Abraham Solvation Parameter Model Research Articles

Application of Abraham's solvation parameter model to extractables and leachables studies in pharmaceutical and medical device industries: A tutorial

The Abraham's solvation parameter model is an important tool to model and predict distribution properties of compounds in numerous partitioning systems in chemistry, environmental chemistry, medicine, and biology. The evaluation of the distribution properties in extractables and leachables (E&L) studies in pharmaceutical and medical device industries is another major application of this model. This tutorial is aimed at illustrating the applications of the model in E&L studies. Specific examples of the application illustrated in this tutorial include: (a) establishment of equivalent or similar solvents; (b) determination of polarity of solvents, biological tissues, and materials; (c) development of drug product simulating solvents; (d) understanding solvent extraction power for a material; (e) selection of solvent and standards in pretreatment of extraction samples; and (f) chromatography retention prediction for E&L.

Determination of experimental solute descriptor values for methyl 3-nitrobenzoate by liquid–liquid partitioning and gas chromatography

ABSTRACT In this study, methyl 3-nitrobenzoate, a popular compound used to protect crops and in the textile industry, was studied using liquid–liquid partitioning and gas chromatography and the Abraham solvation parameter descriptor values were determined for potential applications in QSPR. The solver algorithm in Excel was used to determine the descriptor values for methyl 3-nitrobenzoate, resulting in E = 1.0616, S = 1.4170, A = 0.00, L = 6.1354, B = 0.6198, and V = 1.2468 with a standard deviation of 0.076. In the situations when toxicity and exposure assessment data are scarce, the application of QSPR models, such as the Abraham solvation parameter model, can aid in the estimation of the environmental impact of chemicals. With the objective to facilitate physicochemical property estimations of methyl 3-nitrobenzoate widely used in the textile and agricultural industries, this study offers experimental solute descriptor values of the Abrham’s solvation parameter model.

Comments on “Solid-liquid equilibrium solubility prediction of sulfanilamide in four binary solvent mixtures by using pure solvents solubility data from 278.15 to 318.15 K with the Abraham solvation parameter model, Yalkowsky Log-Linear and extended log-linear solubility thermodynamic models”

The experimental solubility data of sulfanilamide in binary solvent mixtures at temperature ranging from (278.15 to 318.15) K have carefully been reanalyzed and some additional recommendations were discussed.

Characterization of solute-solvent interactions in liquid chromatography systems: A fast method based on Abraham's linear solvation energy relationships

The Abraham's solvation parameter model, based on linear solvation energy relationships (LSER), allows the accurate characterization of the selectivity of chromatographic systems according to solute-solvent interactions (polarizability, dipolarity, hydrogen bonding, and cavity formation). However, this method, based on multilinear regression analysis, requires the measurement of the retention factors of a considerably high number of compounds, turning it into a time-consuming low throughput method. Simpler methods such as Tanaka's scheme are preferred. In the present work, the Abraham's model is revisited to develop a fast and reliable method, similar to the one proposed by Tanaka, for the characterization of columns employed in reversed-phase liquid chromatography and particularly in hydrophilic interaction liquid chromatography. For this purpose, pairs of compounds are carefully selected in order to have in common all molecular descriptors except for a specific one (for instance, similar molecular volume, dipolarity, polarizability, and hydrogen bonding basicity features, but different hydrogen bonding acidity). Thus, the selectivity factor of a single pair of test compounds can provide information regarding the extent of the dissimilar solute-solvent interactions and their influence on chromatographic retention. The proposed characterization method includes the determination of the column hold-up volume and Abraham's cavity term by means of the injection of four alkyl ketone homologues. Therefore, five chromatographic runs in a reversed-phase column (four pairs of test solutes and a mixture of four homologues) are enough to characterize the selectivity of a chromatographic system. Tanaka's method is also analyzed from the LSER point of view.

Evaluation of the Ability of PAMPA Membranes to Emulate Biological Processes through the Abraham Solvation Parameter Model.

Two parallel artificial membrane permeability assay (PAMPA) systems intended for emulating skin permeability have been characterized through the solvation parameter model of Abraham using multilinear regression analysis. The coefficients of the obtained equations have been compared to the ones already established for other PAMPA membranes using statistical tools. The results indicate that both skin membranes are similar to each other in their physicochemical properties. However, they are different from other PAMPA membranes (e.g., intestinal absorption and blood-brain PAMPAs), mainly in terms of hydrophobicity and hydrogen bonding properties. Next, all PAMPA membranes have been compared to relevant biological processes also characterized through the solvation parameter model. The results highlight that skin-PAMPA membranes are a very good choice to emulate skin permeability.

Correlation of Extractables Transfer from Low-Density Polyethylene into Extraction Solvents with Abraham Solvation Parameter Model and Assessment of Thermodynamic and Kinetic Effects in Achieving Exhaustive Extractions in Chemical Characterization of Medical Devices

Correlation of Extractables Transfer from Low-Density Polyethylene into Extraction Solvents with Abraham Solvation Parameter Model and Assessment of Thermodynamic and Kinetic Effects in Achieving Exhaustive Extractions in Chemical Characterization of Medical Devices

Insights into the Solvation Characteristics of Zwitterionic Deep Eutectic Solvents Using Multiple Polarity Scales

Deep eutectic solvents (DESs) formed by mixing zwitterionic hydrogen bond acceptors (HBAs) with diol- and organic acid-based hydrogen bond donors (HBDs) are popular sustainable solvents. In addition to possessing an amphiphilic character, zwitterionic DESs offer unique solvation properties, unlike those composed of halide-containing HBAs. While all other popular classes of DESs have been investigated, no study has attempted to characterize the solvation characteristics of zwitterionic DESs. In this study, the solvation properties of betaine [Bet]-, sulfobetaine-, and l-carnitine [l-Car]-based DESs were thoroughly investigated for the first time using solvatochromic dye methods and inverse gas chromatography (IGC). The Nile red polarity scale revealed that DESs composed of organic acids were generally more polar than diol-based DESs. Kamlet–Taft solvent parameters revealed that glycerol-based DESs offered exceptionally high hydrogen bond donating ability compared to those composed of 1,4-butane diol and triethylene glycol. The Abraham solvation parameter model revealed hydrogen bond basicity to be the most dominant interaction, and it was generally higher for diol-based HBDs compared to organic acid-based HBDs. Additionally, sulfobetaine HBAs possessing longer alkyl chains generally offered higher dispersive-type interactions and hydrogen bond basicity compared to [Bet] and [l-Car] salts. This is the first study to combine and compare results from solvatochromic dye methods and IGC in an attempt to comprehensively explain and predict the solvation characteristics of zwitterionic DESs.

Abraham Solvation Parameter Model: Revised Predictive Expressions for Solute Transfer into Polydimethylsiloxane Based on Much Larger and Chemically Diverse Datasets

Updated Abraham model correlations are reported for the transfer of organic solutes and inorganic gases to a polydimethylsiloxane coating from both water and the gas phase based on published experimental data for more than 220 different compounds. The derived mathematical expressions back-calculate the observed partitioning behavior to within standard deviations of the residuals of 0.206 and 0.176 log units, respectively.

Linear Free-Energy Relationships and Solvation Thermodynamics: The Thermodynamic Basis of LFER Linearity

The Abraham solvation parameter model, known alternatively as the Linear Solvation Energy Relationships (LSER) model, is widely used in numerous applications in the broader chemical, biochemical, and environmental sector with remarkable success. So far, there is no explanation at the fundamental thermodynamic level for the very linearity of this model. This is, however, essential for the evaluation and exchange of thermodynamic quantities between models and databases. The present work offers such an explanation by combining the equation-of-state solvation thermodynamics with the statistical thermodynamics of hydrogen bonding. It shows what this linearity entails and in what way it is interpreted and handled so far. In addition, it proposes new ways of extending it for estimations over a broad range of external conditions and, eventually, in predicting solvent LFER coefficients from the corresponding molecular descriptors, which are known for thousands of compounds. This would enhance significantly the predictive capacity of the model in practical applications, such as solvent screening, solute partitioning, activity coefficients at infinite dilution, or hydration/solvation energies. Various examples of calculations are reported. A critical discussion of perspectives and challenging emerging issues are also presented.

Linear Solvation–Energy Relationships (LSER) and Equation-of-State Thermodynamics: On the Extraction of Thermodynamic Information from the LSER Database

There is a remarkable wealth of thermodynamic information in freely accessible databases, the LSER database being a classical example. The LSER, or Abraham solvation parameter model, is a very successful predictive tool in a variety of applications in the (bio)chemical and environmental sector. The model and the associated database are very rich in thermodynamic information and information on intermolecular interactions, which, if extracted properly, would be particularly useful in various thermodynamic developments for further applications. Partial Solvation Parameters (PSP), based on equation-of-state thermodynamics, are designed as a versatile tool that would facilitate this extraction of information. The present work explores the possibilities of such an LSER–PSP interconnection and the challenging issues this effort is faced with. The thermodynamic basis of the very linearity of the LSER model is examined, especially, with respect to the contribution of strong specific interactions in the solute/solvent system. This is done by combining the equation-of-state solvation thermodynamics with the statistical thermodynamics of hydrogen bonding. It is verified that there is, indeed, a thermodynamic basis of the LFER linearity. Besides the provenance of the sought linearity, an insight is gained on the thermodynamic character and content of coefficients and terms of the LSER linearity equations. The perspectives from this insight for the further development of LSER and related databases are discussed. The thermodynamic LSER–PSP interconnection is examined as a model for the exchange in information between QSPR-type databases and equation-of-state developments and the associated challenges are examined with representative calculations.

Exploring three-dimensional space of extractables and leachables in volatility, hydrophobicity, and molecular weight and assessment of roles of gas and liquid chromatographic methods in their comprehensive analysis

The three-dimensional (3D) global space of organic extractables and leachables (E&L) in volatility, hydrophobicity, and molecular weight (MW), covering the pharmaceutical container-closure system, biopharmaceutical single use equipment, and tissue-contacting medical devices, has been quantitatively explored by an extensive collection of E&L compounds from the publicly available sources. The total number of compounds collected is 776, including name, CAS number, MW, and boiling point (BP). The hydrophobicity of these compounds in logPo/w are computed by Abraham solvation parameter model, using compounds’ descriptors generated by an online computational program “RMG: Solvation Tools”. A “global” 3D space is built to represent the physicochemical property limits of E&L quantitatively, envisioned to cover a variety of materials extracted by different solvents. This 3D space also represents the scope and capability requirements of general-purpose chromatography-based methods to profile unknown material samples, if a limited number of analytical methods are used in a routine laboratory analysis. It is concluded from the study that the 3D space corresponding to MW of 1000 Da are: BP up to 857 °C and hydrophobicity in logPo/w between − 2.3–19. Additionally, the roles of temperature programmed GC (TPGC) and reversed-phase liquid chromatographic (RPLC) methods are quantitively and critically examined in the comprehensive analysis of the 3D space, particularly for RPLC methods in retention and resolution requirements, and it is also concluded that the current concept of analytical E&L testing strategies based on volatility needs to be challenged. Finally, this study proposes a semi-empirical method in correlation and prediction of the retention time of TPGC using Abraham solvation parameter model.

Solid-liquid equilibrium solubility prediction of sulfanilamide in four binary solvent mixtures by using pure solvents solubility data from 278.15 to 318.15 K with the Abraham solvation parameter model, Yalkowsky Log-Linear and extended log-linear solubility thermodynamic models

The industrial application of sulfanilamide solubility in binary solvent mixtures is a critical factor in drug development, assessment, as well as future improvement. The current work eliminates the substantial experimental work, as well as the ability to apply improved and upgraded computed models that include solute physicochemical properties and activity coefficients. The predicted solid–liquid equilibrium data of sulfanilamide in acetone containing binary solvent mixtures at temperatures ranging from 278.15 to 318.15 K were calculated by applying the combined version of Jouyban-Acree model with Abraham solute parameter model, combined version of Jouyban-Acree model with Abraham solvation parameter model, combined version of Jouyban-Acree model with Hansen solubility parameter model, the Yalkowsky Log-Linear model, Extended log-linear model. In comparison to previously published binary solvent solubility data, this paper provides predicted binary solubility data using only mono-solvent solubility data as well as from the computed models. From the solubility trained model the %ARD can be ranked as the combined version of combined version of the Jouyban-Acree model with Abraham Solute parameter model (19.47 %) < the Jouyban-Acree model with Hansen solubility parameter model (23.76 %) < the Yalkowsky model (50.54 %) < the combined version of Jouyban-Acree model with Abraham solvation parameter model (68.83 %) < the Extended log-linear model (615.78 %). The combined version of Jouyban-Acree model with Abraham Solute parameter model giving most reliable predicted solubility results compared to other computed models. The most important outcome of this research will be immensely beneficial in calculating binary solubility data utilizing only mono-solvent solubility data as well as from computed models. The binary solubility predictions were calculated from already reported mono-solvent solubility data from experimentally determined, Hildebrand-Scatchard equation-1 and Hildebrand-Scatchard equation-2.

Abraham Solvation Parameter Model: Calculation of L Solute Descriptors for Large C11 to C42 Methylated Alkanes from Measured Gas–Liquid Chromatographic Retention Data

Abraham model L solute descriptors have been determined for 149 additional C11 to C42 monomethylated and polymethylated alkanes based on published Kovat’s retention indices based upon gas–liquid chromatographic measurements. The calculated solute descriptors, in combination with previously published Abraham model correlations, can be used to predict a number of very important chemical and thermodynamic properties including partition coefficients, molar solubility ratios, gas–liquid chromatographic and HPLC retention data, infinite dilution activity coefficients, molar enthalpies of solvation, standard molar vaporization and sublimation at 298 K, vapor pressures, and limiting diffusion coefficients. The predictive computations are illustrated by estimating both the standard molar enthalpies of sublimation and the enthalpies of solvation in benzene for the monomethylated and polymethylated alkanes considered in the current study.

Calculation of Relative Solubility of Semipolar Solvents by Abraham Solvation Parameter Model for Extractables and Leachables Analysis in Chemical Characterization of Medical Devices

Calculation of Relative Solubility of Semipolar Solvents by Abraham Solvation Parameter Model for Extractables and Leachables Analysis in Chemical Characterization of Medical Devices

Development of Predictive Expressions for Infinite Dilution Activity Coefficients, Molar Solubilities and Partition Coefficients for Solutes Dissolved in 2-Pyrrolidone Based on the Abraham Solvation Parameter Model

Development of Predictive Expressions for Infinite Dilution Activity Coefficients, Molar Solubilities and Partition Coefficients for Solutes Dissolved in 2-Pyrrolidone Based on the Abraham Solvation Parameter Model

Abraham solvation parameter model: updated correlations for describing solute partitioning into plant cuticles from water and from air

ABSTRACT Abraham model correlations are reported for describing the logarithms of water-to-plant cuticle partition coefficients and logarithms of air-to-plant partition coefficients based on experimental values retrieved from the published chemical and environmental literature for 24 different plant species. Data sets containing more than 200 experimental partition coefficients were used in determining each correlation equation. The derived correlations back-calculated the experimental data to within a standard deviation of 0.23 log units.

Abraham Solvation Parameter Model: Prediction of Enthalpies of Vaporization and Sublimation of Mono-methyl Branched Alkanes Using Measured Gas Chromatographic Data

Abraham model L solute descriptors have been determined for 174 additional mono-methyl branched alkanes based on published linear-programmed gas chromatographic retention indices. Standard molar enthalpies of vaporization and sublimation at 298 K are calculated for the 174 mono-methylated alkanes using the reported solute descriptors and our recently published Abraham model correlations. Calculated vaporization and sublimation enthalpies derived from the Abraham model compare very favorable with values based on a popular atom-group additivity model. Unlike the additivity model the Abraham model gives different predicted values for each mono-methyl alkane having a given C n H 2n+2 molecular formula

Hesperetin Solubility in Aqueous Co-solvent Mixtures of Methanol and Ethanol: Solute Descriptors, Solvent Effect and Preferential Solvation Analysis

Solubility data for hesperetin in pure solvents and alcohol-rich regions of aqueous mixtures of methanol and ethanol were used to derive the solute descriptors for solubility prediction of hesperetin by using the Abraham solvation parameter model. Solubility data in aqueous mixtures of methanol and ethanol were analyzed by the linear solvation energy relationships approach to provide detailed insight into the solvent effect. In this regard, energy terms for solute–solvent and solvent–solvent interactions were defined in terms of dipolarity–polarizability, hydrogen bond basicity, hydrogen bond acidity and Hildebrand solvent parameter. Results indicate that the main contribution was from solvent–solvent interactions represented by the cavity term. Preferential solvation analysis was performed with the help of inverse Kirkwood–Buff integrals approach. Local composition and preferential solvation parameter were calculated as a function of mole fraction of methanol and ethanol. Results show that hesperetin is preferentially surrounded by water in water-rich regions, whereas methanol or ethanol are preferred in other compositions. This observation was discussed in terms of the solute hydrophobic hydration and specific hydrogen bonding interactions.

Thermodynamic analysis and applications of the Abraham solvation parameter model in the study of the solubility of some sulfonamides

Se investigó la solubilidad de sulfadiazina (SD), sulfamerazina (SMR) y sulfametazina (SMT) en mezclas codisolventes de octanol + metanol a 278,15 K, 298,15 y 313,15 K. En todos los casos, la solubilidad más baja de cada fármaco se obtuvo en octanol puro a 278,15 K. La solubilidad máxima depende de la polaridad del fármaco, por lo que SMR y SMT alcanzaron su máxima solubilidad en mezclas cosolventes ricas en metanol. Las funciones termodinámicas de solución se calcularon a partir de los datos experimentales de solubilidad, utilizando las ecuaciones de van’t Hoff y Gibbs, siguiendo el enfoque propuesto por Krug et al. La entalpía de la solución es positiva en todos los casos, lo cual es una indicación del proceso endotérmico con un marcado favorecimiento entrópico. La solubilidad teórica y la concentración letal media se calcularon utilizando el modelo de Abraham.

DCA]-based ionic liquids for the extraction of sulfur and nitrogen compounds from fuels: Activity coefficients at infinite dilution

Some petroleum processes need the removal of low level aromatic-sulfur and nitrogen compounds for many products, which are extremely important according to the new strict environmental regulations to reduce sulfur and nitrogen content compounds in liquid fuels. Thus the new, alternative solvents such as ionic liquids (ILs) have been proposed. ILs reveal a high selectivity and capacity of extraction of sulfur- and nitrogen-compounds from alkanes with little solvent loss during the process. The measurements of activity coefficients γ13∞ at infinite dilution of different solutes in the IL shows the effect of interactions between organic solutes, or water on the interfacial and bulk properties of the IL. The new (3-cyanopropyl)pyridinium dicyanamide, [N–C3CNPy][DCA] and (3-cyanopropyl)methylpyrrolidinium dicyanamide, [N–C3CNMPyr][DCA] were investigated in this work. The data were obtained using the gas-liquid chromatography technique. Measurements were undertaken at six temperatures, in 10 K intervals, in the range of (318.15–368.15) K. The solutes studied included both non-polar and polar compounds, as alkanes, alkenes, alkynes, as well as aromatic hydrocarbons, alcohols, water, ethers, ketones, and esters. The most important solutes used were thiophene, pyridine, and 1-nitropropane. Densities, ρ, measurements for a range of temperatures, T (298.15–368.15) K for the chosen ILs were undertaken at pressure, p = 101 kPa. The gas-liquid partition coefficients, KL at infinite dilution were calculated. The fundamental thermodynamic functions such as partial molar excess Gibbs energy, enthalpy and entropy at infinite dilution were calculated from the experimental data measurements to discuss the interaction between solutes and the ILs. The values of selectivity and capacity for three separation cases, viz. heptane/thiophene, heptane/pyridine, and heptane/1-nitropropane were calculated from γ13∞ values and compared to literature data for dicyanamide-based ILs. The Abraham solvation parameter model was presented for all solutes. The obtained results indicated that [N–C3CNPy][DCA] has large selectivity and capacity values for all three of the separation cases studied.