Partition Coefficient

Although weakly hydrophobic chemicals such as volatile organic compounds (VOCs) tend not to persist in sediments, they may nevertheless be present in some sediments because of recent or ongoing releases. Standard methods are not available for assessing risks to benthic invertebrates due to VOCs in sediment. More strongly hydrophobic organic chemicals are frequently assessed by using the equilibrium partitioning (EqP) approach, which predicts the bioavailable fraction of chemical (the concentration dissolved in pore water) from the sediment-sorbed fraction, assuming that partitioning is at equilibrium. As typically applied, the EqP approach is ineffective for assessing VOCs in sediment, because the standard EqP equation fails to account for the contribution of dissolved chemical to the total chemical concentration in sediment. For chemicals with low organic carbon-water partition coefficients (KOCs), this results in nonsensical sediment-quality benchmarks that are more conservative (i.e., lower) than benchmarks calculated by assuming 100% bioavailability. A modified EqP equation is presented that accounts for the dissolved fraction of total chemical concentrations in sediment. Results of the standard and modified EqP equations converge with increasing KOC and are essentially identical at log KOC values exceeding approximately 3.5.

The chromatographic capacity factors (k') of 10 beta-adrenoceptor antagonists ("beta-blockers") were measured on three different immobilized artificial membrane-phosphatidylcholine (IAM-PC) HPLC stationary phases, namely IAM-PC-MG, IAM-PC-DD2, and IAM-PC-DD. The two former phases are made of phosphatidylcholine as found in biomembranes and differ each other in end-capping of free propylamino residues whereas the latter is made of single-chain phosphatidylcholine analogues. On IAM-PC-DD2 we found that structurally unrelated neutral compounds give a single correlation between logk' values and the respective octanol/water partition coefficients (logP), as previously observed on IAM-PC-MG phase. This was not observed on the IAM-PC-DD phase. IAM chromatography was performed at a pH of the aqueous eluent (7.0) close to the physiological pH 7.4. Retention on all IAM phases showed a biphasic pattern, being proportional to logP(N) (lipophilicity of neutral forms) for more l...

A homologous series of new gemini cationic surfactants were synthesized and characterized using micro elemental analysis, FTIR, 1H-NMR and mass spectra. The surface activities of these amphiphiles were determined based on the data of surface tension. Critical micelle concentration, effectiveness of the surface tension reduction, efficiency of adsorption, maximum surface excess, minimum surface area and critical packing parameter were evaluated. The effect of cationic micelles on solubilization of anionic azo dye, sulforhodamine B (Acid Red 52) in aqueous micellar solution of the synthesized gemini cationic surfactants was studied at pH 6.9 ± 0.5 and 25 °C. The results showed that the solubility of dye rose with increasing surfactant concentration as a consequence of some association between the dye and the micelles. It was also observed that the aggregation of surfactant and dye takes place at a surfactant concentration below the CMC of the individual surfactant. The partition coefficients between the bulk water and surfactant micelles as well as the Gibbs energies of distribution of dye between the bulk water and surfactant micelles were calculated using a pseudo-phase model. The effect of the hydrophobic chain length of Gemini cationic surfactants on the distribution parameters was also reported. The results show favorable solubilization of dye in cationic micelles.

Lipophilicity plays a significant role as a determinant of biological properties. Reversed-phase high-performance thin layer chromatography (HP-TLC) was applied to determine the log P values of chelidonine, allocryptopine, sanguinarine chloride and chelerythrine chloride at three different pH values: 3.0, 7.4 and 10.0. The mobile phase was a mixture of acetonitrile and water with different concentrations of acetonitrile (50-75 vol%). The retention factors, R m0 values, for the compounds with known log P and for the analyzed substances were determined. The log P values obtained experimentally were compared with the theoretical data obtained by using known algorithms (miLogP, xLogP, and AlogPs). Additionally, log D values of the examined substances were determined. The highest log P value was observed for chelerythrine chloride in an alkaline environment, while the lowest one was noted for chelidonine at acidic pH.

Utilization of ferric chelate complex of trans-1,2-cyclohexanediaminetetraacetic acid (CDTA) for the oxidative scrubbing of H2S and CH3SH in Kraft mill streams can be beneficial from the standpoints of iron protection against precipitation and oxygen-mediated regenerative oxidation of the ferrous chelate CDTA. The physical solubility of methyl mercaptan in CDTA–Fe(III) complex cannot be measured directly because of oxidation of the sulfur-bearing

This work aims to evaluate the feasibility of using imidazolium ionic liquids (ILs) in the design of multiphase bioreactors for the removal of volatile organic compounds (VOCs). The IL affinity for three model VOCs (dimethyl sulfide, dimethyl disulfide and toluene) was evaluated by ...

For several decades, there has been interest in using the skin as a port of entry into the body for the systemic delivery of therapeutic agents. However, the upper layer of the skin, the stratum corneum, poses a barrier to the entry of many therapeutic entities. Given a compound, passive delivery rate is often dependent on two major physicochemical properties: the partition coefficient and solubility. The use of chemical enhancers and modifications of the thermodynamic activity of the applied drug are two frequently employed strategies to improve transdermal permeation. Chemical enhancers are known to enhance drug permeation by several mechanisms which include disrupting the organized intercellular lipid structure of the stratum corneum [1], ‘fluidizing’ the stratum corneum lipids [2], altering cellular proteins, and in some cases, extracting intercellular lipids [3]. However, the resulting increase in drug permeation using these techniques is rather modest especially for hydrophilic drugs. A number of other physical approaches such as iontophoresis, sonophoresis, ultrasound and the use of microneedles are now being studied to improve permeation of hydrophilic as well as lipophilic drugs. This article presents an overview of the use of iontophoresis alone and in conjunction with other approaches such as chemical enhancement, electroporation, sonophoresis, and use of microneedles and ion-exchange materials.

A review is presented of the physical-chemical properties and reactivity of the phthalate esters including a discussion of how these properties control their partitioning and fate in the environment. The air and water solubilities decrease by orders of magnitude from the short alkyl chain phthalates such as dimethyl phthalate (DMP) to the long alkyl chain phthalates such as di-2-ethylhexyl phthalate

Solvents have been parameterized by scales of dipolarity/polarizability π*, hydrogen-bond donor (HBD) strength α, and hydrogen-bond acceptor strength β. Linear dependence (LSER's) on these solvent parameters are used to correlate and predict a wide variety of solvent effects, as well as to provide an analysis in terms of knowledge and theoretical concepts of molecular structural effects. Some recent applications utilizing this approach are presented. Included are analyses of solvent effects on (a) the free energies of transfer of tetraalkylammonium halide ion pairs and dissociated ions, (b) rates of nucleophilic substitution reactions, (c) the contrast in solvent effects of water (HBD) and dimethyl sulfoxide (non-HBD) on the acidities of m- and p-substituted phenols, (d) partition coefficients of non-HBD solutes between solvent bilayers, and (e) family relationships between proton transfer (and non-protonic Lewis acid) basicities and corresponding β values for monomer HBA. A comprehensive summary of LSER with references is given.