A nonionic type V deep eutectic solvent (DES) combining hydrophobic (−)-menthol and hydrophilic resorcinol was prepared and investigated as a solvent for amphiphilic caffeine. Differential scanning calorimetry and thermogravimetric analysis were first used to determine the eutectic composition and characterize its thermal behavior. The menthol-to-resorcinol molar ratio of 2:1 was subsequently selected for physicochemical investigation. Clear homogeneous solutions containing up to 0.701 mol·kg−1 caffeine were prepared, corresponding to 136 g of caffeine per kilogram of DES. Density, speed of sound, and viscosity were measured over the temperature range from 293.15 to 313.15 K. These data were used to evaluate the thermal expansion, volumetric and acoustic properties, intermolecular free length, and concentration and temperature dependences of viscous flow. The viscosity results were further analyzed using the Arrhenius, Jones–Dole, and Eyring–Feakins approaches and compared with the behavior of caffeine in water, ethylene glycol, and methyl salicylate. DFT calculations and molecular electrostatic potential surfaces were used to examine the local organization of the DES and the possible incorporation of caffeine through interactions with both its polar and less-polar regions. The combined experimental and computational approach provides a molecular and thermodynamic basis for evaluating this DES as a caffeine-solubilizing and delivery medium.

Cationic surfactants are widely used in disinfectants, creating a need for rapid and reliable analytical methods for their determination in complex formulations. In this study, a new hydrophobic ion-pair, 1,3-didecyl-2-methylimidazolium tetrakis(perfluorophenyl)borate (DDMIm–TPFPhB), was developed and applied as an ionophore in a potentiometric sensor. The ion-pair was incorporated into a PVC membrane and evaluated by direct potentiometric measurements and titrations. The sensor exhibited near-Nernstian responses toward selected cationic surfactants (56.8–59.1 mV per decade), low detection limits (1.4–2.2 × 10−6 M), and stable signal behavior, along with good selectivity and stability over a pH range of 3–9. Application on commercial disinfectant samples showed good agreement with a commercial ion-selective electrode. According to the charge decomposition analysis performed using density functional theory calculations, the number of electrons donated from perfluorotetraphenyl borate to 1,3-didecyl-2-methylimidazolium is 0.25 e. In contrast, the back-donation from the cation to the anion is only 0.05 e, indicating a relatively substantial overall charge transfer of 0.20 e. This pronounced charge transfer, together with dominant dispersion interactions, contributes to enhanced ion-pair stability within the membrane phase, which is reflected in reduced signal drift and improved analytical performance. These findings establish a direct link between molecular-level interactions and sensor behavior, providing a rational basis for the design of potentiometric sensors for real-sample analysis.

Hydrophobic eutectic solvent systems (ESSs) were prepared and characterized using temperature-dependent thermophysical and transport property measurements, supported by thermal analysis. The investigated systems comprise terpene-based mixtures, menthol:octanoic acid (1:2) and menthol:decanoic acid (1:1), and thymol-based mixtures, thymol:butanol (1:1), thymol:hexanol (1:1), thymol:octanoic acid (1:1), and thymol:oleic acid (1:1), as well as salt-containing ESSs based on tetrabutylphosphonium bromide (TBPBr), TBPBr:octanoic acid (1:1), and TBPBr:lauric acid (1:1). Density, dynamic viscosity, and electrical conductivity were measured at atmospheric pressure (p = 0.1 MPa) over 293.15–313.15 K. From density data, molar volumes and isobaric thermal expansion coefficients were calculated. The temperature dependence of viscosity was correlated with both Arrhenius and Vogel–Fulcher–Tammann equations. Conductivity results were used to compute molar conductivities, and the coupled conductivity–viscosity behavior was assessed via Walden analysis to quantify deviations from ideal electrolyte behavior and estimate ionicity. Thermal behavior and stability were evaluated by differential scanning calorimetry (DSC) and simultaneous thermogravimetric analysis (TG/DSC). The resulting dataset enables a consistent comparison of volumetric, flow, and ion transport descriptors across fully molecular terpene-based mixtures and TBPBr-containing systems. Overall, the combined transport descriptors, including Walden analysis, provide a practical framework for distinguishing molecular from salt-containing hydrophobic ESS families and support formulation selection for temperature-dependent applications, particularly in biphasic extraction processes.

In this study, the use of terpene‐based hydrophobic deep eutectic solvents (HDESs) in the preparation of polymeric membrane ion‐selective electrodes is presented. HDES obtained from terpenes (menthol and thymol) and octanoic acid are used as a new component of polymeric membrane of potentiometric sensors sensitive to lead ions. Electrodes containing different amounts of HDES in the membrane (from 1 to 12 % wt./wt.) are prepared, and potentiometric measurements are carried out for these electrodes to determine the detection limit, the slope of the characteristic, and the response linear range. Based on the analysis of electrode performance, it is found that the optimum concentration of HDES in the membrane is 5 wt%. For such membranes, a more detailed study is carried out using a solid contact sensor. Selectivity toward interfering species as well as potential stability and reversibility, optimum pH range, effect of light, and presence of gases in the sample solution are investigated for such sensors. The obtained measurement results indicate that the tested sensor containing HDES in the membrane has good analytical parameters, and excellent selectivity (log K ≤ −4.4). It has been successfully used to determine lead in real environmental water samples after a brief pretreatment with XAD‐7 resin.

Solvents prepared from natural terpenes (menthol and thymol), as H-bond acceptors, and a series of organic acids (chain lengths of 8, 10, and 14 C atoms), as H-bond donors, were characterized and tested as reaction media for liquid–liquid extraction purposes. Due to their high hydrophobicity, they seem to be promising alternatives to conventional (nonpolar and toxic) solvents, since they possess relatively less toxic, less volatile, and consequently, more environmentally friendly characteristics. Assuming that the equilibrium is established between solvent and analyte during a ligandless procedure, it can be concluded that those nonpolar solvents can efficiently extract nonpolar analytes from the aqueous environment. Previous investigations showed a wide range of applications, including their use as solvents in extractions of metal cations, small molecules, and bioactive compounds for food and pharmaceutical applications. In this work, hydrophobic solvents based on natural terpenes, which showed chemical stability and desirable physicochemical and thermal properties, were chosen as potential reaction media in the liquid–liquid extraction (LLE) procedure for Pb(II) removal from aqueous solutions. Low viscosities and high hydrophobicities of prepared solvents were confirmed as desirable properties for their application. Extraction parameters were optimized, and chosen solvents were applied. The results showed satisfactory extraction efficiencies in simple and fast procedures, followed by low solvent consumption. The best results (98%) were obtained by the thymol-based solvent, thymol–decanoic acid (Thy-DecA) 1:1, followed by L-menthol-based solvents: menthol–octanoic acid (Men-OctA) 1:1 with 97% and menthol–decanoic acid (Men-DecA) 1:1 with 94.3% efficiency.

La rimozione originaria, in tedesco: Urverdrängung, è un concetto che appartiene all'ambi-to delle necessità metapsicologiche, della prima strutturazione e costruzione del sistema menta-le. Fu postulato da Freud (1911, 1915, 1926, 1937) per spiegare retrospettivamente il mecca-nismo della rimozione (rimozione vera e propria) come un movimento di attrazione da parte di qualcosa che è già presente. Contrariamente alla rimozione vera e propria/rimozione seconda-ria, in Tedesco Nachdrängen, la "pietra angolare" del pensiero psicoanalitico, il concetto di rimozione primaria rimane in parte dimenticato, in parte incomprensibile, anche se le sue con-cettualizzazioni sottostanti hanno attirato una crescente attenzione nel corso degli anni. Questo saggio si avvicina a tale ambito indagando la rappresentabilità e l'irrappresentabili-tà, la dinamica: azione – rappresentazione, e la nascita dello psichico a partire dalle esigenze del lavoro. La prima dualità interna e il primo legame sono introdotti nella vita psichica dai proces-si di rimozione originaria, tensione tra attrazione regressiva e formazione-ricostruzione dei processi psichici. Il materiale clinico viene presentato come illustrazione.

The research presented in this paper is focused on blackberry leaf extract (BLE) as a environmentally friendly corrosion inhibitor for copper in 0.5 M NaCl. The caffeic acid, quercetin-3-O-glucoside and kaempferol-3-O-glucoside were identified in BLE by using high-performance liquid chromatography (HPLC-DAD). The BLE functional groups were identified (ATR-FTIR). The electrochemical methods (potentiodynamic polarization, electrochemical frequency modulation and electrochemical impedance spectroscopy) show that BLE acts as a mixed type of inhibitor (max. IE is 97.19 %). The corrosion process is controlled by diffusion (BLE lower than 15 g/L) and charge transfer (15 g/L BLE).

Selective separation and removal of a metal species from complex matrices of other species is of critical importance in separation sciences and especially in industrial processes. The selectivity and efficiency of Pb(II) ion removal from an aqueous solution in the presence of Ni(II), Zn(II), Co(II), Cu(II), and Cd(II) ions as competing ions in a multi-component aqueous source phase through bulk liquid membrane system were investigated. The influence of the palmitic and oleic acid as supporting surfactants in the membrane phase on the removal of Pb(II) ions was also analyzed. Dicyclohexano-18-crown-6 dissolved in chloroform, proved to be a selective and efficient carrier for Pb(II) ions. In the optimized procedure, 3 hours of equilibrium time was required to achieve the maximum removal efficiency. It was found, that removal of Pb(II) ions was achieved without significant reduction in the efficiency compared to the liquid membrane transport of a single-component system. None of these cations interfered with Pb(II) removal. The presence of the oleic and palmitic acid in the membrane phase increase the content of Pb(II) removed to the receiving phase. In optimal transport conditions, more than 97% efficiencies for the removal of Pb(II) were obtained for a system supported by oleic acid. The excellent efficiency and high degree of selectivity for the Pb(II) ion removal by the proposed BLM system, reveals its potential application for the selective removal, concentration, and purification of lead ions from its different mixtures.