Liquid Aqueous Solutions Research Articles

Strengthened Effect of Surface-Active Ionic Liquids on Curcumin Solubility and Extraction Performance of Curcuminoids

As a kind of bioactive component in the rhizome of natural plant Curcuma longa L. (turmeric), curcumin is almost insoluble in water at neutral and acidic pH, which limits its further utilization and development. At the same time, traditional extraction and separation processes typically require the use of a large number of organic solvents. Ionic liquids (ILs) are organic molten salts with melting points below 100 °C. When an ionic liquid exists in a liquid state at or near room temperature, it is referred to as a room-temperature ionic liquid (RTIL). They have a temperature range, good physical and chemical stability, and good structural designability. They have a strong solubilization enhancement effect for many organic compounds. This study first explored the molecular forms of curcumin in ionic liquid aqueous solutions and the intermolecular interactions between curcumin and ionic liquids using spectral analysis and computational chemistry methods; furthermore, using an ionic liquid aqueous solution as an extraction agent, curcumin-like substances (curcuminoids) were extracted from turmeric powders under ultrasound assisted conditions, revealing the relationship between the structure of the ionic liquid and the extraction efficiency. After that, a kinetic study was conducted for the extraction of curcuminoids from turmeric powders, using second-order kinetics fitting to obtain the rate constant and initial extraction rate during the extraction process. Finally, the comparison with a ComplexGAPI tool and antioxidant experiment was performed on the extraction by using ionic liquids and traditional solvent. The full results can provide reference for the design of IL extractants and their application for natural products.

Surface-induced nano-generator utilizing a thermo-responsive smart window based on ionic liquid aqueous solution that exhibits lower critical solution temperature type phase separation

We demonstrate a surface-induced nano-generator utilizing a thermo-responsive smart window based on ionic liquid aqueous solution that exhibits lower critical solution temperature (LCST) type phase separation. This smart window was fabricated by filling an aqueous solution of [nBu4P][CF3COO] between the glass substrates coated with two different polymers: a polyimide with an alkyl side chain and an amorphous fluoropolymer. Below the LCST, the transmittance of the smart window was 87 %, nearly identical to that of a glass substrate. In contrast, when heated above the LCST, the [nBu4P][CF3COO] aqueous solution undergoes phase separation, causing the [nBu4P] cations and [CF3COO] anions to adsorb onto the polyimide with the alkyl side chain and the amorphous fluoropolymer facilitated by the surface pinning effect. This adsorption process results in the smart window generating electricity while transitioning to an opaque state. Therefore, the proposed smart window functions as an electricity-generating thermo-responsive device that can switch between transparent and opaque states in response to temperature changes.

Investigation of the double layer structure of 1-butyl-3-methylimidazolium thiocyanate at the air-water interface using sum-frequency generation vibrational spectroscopy.

The interfacial structure and adsorption behavior of 1-butyl-3-methylimidazolium thiocyanate ionic liquids (ILs) aqueous solutions were investigated using sum-frequency generation vibrational spectroscopy (SFG-VS) and surface tension measurements. Polarization-dependent measurements revealed a dramatic increase in the SFG signal for both CH and CN stretching modes with increasing ILs concentration, reaching a maximum at a mole fraction of 0.01. This concentration dependence was accompanied by a dramatic drop in surface tension. Upon further increasing the concentration, surface tension varied slightly and reached a constant value, while the SFG signal decreased significantly. Quantitative polarization analysis showed that as the bulk concentration increased, the apparent molecular orientation of the SCN- transition dipole at the interface changed from 51° to 46°, and the tilt angle of CH3 group of the butyl chain attached to the imidazole cationic ring changed from 18° to 32°. The decrease in the SFG signal can be explained by the formation of a double layer adsorption structure at the air/water interface. It was also demonstrated that the anions were adsorbed at the interface simultaneously with the cationic group, rather than by successive adsorption as proposed in a previous study. Using the Shereshefsky model, the thermodynamic Gibbs free energy of adsorption deduced from surface tension data was compared with SFG results.

Dissolution and regeneration of starch in hydroxyl-functionalized ionic liquid aqueous solution

There have been continuous quests for suitable solvents for starch, given the importance of effective starch dissolution in its modification and subsequent materials production. In light of this, the potential of hydroxyl-functionalized ionic liquid (IL) as a promising solvent for starch was investigated. Within this study, a hydroxyl-functionalized IL 1-(2,3-dihydroxypropyl)-3-methylimidazole chloride ([Dhpmim][Cl]) was synthesized, and the dissolution of starch in this IL and its aqueous solutions was examined. Starch (5.35 wt%) was completely dissolved in [Dhpmim][Cl] within 2 h at 100 °C. The solubility of starch in [Dhpmim][Cl]-water mixtures initially increased and then decreased with rising water content. The optimal ratio was found to be 1:9 (wt/wt) water:[Dhpmim][Cl], achieving the highest solubility at 9.28 wt%. Density functional theory (DFT) simulations elucidated the possible interactions between starch and solvents. After dissolution and regeneration in the 1:9 water:[Dhpmim][Cl] mixture, starch showed no discernible change in the molecular structure, with no derivatization reaction observed. Regenerated starch exhibited a transformation in crystalline structure from A-type to V-type, and its relative crystallinity (12.4 %) was lower than that of native starch (25.2 %), resulting in decreased thermal stability. This study suggests that the hydroxyl-functionalized IL, [Dhpmim][Cl], and its aqueous solutions serve as effective solvents for starch dissolution.

Interior and Exterior Surface Modification of Zr-Based Metal-Organic Frameworks for Trace Benzene Removal.

The emission of volatile organic compounds (VOCs) significantly contributes to air pollution and poses a serious threat to human health. Benzene, one of the most toxic VOCs, is difficult for the human body to metabolize and is classified as a Group 1 carcinogen. The development of efficient adsorbents for removing trace amounts of benzene from ambient air is thus of great importance. In this work, we studied the benzene adsorption properties of four Zr-based metal-organic frameworks (Zr-MOFs) through static volumetric and dynamic breakthrough experiments. Two previously reported Zr-MOFs, BUT-12 and STA-26, were prepared with a tritopic carboxylic acid ligand (H3L1) functionalized with three methyl groups, and STA-26 is a 2-fold interpenetrated network of BUT-12. Two new isoreticular Zr-MOFs, BUT-12-Et and STA-26-Et, were synthesized using a similar ligand, H3L2, where the methyl groups are replaced with ethyl groups. There are mesopores in BUT-12 and BUT-12-Et and micropores in STA-26 and STA-26-Et. The four Zr-MOFs all showed high stability in liquid water and acidic aqueous solutions. The microporous STA-26 and STA-26-Et showed much higher benzene uptakes than mesoporous BUT-12 and BUT-12-Et at room temperature under low pressures. Particularly, the benzene adsorption capacity of STA-26-Et was high up to 2.21 mmol/g at P/P0 = 0.001 (P0 = 12.78 kPa), higher than those of the other three Zr-MOFs and most reported solid adsorbents. Breakthrough experiments confirmed that STA-26-Et could effectively capture trace benzene (10 ppm) from dry air; however, its benzene capture capacity was reduced by 90% under humid conditions (RH = 50%). Coating of the crystals of STA-26-Et with polydimethylsiloxane (PDMS) increased the hydrophobicity of the exterior MOF surfaces, leading to a more than 2-fold improvement in its benzene capture capacity in the breakthrough experiment under humid condition. PDMS coating of STA-26-Et likely slowed down the water adsorption process, and thus, the adsorbent afforded more efficient capture of benzene. This work demonstrates that modifying both the interior and exterior surfaces of MOFs can effectively enhance their performance in capturing trace benzene from ambient air, even under humid conditions. This finding is meaningful for the development of new adsorbents for effective air purification applications.

Experimental study on mass transfer comparison of two liquid desiccants aqueous solutions

This paper experimentally studies the mass transfer during the dehumidification/regeneration operation using the hygroscopic material calcium chloride and calcium chloride dehydrate as desiccant. These desiccants are compared on the basis of the same operation conditions. According to the analysis of heat and mass transfer processes, the key influencing factors are relative humidity and regeneration temperature. It can be observed that the CaCl2.2H2O is more rapidly diluted than the CaCl2 at the same time during dehumidification, while the CaCl2 solution can be more dried than CaCl2.2H2O solution during regeneration. Then the CaCl2 is able to absorb more moisture in the cycle of LDCS system. Also, the obtained experimental results can help to select liquid desiccant.

A novel synergistic intensification method for CO2 absorption by metal salt and task-specific ionic liquids hybrid solvent in microchannel reactor

A novel metal salt-promoting mass transfer intensification method for CO2 absorption into task-specific ionic liquids aqueous solution was proposed. The mass transfer intensification and intrinsic mechanisms of different concentrations of metal salts (NaBF4, KBF4, KCl, and CuCl2) with task-specific ionic liquids (1-aminopropyl-3-methylimidazolium tetrafluoroborate [Apmim] [BF4]) aqueous solutions for CO2 capture process were visually investigated using a microchannel reactor. The results showed that adding metal salts could remarkably enhance the interaction between metal cations and ionic liquid anions, thereby decreasing the interaction between anions and cations within the ionic liquid molecules and promoting the chemical reaction between ionic liquid cations and CO2. Under the condition of the same salt concentration, the addition of KBF4 has more obvious enhancement for mass transfer in CO2 absorption process. The mass transfer coefficient increases as the gas-liquid phase flow rate rise under slug flow condition. In addition, based on the effects of metal salt concentration, absorbent density, and gas-liquid phase flow rate on the CO2 volumetric mass transfer coefficient kLa, a new correlation for predicting the volumetric mass transfer coefficient of CO2 absorption into the hybrid solvent in microchannel reactor was proposed and validated.

Experimental Study of Lithium Extraction in the Solid-Liquid Conversion of Low-Grade Solid Potash Ore

There are considerable reserves of low-grade solid potash resources in the shallow part of Mahai Salt Lake in the Qaidam Basin, and the lithium brine resources resulting from solid–liquid conversion and mining are quite abundant. The comprehensive utilization of these resources is an important and urgent problem. In this study, to fully utilize these resources, the shallow low-grade solid potash ore in Mahai Salt Lake was used for systematic simulated ore dissolution experiments, combined with geochemical and X-ray diffraction analyses. The following key results were obtained: (1) Most Li+ in the Mahai mining area was deposited on the soluble salt minerals in silt or clay, and the appropriate concentration of solvent can help to dissolve more Li+ and K+; (2) the saturation time of Li+ was longer than that of K+. Therefore, the dissolution time for the mine can be appropriately extended during the production process to dissolve more Li+; (3) the solid–liquid conversion aqueous solution mining method can separate the lithium part of clay deposits and is associated with salt rock in the brine, which is a potential lithium resource. These experimental results provide a theoretical basis for salt pan production.

Design and simulation of a liquid-microjet time-of-flight mass spectrometer with a femtosecond laser ionization source

A liquid-microjet (LJ) linear time-of-flight (TOF) mass spectrometer, coupled with a femtosecond laser ionization source, has been designed for direct measurements of mass spectra of liquid aqueous solutions. Two main features of our designed spectrometer involve the coupling of a liquid microjet nozzle to a conventional ion optics and the application of femtosecond pulses for mass spectral ionization. The detailed design, construction, and simulation of this new spectrometer are presented. More importantly, we combined the experimental tests with the simulated electric fields and ion trajectories to investigate the performance of the designed spectrometer, especially the kind of disturbances of the nozzle electric field on the conventional ion optics. In our current design, the optimal E/R (E: extractor, R: repeller) electrode voltage ratio was found to be ∼0.71 when the voltages on the R, E and G (ground) electrodes were set to be 1500, 1060 and 0 V, respectively, whilst the voltage on the N nozzle electrode was required to be around 1250 V. The capability of the designed spectrometer has been demonstrated by recording the simulated mass spectra of the water, benzene and cytidine with their mass/charge ratios of 18, 76 and 243, respectively. This work shall be helpful for the development of new all-liquid-phase mass spectral technology to be employed in the diagnosis of diseases by the mass analysis of human body fluids.

Optical trapping of nanoclusters formed in a temperature-responsive ionic liquid aqueous solution under focused near-infrared laser irradiation.

Confining molecules and ions at a specific position in a solution enables the control of chemical reactions and analysis of tiny amounts of substances. Here, we demonstrate local condensation of a temperature responsive ionic liquid using optical tweezers. Two kinds of microdroplets are prepared through phase separation or nanocluster formation under irradiation of a near-infrared laser beam. The droplet formation mechanism is discussed in view of the evolution of an optical potential well and the local temperature distribution.

Methane hydrate phase equilibrium considering dissolved methane concentrations and interfacial geometries from molecular simulations.

Natural gas hydrates, mainly existing in permafrost and on the seabed, are expected to be a new energy source with great potential. The exploitation technology of natural gas hydrates is one of the main focuses of hydrate-related studies. In this study, a large-size liquid aqueous solution wrapping a methane hydrate system was established and molecular dynamics simulations were used to investigate the phase equilibrium conditions of methane hydrate at different methane concentrations and interfacial geometries. It is found that the methane concentration of a solution significantly affects the phase equilibrium of methane hydrates. Different methane concentrations at the same temperature and pressure can lead to hydrate formation or decomposition. At the same temperature and pressure, in a system reaching equilibrium, the size of spherical hydrate clusters is coupled to the solution concentration, which is proportional to the Laplace pressure at the solid-liquid interface. Lower solution concentrations reduce the phase equilibrium temperature of methane hydrates at the same pressure; as the concentration increases, the phase equilibrium temperature gradually approaches the actual phase equilibrium temperature. In addition, the interfacial geometry of hydrates affects the thermodynamic stability of hydrates. The spherical hydrate particles have the highest stability for the same volume. Through this study, we provide a stronger foundation to understand the principles driving hydrate formation/dissociation relevant to the exploitation of methane hydrates.

Role of Chemisorbing Species in Growth at Liquid Metal-Electrolyte Interfaces Revealed by in Situ X-Ray Scattering

Liquid-liquid interfaces offer intriguing possibilities for nanomaterials growth. Especially, growth at liquid metal surfaces has recently received renewed interest. Here, fundamental interface-related mechanisms that control the growth behavior in these systems are studied for the case of Pb halide compound formation at the interface between liquid mercury electrode and aqueous salt solutions, using in situ X-ray reflectivity and grazing incidence X-ray diffraction, supplemented by electrochemical measurements and optical microscopy. The nucleation and growth of these compounds at potentials in the regime of Pb de-amalgamation was investigated in NaX + PbX2 (X = F, Cl, Br) to systematically explore the role of the halide species. X-ray reflectivity studies reveal the rapid formation of well-defined ultrathin precursor adlayers in Cl- and Br-containing solution. This adlayer formation is followed by subsequent quasi-epitaxial growth of Pb(OH)X bulk crystals, that are oriented with the c-axis along the surface normal. In contrast, growth in F-containing solution proceeds by slow formation of a more disordered deposit, resulting in random bulk crystal orientations on the Hg surface. A detailed structural analysis of the Pb(OH)Br and Pb(OH)Cl precursor adlayers reveals that they determine the orientation of the subsequently formed bulk crystals, with the arrangement in the adlayer providing a template. Together with our previous results on the pseudo-epitaxial growth of PbFBr on Hg (A. Elsen, et al., Proc.Nat.Acad.Sci., 2013, 110, 6663), these data reveal the decisive role of the interface chemistry, especially the strong chemisorption of the anions bromide and chloride, in steering the formation of these textured deposits at the liquid metal surface.

Study on the heat transfer characteristics of CO2 and liquid desiccant CaCl2 aqueous solution in the gas cooler and evaporator

The heat exchangers are essential components in the CO2 heat pump-driven liquid desiccant dehumidification system since the heat transfer performance of heat exchangers directly affects the energy efficiency of the system. However, the heat transfer characteristics of CO2 and liquid desiccant in the heat exchanger have yet to be fully revealed, resulting in a lack of appropriate strategies to improve the heat transfer performance. To address this issue, numerical gas cooler and evaporator models are developed and verified. The effects of parameters such as the weight concentration of the CaCl2 aqueous solution, the CO2 inlet pressure, mass flow rates, and the length of the heat exchanger on the heat transfer performance are investigated respectively under various operating conditions. Results show that the heat exchange load of the gas cooler can be significantly impacted by various inlet parameters of both fluids. In particular, the increase in the weight concentration from 36 to 54 wt.% deteriorates the heat exchange load by over 15 %. Nevertheless, the heat exchange load of the evaporator is hardly influenced by the weight concentration. This is attributed to a great gap in the two fluids’ heat capacity rates, causing the evaporator to be in the maximum heat transfer state. The sign of the maximum heat transfer state of the heat exchanger is whether the thermal effectiveness is close to 1, which is related to the heat transfer area. Therefore, modifying the heat exchanger length could avoid the thermal effectiveness approaching 1. Results indicate that the appropriate length of the evaporator is 3–4 m under the designed operating conditions.

Volumetric and UV–Visible Spectroscopic Evaluation of Interactions between Thiamine Hydrochloride and Protic Ionic Liquids in Aqueous Solutions

Volumetric and UV–Visible Spectroscopic Evaluation of Interactions between Thiamine Hydrochloride and Protic Ionic Liquids in Aqueous Solutions

Solvation behavior of phenolic pollutants in aqueous solutions of imidazolium-based ionic liquids: A molecular dynamics simulations study

In this study, the solvation behavior of phenolic pollutants (PPs) in 1-octyl-3-methylimidazolium tetrafluoroborate ([C8MIM][BF4]) ionic liquid (IL) aqueous solutions was simulated using molecular dynamics (MD) simulations. The study found that the cationic part of IL was the most interactive and played the most important role in the extraction of PPs. It also demonstrated that stronger hydrophobic interactions between PPs and the cationic portion resulted in higher extraction efficiency, with the exception of resorcinol, whose stronger hydrogen bonds (HBs) with water molecules reduced extraction efficiency. The study discovered that van der Waals forces governed interaction energies (IEs) between PPs and ILs, while HBs played a minor role. Since the cationic part plays a major role in the extraction process of PPs, the efficiency of the extraction process can be improved by making structural changes to this part.

Ionic liquids with reversible photo-induced conductivity regulation in aqueous solution

Stimulus-responsive ionic liquids have gained significant attention for their applications in various areas. Herein, three kinds of azobenzimidazole ionic liquids with reversible photo-induced conductivity regulation were designed and synthesized. The change of electrical conductivity under UV/visible light irradiation in aqueous solution was studied, and the effect of chemical structure and concentration of ionic liquids containing azobenzene to the regulation of photoresponse conductivity were discussed. The results showed that exposing the ionic liquid aqueous solution to ultraviolet light significantly increased its conductivity. Ionic liquids with longer alkyl chains exhibited an even greater increase in conductivity, up to 75.5%. Then under the irradiation of visible light, the electrical conductivity of the solution returned to its initial value. Further exploration of the mechanism of the reversible photo-induced conductivity regulation of azobenzene ionic liquids aqueous solution indicated that this may attributed to the formation/dissociation of ionic liquids aggregates in aqueous solution induced by the isomerization of azobenzene under UV/visible light irradiation and resulted the reversible conductivity regulation. This work provides a way for the molecular designing and performance regulation of photo-responsive ionic liquid and were expected to be applied in devices with photoconductive switching and micro photocontrol properties.

The Influence of Wet Granulation Parameters on the Compaction Behavior and Tablet Strength of a Hydralazine Powder Mixture.

The aim of this paper was to describe the influence of high-shear wet granulation process parameters on tablet tensile strength and compaction behavior of a powder mixture and granules containing hydralazine. The hydralazine powder mixture and eight types of granules were compacted into tablets and evaluated using the Heckel, Kawakita and Adams analyses. The granules were created using two types of granulation liquid (distilled water and aqueous solution of polyvinylpyrrolidone), at different impeller speeds (500 and 700 rpm) and with different wet massing times (without wet massing and for 2 min). Granulation resulted in improved compressibility, reduced dustiness and narrower particle-size distribution. A significant influence of wet massing time on parameters from the Kawakita and Adams analysis was found. Wet massing time had an equally significant effect on tablet tensile strength, regardless of the granulation liquid used. Granules formed with the same wet massing time showed the same trends in tabletability graphs. Tablets created using a single-tablet press (batch compaction) and an eccentric tablet press showed opposite values of tensile strength. Tablets from granules with a higher bulk density showed lower strength during batch compaction and, conversely, higher strength during eccentric tableting.

Absorption mechanism and thermodynamics of SO2 using pH-buffered ionic liquid aqueous solution

Absorption mechanism and thermodynamics of SO2 using pH-buffered ionic liquid aqueous solution

Wood microchannels with multi-carboxyl groups for selective adsorption of Fe3+ from ionic liquids aqueous solution: Experimental and DFT study

Heavy metal contamination is widely present in the spinning field. Some heavy metal ions such as Fe3+ may accumulate in the coagulation bath using ionic liquids (ILs) as green solvents to prepare regenerated cellulose fibers (RCFs), which seriously affect the performance of RCFs and the subsequent regeneration of ILs. This study proposed a new strategy to selectively adsorb Fe3+ from ILs aqueous solution using carboxyl-functionalized wood microchannel (CW). The CW was optimized by citric acid concentration, reaction time, and temperature using carboxyl group contents as an indicator. The physic-chemical properties of CW were characterized, and its adsorption performance for Fe3+ was also evaluated in a water system. Furthermore, the adsorption selectivity of CW for Fe3+ and ILs was investigated. The results demonstrate that the CW had a high adsorption ratio for Fe3+ (94.73%), while that for ILs was 4.20%. The selective adsorption mechanism, in which the Fe3+ is mainly separated from ILs aqueous solution by complexation with carboxyl group, was confirmed by FTIR, XPS, MIP, and DFT calculation. Accordingly, this paper may provide a new strategy to selectively adsorb Fe3+ from ILs aqueous solution, thus offering an economical and efficient method for ILs recovery and water purification.

Ionic liquids as model systems for the study of the behaviour of electrolytes and surfactants in solutions

Abstract Ionic liquids are among the most studied systems in recent years, and this field is still growing considerably, focusing not only on fundamental research but also on the development of ionic liquids for specific applications. In this paper, the similarities and differences between conventional, “classical” electrolytes and common surfactants and ionic liquids, as well as the surface-active ionic liquids, are discussed to highlight their importance and point out their weaknesses. A brief review of the literature data shows that ionic liquids behave like “classical” electrolytes in solutions and can be described by existing models within the range of their validity. Models that describe concentrated electrolyte solutions well are still lacking, and here ionic liquids, which are less constrained by solubility than ordinary electrolytes, can serve as model systems. The micellization of surface-active ionic liquids in aqueous solutions can be described in the same way as for conventional surfactants, but surface-active ionic liquids offer more opportunities to study specific ion and isomer effects.