Liquid–liquid extraction of levulinic acid from aqueous solutions using hydrophobic tri-n-octylamine/alcohol-based deep eutectic solvent

Levulinic acid(LA)is one of the top-12 most promising biomass-based platform chemicals,which has a wide range of applications in a variety of fields.However,separation and purification of LA from aqueous solution or actual hydrolysate continues to be a challenge.Among various downstream separation technologies,liquid-liquid extraction is a low-cost,effective,and simple process to separate LA.The key breakthrough lies in the development of extractants with high extraction efficiency,good hydrophobicity,and low cost.In this work,three hydrophobic deep eutectic solvents(DESs)based on tri-n-octylamine(TOA)as hydrogen bond acceptor(HBA)and alcohols(butanol,2-octanol,and menthol)as hydrogen bond donors(HBDs)were developed to extract LA from aqueous solution.The molar ratios of HBD and HBA,extraction temperature,contact time,solution pH,and initial LA concentration,DES/water volume ratios were systematically investigated.Compared with 2-octanol-TOA and menthol-TOA DES,the butanol-TOA DES exhibited the superior extraction performance for LA,with a maximum extraction efficiency of 95.79±1.4%.Moreover,the solution pH had a great impact on the LA extraction efficiency of butanol-TOA(molar ratio=3:1).It is worth noting that the extraction equilibrium time was less than 0.5 h.More importantly,the butanol-TOA(3:1)DES possesses good extraction abilities for low,medium,and high concentrations of LA.

Removal of cadmium from aqueous solutions using red mud granulated with cement

A novel adsorbent was prepared from granular red mud mixed with cement and its potential to be a suitable adsorbent for the removal of cadmium ions from aqueous solutions was evaluated. The wet red mud was directly mixed up with cement at different mass fractions of 2%-8% and their properties were investigated. Based on the textural characteristics and strength, the granular red mud with 2% addition of cement maintaining for 6 d is identified to have better properties. The batch adsorption experiments for adsorption of Cd2+ ions from solution were performed at 30, 40 and 50 °C at different initial concentrations under the condition of constant pH of 6.5. The equilibrium adsorption was found to increase with the increase of temperature during the adsorption process. Langmuir adsorption isotherm model was found to match the experimental adsorption isotherm better. The kinetics of adsorption was modeled using a pseudo second order kinetic model and the model parameters were estimated.

A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in aqueous solutions and its applications in binary and ternary aqueous solutions

A universal thermodynamic model of calculating mass action concentrations for structural units or ion couples in ternary and binary strong electrolyte aqueous solution was developed based on the ion and molecule coexistence theory and verified in four kinds of binary aqueous solutions and two kinds of ternary aqueous solutions. The calculated mass action concentrations of structural units or ion couples in four binary aqueous solutions and two ternary solutions at 298.15 K have good agreement with the reported activity data from literatures after shifting the standard state and concentration unit. Therefore, the calculated mass action concentrations of structural units or ion couples from the developed universal thermodynamic model for ternary and binary aqueous solutions can be applied to predict reaction ability of components in ternary and binary strong electrolyte aqueous solutions. It is also proved that the assumptions applied in the developed thermodynamic model are correct and reasonable, i.e., strong electrolyte aqueous solution is composed of cations and anions as simple ions, H2O as simple molecule and other hydrous salt compounds as complex molecules. The calculated mass action concentrations of structural units or ion couples in ternary and binary strong electrolyte aqueous solutions strictly follow the mass action law.

Conformations of Carnosine in Aqueous Solutions by All-Atom Molecular Dynamics Simulations and 2D-NOSEY Spectrum

All-atom molecular simulations and two-dimensional nuclear overhauser effect spectrum have been used to study the conformations of carnosine in aqueous solution. Intramolecular distances, root-mean-square deviation, radius of gyration, and solvent-accessible surface are used to characterize the properties of the carnosine. Carnosine can shift between extended and folded states, but exists mostly in extended state in water. Its preference for extension in pure water has been proven by the 2D nuclear magnetic resonance （NMR） experiment. The NMR experimental results are consistent with the molecular dynamics simulations.

Comparisons of Criteria for Analyzing the Dynamical Association of Solutes in Aqueous Solutions

How to determine accurately the association states of solutes in aqueous systems is of fundamental importance in a variety of chemical, physical, and biological processes, We apply four widely used criteria to analyze the dynamic association processes of solutes, e.g., amphiphilic molecules, and to find the inappropriate selections of representative sites on solutes in these criteria may bring about appreciable influence on the estimation of dynamic association behaviors such as unrealistic packing radii and even misleading packing structures. It would be better to select dynamically representative sites on solute molecules based on the characteristic of solute associations. Our detailed discussions give a guide on how to determine an appropriate criterion to accurately analyze the association behaviors of solute molecules in aqueous solutions.

ADSORPTION OF SULFOXIDES ON SOLID FROM AQUEOUS SOLUTIONS——Ⅲ.THE ADSORPTION ON CARBON BLACK

The adsorption of decylmethylsulfoxide(DEMS)onto carbon black and the effects of temperature,salt(NaCl)and acid (HCl)have been measured.Typical two plateaux type adsorption isotherms were obtained.Applying the two step model of surfactant adsorption on solid/liquld interface and the general adsorption isotherm equation[9]the experimental results were interpreted qualitatively and quantitatively.

Separation of ionic liquids from dilute aqueous solutions using the method based on CO_2 hydrates

Ionic liquids （ILs） have been regarded as the potential novel solvents for improved analytical- and process-scale separation methods.The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydrate formation. For illustration, the dilute aqueous solutions with concentrations of ILs ranging from 2× 10^-3 mol% to 2×10^-1 mol% were concentrated. The results show that the separation efficiency is very impressive and that the new method is applicable to aqueous solutions of both hydrophobic and hydrophilic ILs. Compared to the literature separation method based on the supercritical CO2, the new method is applicable to lower concentrations, and more importantly, its operation condition is mild.

Correlation of ^1H NMR Chemical Shift for Aqueous Solutions by Statistical Associating Fluid Theory Association Model

1H NMR chemical shifts of binary aqueous mixtures of acylamide, alcohol, dimethyl sulphoxide (DMSO), and acetone are correlated by statistical associating fluid theory (SAFT) association model. The comparison between SAPT association model and Wilson equation shows that the former is better for dealing with aqueous solutions. Finally, the specialties of both models are discussed.

Raman and infrared spectroscopic quantification of the carbonate concentration in K_(2)CO_(3)aqueous solutions with water as an internal standard

Carbonate-bearing fluids widely exist in different geological settings,and play important roles in transporting some elements such as the rare earth elements.They may be trapped as large or small fluid inclusions(with the size down to<1μm sometimes),and record critical physical-chemical signals for the formations of their host minerals.Spectroscopic methods like Raman spectroscopy and infrared spectroscopy have been proposed as effective methods to quantify the carbonate concentrations of these fluid inclusions.Although they have some great technical advantages over the conventional microthermometry method,there are still some technical difficulties to overcome before they can be routinely used to solve relevant geological problems.The typical limitations include their interlaboratory difference and poor performance on micro fluid inclusions.This study prepared standard ion-distilled water and K_(2)CO_(3)aqueous solutions at different molarities(from 0.5 to 5.5 mol/L),measured densities,collected Raman and infrared spectra,and explored correlations between the K_(2)CO_(3)molarity and the spectroscopic features at ambient P-T conditions.The result confirms that the Raman O-H stretching mode can be used as an internal standard to determine the carbonate concentrations despite some significant differences among the correlations,established in different laboratories,between the relative Raman intensity of the C-O symmetric stretching mode and that of the O-H stretching mode.It further reveals that the interlaboratory difference can be readily removed by performing one high-quality calibration experiment,provided that later quantifying analyses are conducted using the same Raman spectrometer with the same analytical conditions.Our infrared absorption data were collected from thin fluid films(thickness less than~2μm)formed by pressing the prepared solutions in a Microcompression Cell with two diamond-II plates.The data show that both the O-H stretching mode and the O-H bending mode can be used as internal standards to determine the carbonate concentrations.Since the IR signals of the C-O antisymmetric stretching vibration of the CO32ion,and the O-H stretching and bending vibrations from our thin films are very strong,their relative IR absorbance intensity,if well calibrated,can be used to investigate the micron-sized carbonate-bearing aqueous fluid inclusions.This study establishes the first calibration of this kind,which may have some applications.Additionally,our spectroscopic data suggest that as the K_(2)CO_(3)concentration increases the aqueous solution forms more large water molecule clusters via more intense hydrogen-bonding.This process may significantly alter the physical and chemical behavior of the fluids.

Prediction of Water Activity for Mixed Aqueous Solutions from the Data of Their Binary Constituent Solutions

The equation of Patwardhan and Kumar for water activities of mixed electrolyte solutions is extended to aqueous solutions containing non-electrolytes. This equation and the linear isopiestic relation are used to predict water activities of 56 ternary aqueous solutions in terms of the data of their binary subsystems. Both equation of Patwardhan and Kumar and the linear isopiestic relation can provide good predictions for water activities of the present 40 electrolyte solutions, and the linear isopiestic relation generally yields better predictions. The predictions of the extended equation of Patwardhan and Kumar and the linear isopiestic relation are in general quite reasonable for the present 8 ternary solutions of electrolytes and non-electrolytes, and the results of the linear isopiestic relation are usually better. The predictions of these two methods generally agree well with the experimental data for the 8 non-electrolyte mixtures being studied, and the linear isopiestic relation is better.

Homogeneous Synthesis and Characterization of Quaternized Cellulose Derivatives in NaOH-urea Aqueous Solutions

Quaternized cellulose( QC) derivatives were synthesized by reacting cellulose with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride( CHPTAC) in an aqueous solution of Na OH-urea. The chemical structures and physical properties of the obtained QC derivatives were characterized using nitrogen content analysis,Fourier transform infrared spectroscopy( FT-IR),~1H-nuclear magnetic resonance(1H-NMR),X-ray diffraction( XRD),and thermal gravity analysis( TGA). The FT-IR and ~1H-NMR results confirmed the successful introduction of cationic quaternary ammonium groups into the main chain of cellulose. A series of QC derivatives with the degree of substitution( DS) values ranging from 0. 33 to 0. 80 were derived by adjusting the molar ratio of CHPTAC to anhydroglucose unit( AGU) of cellulose,concentration of cellulose in the Na OH-urea solution,as well as reaction temperature and time. According to the DS values of the QC derivatives,the optimized synthetic conditions were as follows: 25℃ reaction temperature,3% cellulose in Na OH-urea solution,the molar ratio of etherification agent to glycosidic cellulose of 15∶ 1,and 12 h reaction time. The TGA and XRD results revealed that the crystalline structure was destroyed during etherification,and the thermal stability of the QC derivatives was lower than that of cellulose.

Hybrid temperature effect on a quartz crystal microbalance resonator in aqueous solutions

The quartz crystal microbalance（QCM） is an important tool that can sense nanogram changes in mass. The hybrid temperature effect on a QCM resonator in aqueous solutions leads to unconvincing detection results. Control of the temperature effect is one of the keys when using the QCM for high precision measurements. Based on the Sauerbrey＇s and Kanazawa＇s theories, we proposed a method for enhancing the accuracy of the QCM measurement, which takes into account not only the thermal variations of viscosity and density but also the thermal behavior of the QCM resonator. We presented an improved Sauerbrey equation that can be used to effectively compensate the drift of the QCM resonator. These results will play a significant role when applying the QCM at the room temperature.

REMOVAL OF VOCs FROM THE AQUEOUS SOLUTIONS BY PERVAPORATION USING A FILLING-TYPE MEMBRANE

The membranes were prepared by the incorporation of highly hydrophobic silicalite and carbon molecular sieves (CMS) from different precursors into the PDMS casting solutions. The pervaporative removal of VOCs, such as benzene, from aqueous solutions was carried out using the separation factor and permeation flux as the evaluating parameters. The effects of the CMS types and structures, feed concentrations on the pervaporation performance were preliminarily investigated.

Recrystallization of freezable bound water in aqueous solutions of medium concentrations

For aqueous solutions with freezable bound water, vitrification and recrystallization are mingled, which brings difficulty to application and misleads the interpretation of relevant experiments. Here, we report a quantification scheme for the freezable bound water based on the water-content dependence of glass transition temperature, by which also the concentration range for the solutions that may undergo recrystallization finds a clear definition. Furthermore, we find that depending on the amount of the freezable bound water, different temperature protocols should be devised to achieve a complete recrystallization. Our results may be helpful for understanding the dynamics of supercooled aqueous solutions and for improving their manipulation in various industries.

Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields:The Sign Effect

We utilize molecular dynamics simulations to investigate the microstructures of ions and polyelectrolytes in aqueous solutions under external electric fields.By focusing on the multi-body interactions between ionic components and H_(2)O molecules,as well as their responses to the external electric fields,we clarify several nontrivial molecular features of the ionic and polyelectrolyte solutions,such as the solvations of cations and anions,clustering of the ions,and dispersions/aggregations of polyelectrolyte chains,as well as the corresponding responses of H_(2)O molecules in these contexts.Our simulations illustrate the variations in structures of ionic solutions caused by reversing the charge sign of the ions,and elucidate the disparity in structures between anionic and cationic polyelectrolyte solutions in the presence of the external electric fields.This work clarifies the mechanism for the alternations in complex multi-body interactions in aqueous solutions caused by the application electric field,which can contribute to the fundamental understanding of the physical and chemical natures of ion-containing and charged polymeric systems.

The interaction mechanism between zein and folic acid in alkaline aqueous solutions:an experimental and molecular simulation study

Objectives:Folic acid is a vitamin that is not highly soluble in water and is sensitive to the environment.Therefore,it is important to find suitable carriers.This study aimed to exemplify the interaction of folic acid with zein in alkaline aqueous solutions and shed light on how zein can be used as a carrier for folic acid.Materials and Methods:Zein and folic acid were separately dissolved in NaOH solutions with a PH of 11.5.Zein solution and folic acid solution were combined in specific ratios.Various methods including multi-spectroscopy,dynamic light scattering,and electron microscopy combining with molecular dynamics simulations were used to study the interaction mechanism between zein and folic acid in alkaline aqueous solutions.Results:Fluorescence spectroscopy showed that the quenching of zein by folic acid was mainly static,and the main driving force behind this interaction was van der Waals forces and hydrogen bonds.The formation of zein–folic acid complexes was confirmed by ultraviolet–visible spectroscopy,Fourier transform infrared spectroscopy,and circular dichroism spectroscopy.The results also showed that the structure of zein changed when it interacted with folic acid.Dynamic light scattering analysis revealed that the addition of folic acid caused proteins to aggregate.The aggregates of the complexes had an irregular shape and were large,as observed by scanning electron microscopy and transmission electron microscopy.Molecular simulation was used to further investigate the interaction mechanisms.According to these findings,the folic acid molecule interacted with zein in a shallow recess near the protein surface.The dominant forces at play in the zein–folic acid interaction were van der Waals forces and electrostatic forces,including hydrogen bonding.Conclusion:The zein alkali-soluble system is very suitable for folic acid delivery.

Study of the Relationship Between New Ionic Interaction Parameters and Salt Solubility in Electrolyte Solutions Based on Molecular Dynamics Simulation

Studying the relationship between ionic interactions and salt solubility in seawater has implications for seawater desalination and mineral extraction.In this paper,a new method of expressing ion-to-ion interaction is proposed by using molecular dynamics simulation,and the relationship between ion-to-ion interaction and salt solubility in a simulated seawater water-salt system is investigated.By analyzing the variation of distance and contact time between ions in an electrolyte solution,from both spatial and temporal perspectives,new parameters were proposed to describe the interaction between ions:interaction distance(ID),and interaction time ratio(ITR).The best correlation between characteristic time ratio and solubility was found for a molar ratio of salt-to-water of 10:100 with a correlation coefficient of 0.96.For the same salt,a positive correlation was found between CTR and the molar ratio of salt and water.For type 1-1,type 2-1,type 1-2,and type 2-2 salts,the correlation coefficients between CTR and solubility were 0.93,0.96,0.92,and 0.98 for a salt-to-water molar ratio of 10:100,respectively.The solubility of multiple salts was predicted by simulations and compared with experimental values,yielding an average relative deviation of 12.4%.The new ion-interaction parameters offer significant advantages in describing strongly correlated and strongly hydrated electrolyte solutions.

Hydrophobic CHA-ZIFs with a junctional trap between cha and d6r cages for adsorption of 2,3-butanediol in aqueous solution

The adsorption and separation of diols from dilute aqueous solution using hydrophobic materials is very challenging due to the strong diolewater hydrogen-bonding interactions.Herein,we screened hydrophobic zeolitic imidazolate frameworks(ZIFs)with chabazite(CHA)topology for separation of 2,3-butanediol(2,3-BDO)and 1,3-propanediol(1,3-PDO),which had junctional and hydrophobic traps matching the two end methyl groups of the 2,3-BDO molecule.Based on CHA-ZIFs with the same smallsized ligand 2-methylimidazole(mIm)and different large-sized ligand benzimidazole derivatives(RbIm),CHA-ZIFs with larger surface areas were obtained by the addition of excess small-sized ligand mIm in the synthesis process.We showed that all of the hydrophobic CHA-ZIFs preferentially adsorbed 2,3-BDO over 1,3-PDO by static batch adsorption and dynamic column adsorption experiments.But ZIF-301 and ZIF-300 with halogen groups exhibited better adsorptive separation performance for 2,3-BDO/1,3-PDO than ZIF-302 with methyl groups.For a typical ZIF-301,its adsorption capacity for 2,3-BDO was 116.4 mg$g1 and selectivity for 2,3-BDO/1,3-PDO was 3.8 in dynamic column adsorption of the binarycomponent system(2,3-BDO/1,3-PDO:50 g·L^(-1)/50 g·L^(-1)).Computational simulations revealed that 2,3-BDO preferentially adsorbed in a trap at the junction between the cha and d6r cages of CHA-ZIFs,meaning the strong hosteguest interactions.Therefore,the hydrophobic CHA-ZIFs with a junctional trap were promising candidate materials for adsorbing 2,3-BDO,which also provided a new perspective for separating diols in dilute aqueous solutions.

Equations of state for aqueous solutions under mantle conditions

With unique physical and chemical properties, aqueous solutions in the mantle may play important roles for a number of geochemical and geodynamical processes. However, since experimental data available are very limited, people still know little about the aqueous solutions and their interactions with surrounding rocks and melts. From the perspective of thermodynamics, equation of state(EOS) is the key to push forward the modeling of aqueous solutions. Nevertheless, up to now accurate EOSs suitable for the mantle conditions are still in shortage. With discussions over several recognized EOSs, we summarize several ways to enhance the predictability of EOS: utilizing high quality data from molecular simulations, choosing functions with sound physical background, and improving the regression procedures for the empirical parameters. In the meantime, we find that the ion-bearing systems are still the focus of challenges in this area. New developments of experiments and computer simulations effectively deal with these challenges and in-depth understandings of aqueous solutions in the mantle are expected in the near future.

A new association state of solutes in nanoconfined aqueous solutions

Recently, we have found a reversible transition between the dispersion and aggregation states of solute molecules in aqueous solutions confined in nanoscale geometry, where solutes exhibit distinct behavior in a new association state from that in the dispersion and aggregation states observed usually in macroscopic systems. However, it remains unknown whether this new association state of solute molecules found in nanoconfined systems would vanish with the system size increasing and approaching the macroscopic scale. Here, we achieve the phase diagram of solute association states by making the analyses of Gibbs free energy of solutes in nanoconfined aqueous solutions in detail. In the phase diagram, we observe a closed regime with a finite system size of nanoconfined aqueous solutions and a solute concentration range, only in which there exists the new association state of solutes with the reversible transition between the aggregation and dispersion states, and there indeed exists an upper limit of the system size for the new association state, around several tens nanometers. These findings regarding the intimate connection between the system size and the solute association behavior provides the comprehensive understanding of the association dynamics of solutes in nanoconfined environment.