Low-melting mixture solvents:extension of deep eutectic solvents and ionic liquids for broadening green solvents and green chemistry

Green solvents such as water and ionic liquids(ILs)are pillars of the great mansion of green chemistry and green processing.Initially proposed as a new family of ILs,deep eutectic solvents(DESs)have received fast development in the past two decades.In this contribution,DESs are reviewed critically and the concept is extended to lowmelting mixture solvents(Lo MMSs),which cover all kinds of materials including ionic compounds,molecular compounds,and metals.Six classes of Lo MMSs are proposed as the new classification system and examples are given.Finally,several thermodynamic issues concerning Lo MMSs are discussed.Two new concepts,robustness of Lo MMSs and high-entropy Lo MMSs,are proposed.

Influence of solvent mixtures on HPMCAS-celecoxib microparticles prepared by electrospraying

Hypromellose acetate succinate(HPMCAS) microparticles containing the poorly-water soluble drug celecoxib(CEL) were prepared by electrospraying intended for oral drug delivery. Various solvent mixtures with different solubility for CEL and HPMCAS were used to induce changes in the polymer structural conformation of the microparticles. The performance of the prepared microparticles was evaluated by studying the solid state from, particle size and morphology, radial drug distribution and drug release. CEL was amorphous in all electrosprayed HPMCAS microparticles. The particle size and morphology was dependent on the solubility of HPMCAS in the solvent mixture used with poorer solvents resulting in smaller microparticles with rougher appearance. The CEL distribution on the particles surface was relatively homogeneous and similar for all microparticles. Drug release from the microparticles was observed at a higher rate depending on the solubility of HPMCAS in the solvent used for electrospraying, and in all cases an at least 4-fold higher rate was observed compared with the crystalline drug. Drug precipitation from the supersaturated solution was inhibited by HPMCAS for all microparticles based on its parachute effect while crystalline CEL did not reach supersaturation. This study demonstrated that electrospraying can be used to produce microparticles with tailored properties for pharmaceutical application by adjusting solvent selection.

Phase behavior of heavy oil-solvent mixture systems under reservoir conditions

A novel experimental procedure was proposed to investigate the phase behavior of a solvent mixture(SM)(64 mol%CH4,8 mol%CO2,and 28 mol%C3 H8)with heavy oil.Then,a theoretical methodology was employed to estimate the phase behavior of the heavy oil-solvent mixture(HO-SM)systems with various mole fractions of SM.The experimental results show that as the mole fraction of SM increases,the saturation pressures and swelling factors of the HO-SM systems considerably increase,and the viscosities and densities of the HO-SM systems decrease.The heavy oil is upgraded in situ via asphaltene precipitation and SM dissolution.Therefore,the solvent-enriched oil phase at the top layer of reservoirs can easily be produced from the reservoir.The aforementioned results indicate that the SM has promising application potential for enhanced heavy oil recovery via solvent-based processes.The theoretical methodology can accurately predict the saturation pressures,swelling factors,and densities of HO-SM systems with various mole fractions of SM,with average error percentages of1.77%for saturation pressures,0.07%for swelling factors,and 0.07%for densities.

Determination of physical properties for the mixtures of [BMIM]Cl with different organic solvents

Physical properties including refractive index, density, viscosity and conductivity for binary mixtures of l-butyl- 3-methyl imidazolium chloride （[BMIM]CI） and different organic solvents at 298.15 K have been investigated. Ex- cess molar volumes have been calculated and obtained data has been fitted by the Redlich-Kister equation. The density and refractive index were found to increase with increasing concentration of [BMIM]CI, however, excep- tions do exist as in the case of dimethyl sulfoxide （DMSO）/[BMIM]CI. For DMSO/[BMIM]CI, the density decreases with increasing concentration. The addition of different organic solvents was able to disrupt the interactions within mixtures, leading to free mobility of ions. The free mobility of ions has been found to enhance conductivity and decrease viscosity to varying extents in all mixtures studied. It has been observed that solubility parameters, dielectric constants and composition of the solvents used play a vital role in determining the resultant properties. The data obtained will play an important role in understanding the effect of the addition of organic solvents in ILs to enhance their applicability.

Crystal Growth of Calcite at Conditions of Gas Processing in Solvent Mixtures of Monoethylene Glycol and Water

Growth kinetics of the most stable polymorph of calcium carbonate,calcite,has been studied in seeded stirred batch experiments in MEG-water solutions at 40 ℃ and 70 ℃,conditions relevant for the processing of natural gas.It was found that MEG changes the growth order from two in pure water to one in solvent mixtures of MEG and water.Assuming parabolic growth (growth order is equal to two),it could be shown that MEG decreases the growth rate constant for calcite from 0.52 nm/s to 0.11 nm/s (70 ℃) when the MEG-content is increased from 0 wt% MEG to 65 wt% MEG.Decreasing the temperature from 70 ℃ to 40 ℃ has a similar effect on the growth rate constant as raising the level of MEG to 65 wt%.

Thickness Uniformity Adjustment of Inkjet Printed Light-emitting Polymer Films by Solvent Mixture

In this paper, thickness uniformity of poly（9,9-di-n-octylfluorene） films patterned by inkjet printing was im- proved by the use of solvent mixtures （a solvent with higher volatility, higher surface energy and lower viscosity, with another solvent with lower volatility, lower surface energy and higher viscosity）. The average thickness of inkjet printed poly（9,9-di-n-octylfluorene） films was increased from ca. 30 nm to ca. 100 nm when solvent mixtures were used instead of pure chlorobenzene. More flat PFO films were formed instead of the original films with con- cave-lens like cross-section formed by coffee ring effect. This improvement was explained by combination of in- tense Marangoni flow at early drying process and weak complementary flow at the later drying process formed in the solvent mixture. Patterned poly（9,9-di-n-octylfluorene） films were used for fabrication of electroluminescence devices with improved electronic property. Array of pixels with about 80% effective light-emitting area was ob- tained.

Design of solvent mixtures for removal of phenol from wastewater using a non-linear programming model with a multi-start method

The optimization-based design of solvent mixtures used for phenolic wastewater treatment was investigated in this work.A nonlinear programming(NLP)model was formulated based on the concepts of computer-aid molecule design(Computer-Aided Molecular Design,CAMD)to select solvent mixtures with the best extraction performance considering the constraints of extraction process and the environmental impact.Due to the complexity of the NLP model,multi-start method was adopted to solve this problem in order to get near global optimal solution.The results of the calculations suggested that the optimal mixture consisted of 70.1%n-octanol and 29.9%2-octanone(molar fraction).The 119 sets of experimental results showed that the extraction ability of the optimal solvent mixture identified by CAMD technique was among the top 6 sets compared to the experiment results.The results suggested that the developed NLP model could be able to screen the optimal solvent mixture in phenolic wastewater treatment.

To gel or not to gel：A prior prediction of gelation in solvent mixtures

The gelation behaviours of low molecular weight gelators 1,3：2,5：4.6-tris（3,4-dichlorobenzylidene）-Dmannitol（G1） and 2,4-（3.4-dichlorobenzylidene）-N-（3-aminopropyl）-D-gluconamide（G2） in 34 solvents have been studied.We found that sample dissolved at low concentrations may become a gel or precipitate at higher concentrations.The Hansen solubility parameters（HSPs） and a Teas plot were employed to correlate the gelation behaviours with solvent properties,but with no success if the concentration of the tests was not maintained constant.Instead,on the basis of the gelation results obtained for the G1 and G2 in single solvents,we studied the gelation behaviours of G1 and G2 in23 solvent mixtures and found that the tendency of a gelator to form a gel in mixed solvents is strongly correlated with its gelation behaviours in good solvents.If the gelation occurs in a good solvent at higher concentrations,it will take place as well in a mixed solvent（the good solvent plus a poor solvent） at a certain volume ratio.In contrast,if the gelator forms a precipitate in a good solvent at higher concentrations,no gelation is to be observed in the mixed solvents.A gelation rule for mixed solvents is thus proposed,which may facilitate decision making with regard to solvent selection for gel formation in the solvent mixtures in practical applications.

Polymer Solar Cells with Improved Power Conversion Efficiency Using Solvent Mixtures

In this paper, the effects of solvent mixtures on the morphology, charge transport, and light trapping of poly[N-900-hepta-decanyl-2,7-carbazole-alt-5,5-（40,70-di-2-thienyl-20,10,30-benzothiadiazole）]（PCDTBT） and [6,6]-phenyl C71-butyric acid methyl ester（PC71BM） based solar cells were investigated. As a good solvent for PCDTBT, o-dichlorobenzene（ODCB） was selected to mix with chloroform（CF）, chlorobenzene（eB）, and 1,2,4-Trichloroben-zene（TCB） for optimizing the morphology of the PCDTBT：PCTIBM active layer. It can be found that the device performance of polymer solar cells（PSCs） has been greatly improved when using a optimal blend ratio. Especially, the PSCs fabricated via ODCB（90%）/CF（10%, volume fraction） mixture exhibit a remarkable enhancement of photon-to-current efficiency（PCE） from 5.16% to 7.47%. The enhanced performance of the PSCs can be attributed to the higher absorption, the lower resistance, and the optimized surface morphology of the active layers modified by the solvent mixtures.