The relevance of the Laplacian of intracule and extracule density distributions for analyzing electron-electron interactions in molecules

A topological analysis of intracule and extracule densities and their Laplacians computed within the Hartree-Fock approximation is presented. The analysis of the density distributions reveals that among all possible electron-electron interactions in atoms and between atoms in molecules only very few are located rigorously as local maxima. In contrast, they are clearly identified as local minima in the topology of Laplacian maps. The conceptually different interpretation of intracule and extracule maps is also discussed in detail. An application example to the C2H2, C2H4, and C2H6 series of molecules is presented

The aromatic fluctuation index (FLU): a new aromaticity index based on electron delocalization

In this work, the aromatic fluctuation index (FLU) that describes the fluctuation of electronic charge between adjacent atoms in a given ring is introduced as a new aromaticity measure. This new electronic criterion of aromaticity is based on the fact that aromaticity is related to the cyclic delocalized circulation of π electrons. It is defined not only considering the amount of electron sharing between contiguous atoms, which should be substantial in aromatic molecules, but also taking into account the similarity of electron sharing between adjacent atoms. For a series of rings in 15 planar polycyclic aromatic hydrocarbons, we have found that, in general, FLU is strongly correlated with other widely used indicators of local aromaticity, such as the harmonic-oscillator model of aromaticity, the nucleus independent chemical shift, and the para-delocalization index (PDI). In contrast to PDI, the FLU index can be applied to study the aromaticity of rings with any number of members and it can be used to analyze both the local and global aromatic character of rings and molecules

Relacions estructura-propietat per un conjunt d'hidrocarburs a partir de nous descriptors tridimensionals derivats de la semblança molecular quàntica

En aquest article es defineixen uns nous índexs tridimensionals per a la descripció de les molècules a partir de paràmetres derivats de la Teoria de la Semblança Molecular i de les distàncies euclidianes entre els àtoms i les càrregues atòmiques efectives. Aquests indexs, anomenats 3D, s'han aplicat a l'estudi de les relacions estructura-propietat d'una família d'hidrocarburs, i han demostrat una capacitat de descripció de tres propietats de la família (temperatura d'ebullició, temperatura de fusió i densitat) molt més acurada que quan s'utilitzen els indexs 2D clàssics

Alkyl nitrates in outflow from North America over the North Atlantic during Intercontinental Transport of Ozone and Precursors 2004

This paper is based on alkyl nitrate measurements made over the North Atlantic as part of the International Consortium for Research on Atmospheric Transport and Transformation (ICARTT). The focus is on the analysis of air samples collected on the UK BAe-146 aircraft during the Intercontinental Transport of Ozone and Precursors (ITOP) project, but air samples collected on board the NASA DC-8 and NOAA WP-3D aircraft as part of a Lagrangian experiment are also used. The ratios between the alkyl nitrates and their parent hydrocarbons are compared with those expected from chemical theory. Further, a box model is run to investigate the temporal evolution of the alkyl nitrates in three Lagrangian case studies and compared to observations. The air samples collected during ITOP do not appear to be strongly influenced by oceanic sources, but rather are influenced by emissions from the N.E. United States and from Alaskan fires. There also appears to be a widespread common source of ethyl nitrate and 1-propyl nitrate other than from their parent hydrocarbons. The general agreement between the alkyl nitrate data and photochemical theory suggests that during the first few days of transport from the source region, photochemical production of alkyl nitrates, and thus ozone, had taken place. The observations in the more photochemically processed air masses are consistent with the alkyl nitrate production reactions no longer dominating the peroxy radical self/cross reactions. Further, the results also suggest that the rates of photochemical processing in the Alaskan smoke plumes were small.

A preliminary investigation of the release of oil from contaminated clays and other fine-grained sediments during consolidation

Fine-grained sediments on land, or in a freshwater or marine environment, may become contaminated with a wide range of pollutants including hydrocarbons. This paper is concerned with preliminary studies of the mobilization and transportation of hydrocarbons, during the process of consolidation, to adjacent sediments or water bodies. A modified Rowe Cell was used to measure the consolidation properties of prepared kaolinite and bentonite clay-water slurries, with and without the addition of oil, along with hydrocarbon-bearing drill-cuttings samples taken from the sea-bed adjacent to two North Sea oil-well platforms. The consolidation properties of the kaolinite and bentonite clay slurries were little altered by the addition of oil, which was present at concentrations of between 8073 and 59 572 mg kg(-1). During each consolidation stage, samples of the expelled pore-fluids were collected and analysed for oil content. These values were very low in comparison with the original oil concentration in the samples and changed little between each consolidation stage. Analysis of the slurry samples both before and after consolidation confirms that, proportionally, little oil is removed as a result of consolidation. The implication of these results is that, for the range of samples tested, the very high hydraulic gradients and particle rearrangements that occur during the process of consolidation are capable of releasing only proportionally small amounts of oil bound to the fine-grained clay and silt particles.

Remediation of soils contaminated with petrol and diesel with lime

Lime treatment of hydrocarbon-contaminated soils offers the potential to stabilize and solidify these materials, with a consequent reduction in the risks associated with the leachate emanating from them. This can aid the disposal of contaminated soils or enable their on-site treatment. In this study, the addition of hydrated lime and quicklime significantly reduced the leaching of total petroleum hydrocarbons (TPH) from soils polluted with a 50:50 petrol/diesel mixture. Treatment with quicklime was slightly more effective, but hydrated lime may be better in the field because of its ease of handling. It is proposed that this occurs as a consequence of pozzolanic reactions retaining the hydrocarbons within the soil matrix. There was some evidence that this may be a temporary effect, as leaching increased between seven and 21 days after treatment, but the TPH concentrations in the leachate of treated soils were still one order of magnitude below those of the control soil, offering significant protection to groundwater. The reduction in leaching following treatment was observed in both aliphatic and aromatic fractions, but the latter were more affected because of their higher solubilty. The results are discussed in the context of risk assessment, and recommendations for future research are made.

A preliminary investigation of the release of oil from contaminated clays and other fine-grained sediments during consolidation

Fine-grained sediments on land, or in a freshwater or marine environment, may become contaminated with a wide range of pollutants including hydrocarbons. This paper is concerned with preliminary studies of the mobilization and transportation of hydrocarbons, during the process of consolidation, to adjacent sediments or water bodies. A modified Rowe Cell was used to measure the consolidation properties of prepared kaolinite and bentonite clay-water slurries, with and without the addition of oil, along with hydrocarbon-bearing drill-cuttings samples taken from the sea-bed adjacent to two North Sea oil-well platforms. The consolidation properties of the kaolinite and bentonite clay slurries were little altered by the addition of oil, which was present at concentrations of between 8073 and 59 572 mg kg(-1). During each consolidation stage, samples of the expelled pore-fluids were collected and analysed for oil content. These values were very low in comparison with the original oil concentration in the samples and changed little between each consolidation stage. Analysis of the slurry samples both before and after consolidation confirms that, proportionally, little oil is removed as a result of consolidation. The implication of these results is that, for the range of samples tested, the very high hydraulic gradients and particle rearrangements that occur during the process of consolidation are capable of releasing only proportionally small amounts of oil bound to the fine-grained clay and silt particles.

Flavour characterization of fresh and processed pennywort (Centella asiatica L.) juices

The flavour characteristics of fresh and processed pennywort juices treated by pasteurization, sterilization and high pressure processing (HPP) were investigated by using solid-phase micro-extraction combined with gas chromatography-mass spectrometry. Sesquiterpene hydrocarbons comprised the major class of volatile components present and the juices had a characteristic smell due to the presence of volatile compounds including β-caryophyllene, humulene, E-β-farnesene, α-copaene, alloaromadendrene and β-elemene. All processing operations caused a reduction in the total volatile concentration, but HPP caused more volatile acyclic alcohols, aldehydes and oxygenated monoterpenoids to be retained than pasteurization and sterilization. Ketones were not present in fresh pennywort juice, but 2-butanone and 3-nonen-2-one were generated in all processed juices, and 2-nonanone and 2-hexanone were present in pasteurized and sterilized juices. Other chemical changes including isomerization were also reduced by HPP compared to pasteurization, and sterilization.

Radiative forcing due to changes in ozone and methane caused by the transport sector

The year 2000 radiative forcing (RF) due to changes in O3 and CH4 (and the CH4-induced stratospheric water vapour) as a result of emissions of short-lived gases (oxides of nitrogen (NOx), carbon monoxide and non-methane hydrocarbons) from three transport sectors (ROAD, maritime SHIPping and AIRcraft) are calculated using results from five global atmospheric chemistry models. Using results from these models plus other published data, we quantify the uncertainties. The RF due to short-term O3 changes (i.e. as an immediate response to the emissions without allowing for the long-term CH4 changes) is positive and highest for ROAD transport (31mWm-2) compared to SHIP (24 mWm-2) and AIR (17 mWm-2) sectors in four of the models. All five models calculate negative RF from the CH4 perturbations, with a larger impact from the SHIP sector than for ROAD and AIR. The net RF of O3 and CH4 combined (i.e. including the impact of CH4 on ozone and stratospheric water vapour) is positive for ROAD (+16(±13)(one standard deviation) mWm-2) and AIR (+6(±5) mWm-2) traffic sectors and is negative for SHIP (-18(±10) mWm-2) sector in all five models. Global Warming Potentials (GWP) and Global Temperature change Potentials (GTP) are presented for AIR NOx emissions; there is a wide spread in the results from the 5 chemistry models, and it is shown that differences in the methane response relative to the O3 response drive much of the spread.

Headspace volatile markers for sensitivity of cocoa (Theobroma cacao L.) somatic embryos to cryopreservation

The mechanisms that reduce the viability of plant somatic embryos following cryopreservation are not known. The objective of the present study was to evaluate the sensitivity of cocoa (Theobroma cacao L.) somatic embryos at different stages of an encapsulation-dehydration protocol using stress-related volatile hydrocarbons as markers of injury and recovery. The plant stress hormone ethylene and volatile hydrocarbons derived from hydroxyl radicals (methane) and lipid peroxidation (ethane) were determined using gas chromatography headspace analysis. Ethylene and methane were the only volatiles detected, with both being produced after each step of the cryogenic protocol. Ethylene production was significantly reduced following exposure to liquid nitrogen, but then increased in parallel with embryo recovery. In contrast, the production of methane was cyclic during recovery, with the first cycle occurring earlier for embryos recovered from liquid nitrogen and desiccation than those recovered from earlier steps in the protocol. These results suggest that loss of somatic embryo viability during cryopreservation may be related to the oxidative status of the tissue, and its capacity to produce ethylene. This study has demonstrated that headspace volatile analysis provides a robust non-destructive analytical approach for assessing the survival and recovery of plant somatic embryos following cryopreservation.

Effects of dredging in Goteborg Harbor, Sweden, assessed by biomarkers in eelpout (Zoarces viviparus)

We used a battery of biomarkers in fish to study the effects of the extensive dredging in Goteborg harbor situated at the river Gota alv estuary, Sweden. Eelpout (Zoarces viviparus) were sampled along a gradient into Goteborg harbor, both before and during the dredging. Biomarker responses in the eelpout before the dredging already indicated that fish in Goteborg harbor are chronically affected by pollutants under normal conditions compared to those in a reference area. However, the results during the dredging activities clearly show that fish were even more affected by remobilized pollutants. Elevated ethoxyresorufin-O-deethylase activities and cytochrome P4501A levels indicated exposure to polycyclic aromatic hydrocarbons. Elevated metallothionein gene expression indicated an increase in metal exposure. An increase in general cell toxicity, measured as a decrease in lysosomal membrane stability, as well as effects on the immune system also could be observed in eelpout sampled during the dredging. The results also suggest that dredging activities in the Gota alv estuary can affect larger parts of the Swedish western coast than originally anticipated. The present study demonstrates that the application of a set of biomarkers is a useful approach in monitoring the impact of anthropogenic activities on aquatic environments.

Haem peroxidase activity in Daphnia magna: A biomarker for sub-lethal toxicity assessments of kerosene-contaminated groundwater

A novel biomarker was developed in Daphnia magna to detect organic pollution in groundwater. The haem peroxidase assay, which is an indirect means of measuring oxidase activity, was particularly sensitive to kerosene contamination. Exposure to sub-lethal concentrations of kerosene-contaminated groundwater resulted in a haem peroxidase activity increase by dose with a two-fold activity peak at 25%. Reproduction in D. magna remained unimpaired when exposed to concentrations below 25% for 21 days, and a decline in fecundity was only observed at concentrations above the peak in enzyme activity. The measurement of haem peroxidase activity in D. magna detected sublethal effects of kerosene in just 24 h, whilst offering information on the health status of the organisms. The biomarker may be useful in determining concentrations above which detrimental effects would occur from long-term exposure for fuel hydrocarbons. Moreover, this novel assay detects exposure to chemicals in samples that would normally be classified as non-toxic by acute toxicity tests.

Multivariate relationships between groundwater chemistry and toxicity in an urban aquifer

Multivariate statistical methods were used to investigate file Causes of toxicity and controls on groundwater chemistry from 274 boreholes in an Urban area (London) of the United Kingdom. The groundwater was alkaline to neutral, and chemistry was dominated by calcium, sodium, and Sulfate. Contaminants included fuels, solvents, and organic compounds derived from landfill material. The presence of organic material in the aquifer caused decreases in dissolved oxygen, sulfate and nitrate concentrations. and increases in ferrous iron and ammoniacal nitrogen concentrations. Pearson correlations between toxicity results and the concentration of individual analytes indicated that concentrations of ammoinacal nitrogen, dissolved oxygen, ferrous iron, and hydrocarbons were important where present. However, principal component and regression analysis suggested no significant correlation between toxicity and chemistry over the whole area. Multidimensional Scaling was used to investigate differences in sites caused by historical use, landfill gas status, or position within the sample area. Significant differences were observed between sites with different historical land use and those with different gas status. Examination of the principal component matrix revealed that these differences are related to changes in the importance of reduced chemical species.

A mechanistic study of the low pressure pyrolysis of linear siloxanes

Matrix isolation IR spectroscopy has been used to study the vacuum pyrolysis of 1,1,3,3-tetramethyldisiloxane (L1), 1,1,3,3,5,5-hexamethyltrisiloxane (L2) and 3H,5H-octamethyltetrasiloxane (L3) at ca. 1000 K in a flow reactor at low pressures. The hydrocarbons CH3, CH4, C2H2, C2H4, and C2H6 were observed as prominent pyrolysis products in all three systems, and amongst the weaker features are bands arising from the methylsilanes Me2SiH2 (for L1 and L2) and Me3SiH (for L3). The fundamental of SiO was also observed very weakly. By use of quantum chemical calculations combined with earlier kinetic models, mechanisms have been proposed involving the intermediacy of silanones Me2Si = O and MeSiH = O. Model calculations on the decomposition pathways of H3SiOSiH3 and H3SiOSiH2OSiH3 show that silanone elimination is favoured over silylene extrusion.

Low molecular weight organogelators from self-assembling synthetic tripeptides with coded amino acids: morphological, structural, thermodynamic and spectroscopic investigations

A series of self-assembling terminally blocked tripeptides (containing coded amino acids) form gels in various aromatic solvents including benzene, toluene, xylenes at low concentrations. However these tripeptides do not form gels in aliphatic hydrocarbons like n-hexane, cyclohexane, n-decane etc. Morphological studies of the dried gel indicate the presence of an entangled fibrous network, which is responsible for gelation. Differential scanning calorimetric (DSC) studies of the gels produced by peptide 1 clearly demonstrates thermoreversible nature of the gel and tripeptide-solvent complex may be produced during gel formation. FT-IR and H-1 NMR studies of the gels demonstrate that an intermolecular hydrogen-bonding network is formed during gelation. Single crystal X-ray diffraction studies for peptides 1, 2 and 3 have been performed to investigate the molecular arrangement that might be responsible for forming the fibrous network of these self-assembling peptide gelators. It has been found that the morph responsible for gelation of peptides 1, 2 and 3 in benzene is somewhat different from that of its xerogel.