Dissociation processes of ionized freons: CHFCl2+ and CF2Cl2+ in the gas phase.

The present study reveals the effects of symmetry on how the distribution and flow of energy play out on the decomposition of small halocarbons. Unimolecular decay of the freons CHFCl2 and CF2Cl2 when ionized has been investigated. Mass spectrometric results that encompass isotope effects (peak heights) and energy distribution in the exit channel (peak shapes) are interpreted by computational methods. Non-statistical processes of electronic predissociation and isolated state decay are shown to be directly associated with molecular symmetry.

Interaction between indigenous hydrocarbon-degrading bacteria in reconstituted mixtures for remediation of weathered oil in soil.

It has been demonstrated that biostimulation is necessary to investigate the interactions between indigenous bacteria and establish an approach for the bioremediation of soils contaminated with weathered oil. This was achieved by adjusting the carbon (C)/nitrogen (N)/phosphorus (P) ratio to 100/10/1 combined with the application of 0.8 mL/kg Tween-80. In addition, three indigenous bacteria isolated from the same soil were introduced solely or combined concomitantly with stimulation. Removal of n-alkanes and the ratios of n-heptadecane to pristane and n-octadecane to phytane were taken to indicate their biodegradation performance over a period of 16 weeks. One strain of Pseudomonas aeruginosa D7S1 improved the efficiency of the process of stimulation. However, another Pseudomonas aeruginosa, D5D1, inhibited the overall process when combined with other bacteria. One strain of Bacillus licheniformis D1D2 did not affect the process significantly. The Fourier transform infrared analysis of the residual hydrocarbons supported the conclusions pertaining to the biodegradation processes when probing the modifications in densities and stretching. The indigenous bacteria cannot mutually benefit from their metabolisms for bioremediation if augmented artificially. However, the strain Pseudomonas. aeruginosa D7S1 was able to perform better alone than in a consortium of indigenous bacteria.

Molecular Transport across Oil-Brine Interfaces Impacts Interfacial Tension: Time-Effects in Buoyant and Pendant Drop Measurements.

The buoyant drop method is a ubiquitous tool for addressing phenomena at the liquid-liquid interface via the determination of the interfacial tension (IFT) between two immiscible phases. Here, the focus is on how electrolytes (in an aqueous phase) and carboxylic acids (in a decane phase) impact the interfacial layer between the two phases. The IFT measurement provides a single number, which is not fulfilling when it comes to deducing information about a complex multiparameter system. Furthermore, the temporal evolution of IFT does not always reach a steady-state value on a time scale, which is realistic to use for comparative studies. We have investigated the temporal evolution of IFT in a series of experiments with varying compositions of the decane-carboxylic acid phase and the brine phase. The results show that there are at least two opposing effects in play. For water-soluble acids, the IFT initially increases with time until a turnover point is reached from where there is a gradual decay. The IFT at the turnover point is close to that of the pure water-decane system. For a poorly water-soluble acid, the IFT shows a much smaller increase and the turnover happens much faster. For a water-soluble acid, there is a high degree of sensitivity toward the electrolyte; it determines the position (in time) of the IFT peak and the steepness of the subsequent decay. Now, if the phases are reversed, that is, by placing a drop of brine in the decane-surfactant phase, the IFT decreases with time regardless of the acid and with little impact of the electrolyte and its concentration in the brine. We propose an explanation for the observed behavior (supported by COSMO-RS calculations), which is based on diffusion in and out of the two phases, solubility, and interfacial reactivity (i.e., aggregation between electrolytes and carboxylic acids).

Real-time monitoring of oil-induced micellar transitions in viscoelastic surfactants by small-angle X-ray scattering.

HYPOTHESIS: Viscoelastic surfactant solutions with entangled wormlike micelles (WLMs) display dramatic changes in rheological properties when exposed to hydrophobic substances. This change is key in the oil and gas industry and for drug delivery. The changes in viscoelastic properties are believed to be a result of changes in micellar shape due to the oil solubilization. The time dependence of the process has practical importance, yet its mechanism is unknown. We set out to map the structural changes with time using small-angle x-ray scattering (SAXS). EXPERIMENT: A surfactant system with erucamidopropyl hydroxypropyl sulfobetaine as the active ingredient was homogenized with three concentrations of n-decane (70 mM, 140 mM, 280 mM) in 600 mM CaCl2. The samples were monitored with time using SAXS. Model fits were used to determine the structures present in the sample at each time interval. FINDINGS: The entangled WLMs disappeared while spherical decane-swollen micelles formed with time, explaining the sharp decrease in viscosity. It was shown that the time at which the spherical swollen micelles appeared depends on the concentration of n-decane. This insight allows control of the spherical micelle appearance time, which is important for the successful application of WLMs in sectors that require WLMs to persist for a set time before they transform.

Tuning and Tracking of Coherent Shear Waves in Molecular Films.

We have determined the time-dependent displacement fields in molecular sub-micrometer thin films as response to femtosecond and picosecond laser pulse heating by time-resolved X-ray diffraction. This method allows a direct absolute determination of the molecular displacements induced by electron-phonon interactions, which are crucial for, for example, charge transport in organic electronic devices. We demonstrate that two different modes of coherent shear motion can be photoexcited in a thin film of organic molecules by careful tuning of the laser penetration depth relative to the thickness of the film. The measured response of the organic film to impulse heating is explained by a thermoelastic model and reveals the spatially resolved displacement in the film. Thereby, information about the profile of the energy deposition in the film as well as about the mechanical interaction with the substrate material is obtained.

A health equity impact assessment umbrella program (AAPRISS) to tackle social inequalities in health: program description.

BACKGROUND: The failure to simultaneously address two objectives (increasing the average health of the population and reducing health inequalities) may have led to what has been observed in France so far: an overall decrease in mortality and increase in inequality. OBJECTIVE: The Apprendre et Agir pour Réduire les Inégalités Sociales de Santé (AAPRISS) methodology is to analyze and modify interventions that are already underway in terms of their potential impact on health inequalities. It relies on partnership between researchers and actors in the health field, as well as policy makers. In this paper, we describe the program and discuss its feasibility and acceptability. METHODS: This program is not a single intervention, but a process aiming at assessing and reshaping existing health programs, therefore acting as a kind of meta-intervention. The program develops scientific and methodological support stemming from co-construction methods aimed at increasing equity within the programs. Stakeholders from prevention policy-making and the health care system, as well as researchers, collaborate in defining interventions, monitoring their progress, and choosing indicators, methods and evaluation procedures. The target population is mainly the population of the greater Toulouse area. The steps of the process are described: (1) establishment of AAPRISS governance and partnerships; (2) inclusion of projects; and (3) the projects' process. DISCUSSION: Many partners have rallied around this program, which has been shown to be feasible and acceptable by partners and health actors. A major challenge is understanding each partner's expectations in terms of temporality of interventions, expected outcomes, assessment methods and indicators. Analyzing the projects has been quite feasible, and some modifications have been implemented in them in order to take inequalities in health into account.

Hydrocarbon binding by proteins: structures of protein binding sites for ≥C10 linear alkanes or long-chain alkyl and alkenyl groups.

In order to identify potential de novo enzyme templates for the cleavage of C­C single bonds in long-chain hydrocarbons, we analyzed protein structures that bind substrates containing alkyl and alkenyl functional groups. A survey of ligand-containing protein structures deposited in the Protein Data Bank resulted in 874 entries, consisting of 194 unique ligands that have ≥10 carbons in a linear chain. Fatty acids and phospholipids are the most abundant types of ligands. Hydrophobic amino acids forming α-helical structures frequently line the binding pockets. Occupation of these binding sites was evaluated by calculating both the buried surface area and volume employed by the ligands; these quantities are similar to those computed for drug­protein complexes. Surface complementarity is relatively low due to the nonspecific nature of the interaction between the long-chain hydrocarbons and the hydrophobic amino acids. The selected PDB structures were annotated on the basis of their SCOP and EC identification numbers, which will facilitate design template searches based on structural and functional homologies. Relatively low surface complementarity and ∼55% volume occupancy, also observed in synthetic-host, alkane-guest systems, suggest general principles for the recognition of long-chain linear hydrocarbons.

[Territorial translation of the National Health and Nutrition Program in Midi-Pyrénées, France]. / La traduction rerritoriale du Programme national nutrition santé (PNNS) en Midi-Pyrénées, France.

Inspired by the Hygienist Movement, which associates good health with regular, moderate exercise, the National Health and Nutrition Program identifies a lack of physical activity as a risk factor for many chronic diseases. As such, the Program encourages people to take care of their bodies by inciting a moral obligation to develop a physically active lifestyle and follow a healthy diet. With the overall goal of improving the health of the population by acting on nutrition, the Program focuses on primary prevention, screening and early treatment of conditions like heart disease, cancer, obesity, osteoporosis and diabetes. As an incentive program developed in keeping with the biopolitical views of the 1970s that saw education as an alternative means to hospitals for achieving good health, the Program is also a good public action tool for controlling costs.

Synthetic and mechanistic insight into nosylation of glycine residues.

The Fukuyama-Mitsunobu alkylation procedure is widely used to introduce alkyl substituents to amino groups in general and N-alkylation of peptides in particular. Here we have investigated the procedure in detail for N-alkylation of peptides with N-terminal glycine residues, based on the observation that standard conditions lead to substantial bis-nosylation of the glycine amino group. A systematic evaluation of this observation was carried out and it was demonstrated that for peptides with alanine, ß-alanine or γ-aminobutyric acid (GABA) as N-terminal residues mono-nosylation was observed under the same conditions. Moreover, bis-nosylation was independent of the type of resin, neighboring amino acid and nature of the peptide. Calculations suggest that the reason for the bis-nosylation is the fact that the deprotonated mono-nosyl species is particularly stable in the case of the terminal Gly residue because the N(-) residue can become closer to the SO(2) unit. Finally, the mono-nosylated N-terminal glycine could be obtained by careful optimization of the procedure, adding only one equivalent of 2-nitrobenzenesulfonyl chloride.