Tetrathiafulvalene esters with high redox potentials and improved solubilities for non-aqueous redox flow battery applications

The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.

Measurement of Solubilities of o-Phenylphenol in Petroleum Ether and DDP in Acetone+Water Solution

[（6-oxide-6H-dibenze（c, e）（1, 2）oxaphosphorin-6-yl）methyl]-butanedioic acid （DDP） was prepared and characterized. Solubilities of o-phenylphenol（OPP） in petroleum ether and DDP in acetone ＋ water solution were measured by a gravimetrical method. The solubility data of OPP were well correlated using Francis equation. For the solubility of DDP in acetone aqueous solution, it was found that at each fixed temperature there existed a maximum when the acetone mass fraction in the solvent reached a certain concentration. The experiment shows that the fraction is approximately 0.6. The solubility data would be helpful for their industrial crystallization process.

Experimental determination of solubilities and＇supersolubilities of 2,2＇,4,4＇,6,6＇-hexanitrostilbene in different organic solvents

The laser monitor technique was used to determine solubilities and supersolubilities of HNS in N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methyl-2-pyrrolidone and 1,4-butyrolactone. The experimental solubility values were correlated with λh equation, modified Apelblat equation and NRTL model. Furthermore, the dissolution enthalpy, dissolution entropy and the Gibbs energy of HNS were calculated by the experimental data. The results show that the solubilities of HNS in the above solvents increase with the increasing temperature. Besides, at the same temperature, the order of solubility is N-methyl-2-pyrrolidone > dimethyl sulfoxide > N,N-dimethylformamide > 1,4-butyrolactone > acetonitrile. The temperature dependence of predicted solubility is in agreement with the experimental data.

DETERMINATION OF THE SOLUBILITIES OF 2,4-DICHLOROBENZALDEHYDE IN ORGANIC SOLVENTS

Solubilities of 2,4-dichlorobenzaldehyde in five single organic solvents,namely,n-propanol,n-butanol.cyclohexane,chloroform and dichloromethane as well as in two mixed solvents,namely,cyclohexane-acetone and cyclohexane n-butanol,have been measured.These data are correlated withWilson,NRTL and UNIQUAC activity coefficient models and can be used for the process design inthe purification of 2,4-dichlorobenzaldehyde.

Solubilities of CO_2, CH_4,H_2,CO and N_2 in choline chloride/urea

Solubilities of CO_2, CH_4, H_2, CO and N_2 in choline chloride/urea(ChCl/Urea) were investigated at temperatures ranging from 308.2 to328.2 K and pressures ranging from 0.6 to 4.6 MPa. The results show that the solubilities of gases increase with increasing pressure and decreasing temperature. The solubility of CO_2 is higher than that of CH_4, H_2, CO and N_2, which indicates that ChCl/Urea may be used as a potential solvent for CO_2 capture from the gas mixture. Solubility of CO_2 in ChCl/Urea was fitted by Non-Random Two-Liquid and Redlich-Kwong(NRTL-RK) model, and solubility of CH_4, H_2, CO or N_2 in ChCl/Urea was fitted by Henry's Law. The standard enthalpy, standard Gibbs energy and standard entropy of gases were calculated. Additionally, the CO_2/CH_4 selectivities in water, dry ChCl/Urea and aqueous ChCl/Urea were further discussed.

Solubilities,Densities,Refractive Indices of Aqueous Ternary Systems PEG400-NaCl/KCl-H2O at 298 K

Phase equilibria for the NaCl/KCl-PEG400-H2O aqueous ternary systems at 298 K were studied using an isothermal dissolution method.In addition,the densities and refractive indices were determined.The corresponding phase diagrams,as well as the density vs.composition and refractive index vs.composition diagrams,were plotted.Results revealed that over the entire PEG400 composition range studied at 298 K only 1 liquid phase was obtained,without the formation of a biphase region.The phase diagrams of these 2 systems consist of 1 homogeneous area with unsaturated liquid (L) and an equilibrium area containing the solid phase of NaCl/KCl and the saturated liquid phase (S+L).The solubility of NaCl/KCl decreases with the addition of PEG400 at 298 K.

Prediction of the Aqueous Solubilities of Polychlorinated Biphenyls

Using the molecular electronegativity distance vector descriptors derived directly from the molecular topological structures, the aqueous solubilities of polychlorinated biphenyls (PCBs) were predicted. A three-variable regression equation with correlation coefficient of 0.9739 and the root mean square errors of 0.26 was developed. The descriptors included in the equation represent three interactions between three pairs of atomic types, i.e., atom -C= and >C=, -C= and -Cl, and -Cl and -Cl. It has been proved that the aqueous solubilities of 137 PCB congeners can be accurately predicted as long as there are more than 65 calibration compounds.

Determination of the subcooled liquid solubilities of PAHs in partitioning batch experiments

Subcooled liquid solubility is the water solubility for a hypothetical state of liquid. It is an important parameter for multicomponent nonaqueous phase liquids （NAPLs） containing polycyclic aromatic hydrocarbons （PAHs）, which can exist as liquids even though most of the solutes are solid in their pure form at ambient temperature. So far, subcooled liquid solubilities were estimated from the solid water solubility and fugacity ratio of the solid and （subcooled） liquid phase, but rarely derived from experi- mental data. In our study, partitioning batch experiments were performed to determine the subcooled liquid solubility of PAHs in NAPL-water system. For selected PAH, a series of batch experiments were carried out at increased mole fractions of the target component in the NAPL and at a constant NAPL/ water volume ratio. The equilibrium aqueous PAH concentrations were measured with HPLC and/or GC- MS. The suhcooled liquid solubility was derived by extrapolation of the experimental equilibrium aqueous concentration to a mole fraction of unity. With the derived subcooled liquid solubility, the fugacity ratio and enthalpy of fusion of the solute were also estimated. Our results show a good agreement between the experimentally determined and published data.

SOLUBILITIES OF CARBON DIOXIDE IN MIXTURES OF n-DECANE-n-HEXADECANE AND n-HEPTANE-TOLUENE

Solubilities of CO2 in binary mixtures of n-decane-n-hexadecane and n-heptane-toluenewere measured in a glass apparatus by a synthetic method.Henry’s constants at several temperaturesand solvent compositions were reported.While the Henry’s constants of CO2 in mixtures of decaneand hexadecane can be satisfactorily predicted by a simple linear interpolation,prediction of Henry’sconstants for CO2 in mixtures of heptane and toluene requires excess Gibbs energy of the solvent mix-tures.The standard thermodynamic functions of solution（ΔH0,ΔG0,and ΔS0）were reported.

SOLUBILITIES OF VINYL CHLORIDE IN EMULSIFIER SOLUTIONS

1 INTRODUCTIONVinyl chloride（VC）is a slightly water-soluble monomer.But its solubility in water(～10g·L-1)is much higher than that of olefins(0.1～1g·L-1).The solubilityof VC is an important parameter in suspension,emulsion and miniemulsionpolymerizations.The presence of emulsifier in aqueous medium will enhance the solubil-ity of VC.The solubility of VC depends not only on the types and concentration of theemulsifier,but also on the temperature and pressure.Unfortunately,the solubilities ofVC in emulsifier solutions are rarely reported in literatures.

SOLUBILITIES OF Ce,Nd AND Y IN α-Fe

The solubilities of Ce,Nd and Y in α-Fe at 873 to 1153 K have been deter mined by means of electron microprobe quantitative analyses.The temperature dependences of the solubilities were obtained from the experimental data.The results have been compared with those deter- mined by three other technigues,very good agreement was obtained between the results of all these techniques.

Effects of High Hydrostatic Pressure on the Solubilities and Structures of Alaska Pollock Protein

Alaska pollock is an important protein source which is extensively used in the food industry. Pollock protein isolates(PPI) with significantly enriched protein contents could be prepared using isoelectric solubilization/precipitation(ISP) processing; however, the functional properties of this process is limited by the large amount of water-insoluble proteins. In this study, we investigated the influence of high hydrostatic pressure(HHP) treatment on the solubility and structural changes of PPI. PPI obtained using ISP is treated with hydrostatic pressures of 200, 300, 400, and 500 MPa for up to 15 min, and the HHP-treated samples were observed to exhibit significantly improved solubilities. Further biochemical assays reveal that the continuous HHP treatments reduce the contents of free sulfhydryl groups and promote the formation of macromolecules with better water solubilities, which may induce the solubility improvements of the HHP-treated PPI. Our results indicate that HHP can be utilized to effectively prepare highly water-soluble Alaska pollock protein in food processing.

FACTORS INFLUENCING SOLID SOLUBILITIES OFRARE-EARTHS IN Pd

A parameter describing the solid solubilities of mre-earths in Pd, Nf/aX(TR - rPd),was proposed, where N is the fshell filled electron nutnben △X the electronegativity dtherence between Palladium and rare-earths, rR the atotnic radii of rare-earth elementand rPd of Pd. The marimum solid solubilities are linear relation to this parnmeterexcept La, Nd and Ce.

Description and Prediction of the Solid Solubilities of Binary Alloys Based on the Actinide Metals

The solid solubilities of 207 binary alloys based on the three actinide metals (Th, U and Pu) at room tem- perature are studied with the two theoretical schemes suggested by one of the present authors (ZBW).The re- sults show that the soluble elements can be distinguished from the insoluble ones by a parabola y_1=a--bx^2 or an ellipse (x_2,-m)~2/c^2+(y_2-n)~2/d^2=l with the total reliabilities of 87.9% and 92.3% respectively for the 207 binary alloys. The contants a and b in the parabola equation, and c, d, m and n in the ellipse equation can be related to some appropriate parameters for each host metal respectively. The reasons are discussed. From the theories the soluble elements in these actinide host metals that have not been measured yet can be predicted in the accuracies of the schemes.

SOLID SOLUBILITIES OF Ce, Nd AND Y IN α—Fe AT ROOM TEMPERATURE

Using the thermodynamic formula of solid solubility in dilute solution, the solid solubilities of Ce. Nd and Y in α-Fe at room temperature have been calculated The results are 48, 32 and 1(×10-4wt. -％) respectively and the mechanism influencing the values of solid solubilities are also discussed.

CALCULATION OF GOLD SOLUBILITIES IN THE WINDOW OF T & P

Calculations based on the newest thermodynamic properties and supposed ore-fluid conditions suggest that gold solubilities in aqueous hydrosulphide and chloride fluids wi1l change with both temperature and pressure.At given 100 MPa, the gold solubility in aqueous hydrosulphide fluids will increase as the temperature increases, and reach the peak at 400℃, then decrease as the temperature increases;at 150 MPa, the peak of gold solubility is located at 500℃. At 100 MPa, however, the gold solubility in aqueous chloride fluids will also increase as the temperature increases, and reach the peak at 500℃, then decrease as the temperature increases ; at 150 MPa, the peak of gold solubility is shifted to 600℃ or higher. On the other hand, at given 300℃ and below 300℃,the gold solubility in aqueous hydrosulphide and chloride fluids changes very little as the pressure increases ; however, above 400℃ the gold solubility will increase sharply with pressure. This certifies that the pressure plays a very important role on the gold solubility at high temperature, At some content,the influence of pressure on the gold solubility is the same as that of temperature. Peaks of gold solubilities in aqueous hydrosulphide and chloride fluids in the window of T & P will form a trajectory respectively in the crust. The two trajectories will form a belt which is a favorite region for gold transportation in ore-forming fluids. Outside of this region, gold will be deposited from the ore-forming fluids. It is possible that the positions of gold deposits wou1d be inferred with this diagram in the future.

Absorption characteristics,model,and molecular mechanism of hydrogen sulfide in morpholine acetate aqueous solution

The solubility of H_(2)S was measured in solutions of N-butyl-N-methylmorpholine acetate([Bmmorp][Ac])containing 20%-40%(mass)water at experimental temperatures ranged from 298.15 to 328.15 K and pressures up to 320 k Pa.The total solubility of H_(2)S increased with higher temperatures,lower pressures,and reduced water content.The reaction equilibrium thermodynamic model was used to correlate the solubility data.The results indicate that the chemical reaction equilibrium constant decrease with increasing water content and temperature,whereas Henry constant increase with increasing water content and temperature.Compared with other ionic liquids,H_(2)S exhibits a higher physical absorption enthalpy and a lower chemical absorption enthalpy in[Bmmorp][Ac]aqueous solution.This suggests that[Bmmorp][Ac]has a strong physical affinity for H_(2)S and low energy requirement for desorption.Quantum chemical methods were used to investigate the molecular mechanism of H_(2)S absorption in ionic liquids.The interaction energy analysis revealed that the binding of H_(2)S with the ionic liquid in a1:2 ratio is more stable.Detailed analyses by the methods of the interaction region indicator and the atoms in molecules were conducted to the interactions between H_(2)S and the ionic liquid.

Mapping out the reaction network of humin formation at the initial stage of fructose dehydration in water

The formation of humins hampers the large-scale production of 5-hydroxymethylfurfural(HMF)in biorefinery.Here,a detailed reaction network of humin formation at the initial stage of fructose-to-HMF dehydration in water is delineated by combined experimental,spectroscopic,and theoretical studies.Three bimolecular reaction pathways to build up soluble humins are demonstrated.That is,the intermolecular etherification of β-furanose at room temperature initiates the C12 path,whereas the C-C cleavage of a-furanose at 130-150℃ leads to C11 path,and that of open-chain fructose at 180℃ to C11' path.The successive intramolecular dehydrations and condensations of the as-formed bimolecular intermediates lead to three types of soluble humins.We show that the C12 path could be restrained by using HCl or AlCl_(3) catalyst,and both the C12 and C110 paths could be effectively inhibited by adding THF as a co-solvent or accelerating heating rate via microwave heating.

MIR1868 negatively regulates rice cold tolerance at both the seedling and booting stages

Low temperature causes rice yield losses of up to 30%–40%,therefore increasing its cold tolerance is a breeding target.Few genes in rice are reported to confer cold tolerance at both the vegetative and reproductive stages.This study revealed a rice-specific 24-nt miRNA,miR1868,whose accumulation was suppressed by cold stress.Knockdown of MIR1868 increased seedling survival,pollen fertility,seed setting,and grain yield under cold stress,whereas its overexpression conferred the opposite phenotype.Knockdown of MIR1868 increased reactive oxygen species(ROS)scavenging and soluble sugar content under cold stress by increasing the expression of peroxidase genes and sugar metabolism genes,and its overexpression produced the opposite effect.Thus,MIR1868 negatively regulated rice cold tolerance via ROS scavenging and sugar accumulation.

Machine learning with active pharmaceutical ingredient/polymer interaction mechanism:Prediction for complex phase behaviors of pharmaceuticals and formulations

The high throughput prediction of the thermodynamic phase behavior of active pharmaceutical ingredients(APIs)with pharmaceutically relevant excipients remains a major scientific challenge in the screening of pharmaceutical formulations.In this work,a developed machine-learning model efficiently predicts the solubility of APIs in polymers by learning the phase equilibrium principle and using a few molecular descriptors.Under the few-shot learning framework,thermodynamic theory(perturbed-chain statistical associating fluid theory)was used for data augmentation,and computational chemistry was applied for molecular descriptors'screening.The results showed that the developed machine-learning model can predict the API-polymer phase diagram accurately,broaden the solubility data of APIs in polymers,and reproduce the relationship between API solubility and the interaction mechanisms between API and polymer successfully,which provided efficient guidance for the development of pharmaceutical formulations.