a hydrogen bond acceptor with all components of the studied systems with the highest affinities to ion pairs of ETA and GLE. Finally, the linear regression model was formulated, which can accurately estimate edaravone solubility utilizing molecular descriptors obtained from COSMO-RS computations. This enables the screening of new eutectic solvents for finding greener replacers of designed solvents. The theoretical analysis of tautomeric equilibria confirmed that keto-isomer edaravone is predominant in the bulk liquid phase of all considered deep eutectic solvents (DES). Full article

The common Deep Eutectic Solvent (DES) ‘ethaline’ (1:2 choline chloride:ethylene glycol) was examined here as a basis for the self-assembly of the surfactant dodecyltrimethylammonium bromide (C₁₂TAB). A phase diagram was constructed, showing evidence for a L₁ (micellar) phase, confirmed by tensiometry to have a room temperature critical micelle concentration (CMC) of 1.2 wt.%. Small angle neutron scattering (SANS) measurements indicate formation of interacting globular micelles with slightly smaller apparent radii than in water. The apparent mesophase/multiphase region was studied using SWAXS, demonstrating rich mesoscopic lyotropic liquid crystalline phase behaviour, with evidence for lamellar L_α peaks, alongside potential co-crystalline phases. We attempted to tailor the self-assembly by studying binary DES containing longer diols including 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol, and ternary DES where the HBD component was a 1:1 ethylene glycol:diol mixture. However, synchrotron SAXS showed that only ternary ‘propethaline’ mixtures displayed signs of self-assembly and micellization, perhaps due to the reduction in calculated Gordon parameter, which decreases linearly with increasing alkyl chain length. Systematic differences were thus observed in the ability of the solvents to modulate assembly, from globular micelles in ChCl:EG, to weaker assembly in long-tail DES, and complete solubilisation in butaline and pentaline. Full article

A new class of solid-state miniaturised reference electrodes with a deep eutectic solvent as an alternate enhancement electrode system is described. A simple and accurate stable electrochemical sensor was prepared by developing a conventional reference electrode using an Ag/AgCl planar micro-reference electrode covered with a PVC polymer. A conductive deep eutectic solvent (DES), ethaline, was added in small quantities and mixed with an internal electrolyte to maintain the Cl⁻ ion concentration in the constructed electrode. The fabricated microelectrode showed good stability, reproducibility, and long-term stability against varying concentrations of different ions. The potential response of the fabricated microelectrode was studied under varying concentrations of Cl⁻ ions in the presence of 0.1 to 1.0% DES in a concentrated electrolyte system (20 mM Na₂SO₄). The stability of the fabricated microelectrode was addressed against Br⁻ and Cl⁻ ions using different inorganic salts, and the potential measurements were found to be insensitive toward all responsive ions. The stability response of the fabricated microelectrode against Cl⁻ ions was optimised in the presence of 1.0% DES. The experimental data showed good agreement with the potential change of the fabricated electrode in the presence of the supporting DES electrolyte. The liquid junction-free PVC solid-state miniaturised reference electrode demonstrated a constant potentiometric measurement over a long period of time. The concentrated supporting DES electrolyte solution (20 mM) exhibited better stability values and was a more suitable fabricated microelectrode than other additive concentrations. The long-term stability of the developed microelectrode displayed a good lifetime and high stability of around 60 days. Full article

Redox flow batteries hold promise as large-scale energy storage systems for off-grid electrification. The electrolyte is one of the key components of redox batteries. Inspired by the mechanism involved in solvents for extraction, a ternary deep eutectic solvent (DES) is demonstrated, in which glycerol is introduced into the original binary ethaline DES. Redox pairs (active substance) dissolved in the solvent have low charge transfer resistance. The results show that the viscosity of the solvent with the ratio of choline chloride to ethylene glycol to glycerol of 1:2:0.5 decreases from 51.2 mPa·s to 40.3 mPa·s after adding the redox pair, implying that the mass transfer resistance of redox pairs in this solvent is reduced. Subsequent cyclic voltammetry and impedance tests show that the electrochemical performance with the ternary DES as the electrolyte in redox flow batteries is improved. When the ratio of 1:2:0.5 ternary DES is used as the electrolyte, the power density of the battery (9.01 mW·cm⁻²) is 38.2% higher than that of the binary one (6.52 mW·cm⁻²). Fourier transform infrared spectroscopy further indicates that the introduction of glycerol breaks the hydrogen bond network of the solvent environment where the redox pair is located, unraveling the hydrogen bond supramolecular complex. Rational solvent design is an effective strategy to enhance the electrochemical performance of redox batteries. Full article

A novel hybrid composite of conductive poly(methylene blue) (PMB) and carbon nanotubes (CNT) was prepared for the detection of 5-aminosalicylic acid (5-ASA). Electrosynthesis of PMB with glassy carbon electrode (GCE) or with carbon nanotube modified GCE was done in ethaline deep eutectic solvent of choline chloride mixed with ethylene glycol and a 10% v/v aqueous solution. Different sensor architectures were evaluated in a broad range of pH values in a Britton-Robinson (BR) buffer using electrochemical techniques, chronoamperometry (CA), and differential pulse voltammetry (DPV), to determine the optimum sensor configuration for 5-ASA sensing. Under optimal conditions, the best analytical performance was obtained with CNT/PMB_DES/GCE in 0.04 M BR buffer pH 7.0 in the range 5–100 µM 5-ASA using the DPV method, with an excellent sensitivity of 9.84 μA cm⁻² μM⁻¹ (4.9 % RSD, n = 5) and a detection limit (LOD) (3σ/slope) of 7.7 nM, outclassing most similar sensors found in the literature. The sensitivity of the same sensor obtained in CA (1.33 μA cm⁻² μM⁻¹) under optimal conditions (pH 7.0, E_app = +0.40 V) was lower than that obtained by DPV. Simultaneous detection of 5-ASA and its analogue, acetaminophen (APAP), was successfully realized, showing a catalytic effect towards the electro-oxidation of both analytes, lowering their oxidation overpotential, and enhancing the oxidation peak currents and peak-to-peak separation as compared with the unmodified electrode. The proposed method is simple, sensitive, easy to apply, and economical for routine analysis. Full article

Deep eutectic solvents (DESs) are emerging green solvents with very unique characteristics. Their contribution to atmospheric pollution is negligible, and they can be “designed” for desired properties. In this study, the feasibility of applying DESs (Reline, Ethaline, or Glyceline) as absorbents in absorption refrigeration cycles was investigated. The sophisticated cubic-plus-association (CPA) equation of state, considering the strong intermolecular interactions of such complex systems, was used to estimate the thermodynamic properties. At a fixed set of base case operating conditions, the coefficients of performance were calculated to be 0.705, 0.713, and 0.716 for Reline/water, Ethaline/water, and Glyceline/water systems, respectively, while the corresponding mass flow rate ratios were 33.73, 11.53, and 16.06, respectively. Furthermore, the optimum operating conditions of each system were estimated. To verify the feasibility, results were compared to literature systems, including LiBr/water and various ionic liquid/water systems. The results indicate that DES/water working fluids have the potential to be used in such cycles. Since DESs have the characteristic to be tuned (designed) to desired properties, including their solvent power and their enthalpies of absorption, much further research needs to be done to propose new DESs with higher energy efficiencies. Full article