Hansen Solubility Parameters Values Research Articles

Application of Multivariate Adaptive Regression Splines (MARSplines) for Predicting Hansen Solubility Parameters Based on 1D and 2D Molecular Descriptors Computed from SMILES String

A new method of Hansen solubility parameters (HSPs) prediction was developed by combining the multivariate adaptive regression splines (MARSplines) methodology with a simple multivariable regression involving 1D and 2D PaDEL molecular descriptors. In order to adopt the MARSplines approach to QSPR/QSAR problems, several optimization procedures were proposed and tested. The effectiveness of the obtained models was checked via standard QSPR/QSAR internal validation procedures provided by the QSARINS software and by predicting the solubility classification of polymers and drug-like solid solutes in collections of solvents. By utilizing information derived only from SMILES strings, the obtained models allow for computing all of the three Hansen solubility parameters including dispersion, polarization, and hydrogen bonding. Although several descriptors are required for proper parameters estimation, the proposed procedure is simple and straightforward and does not require a molecular geometry optimization. The obtained HSP values are highly correlated with experimental data, and their application for solving solubility problems leads to essentially the same quality as for the original parameters. Based on provided models, it is possible to characterize any solvent and liquid solute for which HSP data are unavailable.

Evaluation of adsorption of organic solvents to modified hydrophobic silica adsorbents based on Hansen solubility parameter

• Adsorption of organic substances in aqueous solution was carried out using hydrophobic silica adsorbent. • Adsorbed amount was estimated using HSP theory. • An adsorption amount estimation formula using the difference R a of HSP values was constructed. • It was suggested that affinity is an important factor in adsorption. Adsorption is an effective methodology for the removal of organic matter. Several studies have shown that adsorption performance is dependent on pore size, specific surface area, and the affinity between the adsorbent and adsorbed material. In this study, we concentrated on the effect of the affinity between the surface of the adsorbent and the adsorbed matter by examining the adsorption of organic solvents from organic/aqueous mixtures using three types of hydrophobic silica adsorbents. The Hansen solubility parameters (HSPs) of the adsorbents were determined using the group contribution method. A linear relationship between the logarithm of the amount of adsorbed organic solvent and the difference between the HSP values of the organic solvents and adsorbents was obtained with a high correlation coefficient. These experimental results suggest that the affinity between the adsorbent and adsorbed matter can be well-described by the HSPs of the components.

Influence of Hansen solubility parameters on exfoliation of organophilic fluoromica

The influence of different surface energies described by Hansen solubility parameters (HSP) on the exfoliation of organophilic fluoromicas is investigated. HSP values of four synthetic organophilic fluoromica with different surfactants have been predetermined. Those surfactants change the fluoromica surface energies described by HSP. The HSP are used to calculate the dispersibility of the various organophilic fluoromica in chloroform via Flory-Huggins (F-H) theory. The F-H parameter (χ) describes the effective difference in HSP related surface energies of particles and chloroform molecules, which is related to the energy cost of exfoliation. An influence of F-H parameter is detected on the delamination state of organophilic fluoromica. The delamination state is evaluated quantitatively using atomic force microscopy (AFM). In the case of a high F-H parameter (χ > 0.15), aggregated and unstable fluoromica dispersions are obtained. Whereas in the case of F-H parameters near zero, exfoliated and stable fluoromica dispersions are achieved. The presence of surfactant on the surface of exfoliated fluoromica flakes is proven by Fourier-transform infrared spectroscopy (FT-IR), and density functional theory (DFT) calculation.

Measurement of Hansen solubility parameters for organophilic fluoromica and evaluation of potential solvents for exfoliation

Abstract A method to measure Hansen solubility parameters for organophilic fluoromica is developed. For this purpose, fluoromica with four different intercalated molecules (surfactants) have been dispersed in various solvents. These surfactants change the fluoromica surface energies described by Hansen solubility parameters (HSP). The three Hansen solubility parameters (dispersion, polar and hydrogen bonding) of different organophilic fluoromicas have been obtained by using gravimetric analysis. The dispersion parameters for all four organophilic fluoromicas are almost identical, with a value around 17 MPa . Whereas polar and H-bonding parameters are varying with the used surfactants. Surprisingly the polar and hydrogen bonding values for hydrophobic alkyl chain tailored surfactants are higher than those for a hydrophilic surfactant with poly(ethylene glycol) chains. The determined HSP values allow calculating the dispersibility of the organophilic fluoromica in solvents via the Flory-Huggins (F-H) parameter. These F-H parameters describes the effective difference in HSP related surface energies of particles and solvent molecules and are used to identify potential solvents for an exfoliation process. With this approach, beside known solvents such as chloroform, also new potential candidates such as trichloroethylene, and benzyl ethyl ether are identified for dispersing/exfoliating modified organophilic fluoromica. This work is accompanied by X-ray diffraction (XRD) measurements to gain knowledge about the interlayer space of the different organophilic fluoromicas.

Soluble Metal Oxo Alkoxide Inks with Advanced Rheological Properties for Inkjet-Printed Thin-Film Transistors.

Semiconductor inks containing an indium-based oxo alkoxide precursor material were optimized regarding rheology requirements for a commercial 10 pL inkjet printhead. The rheological stability is evaluated by measuring the dynamic viscosity of the formulations for 12 h with a constant shear rate stress under ambient conditions. It is believed that the observed superior stability of the inks is the result of effectively suppressing the hydrolysis and condensation reaction between the metal oxo alkoxide precursor complex and atmospheric water. This can be attributed to a strong precursor coordination and the resulting reduction in ligand exchange dynamics of the solvent tetrahydrofurfuryl alcohol which is used as the main solvent in the formulations. It is also shown that with a proper selection of cosolvents, having high polar Hansen solubility parameter values, the inks drop formation properties and wettability can be fine-tuned by maintaining the inks rheological stability. Good drop jetting performance without satellite formation and high drop velocities of 8.25 m/s were found with the support of dimensionless numbers and printability windows. By printing single 10 pL ink dots onto short channel indium-tin-oxide electrodes, In2O3 calcination at 350 °C and a solution-processed back-channel protection, high average saturation mobility of approximately 10 cm2/(V s) are demonstrated in a bottom-contact coplanar thin-film transistor device structure.

Establishing the importance of oil-membrane interactions on the transmembrane diffusion of physicochemically diverse compounds

The diffusion process through a non-porous barrier membrane depends on the properties of the drug, vehicle and membrane. The aim of the current study was to investigate whether a series of oily vehicles might have the potential to interact to varying degrees with synthetic membranes and to determine whether any such interaction might affect the permeation of co-formulated permeants: methylparaben (MP); butylparaben (BP) or caffeine (CF). The oils (isopropyl myristate (IPM), isohexadecane (IHD), hexadecane (HD), oleic acid (OA) and liquid paraffin (LP)) and membranes (silicone, high density polyethylene and polyurethane) employed in the study were selected such that they displayed a range of different structural, and physicochemical properties. Diffusion studies showed that many of the vehicles were not inert and did interact with the membranes resulting in a modification of the permeants’ flux when corrected for membrane thickness (e.g. normalized flux of MP increased from 1.25±0.13μgcm−1h−1 in LP to 17.94±0.25μgcm−1h−1in IPM). The oils were sorbed differently to membranes (range of weight gain: 2.2±0.2% for polyurethane with LP to 105.6±1.1% for silicone with IHD). Membrane interaction was apparently dependent upon the physicochemical properties including; size, shape, flexibility and the Hansen solubility parameter values of both the membranes and oils. Sorbed oils resulted in modified permeant diffusion through the membranes. No simple correlation was found to exist between the Hansen solubility parameters of the oils or swelling of the membrane and the normalized fluxes of the three compounds investigated. More sophisticated modelling would appear to be required to delineate and quantify the key molecular parameters of membrane, permeant and vehicle compatibility and their interactions of relevance to membrane permeation.

Solubility of Oxygen in Organic Solvents and Calculation of the Hansen Solubility Parameters of Oxygen

The solubility of oxygen in 21 pure organic solvents was measured at 298.2 K and 101.33 kPa using the static method. The Hansen solubility parameters (HSPs) of oxygen were determined from the measured solubilities in the pure solvents. The HSPs of oxygen were δd = 6.7 MPa1/2, δp = 0.0 MPa1/2, and δh = 3.8 MPa1/2, where d, p, and h stand for dispersion forces, dipole interaction, and hydrogen bonding, respectively. A linear relationship between the log of the gas solubility (log xG) in pure solvents and the difference between the HSP values of oxygen and the pure solvents was obtained with a high correlation coefficient of 0.944. In addition, the solubilities of oxygen in mixed solvents were measured, and these were compared with the oxygen gas solubility calculated from the HSPs of oxygen.

Extraction of natural dye from Gardenia and chromaticity analysis according to chi parameter

Various methods of extracting natural dyes have been studied because of the increase of eco-friendly, non-toxic natural dyes. In this study, the natural dyes extraction process was optimized using Gardenia jasminoides Ellis containing crocin. Hansen solubility parameter values and chi parameter values (χ12) of various organic solvents and crocin were calculated, and the extracted pigments were analyzed by experiments. Comparing to calculated values and analyzed values, the relevancy was found and the solvents yielding color close to the target color were selected. Four kinds of solvents (methanol, ethanol, 1-propanol, and 2-propanol) having color close to the target color were selected because their χ12 values were small and their Hansen solubility parameter values were similar to the Hansen solubility parameter value of crocin. These selected solvents were each mixed with distilled water at various volume ratios, and the extraction process was conducted. The results showed that L,a,b values closest to the target color were obtained when using 40–60vol% of the solvents. Also, trends of χ12 values and the color difference (ΔE*) values were well matched up with UV absorbance.

Comparison of Hansen Solubility Parameter of Asphaltenes Extracted from Bitumen Produced in Different Geographical Regions

The Hansen solubility parameters (HSPs) of asphaltenes extracted from oil sand bitumen samples produced at Athabasca in Canada and also from a vacuum residue fraction (VR) produced in the Middle East were determined by the Hansen solubility sphere method. For calculation of HSPs, the solubilities of asphaltenes were determined using a dynamic light scattering (DLS) method by dissolving or dispersing the asphaltenes in various solvents and measuring the particle size distributions thereof. The particle diameters of asphaltenes in good solvents were lower than its detection limit (<1 nm). It was demonstrated in the present study that asphaltenes differing in elemental composition had different HSP values corresponding to dispersion, dipole interaction, and hydrogen-bonding forces (δd, δp, and δh, respectively). Experimental results suggested that the differences in HSP values of the asphaltenes were influenced by the H/C ratio, oxygen content, and average asphaltene molecular weight.

Rational formulation design

To be efficacious and to satisfy the requirements for claim substantiation, a cosmetic formulation must achieve effective targeting of an active in the skin. Although the basic principles governing the skin permeation and disposition of molecules have been known for many years, attention has been far less focused on the role of the vehicle, particularly at cosmetically relevant doses. In this article, we discuss the necessity to understand the fate of the formulation components as well as the active once applied onto skin. Recent data confirm that the residence time of the formulation constituents can have a profound impact on the fate of the active. Approaches to identify the ideal vehicle for skin delivery are considered critically, specifically the recent work on 'formulating for efficacy' (FFE) by the late Johann Wiechers. Essentially, FFE aims to match the active with the optimal vehicle for skin delivery based on matching polarity/solubility values of the trinity of skin, active and vehicle. The emerging importance of techniques that provide insight to how the vehicle distributes in and on skin is highlighted.

Molecular solubility and hansen solubility parameters for the analysis of phase separation in bulk heterojunctions

AbstractAlthough the fabrication procedures for bulk heterojunction (BHJ) solar cells are routinely optimized to accommodate new organic materials, the influence of solvent properties and cohesive forces on the film‐forming process and the self‐assembly of donor and acceptor molecules on the nanoscale are poorly understood. In this study, we measure the solubility of a variety of organic semiconductors in a range of solvents and calculate cohesive forces including dispersion forces, dipole interactions, and hydrogen bonding via Hansen Solubility Parameters (HSPs). HSPs were calculated by measuring the solubilities of various organic semiconductors in 27 solvents and the influence of solvent identity on film morphology of different BHJ mixtures was explored via atomic force microscopy (AFM). The possibility of correlations between HSPs and film morphology was considered; however, it is apparent that the HSP values alone do not play a critical role in determining the morphology of the films of conjugated polymers and molecules. This collection of solubility data constitutes the first of its type for organic semiconducting materials, and may act as a useful reference for the organic semiconductor community to aid in the understanding and selection of solvents for donor–acceptor BHJ mixtures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012

On the Applicability of the Regular Solution Theory to Asphaltene + Diluent Mixtures

The similarity of the Hildebrand or Hansen solubility parameter is frequently used in petroleum science as a measure of the compatibility of constituents and for interpreting and correlating properties of asphaltene + diluent mixtures. A partial specific volume at near infinite dilution and enthalpies of solution are sensitive measures of solute–solvent interactions derived from high precision density and calorimetry measurements for dilute mixtures. In this contribution, the partial specific volumes and enthalpies of solution of pyrene and various Athabasca and Maya asphaltenes at near infinite dilution on a mole fraction basis, in decane, toluene, 1-methylnaphthalene, quinoline, anisole, 2,6-lutidine, pyridine, methylene chloride, and tetrahydrofuran are reported over the temperature range of 20–80 °C. At 20 °C, these diluents possess solubility parameters ranging from 15 MPa0.5 (decane) to 22 MPa0.5 (quinoline). The properties of pyrene + diluent mixtures are used to illustrate the application and misapplication of the regular solution theory to such mixtures. Thermodynamic measurements, partial specific volume, and enthalpy of solution are shown to be independent of both Hildebrand and Hansen solubility parameter values. These results do not support the use of the solubility parameter or other simple solution thermodynamic concepts to describe asphaltene + diluent mixture behavior. The need for a more detailed description of physiochemical phenomena arising upon mixing asphaltenes with diluents is discussed.

Mapping and Multivariate Analysis for a Rapid Evaluation of New Green Solvents Characteristics and Efficiency

Current regulations require the substitution of toxic solvents by safer ones. Succinic acid diesters, which are among promising bio-based candidates, have been compared to petrochemical solvents through two complementary approaches. The first one deals with a prediction of solvents dissolution power based on Hansen Solubility Parameters (HSP). HSP values obtained with the model developed by Stefanis-Panayiotou showed good agreement with experimental miscibility maps. The second one explores the physicochemical properties with multivariate statistical methods. Principal Components Analysis and Agglomerative Hierarchical Clustering led to a partition of green solvents into clusters together with toxic solvents, suggesting favourable substitutions in further applications.

A new procedure for calculating Hansen solubility parameters of carbon nanotube/polymer composites

In this article, a new modeling and optimization procedure for Hansen solubility parameters (HSP) is developed. HSP values and the radius of interaction sphere for a solute can be determined by using this method based on experimental data at room temperature. The newly developed method could fit the experimental data better and get smaller radius of interaction sphere compared with the classical Hansen’s method. The HSP values of carbon nanotubes and polymer matrix are calculated to show the accuracy of the proposed approach. The physical affinity between the carbon nanotubes and polymer in the filler-polymer matrix system composite has been evaluated by their HSP spheres interaction.

Hollow fiber supported liquid membrane for extraction of ethylbenzene and nitrobenzene from aqueous solution: A Hansen Solubility Parameter approach

A hollow fiber supported liquid membrane (HFSLM) method was developed to extract organic pollutants (ethylbenzene and nitrobenzene) from aqueous solution, which provided a high selectivity and extraction efficiency. It was a two-phase system. The microporous hydrophobic polyethersulfone (PES) hollow fiber membrane which was made in our laboratory was used as the solid support for the liquid membrane. n-undecane, n-dodecane, n-heptanol and n-octanol were used as organic extractants which were located inside the pores and the lumens of the hollow fibers. The organic pollutants were extracted from aqueous phase into organic phase. A new approach of choosing the organic extractants which was based on Hansen Solubility Parameters (HSP) theory was proposed. The selectivity and extraction performance of organic extractants to ethylbenzene and nitrobenzene were successfully related to HSP values. The effect of different parameters such as operation temperature, flow rates of aqueous phase and organic phase, initial concentration of organic pollutants and pH value in aqueous phase was also studied.

Determination of Flory interaction parameters between polyimide and organic solvents by HSP theory and IGC

Flory-Huggins interaction parameter χ12 is an important parameter used for characterizing the interaction intensity between polymer and solvent. In this work, two methods were used to calculate the χ12 values of a polyimide (HQDPA-DMMDA) and twelve organic solvents. One method was inverse gas chromatography (IGC) technique, another was Hansen Solubility Parameters (HSP) theory. For the IGC experiment, χ12 was measured with an extrapolation method for the carrier gas when the temperature was changed from 50circC to 80°C. For the HSP approach, the Beerbower group contribution method was used to calculate the HSP values of the polyimide. It was found that the χ12 values of the polyimide and the organic solvents calculated from the two methods were similar. Consequently, the Beerbower group contribution method can be used to calculate HSP, and the HSP can be used to rapidly estimate the Flory–Huggins interaction parameter χ12.

New procedure for the determination of Hansen solubility parameters by means of inverse gas chromatography

The Hansen solubility parameter (HSP) seems to be a useful tool for the thermodynamic characterization of different materials. Unfortunately, estimation of the HSP values can cause some problems. In this work different procedures by using inverse gas chromatography have been presented for calculation of pharmaceutical excipients’ solubility parameter. The new procedure proposed, based on the Lindvig et al. methodology, where experimental data of Flory–Huggins interaction parameter are used, can be a reasonable alternative for the estimation of HSP values. The advantage of this method is that the values of Flory–Huggins interaction parameter χ for all test solutes are used for further calculation, thus diverse interactions between test solute and material are taken into consideration.

Calculation of Hansen Solubility Parameter Values for a Range of Pressure and Temperature Conditions, Including the Supercritical Fluid Region

Starting from the original definition of the cohesive energy density and the Hildebrand solubility parameter, an approach utilizing an equation of state of the form P = f(ρ,T) is used for calculating Hildebrand solubility parameters for a range of temperatures and pressures, including the supercritical fluid region. In addition, an approach is presented to determine Hansen solubility parameters over the same range of temperatures and pressures. The pure fluid used in these calculations is carbon dioxide (CO2). CO2 has been extensively studied, and its use as a supercritical fluid is well established in high-pressure chromatography and fluid extraction applications.