Correlation and estimation of gas–chloroform and water–chloroform partition coefficients by a linear free energy relationship method

Abraham, Michael H.; Platts, James Alexis; Hersey, Anne; Leo, Albert J.; Taft, Robert W.

doi:10.1021/js990008a

Cited by 101 publications

(78 citation statements)

References 55 publications

(67 reference statements)

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“…1b). This choice of small molecules was taken from the Minnesota solvation database40 and Abraham et al, 1999 41. Although the Minnesota solvation database contains in excess of 3000 data points, our dataset for this study was limited to molecules for which (a) experimental solvation free energies were available in multiple organic solvents, and (b) these multiple organic solvents had parameters available in the amoeba09 or chloroalkane AMOEBA force fields 39, 42.…”

Section: Methodsmentioning

confidence: 99%

Evaluation of solvation free energies for small molecules with the AMOEBA polarizable force field

2016

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The effects of electronic polarization in biomolecular interactions will differ depending on the local dielectric constant of the environment, such as in solvent, DNA, proteins, and membranes. Here the performance of the AMOEBA polarizable force field is evaluated under nonaqueous conditions by calculating the solvation free energies of small molecules in four common organic solvents. Results are compared with experimental data and equivalent simulations performed with the GAFF pairwise‐additive force field. Although AMOEBA results give mean errors close to “chemical accuracy,” GAFF performs surprisingly well, with statistically significantly more accurate results than AMOEBA in some solvents. However, for both models, free energies calculated in chloroform show worst agreement to experiment and individual solutes are consistently poor performers, suggesting non‐potential‐specific errors also contribute to inaccuracy. Scope for the improvement of both potentials remains limited by the lack of high quality experimental data across multiple solvents, particularly those of high dielectric constant. © 2016 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.

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Section: Methodsmentioning

confidence: 99%

Evaluation of solvation free energies for small molecules with the AMOEBA polarizable force field

2016

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“…The solvation parameter model of Abraham [4][5][6][7][8][9][10][11] is one of the most useful approaches for the analysis and prediction of partition and sorption coefficients. The basic model relies on two linear free energy relationships, one for solute transfer between two condensed phases SP = c + e·E + s·S + a·A + b·B + v·V (1) and one for processes involving gas to condensed phase transfer SP = c + e·E + s·S + a·A + b·B + l·L (2) The dependent variable, SP, is some property of a series of solutes in a fixed phase.…”

Section: Solid-phase Microextraction (Spme) Is a Versatile Analyticalmentioning

confidence: 99%

Characterization of the sorption of gaseous and organic solutes onto polydimethyl siloxane solid-phase microextraction surfaces using the Abraham model

Sprunger

Proctor

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et al. 2007

Journal of Chromatography A

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106

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Water-to-polydimethylsiloxane (PDMS) and gas-to-PDMS sorption coefficients have been compiled for 170 gaseous and organic solutes. Both sets of sorption coefficients were analyzed using the Abraham solvation parameter model. Correlations were obtained for both "dry" headspace solid-phase microextraction and conventional "wet" PDMS coated surfaces. The derived equations correlated the experimental water-to-PDMS and gas-to-PDMS data to better than 0.17 and 0.18 log units, respectively. In the case of the gas-to-PDMS sorption coefficients, the experimental values spanned a range of approximately 11 log units.

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“…The Abraham general solvation model is based upon two particular linear free-energy relationships for describing the partition of solutes between water and a given solvent (1)(2)(3)(4)(5)(6)(7)(8) log…”

Section: Resultsmentioning

confidence: 99%

“…P o vap can be transformed into the gas-phase concentration, C G , and the gas-water and gas-solvent partitions, L W and L S , can be obtained through Eqs. (4,5), respectively…”

Section: Resultsmentioning

confidence: 99%

“…As additional experimental data became available, researchers expanded their studies to include more organic solvents, as well as aqueous micellar solvent media. In this regard, Abraham and co-workers (1)(2)(3)(4)(5)(6)(7)(8) developed expressions for describing the partition of solutes between water and an organic solvent and between the gas phase and a given solvent. To date, mathematical expressions have been deduced for approximately 40 dry solvents.…”

Section: Introductionmentioning

confidence: 99%

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Acree

Abraham

2002

Journal of Solution Chemistry

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The Abraham general solvation model is used to calculate the numerical values of the solute descriptors for benzil from experimental solubilities in organic solvents. The mathematical correlations take the formwhere C S and C W refer to the solute solubility in the organic solvent and water, respectively, C G is a gas-phase concentration, R 2 is the solute excess molar refraction, V x is the McGowan volume of the solute, fi H 2 and fl H 2 are measures of the solute hydrogenbond acidity and basicity, … H 2 denotes the solute dipolarity/polarizability descriptor, and L [16] is the solute gas-phase dimensionless Ostwald partition coefficient into hexadecane at 25 • C. The remaining symbols in the above expressions are known solvent coefficients, which have been determined previously for a large number of gas/solvent and water/solvent systems. We estimate R 2 as 14.45 cm 3 -mol −1 and calculate V x as 163.74 cm 3 -mol −1 , and then solve a total of 51 equations to yield … H 2 = 1.59, fl H 2 = 0.620 and log L [16] = 7.6112. These descriptors reproduce the 51 observed log(C S /C W ) and log(C S /C G ) values with a standard deviation of only 0.115 log units.

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Correlation and estimation of gas–chloroform and water–chloroform partition coefficients by a linear free energy relationship method

Cited by 101 publications

References 55 publications

Evaluation of solvation free energies for small molecules with the AMOEBA polarizable force field

Evaluation of solvation free energies for small molecules with the AMOEBA polarizable force field

Characterization of the sorption of gaseous and organic solutes onto polydimethyl siloxane solid-phase microextraction surfaces using the Abraham model

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