Yes / We have set out an equation for partition of 87 neutral molecules from water to o-nitrophenyl octyl ether, NPOE, an equation for partition of the 87 neutral molecules and 21 ionic species from water to NPOE, and an equation for partition of 87 neutral molecules from the gas phase to NPOE. Comparison with equations for partition into other solvents shows that, as regards partition of neutral (nonelectrolyte) compounds, NPOE would be a good model for 1,2-dichloroethane and for nitrobenzene. In terms of partition of ions and ionic species, NPOE is quite similar to 1,2-dichloroethane and not far away from other aprotic solvents such as nitrobenzene.

Experimental mole fraction solubilities of several carboxylic acids (2-methoxybenzoic acid, 4-methoxybenzoic acid, 4-nitrobenzoic acid, 4-chloro-3-nitrobenzoic acid, 2-chloro-5-nitrobenzoic acid,2-methylbenzoic acid and ibuprofen) and 9-fluorenone, thianthrene and xanthene were measured in a wide range of solvents of varying polarity and hydrogen-bonding characteristics. Results of these measurements were used to calculate gas-to-organic solvent and water-to-organic solvent solubility ratios, which were then substituted into known Abraham process partitioning correlations. The molecular solute descriptors that were obtained as the result of these computations described the measured solubility data to within an average absolute deviation of 0.2 log units. The calculated solute descriptors also enable one to estimate many chemically, biologically and pharmaceutically important properties for the ten solutes studied using published mathematical correlations.

No / We describe the Δlog P method for the assessment of intramolecular hydrogen bonds (IMHBs), and show that it is not a very general method of distinguishing between molecules in which there is an IMHB and molecules in which there is no IMHB. The ‘double’ Δlog P method of Shalaeva et al. is a much more reliable method for the assessment of IMHB but requires the synthesis of a model compound and the determination of no less than four water-solvent partition coefficients. In addition, it is difficult to apply to compounds that contain more than one hydrogen bond acidic group capable of IMHB. We then describe our NMR method of assessing IMHB, based on 1H NMR chemical shifts in solvents DMSO and CDCl3. We have determined 1H NMR chemical shifts for a number of ortho-substituted anilines and show that the only compound we have studied that forms an IMHB is methyl 2-methylaminobenzoate though there is no IMHB present in methyl 2-aminobenzoate. This apparently anomalous result is supported by both MM and ab initio calculations. The NMR method is much simpler and less time consuming than other methods for the assessment of IMHB. It provides a quantitative assessment of IMHB and can be applied to molecules with more than one hydrogen bond acidic group.

Yes / We describe the Δlog P method for the assessment of intramolecular hydrogen bonds (IMHBs), and show that it is not a very general method of distinguishing between molecules in which there is an IMHB and molecules in which there is no IMHB. The ‘double’ Δlog P method of Shalaeva et al. is a much more reliable method for the assessment of IMHB but requires the synthesis of a model compound and the determination of no less than four water-solvent partition coefficients. In addition, it is difficult to apply to compounds that contain more than one hydrogen bond acidic group capable of IMHB. We then describe our NMR method of assessing IMHB, based on 1H NMR chemical shifts in solvents DMSO and CDCl3. We have determined 1H NMR chemical shifts for a number of ortho-substituted anilines and show that the only compound we have studied that forms an IMHB is methyl 2-methylaminobenzoate though there is no IMHB present in methyl 2-aminobenzoate. This apparently anomalous result is supported by both MM and ab initio calculations. The NMR method is much simpler and less time consuming than other methods for the assessment of IMHB. It provides a quantitative assessment of IMHB and can be applied to molecules with more than one hydrogen bond acidic group.

Les matériaux plastiques contiennent des additifs, qui ne sont pas fixés dans la matrice polymère et risquent migrer dans les aliments. La directive européenne 2002/72 a introduit la possibilité de démontrer l’aptitude au contact alimentaire de ces matériaux à partir d’approches prédictives, dont l’application est limitée par la disponibilité de données de formulation et de physico-chimie. Ces travaux visent à adapter et développer des approches analytiques rapides pour identifier et quantifier les substances majoritaires contenues dans les plastiques et à développer une approche générique de prédiction des coefficients de partage entre des polymères et les simulants de l’aliment. Des méthodes conventionnelles d’extraction par solvant et de quantification en CLHP-UV-DEDL et CPG-DIF ont été comparées pour quatre formulations modèles de PEHD et PS. Une méthode rapide de déconvolution de spectres infrarouge d’extraits de PEHD a été développée pour identifier et quantifier les additifs. Un modèle prédictif des coefficients d’activité dans les PE et les simulants est proposé. Les contributions enthalpique et entropique non configurationnelle sont évaluées à partir d’un échantillonnage des énergies de contact paire à paire. Il est démontré que la contribution entropique configurationnelle est indispensable à la description de l’affinité de molécules de grande taille dans les simulants polaires ou non constitués de petites molécules. Des arbres de décision combinant approche expérimentale et modèle sont finalement discutés dans la logique de démonstration de la conformité et de veille sanitaire / Plastic packagings are formulated with additives, which can migrate from materials into foodstuffs. According to European directive 2002/72/EC, the ability of plastic materials to be used in contact with food can be demonstrated using modelling tools. Their use is however limited due to availability of some data, like the formulation of materials and partition coefficients of substances between plastics and food. On the one hand this work aims to develop the ability of laboratories to identify and quantify the main substances in plastic materials, and on the other hand it aims to develop a new method to predict partition coefficients between polymers and food simulants. Four formulations of both HDPE and PS were chosen and used during the work. Standard extraction methods and quantification methods using HPLC-UV-ELSD and GC-FID were compared. A new deconvolution process applied on infrared spectra of extracts was developed to identify and quantify additives contained in HDPE. Activity coefficients in both phases were approximated through a generalized off-lattice Flory-Huggins formulation applied to plastic materials and to liquids simulating food products. Potential contact energies were calculated with an atomistic semi-empirical forcefield. The simulations demonstrated that plastic additives have a significant chemical affinity, related to the significant contribution of the positional entropy, for liquids consisting in small molecules. Finally, decision trees, which combine both experimental and modelling approaches to demonstrate the compliance of plastic materials, were discussed

Drei Verteilungskoeffizienten, die für physiologie-basierte Pharmakokinetik (PBPK)-Modelle relevant sind, wurden mit verschiedenen Ansätzen modelliert. Für den Blut/Luft-Verteilungskoeffizienten wurde ein auf linearen Solvatations-Energie-Beziehungen (LSER) beruhendes Literaturmodell angewendet und diskutiert. Mit einer schematischen Aufteilung des Blutkompartiments in Wasser und einen organischen Teil wurde der Blut/Luft-Verteilungskoeffizient mit einer linearen Regression von anderen Verteilungskoeffizienten vorhergesagt. Zusätzlich wurde ein Fragmentmodell entwickelt. Der Fett/Luft-Verteilungskoeffizient wurde mit dem LSER-Ansatz und mit anderen Verteilungskoeffizienten modelliert. Der Koeffizient Fett/Blut wurde aus den ersten beiden errechnet. Da der inverse dimensionslose Henry-Koeffizient Wasser/Luft-Verteilungskoeffizient bei der Blut/Luft-Modellierung zum Einsatz kommt und dieser aus dem Dampfdruck und der Wasserlöslichkeit gewonnen werden kann, wurde der Dampfdruck ebenfalls modelliert.

Volatile elements released from the subducting slab play a fundamental role during the formation of arc magmas in the mantle wedge. Advances of melt inclusion studies enlarged the data on volatile abundance in arc magmas, and it is now possible to characterize some volatile contents in arc primary magmas, in particular F and Cl. A recent study of Mt Shasta melt inclusions (LeVoyer et al., 2010) shows that fractionation of F and Cl potentially contains information about arc magma genesis. In order to trace the source of arc magmas, fluorine and chlorine partitioning was investigated. Here, I present new experimental determinations of Cl and F partition coefficients between dry and hydrous silicate melts and mantle minerals: olivine, orthopyroxene, clinopyroxene, plagioclase, garnet and also pargasite and phlogopite. The values were compiled from more than 300 measurements in 24 melting experiments, conducted between 8 and 25 kbars and between 1180 and 1430˚C. The low abundance F, Cl measurements in minerals were done by Cameca IMF 1280 at WHOI using the negative secondary ion mode. The results show that DOpx/meltF ranges from 0.123 to 0.021 and DCpx/meltF ranges from 0.153 to 0.083, while Cl partition coefficient varies from DOpx/meltCl from 0.002 to 0.069 and DCpx/meltCfrom 0.008 to 0.015, as well. Furthermore, DOl/meltF ranges from 0.116 to 0.005 and DOl/meltCl from 0.001 to 0.004; DGrt/meltF ranges from 0.012 to 0.166 and DGrt/meltCl from 0.003 to 0.087 with the increasing water amount and decreasing temperature. I also show that F is compatible in phlogopite DPhl/meltF > 1.2) while DAmp/meltF is incompatible in pargasite DAmp/meltF from 0.36 to 0.63). On the contrary, Cl is more incompatible in phlogopite (DPhl/meltCl > 1.2 on average 0.09 ± 0.02), than in pargasite (DPhl/meltCl from 0.12 to 0.38). This study demonstrates that F and Cl are substituted in specific oxygen site in minerals that lead then to be more sensitive than trace elements to crystal chemistry and water amount variations thus melting conditions. Using those new partition coefficients, I modelled melting of potential sub-arc lithologies with variable quantity aqueous-fluid. This model is able to decipher 1) amount of aqueous-fluid involved in melting, 2) melting induced by fluid or melting of an hydrous mineral-bearing source and 3) melting of either pargasite-bearing lithology or phlogopite-bearing lithology and shows that sources of some primitive melts, for instance from Italy, bear pargasite and phlogopite, while some primitve melts seem to be the results of fluid-induced melts.

Arsenik är en naturligt förekommande halvmetall som orsakar stora hälsoproblem genom exponering t.ex. via dricksvatten. På grund av arseniks negativa effekter på människors hälsa sänktes den tillåtna gränsen i dricksvatten från 50 μg/l till 10 μg/l 2003 av WHO. Arsenik förekommer i huvudsak i två oorganiska former, arsenat (AsO43-) och arsenit (AsO33-), där arsenit är en betydligt mer mobil och toxisk form. Vilken form som dominerar påverkas i första hand av redoxförhållanden men även av pH. Reduktion från arsenat till arsenit är gynnsamma vid lägre pH och vid syrefria (reducerade) förhållanden. I Sverige har tidigare användning av arsenik, t.ex. vid impregneringsanläggningar, orsakat föroreningar som än idag ligger kvar. I Hjältevad i Eksjö kommun drev Televerket under 1940- till 1980-talet en impregneringsanläggning för telefonstolpar. Impregneringsvätska, innehållande bland annat arsenik, kunde spridas inom området till största del på grund av en tank som började läcka under 1960-talet. En omfattande sanering med jordtvätt genomfördes 1997. Senare kontroller har dock påvisat stadigt ökade halter. Med anledning av de ökade halterna har ett arbete inletts för att kartlägga föroreningssituationen. Syftet med examensarbetet är att utvärdera grundvattenkemin i Hjältevad genom att visualisera föroreningsföroreningsplymen, undersöka mobiliteten genom att undersöka samband mellan halten arsenik och kemiska parametrar samt göra en fördjupad analys av spridningsrisken med hjälp av Kd-värden. Data från jord- och grundvattenprovtagningar genomförda under augusti och september 2017 bearbetades med hjälp av ArcMap och Excel. Resultatet visade att låga redoxförhållanden sannolikt har bidragit till ökad spridning av arsenik vilket till stor del förekom i den reducerade formen arsenit. De högsta halterna var koncentrerade till området kring den f.d. läckande tanken, där halter så höga som 2200 μg/l kunde uppmätas i grundvattnet. Vidare visade provtagningsresultaten att mängden förorenad jord missbedömdes vid saneringen 1997 (halter på 238 mg/kg kunde uppmätas i jorden). Slutsatsen drogs att redoxförhållanden inom området är gynnsamma för att arsenik ska förekomma i den reducerade formen arsenit, att arseniks mobilitet med stor sannolikhet är betydligt högre än vad som tidigare bedömdes samt att risker föreligger om inga åtgärder vidtas. / Arsenic is a naturally occurring metalloid that causes major health problems for people affected by exposure, e.g. through their drinking water. Due to the negative effects on human health, the permissible concentration in drinking water was lowered in 2003, from 50 μg/l to 10 μg/l. Arsenic predominantly exists in two inorganic forms, arsenate (AsO43-) and arsenite (AsO33-), where arsenite is a more mobile and toxic. Which forms that dominates is controlled by pH and redox potential. Reduction from arsenate to arsenite is favorable at lower pH and at anoxic (reduced) conditions. In Sweden previous use of arsenic, e.g. at impregnation plants, caused pollution still affecting soils and groundwater. In Hjältevad, Eksjö municipality, an impregnation plant for telephone poles was run by Televerket during the 1940s to 1980s. Impregnating fluid, including arsenic, was spread in the area, mainly due a leaky storage tank during the 1960s. The site was remediated in 1997 using soil washing. However, monitoring program demonstrated steadily increased levels in a well situated downstream the contaminated area. Due to the increased contamination levels of arsenic in the ground water, a detailed investigation was initiated to identify the pollution situation. The main objective was to investigate about the chemical and physical processes affecting the mobilization of arsenic. Groundwater and soil materials were sampled from the area and evaluated using ArcMap and Excel. In support of this evaluation, distribution coefficients (Kd) for soil materials from the aqvifer were obtained by leaching tests performed at oxidized conditions. The result showed that reducing conditions in the aquifer appeared to have caused increased mobilization of arsenic in the area and that large amounts of pollution was not removed at the remediation in 1997 (levels of 238 mg/kg arsenic could be detected in the soil). In the collected samples, arsenic mainly occurred in the reduced form arsenite. The highest levels in the groundwater were found in the area around the former leaky tank, where concentrations up to 2200 μg/l was measured. The conclusion was that large amounts of pollution was not removed at the remediation in 1997, and that arsenic mobility seems to be significantly higher than previously assessed and that action needs to be taken to stop the spread.

Drei Verteilungskoeffizienten, die für physiologie-basierte Pharmakokinetik (PBPK)-Modelle relevant sind, wurden mit verschiedenen Ansätzen modelliert. Für den Blut/Luft-Verteilungskoeffizienten wurde ein auf linearen Solvatations-Energie-Beziehungen (LSER) beruhendes Literaturmodell angewendet und diskutiert. Mit einer schematischen Aufteilung des Blutkompartiments in Wasser und einen organischen Teil wurde der Blut/Luft-Verteilungskoeffizient mit einer linearen Regression von anderen Verteilungskoeffizienten vorhergesagt. Zusätzlich wurde ein Fragmentmodell entwickelt. Der Fett/Luft-Verteilungskoeffizient wurde mit dem LSER-Ansatz und mit anderen Verteilungskoeffizienten modelliert. Der Koeffizient Fett/Blut wurde aus den ersten beiden errechnet. Da der inverse dimensionslose Henry-Koeffizient Wasser/Luft-Verteilungskoeffizient bei der Blut/Luft-Modellierung zum Einsatz kommt und dieser aus dem Dampfdruck und der Wasserlöslichkeit gewonnen werden kann, wurde der Dampfdruck ebenfalls modelliert.

[pt] O coeficiente de partição octanol-água do composto 1,2-dipalmitoilsn-glicero-3-fosfatidilcolina (DPPC) foi investigado utilizando os métodos de integração termodinâmica e amostragem guarda-chuva através de simulações de dinâmica molecular atomística. Os campos de força AMBER/GAFF e CHARMM/CGenFF foram usados com seis modelos de água (SPC, TIP3P, TIP4P, TIP5P, OPC3 e OPC4) amplamente utilizados em simulações de dinâmica molecular. Dentre os modelos utilizados, o modelo de água OPC4 com os dois campos de força em estudo forneceu a melhor concordância com o coeficiente de partição experimental octanol-água do DPPC. No entanto, ainda existe muito espaço para melhorias nos modelos de água que estimam a tensão superficial de forma apropriada. Usando o modelo de água OPC4, a energia livre de Gibbs de transferência do DPPC do octanol para a fase aquosa foi calculada em 19,8(mais ou menos)0,3 e 20,2(mais ou menos)0,3 kcal mol-1 , estimando um coeficiente de partição octanol-água de 14,5(mais ou menos)0,4 e 14,8(mais ou menos)0,3 para os campos de força AMBER/GAFF e CHARMM/CGenFF, respectivamente. A amostragem guarda-chuva apresentou problemas de arrastes de moléculas de uma fase para outra, gerando artefatos e consequentemente subestimando os valores de energia livre e de coeficiente de partição octanol-água. Este estudo mostra a importância do desenvolvimento de novos modelos de água que reproduzam com precisão todas as suas características experimentais. A conciliação entre medições experimentais e cálculos teóricos do coeficiente de partição de moléculas anfifílicas poderia ser resolvida através do ajuste dos parâmetros do modelo de água. Este estudo possui grande importância na simulação de propriedades moleculares de importância em muitas áreas de aplicações científicas e industriais, tais como biofísica, surfactante, coloides, membranas, medicina, nanotecnologia, e indústrias alimentícias e farmacêuticas. / [en] The octanol-water partition coefficient of the compost 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) molecule wasinvestigated using the methods of thermodynamic integration and umbrellasampling through atomistic molecular dynamics simulations. TheAMBER/GAFF and CHARMM/CGenFF force fields were used with sixwater models (SPC, TIP3P, TIP4P, TIP5P, OPC3, and OPC4) widely usedin molecular dynamics simulations. Among the models used, the OPC4water model with the two force fields provided the best agreement with theexperimental octanol-water partition coefficient of the DPPC. However,there is still much room for improvement in water models that correctlyestimate the surface tension. Using the OPC4 water model, the Gibbs freeenergy of transferring DPPC from octanol to the aqueous phase wascalculated to be 19.8(plus minus)0.3 and 20.2(plus minus)0.3 kcal mol-1, estimating an octanolwater partition coefficient of 14.5(plus minus)0.4 and 14.8(plus minus)0.3 for the AMBER/GAFFand CHARMM/CGenFF force fields, respectively. Umbrella samplingpresented issues of molecules being dragged between the two phases,generating artifacts, and consequently underestimating the values of freeenergy and octanol-water partition coefficient. This study shows theimportance of developing new models of water that accurately reproduceall its experimental characteristics. The reconciliation betweenexperimental measurements and theoretical calculations of partitioncoefficients of amphiphilic molecules. This study may have greatimportance in many areas of scientific and industrial applications, such asbiophysics, surfactant, colloids, membranes, medicine, nanotechnology,and food and pharmaceutical industries.