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Partition Coefficient (partition + coefficient)
Kinds of Partition Coefficient Selected AbstractsPrediction of the Solubility, Activity Coefficient and Liquid/Liquid Partition Coefficient of Organic CompoundsMOLECULAR INFORMATICS, Issue 9 2004H. Hilal Abstract Solvation models, based on fundamental chemical structure theory, were developed in the SPARC mechanistic tool box to predict a large array of physical properties of organic compounds in water and in non-aqueous solvents strictly from molecular structure. The SPARC self-interaction solvation models that describe the intermolecular interaction between like molecules (solute-solute or solvent-solvent) were extended to quantify solute-solvent interaction energy in order to estimate the activity coefficient in almost any solvent. Solvation models that include dispersion, induction, dipole-dipole and hydrogen bonding interactions are used to describe the intermolecular interaction upon placing an organic solute molecule in any single or mixed solvent system. In addition to estimation of the activity coefficient for 2674 organic compounds, these solvation models were validated on solubility and liquid/liquid distribution coefficient in more than 163 solvents including water. The RMS deviations of the calculated versus observed activity coefficients, solubilities and liquid/liquid distribution coefficients were 0.272,log mole fraction, 0.487,log mole fraction and 0.44,log units, respectively. [source] Solvatochromic Analysis of Partition Coefficients in the o -Nitrophenyl Octyl Ether (o -NPOE)/Water SystemHELVETICA CHIMICA ACTA, Issue 11 2003Xiangli Liu The objective of this study was to unravel the structural properties responsible for the partitioning of solutes in o -nitrophenyl octyl ether (o -NPOE)/H2O, a new solvent system for the determination of the partition coefficients of ions. A set of 88 compounds (including drugs) was selected to allow a regular and broad distribution of property spaces. Partition coefficients in o -NPOE/H2O (log,Pnpoe) were measured by the shake-flask or the potentiometric method. Linear solvation free-energy relationship (LSER) analyses showed that Van der Waals volume, H-bond-acceptor basicity, and H-bond-donor acidity are the three molecular descriptors of solutes determining their log,Pnpoe values. The partitioning mechanism of the investigated compounds in o -NPOE/H2O is controlled by the same structural properties as it is in 1,2-dichloroethane (DCE)/H2O. ,log,Poct,npoe Values (difference between log,Poct and log,Pnpoe) express mainly dipolarity/polarizability and H-bond-donor acidity. The solvent o -NPOE is shown to be a good candidate to replace DCE in measurements of lipophilicity. [source] Electronic Speckle Pattern Interferometry: A Tool for Determining Diffusion and Partition Coefficients for Proteins in GelsBIOTECHNOLOGY PROGRESS, Issue 6 2002David Karlsson The aim of this study was to demonstrate electronic speckle pattern interferometry (ESPI) as a powerful tool in determining diffusion coefficients and partition coefficients for proteins in gels. ESPI employs a CCD camera instead of a holographic plate as in conventional holographic interferometry. This gives the advantage of being able to choose the reference state freely. If a hologram at the reference state is taken and compared to a hologram during the diffusion process, an interferometric picture can be generated that describes the refraction index gradients and thus the concentration gradients in the gel as well as in the liquid. MATLAB is then used to fit Fick's law to the experimental data to obtain the diffusion coefficients in gel and liquid. The partition coefficient is obtained from the same experiment from the flux condition at the interface between gel and liquid. This makes the comparison between the different diffusants more reliable than when the measurements are performed in separate experiments. The diffusion and partitioning coefficients of lysozyme, BSA, and IgG in 4% agarose gel at pH 5.6 and in 0.1 M NaCl have been determined. In the gel the diffusion coefficients were 11.2 ± 1.6, 4.8 ± 0.6, and 3.0 ± 0.3 m2/s for lysozyme, BSA, and IgG, respectively. The partition coefficients were determined to be 0.65 ± 0.04, 0.44 ± 0.06, and 0.51 ± 0.04 for lysozyme, BSA, and IgG, respectively. The current study shows that ESPI is easy to use and gives diffusion coefficients and partition coefficients for proteins with sufficient accuracy from the same experiment. [source] Preparation of novel acrylamide-based thermoresponsive polymer analogues and their application as thermoresponsive chromatographic matricesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2008Yoshikatsu Akiyama Abstract New thermoresponsive polymers based on poly(N -(N, -alkylcarbamido)propyl methacrylamide) analogues were designed with increased hydrophobic content to facilitate temperature-dependent chromatographic separations of peptides and proteins from aqueous mobile phases. These polymer solution exhibited a lower critical solution temperature (LCST) when the alkyl group is methyl, ethyl, isopropyl, propyl, butyl, and isobutyl. However, larger alkyl groups such as hexyl and phenyl were not soluble in aqueous solutions at any temperature. Phase transition temperatures were lower for larger alkyl groups and increased with decreasing polymer molecular weight and concentration in solution. LCST dependence on polymer molecular weight and concentration is more significant compared with well-studied poly(N -isopropylacrylamide) (PIPAAm). Partition coefficient (log P) values for N -(N, -butylcarbamide)propylmethacrylamide and N -(N, -isobutylcarbamide)propyl methacrylamide (iBuCPMA) monomers are larger than that for IPAAm monomer, suggesting higher hydrophobicity than IPAAm. Chromatographic evaluation of poly(N -(N, -isobutylcarbamide)propyl methacrylamide) (PiBuCPMA) grafted silica particles in aqueous separations revealed larger k, values for peptides, insulin, insulin chain B, and angiotensin I than PIPAAm-grafted silica beads. In particular, k, values for insulin obtained from PiBuCPMA-grafted silica separations were much larger than those from PIPAAm-grafted surface separations, indicating that PiBuCPMA should be more hydrophobic than PIPAAm. These results support the introduction of alkylcarbamido groups to efficiently increase thermoresponsive polymer hydrophobicity of poly(N -alkylacrylamides) and poly(N -alkylmethacrylamides). Consequently, poly(N -(N, -alkylcarbamido)propyl methacrylamide) analogues such as PiBuCPMA and poly(N -(N, -alkylcarbamido)alkylmehacrylamide) are new thermoresponsive polymers with appropriate hydrophobic partitioning properties for protein and peptide separations in aqueous media, depending on selection of their alkyl groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5471,5482, 2008 [source] The sorptive capacity of animal proteinENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 9 2007Adrian M.H. deBruyn Abstract Partition coefficients that are used to predict concentrations of hydrophobic organic chemicals in biota (e.g., the bioconcentration factor) often assume that the sorptive capacity of an organism or tissue is adequately represented by its lipid content. In lean organisms and tissues, however, theory suggests that partitioning may be strongly influenced by the sorptive capacity of nonlipid materials, such as protein. Little is known about the sorptive capacity of proteins for hydrophobic organic chemicals, and methods to include proteins in bioaccumulation models do not exist. Here, we present a compilation and meta-analysis of published data to estimate the relative sorptive capacities of animal proteins and lipids for neutral organic chemicals. We found that the estimated sorptive capacity of protein in solid animal tissues ranged from around 1 to 10% that of lipid for compounds with a log octanol/water partition coefficient (KOW) of greater than two. The sorptive capacity of blood protein (albumin) appeared to be substantially higher than this, especially for low- KOW chemicals. For modeling purposes, we recommend estimating the sorptive capacity of animal protein as 5% that of lipid. According to this estimate, the sorptive capacity of an animal or tissue will be dominated by the contribution from protein if the lipid content makes up less than 5% of the dry-weight organic content. In such situations, a consideration of the sorptive capacity of nonlipid constituents, such as protein, will permit more accurate predictions of chemical accumulation and distribution. [source] Solvatochromic Analysis of Partition Coefficients in the o -Nitrophenyl Octyl Ether (o -NPOE)/Water SystemHELVETICA CHIMICA ACTA, Issue 11 2003Xiangli Liu The objective of this study was to unravel the structural properties responsible for the partitioning of solutes in o -nitrophenyl octyl ether (o -NPOE)/H2O, a new solvent system for the determination of the partition coefficients of ions. A set of 88 compounds (including drugs) was selected to allow a regular and broad distribution of property spaces. Partition coefficients in o -NPOE/H2O (log,Pnpoe) were measured by the shake-flask or the potentiometric method. Linear solvation free-energy relationship (LSER) analyses showed that Van der Waals volume, H-bond-acceptor basicity, and H-bond-donor acidity are the three molecular descriptors of solutes determining their log,Pnpoe values. The partitioning mechanism of the investigated compounds in o -NPOE/H2O is controlled by the same structural properties as it is in 1,2-dichloroethane (DCE)/H2O. ,log,Poct,npoe Values (difference between log,Poct and log,Pnpoe) express mainly dipolarity/polarizability and H-bond-donor acidity. The solvent o -NPOE is shown to be a good candidate to replace DCE in measurements of lipophilicity. [source] Syntheses and Properties of Fluorous Quaternary Phosphonium Salts that Bear Four Ponytails; New Candidates for Phase Transfer Catalysts and Ionic LiquidsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 12-13 2006Charlotte Emnet Abstract The fluorous tertiary phosphine [Rf6(CH2)2]3P [Rfn=CF3(CF2)n,1] and excess PhCH2Br, CH3(CH2)3OSO2CF3, or Rf6(CH2)2OSO2CF3 react (CF3C6H5, 45,110,°C) to give the phosphonium salts (PhCH2)[Rf6(CH2)2]3P+ Br, (2, 71,%), [CH3(CH2)3][Rf6(CH2)2]3P+ CF3SO3, (3, 65,%), or [Rf6(CH2)2]4P+ CF3SO3, (4, 83,%). The phosphines [Rf6(CH2)2]2[Rf8(CH2)2]P and [Rf8(CH2)2]3P are similarly elaborated with Rf6(CH2)2I, Rf8(CH2)2I, or Rf8(CH2)2Br (DMF, 115,°C) to [Rf8(CH2)2]4- x[Rf6(CH2)2]xP+ I, (x=3, 7; 2, 8; 1, 9; 0, 10) or [Rf8(CH2)2]4P+ Br, (80,60,%). The salts exhibit melting points between 110,°C and 43,°C, with lower values favored by less symmetrical cations, Rf6 segments, and triflate and bromide anions. Solubilities decrease in the solvent sequence CF3C6F5 (all salts at least moderately soluble, room temperature)>acetone>THF>CF3C6H5>CF3C6F11>CH3C6H5, Et2O, CH2Cl2, hexane (all salts insoluble at elevated temperatures); some appreciably increase upon heating. Partition coefficients are very biased towards fluorous phases (>93:<7). The salts can be quite efficient at extracting picrate from water into CF3C6F5 (97,86,% for 2, 4, 9, 10) or CF3C6H5 (85,66,% for 2 - 4), demonstrating their potential for phase transfer catalysis. A CF3C6F5 solution of Rf8(CH2)3I and aqueous NaCl react at 100,°C in the presence (but not the absence) of 9 to give Rf8(CH2)3Cl. [source] Retention of aroma compounds: an interlaboratory study on the effect of the composition of food matrices on thermodynamic parameters in comparison with waterJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 8 2010Mirela Kopjar Abstract BACKGROUND: Partition coefficients give an indication of the retention of aroma compounds by the food matrix. Data in the literature are obtained by various methods, under various conditions and expressed in various units, and it is thus difficult to compare the results. The aim of the present study was first to obtain gas/water and gas/matrix partition coefficients of selected aroma compounds, at different temperatures, in order to calculate thermodynamic parameters and second to compare the retention of these aroma compounds in different food matrices. RESULTS: Yogurts containing lipids and proteins induced a higher retention of aroma compounds than model gel matrices. The observed effects strongly depend on hydrophobicity of aroma compounds showing a retention for ethyl hexanoate and a salting out effect for ethyl acetate. A small but noticeable decrease in enthalpy of affinity is observed for ethyl butyrate and ethyl hexanoate between water and food matrices, suggesting that the energy needed for the volatilization is lower in matrices than in water. CONCLUSION: The composition and complexity of a food matrix influence gas/matrix partition coefficients or aroma compounds in function of their hydrophobicity and to a lower extent enthalpy of vaporization. Copyright © 2010 Society of Chemical Industry [source] Partition Coefficient Kow of Benzene, Ethanol and Aniline in Benzene-ethanol and Aniline-benzene Mixtures and Coefficient of Distribution Kmix of these MixturesMOLECULAR INFORMATICS, Issue 4 2006M. Rucki Abstract The study related to partition coefficients between n-octanol and water Kow of compounds in binary mixtures benzene-ethanol and benzene-aniline was carried out. Partition coefficients of benzene, aniline and ethanol for different values of molar ratio of benzene and different total concentration of compounds in the mixtures benzene-ethanol and benzene-aniline were determined. Coefficient of distribution Kmix was determined for both mixtures. In benzene-ethanol mixture collected results show statistically significant deviations the Kow of benzene from values for pure compound. For ethanol, there are no statistically significant deviations from values for pure compound. But also there are some trends of changes of Kow. In benzene-aniline mixture collected results show statistically significant deviations of the Kow of benzene and aniline from values for pure compounds. Changes of Kow were used for explanation of acute toxicity of binary mixtures benzene-ethanol and aniline-benzene. [source] Use of affinity capillary electrophoresis for characterizing pharmaceutical colloidal vehicle systems thermodynamicallyBIOPHARMACEUTICS AND DRUG DISPOSITION, Issue 7-8 2001Neubert Reinhard Abstract This review offers a detailed discussion of the interaction between pharmaceutical compounds and vehicles using the affinity capillary electrophoresis and the microemulsion electrokinetic chromatography. Partition coefficients of drugs were calculated between a micelle and an aqueous phases from the measurement of the migration time, provided the critical micelle concentration and the phase ratio are known. Thermodynamic quantities such as enthalpy and entropy changes of micellar solubilization were calculated from the temperature dependence of the partition coefficients. Partial specific volumes were measured using dynamic light scattering. The logarithm of the partition coefficients and the capacity factor in the micellar system were correlated with the logarithm of the n-octanol/water partition coefficients. Copyright © 2001 John Wiley & Sons, Ltd. [source] Concentration of mammalian genomic DNA using two-phase aqueous micellar systemsBIOTECHNOLOGY & BIOENGINEERING, Issue 6 2009Foad Mashayekhi Abstract The concentration of biomarkers, such as DNA, prior to a subsequent detection step may facilitate the early detection of cancer, which could significantly increase chances for survival. In this study, the partitioning behavior of mammalian genomic DNA fragments in a two-phase aqueous micellar system was investigated using both experiment and theory. The micellar system was generated using the nonionic surfactant Triton X-114 and phosphate-buffered saline (PBS). Partition coefficients were measured under a variety of conditions and compared with our theoretical predictions. With this comparison, we demonstrated that the partitioning behavior of DNA fragments in this system is primarily driven by repulsive, steric, excluded-volume interactions that operate between the micelles and the DNA fragments, but is limited by the entrainment of micelle-poor, DNA-rich domains in the macroscopic micelle-rich phase. Furthermore, the volume ratio, that is, the volume of the top, micelle-poor phase divided by that of the bottom, micelle-rich phase, was manipulated to concentrate DNA fragments in the top phase. Specifically, by decreasing the volume ratio from 1 to 1/10, we demonstrated proof-of-principle that the concentration of DNA fragments in the top phase could be increased two- to nine-fold in a predictive manner. Biotechnol. Bioeng. 2009;102: 1613,1623. © 2008 Wiley Periodicals, Inc. [source] Combined AFM and Two-Focus SFCS Study of Raft-Exhibiting Model Membranes,CHEMPHYSCHEM, Issue 11 2006Salvatore Chiantia Abstract Dioleoylphosphatidylcholine/sphingomyelin/cholesterol (DOPC/SM/cholesterol) model membranes exhibit liquid,liquid phase separation and therefore provide a physical model for the putative liquid-ordered domains present in cells. Here we present a combination of atomic force microscopy (AFM) imaging, force measurements, confocal fluorescence imaging and two-focus scanning fluorescence correlation spectroscopy (two-focus SFCS) to obtain structural and dynamical information about this model membrane system. Partition coefficients and diffusion coefficients in the different phases were measured with two-focus SFCS for numerous fluorescent lipid analogues and proteins, while being directly related to the lateral organization of the membrane and its mechanical properties probed by AFM. Moreover we show how the combination of these different approaches is effective in reducing artifacts resulting from the use of a single technique. [source] A quantitative approach to probe the dependence and correlation of food-effect with aqueous solubility, dose/solubility ratio, and partition coefficient (Log P) for orally active drugs administered as immediate-release formulationsDRUG DEVELOPMENT RESEARCH, Issue 2 2005Brahma N. Singh Abstract The purpose of the present review was to systematically evaluate if aqueous solubility, dose/solubility ratio, and partition coefficient (Log P) could be used as useful parameters to quantitatively probe the dependence and correlation of in vivo food effects with these physicochemical properties of orally active drugs administered as immediate-release (IR) formulations. Mean AUC data obtained under fasted and fed states of over 100 structurally diverse orally active drugs with different physicochemical properties were obtained from the primary literature. Correlations of AUC ratio (Fed/Fasted) with aqueous solubility, dose/solubility ratio, and Log P were derived and statistically evaluated by Pearson's correlation test (two-tailed). A negative correlation was obtained between the logarithm of the aqueous solubility and the AUC ratio (r=,0.5982, N=93), whereas a positive correlation existed between AUC ratio and Log P (r=0.5147, N=110) and between AUC ratio and dose/solubility ratio (r=0.5511, N=87). All these correlations were significant (P<0.0001). Based on this study, the estimated range within which a drug is not expected to be significantly affected by food falls between 0.148,89.39 mg/ml for aqueous solubility and between 0.23,624 ml for the dose:solubility ratio. The corresponding range of Log P for expecting a lack of food-effect lies between ,1.13 and 2.98. Quantitatively, the effect of food was most pronounced for lipophilic, poorly water-soluble drugs (with only a few exceptions), irrespective of whether the drug is acidic, basic, or neutral. It is concluded that aqueous solubility, dose/solubility ratio, and partition coefficient can be used as useful parameters to probe the dependence and correlation of food-effect with these physicochemical parameters for immediate-release formulations. Drug Dev. Res. 65:55,75, 2005. © 2005 Wiley-Liss, Inc. [source] Rapidly profiling blood,brain barrier penetration with liposome EKCELECTROPHORESIS, Issue 14 2007Yongjun Wang Abstract This report intended to study the potential of liposome EKC (LEKC) as a convenient and high-throughput screening tool to assess drug penetration across the blood,brain barrier (BBB). The retention factors (k) of 24 structurally diverse compounds were determined with LEKC and vesicle EKC (VEKC), respectively. Principal component analysis of the steady-state concentrations ratio of compounds in the brain and in the blood expressed as log,BB, log,kLEKC, log,kVEKC, and other lipophilic descriptors including octanol/water partition coefficient (Clog,P), octanol/water distribution coefficients (log,D7.4), and polar surface area (PSA), showed the maximum similarity of partitioning processes in LEKC to drug penetration across the BBB. Furthermore, the log,BB were correlated with the above five lipophilic descriptors, and the results showed that log,kLEKC gave the better correlation coefficient (r2,=,0.811, p <0.0001) than those of log,D7.4, Clog,P, PSA, and log,kVEKC (r2,=,0.730, 0.672, 0.627, and 0.620, p <0.0001). This is the first report of the use of LEKC as a promising rapid tool to profile drug penetration across the BBB. [source] Comparison of methanol and acetonitrile as solvents for the separation of sertindole and its major metabolites by capillary zone electrophoresisELECTROPHORESIS, Issue 17 2005Xavier Subirats Abstract Sertindole (1-[2-[4-[5-chloro-1-(4-fluorophenyl)-1H -indol-3-yl]-1-piperidinyl]ethyl]-2-imidazolidinone), an atypical antipsychotic drug, was separated by capillary electrophoresis from its two main metabolites norsertindole and dehydrosertindole. The low solubility of the analytes in water (octanol-water partition coefficient is about 105) is overcome by the use of methanol (MeOH) and acetonitrile (ACN) as solvents for the background electrolyte (BGE). Mobilities were measured in BGEs with defined pH in a broad range. It was found that in MeOH the mobility of the analytes is mainly governed by acid,base equilibria, whereas in ACN other reactions like ion pairing and homoconjugation play a pronounced role and lead to a complex pattern of the mobility as function of the pH. However, separation can be obtained in less than 10,min in both solvent systems. [source] QSARs for aromatic hydrocarbons at several trophic levelsENVIRONMENTAL TOXICOLOGY, Issue 2 2006Walter Di Marzio Abstract Quantitative structure,activity relationships (QSARs) with aromatic hydrocarbons were obtained. Biological response was measured by acute toxicity of several aquatic trophic levels. The chemicals assayed were benzene, toluene, ethylbenzene, o -xylene, m -xylene, p -xylene, isopropylbenzene, n -propylbenzene, and butylbenzene. Acute toxicity tests were carried out with Scenedesmus quadricauda, as representative of primary producers; Daphnia spinulata, a zooplanctonic cladoceran; Hyalella curvispina, a benthic macroinvertebrate; and Bryconamericus iheringii, an omnivorous native fish. The EC50 or LC50 was calculated from analytical determinations of aromatic hydrocarbons. Nonlinear regression analysis between the logarithm of the octanol,water partition coefficient (log Kow) of each compounds and the toxicity end points was performed. QSARs were positively related to increases in log Kow at all trophic levels. Intertaxonomic differences were found in comparisons of algae with animals and of invertebrates with vertebrates. We observed that these differences were not significant with a log Kow higher than 3 for all organisms. Aromatic hydrocarbons with log Kow values of less than 3 showed different toxicity responses, with algae more resistant than fish and invertebrates. We concluded that this was a result of the narcotic mode of action related to liposolubility and the ability of the compound to reach its target site in the cell. The bioconcentration factor (BCF) achieved to start nonpolar narcosis fell almost 1 order of magnitude below the BCF expected from the log Kow. Predicted critical body residues for nonpolar narcosis ranged between 2 and 1 mM. © 2006 Wiley Periodicals, Inc. Environ Toxicol 21: 118,124, 2006. [source] Persistent or not persistent?ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2009Polychlorinated biphenyls are readily depurated by grizzly bears (Ursus arctos horribilis) Abstract Major pharmacokinetic processes influencing polychlorinated biphenyl (PCB) accumulation in mammals include uptake, biotransformation, respiration, and excretion. We characterized some of the factors underlying PCB accumulation/loss by evaluating PCB concentrations and patterns in pre- and posthibernation grizzly bears (Ursus arctos horribilis) and their prey. The PCB congeners with vicinal meta - and para -chlorine unsubstituted hydrogen positions consistently showed loss both before and during hibernation, supporting the idea of a dominant role for biotransformation. Retention of all other studied congeners relative to that of PCB 194 varied widely (from <1 to 100%) and was highly correlated with log octanol--water partition coefficient (p < 0.0001). A lack of loss for most of these other congeners during hibernation supports the notion that excretion (e.g., fecal or urinary) or lack of uptake during the feeding season underlies their lack of accumulation, because hibernating bears do not eat or excrete. We estimate that grizzly bears retain less than 10% of total PCBs taken up from their diet. Our results suggest that for grizzly bears, depuration of PCBs via biotransformation is important (explaining ,40% of loss), but that nonbiotransformation processes, such as excretion, may be more important (explaining ,60% of loss). These findings, together with the approximately 91% loss of the persistent PCB 153 congener relative to PCB 194 in grizzly bears, raise important questions about how one defines persistence of PCBs in wildlife and may have bearing on the interpretation of food-web biomagnification studies. [source] Evaluation of poly(ethylene-co-vinyl acetate-co-carbon monoxide) and polydimethylsiloxane for equilibrium sampling of polar organic contaminants in waterENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 9 2009Jörgen A Magnér Abstract Abstract-The aim of the present study was to develop a passive a bsorptive equilibrium sampler that would enable the determination of the concentrations of polar organic compound (POC) in water more efficiently than existing techniques. To this end, a novel plastic material, poly(ethylene-co-vinyl acetate-co-carbon monoxide) (PEVAC), was evaluated and the results were compared with an existing silicone-based passive absorptive equilibrium device. Seven compounds (imidacloprid, carbendazim, metoprolol, atrazin, carbamazepine, diazinon, and chlorpyrifos), a mixture of pharmaceuticals, and pesticides with a logarithmic octanol-water partition coefficient ranging from 0.2 to 4.77 were selected as model substances for the experiments. The results showed that six of the seven selected POCs reached distribution equilibrium within 4 d in the two materials tested. A linear relation with a regression coefficient of more than 0.8906 between the established logarithmic absorbent-water partition coefficient and the calculated logarithmic dissociation partition coefficient of the selected compounds in the two polymers was observed. The correlation between these two coefficients was within one order of magnitude for the compounds that reached equilibrium in the two polymers, which demonstrates that both materials are suitable for mimicking biological uptake of POCs. The PEVAC material showed an enhanced sorption for all selected compounds compared to the silicone material and up to five times higher enrichment for the most polar compound. Fluorescence analysis of the sampler cross-section, following the uptake of fluoranthene, and proof that the sorption was independent of surface area variations demonstrated that the PEVAC polymer possessed absorptive rather than adsorptive enrichment of organic compounds. [source] Technical basis for polar and nonpolar narcotic chemicals and polycyclic aromatic hydrocarbon criteria.ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 7 2009Abstract A method is presented for extending the target lipid model (TLM) of narcotic toxicity to polar narcotic chemicals. The proposed polyparameter TLM extends the applicability of the TLM by including polar compounds and removing explicit chemical class corrections. The validity of the model is tested using a data set of 1,687 acute toxicity tests for 42 aquatic species, including fish, amphibians, arthropods, mollusks, polychaetes, coelenterates, protozoans, and algae, and 398 chemicals. The target lipid-water partition coefficient is computed using the Abraham polyparameter model. This replaces use of the octanol-water partition coefficient so that the partitioning of polar narcotic chemicals can be described correctly. The model predicts the log median lethal concentration with a root mean square error of 0.460 for nonpolar and polar chemicals and 0.501 for only polar chemicals. [source] Influence of soil pH on the sorption of ionizable chemicals: Modeling advancesENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2009Antonio Franco Abstract The soil,water distribution coefficient of ionizable chemicals (Kd) depends on the soil acidity, mainly because the pH governs speciation. Using pH-specific Kd values normalized to organic carbon (KOC) from the literature, a method was developed to estimate the KOC of monovalent organic acids and bases. The regression considers pH-dependent speciation and species-specific partition coefficients, calculated from the dissociation constant (pKa) and the octanol,water partition coefficient of the neutral molecule (log Pn). Probably because of the lower pH near the organic colloid,water interface, the optimal pH to model dissociation was lower than the bulk soil pH. The knowledge of the soil pH allows calculation of the fractions of neutral and ionic molecules in the system, thus improving the existing regression for acids. The same approach was not successful with bases, for which the impact of pH on the total sorption is contrasting. In fact, the shortcomings of the model assumptions affect the predictive power for acids and for bases differently. We evaluated accuracy and limitations of the regressions for their use in the environmental fate assessment of ionizable chemicals. [source] Determination of physicochemical properties of tetrabromobisphenol AENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2008Hidetoshi Kuramochi Abstract Aqueous solubility (Sw), 1-octanol/water partition coefficient (KOW), and vapor pressure of the nonionic form of 2,2,,6,6,-tetrabromo-4,4,-isopropylidenediphenol (tetrabromobisphenol A or TBBP-A) were measured. From this, enthalpies of solution and vaporization were estimated. Furthermore, enthalpy of fusion and melting point were measured to estimate subcooled liquid vapor pressure, the infinite dilution activity coefficient, and Henry's law constant. Since TBBP-A is expected to exit in both ionic and nonionic forms at near neutral pH, pH effects on physicochemical properties were also examined. Because of the ionization of TBBP-A, Sw increased by five orders of magnitude, while KOW decreased by eight orders of magnitude. Furthermore, an analytical model based on mass balance and dissociation of TBBP-A was applied to represent the pH dependence. [source] Estimation of the soil,water partition coefficient normalized to organic carbon for ionizable organic chemicals,ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 10 2008Antonio Franco Abstract The sorption of organic electrolytes to soil was investigated. A dataset consisting of 164 electrolytes, composed of 93 acids, 65 bases, and six amphoters, was collected from literature and databases. The partition coefficient log KOW of the neutral molecule and the dissociation constant pKa were calculated by the software ACD/Labs®. The Henderson-Hasselbalch equation was applied to calculate dissociation. Regressions were developed to predict separately for the neutral and the ionic molecule species the distribution coefficient (Kd) normalized to organic carbon (KOC) from log KOW and pKa. The log KOC of strong acids (pKa < 4) was not correlated to these parameters. The regressions derived for weak acids and bases (undissociated at environmental pH) were similar. The highest sorption was found for strong bases (pKa > 7.5), probably due to electrical interactions. Nonetheless, their log KOC was highly correlated to log KOW. For bases, a nonlinear regression was developed, too. The new regression equations are applicable in the whole pKa range of acids, bases, and amphoters and are useful in particular for relatively strong bases and amphoters, for which no predictive methods specifically have been developed so far. [source] Water-column concentrations and partitioning of polybrominated diphenyl ethers in the New York/New Jersey Harbor, USAENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 8 2008Archil Zarnadze Abstract Despite the emerging concern regarding polybrominated diphenyl ethers (BDEs), very few measurements of BDE concentrations in ambient water have been published. In the present study, BDEs were measured in water samples from the New York/New Jersey Harbor (USA). Samples were taken in Raritan Bay west of Sandy Hook during four intensive sampling campaigns in 2000 and 2001. Congeners 17, 47, 99, 100, 153, 154, 183, and 209 were detected. Total BDE (,BDE) concentrations (average ± standard deviation) were 175 ± 75 ng/g in the particle phase and 110 ± 72 pg/L in the apparent dissolved phase. The deca-congener, BDE 209, constituted 85 and 9% of ,BDEs in the particle and apparent dissolved phases, respectively. The ,BDE levels are significantly higher than those measured in Lake Ontario, USA, and in The Netherlands, but they are similar to concentrations measured in Lake Michigan and San Francisco Bay (both USA). Calculated values of the organic carbon-water partition coefficient (KOC) were strongly correlated with literature values of the octanol-water partition coefficient (KOW). The data suggest that sorption of BDEs to colloids is important in this system, although quantifying the extent of colloid sorption is difficult. [source] Adsorption of hydrophobic organic compounds onto a hydrophobic carbonaceous geosorbent in the presence of surfactants,ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 6 2008Peng Wang Abstract The adsorption of hydrophobic organic compounds (HOCs; atrazine and diuron) onto lampblack was studied in the presence of nonionic, cationic, and anionic surfactants (Triton® X-100), benzalkonium chloride [BC], and linear alkylbenzene sulfonate [LAS]) to determine the effect of the surfactant on HOC adsorption onto a hydrophobic carbonaceous geosorbent. Linear alkylbenzene sulfonate showed an adsorption capacity higher than that of BC but similar to that of Triton X-100, implying the charge property of a surfactant is not a useful indicator for predicting the surfactant's adsorption onto a hydrophobic medium. The results also indicated that the octanol-water partition coefficient (Kow) of a surfactant is not a good predictor of that surfactant's sorption onto a hydrophobic medium. Under subsaturation adsorption conditions (i.e., before sorption saturation is reached), surfactant adsorption reduced HOC adsorption to a significant extent, with the reduction in HOC adsorption increasing monotonically with the amount of surfactant adsorbed. Among the three surfactants, Triton X-100 was the most effective in reducing HOC adsorption, whereas BC and LAS showed similar effectiveness in this regard. Under the same amount of the surfactant sorbed, the reduction in atrazine adsorption was consistently greater than that for diuron because of atrazine's lower hydrophobicity. No significant difference was observed in the amount of the HOC adsorbed under different adsorption sequences. Our results showed that the presence of surfactant can significantly decrease HOC adsorption onto hydrophobic environmental media and, thus, is important in predicting HOC fate and transport in the environment. [source] Effects of estimates from different geochemical models on metal fate predicted by coupled speciation-fate models,ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 5 2008Satyendra P. Bhavsar Abstract Coupled metal speciation-fate models are an improvement over stand-alone fate-transport models for accurately assessing metal fate and transport. These coupled models estimate fate-controlling partition coefficients using geochemical speciation/complexation models. Commercially available geochemical models are practical options for a two-step, loose coupling with fate-transport models. These models differ in their partitioning estimates because of differences in assumptions, databases, and so on. The present study examines the effects of differences in estimates from geochemical models on estimates of cationic metal fate using two geochemical models: the Windermere humic aqueous model (WHAM) and the minicomputer equilibrium+ model (MINEQL+). The results from each geochemical model were used as input to the fate module of TRANSPEC (a general, coupled metal transport and speciation model). The two versions of the TRANSPEC model were then used to assess the fate of five cationic metals (Cd, Cu, Ni, Pb, and Zn) in Ross Lake (Flin Flon, MB, Canada; alkaline, eutrophic, mine impacted), Kelly Lake (Sudbury, ON, Canada; circumneutral, mesotrophic, mine influenced), and Lake Tantaré (Quebec City, QC, Canada; acidic, oligotrophic, pristine). For relatively soluble metals (Cd, Ni, and Zn), the WHAM and MINEQL+ estimates of speciation/complexation were similar for Ross and Kelly lakes but differed for Lake Tantaré. These differences, however, did not result in significant differences in overall fate estimates. Marked differences were observed between the WHAM and MINEQL+ estimates of partition coefficient, Kd, for more particle-reactive Cu and Pb that translated into the greatest impact on fate in mesotrophic Kelly Lake, in which particle movement is important for fate. [source] The sorptive capacity of animal proteinENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 9 2007Adrian M.H. deBruyn Abstract Partition coefficients that are used to predict concentrations of hydrophobic organic chemicals in biota (e.g., the bioconcentration factor) often assume that the sorptive capacity of an organism or tissue is adequately represented by its lipid content. In lean organisms and tissues, however, theory suggests that partitioning may be strongly influenced by the sorptive capacity of nonlipid materials, such as protein. Little is known about the sorptive capacity of proteins for hydrophobic organic chemicals, and methods to include proteins in bioaccumulation models do not exist. Here, we present a compilation and meta-analysis of published data to estimate the relative sorptive capacities of animal proteins and lipids for neutral organic chemicals. We found that the estimated sorptive capacity of protein in solid animal tissues ranged from around 1 to 10% that of lipid for compounds with a log octanol/water partition coefficient (KOW) of greater than two. The sorptive capacity of blood protein (albumin) appeared to be substantially higher than this, especially for low- KOW chemicals. For modeling purposes, we recommend estimating the sorptive capacity of animal protein as 5% that of lipid. According to this estimate, the sorptive capacity of an animal or tissue will be dominated by the contribution from protein if the lipid content makes up less than 5% of the dry-weight organic content. In such situations, a consideration of the sorptive capacity of nonlipid constituents, such as protein, will permit more accurate predictions of chemical accumulation and distribution. [source] Biomagnification and polychlorinated biphenyl congener distribution in an aquatic predator-prey, host-parasite systemENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 5 2007Maria E. Persson Abstract Biomagnification and polychlorinated biphenyl (PCB) congener distribution was examined in a predator-prey, hostparasite system, in which Atlantic salmon (Salmo salar) preyed upon sprat (Sprattus sprattus). Eubothrium crassum was an intestinal parasite in salmon that also "preyed upon" sprat, because the parasites gained access to foodstuffs via the host (salmon) gut. Salmon contained significantly higher concentrations of total PCBs compared to both parasites and prey (sprat), but no difference in PCB concentration was found between sprat and E. crassum. Salmon biomagnified several PCB congeners from their diet (sprat), whereas parasites did not, despite the fact that both salmon and their parasites ingested the same prey. Differences in nutrient uptake mechanisms between the host and their parasites, in addition to the lack of a gastrointestinal tract in the cestode, may explain the lack of biomagnification in E. crassum. No difference was found in PCB congener distribution between parasites, salmon, and sprat, and none of the animal types showed a preference for accumulating more or less lipophilic congeners (congeners with a high or low octanol/water partition coefficient [KOW]). Biomagnification factors for individual congeners in salmon did not increase with KOW; rather, they were constant, as shown by a linear relationship for congener concentration in prey and predator. [source] Bioconcentration of persistent organic pollutants in four species of marine phytoplanktonENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2005Antje Gerofke Abstract The uptake of polychlorinated biphenyls (PCBs) was studied in four species of marine algae. A novel experimental system to establish and maintain constant dissolved concentrations of PCBs was employed. Headspace sampling was used to verify that the freely dissolved concentrations remained constant with time. The headspace analysis also allowed sorption to dissolved organic carbon (DOC) to be quantified for all but the most lipophilic PCB congeners. Equilibration with the dissolved phase was rapid for three of the four algae species (<1 d for the majority of congeners). Organic carbon,normalized algae/water partition coefficients (KAlgW) were similar for three of the four species, but were lower by a factor of 10 to 20 for Phaeodactylum tricornutum. The KAlgW values of the first three species were similar to the octanol/water partition coefficient (KOW) for those PCB congeners for which DOC sorption could be quantified. These KAlgW values also agreed well with organic carbon,normalized bioconcentration factors for PCBs in suspended particulate matter (BCFSPM) sampled in Baltic Sea surface water during the summer. [source] Predicting single and mixture toxicity of petrogenic polycyclic aromatic hydrocarbons to the copepod Oithona davisaeENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2005Carlos Barata Abstract In the present study, the acute toxicity of 10 polycyclic aromatic hydrocarbons (PAH) associated with the Prestige fuel oil spill (Spain, 2002) were evaluated, either as single substances or in mixtures, in adults of the copepod Oithona davisae. All but dimethylphenanthrene had negative effects on O. davisae survival at concentrations below their water solubility, with 48-h median lethal concentrations for naphthalene and pyrene of 56.1 and 0.8 ,mol/L, respectively, making these the least and most toxic compounds. Polycyclic aromatic hydrocarbons had narcotic effects on copepods, as evidenced by the lack of motility at lower concentrations than those causing death. Naphthalene showed the greatest narcotic effects, and phenanthrene showed minor effects. Acute toxicity of the tested PAHs was inversely related (r2 = 0.9) with their octanol,water partition coefficient, thereby confirming the validity of the baseline quantitative structure,activity regression models for predicting the toxicity of PAH compounds in copepod species. When supplied in mixtures, the toxic effect of PAHs was additive. These results indicate that the many PAHs in an oil spill can be considered unambiguous baseline toxicants (class 1) acting additively as nonpolar narcotics in copepods; hence, their individual and combined toxicity can be predicted using their octanol,water partition coefficient. [source] Biomimetic solid-phase microextraction to predict body residues and toxicity of chemicals that act by narcosisENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 2 2002Heather A. Leslie Abstract A biomimetic extraction technique using solid-phase microextraction (SPME) fibers has been developed for the risk assessment of contaminants with a narcotic mode of action. Our goal is to apply this technique in the future for the prediction of total baseline toxicity of environmental water and effluent samples. Validation of this method requires establishing the relationship between contaminant accumulation and toxicity in biota and accumulation in the surrogate solid phase (the SPME fiber coating). For this purpose, we determined the median lethal concentration (LC50) values for Chironomus riparius midge larvae exposed to two halogenated aromatic compounds separately and measured body residues in the exposed larvae. Solid-phase microextraction fibers with an 85-,m polyacrylate (PA) coating served as the surrogate hydrophobic phase, mimicking the uptake of the compounds by midge larvae. The toxicant concentrations in SPME fibers measured directly by gas chromatography/mass spectrometry (GCMS) or calculated from the SPME fiber,water partition coefficient, KSPME, were related to the toxicant concentrations found in midge larvae. Our results demonstrated that the biomimetic SPME method enables the estimation of body residues in biota and prediction of the degree of baseline toxicity of a water medium. [source] | |||||||||||||||||||||||||||||||||||||||||||