Evolution of the source apportionment of the lipidic fraction from sediments along the Fensch River, France: a multimolecular approach

The Fensch River (FR) is one of the most contaminated rivers in France due to the population density and the concentration of industrial activities in this small watershed area. From upstream to downstream, the organic matter extracted from sediments has been analyzed by gas chromatography-mass spectrometry and molecules have been quantified and classified into natural, petrogenic, pyrogenic and sewage water (SW) markers. Upstream the river, anthropogenic molecules are already predominant and represent 87.1% of the molecules quantified. This proportion increases from upstream to downstream and rises to 96.8% at the confluence of the FR with the Moselle River. In the upper part of the FR the contamination is mainly due to human waste (coprostanol: 36.44 microg/g; 42.1% of anthropogenic markers). In the lower part, the contribution of SW markers decreases from 42.1 to 2.4% and the proportion of pyrogenic molecules increases from 29.6 to 59.6%. The major sources of pyrogenic organic matter have been determined by calculation of specific ratios on polycyclic aromatic hydrocarbons and by comparison with reported data. Coal tar, road runoff and atmospheric depositions of urban particles seem to be the major pyrogenic sources. Along the river, the proportion of petrogenic molecules remains constant and those molecules seem to be mainly inherited from road runoff, in the upper part of the FR. Industrial lubricants that occur in steel plant sludge are an additional source in the lower part of the river.     

Methodology for developing a high-precision ultrasound flow meter and fluid velocity profile reconstruction

This article reports the methodology used to develop a high-precision ultrasound transit time flow meter dedicated to liquid hydrocarbons. This kind of flow meter is designed for custody transfer applications requiring accuracy better than 0.15% of reading. We focus here on certain specific points to achieve this accuracy. The transit time method needs to estimate accurately the time delay between signals received by a pair of transducers. In this study, we review different ways of estimating this time delay. We also propose a specific configuration of the flow meter paths. In particular, this configuration compensates for the swirl phenomenon, which has a significant impact on the accuracy of the flow meter. We also propose a theoretical parametric profile to reconstruct the fluid velocity profile in order to perform in situ diagnosis of the flow. The parameters of the model are estimated from the measurements of the flow meter. Simulations and experimental results showed that this method provides characterization of the flow in disturbed and undisturbed flow conditions.     

Electric‐Field‐Controlled Alignment of Rod‐Shaped Fluorescent Nanocrystals in Smectic Liquid Crystal Defect Arrays

Periodic micro‐arrays of straight linear defects containing nanoparticles can be created over large surface areas at the transition from the nematic to smectic‐A phase in a nanoparticle–liquid crystal (LC) composite material confined under the effect of conflicting anchoring conditions (unidirectional planar vs normal) and electric fields. Anisomeric dichroic dye molecules and rod‐shaped fluorescent semiconductor nanocrystals (dot‐in‐rods) with large permanent electric dipole and high linearly polarized photoluminescence quantum yield align parallel to the local LC molecular director and follow its reorientation under application of the electric field. In the nano‐sized core regions of linear defects, where the director is undefined, anisotropic particles align parallel to the defect whereas spherical quantum dots do not show any particular interaction with the defect. Under application of an electric field, ferroelectric semiconductor nanoparticles in the core region align along the field, perpendicular to the defect direction, whereas dichroic dyes remain parallel to the defect. This study provides useful insights into the complex interaction of anisotropic nanoparticles and anisotropic soft materials such as LCs in the presence of external fields, which may help the development of field‐responsive nanoparticle‐based functional materials.     

Analysis of an intact G-protein coupled receptor by MALDI-TOF mass spectrometry: molecular heterogeneity of the tachykinin NK-1 receptor

Integral membrane proteins are among the most challenging targets for biomedical research as most important cellular functions are tied to these proteins. To analyze intrinsically their structure/function, their transduction mechanism, or both, these proteins are commonly expressed in cultured cells as recombinant proteins. However, it is not possible to check whether these recombinant proteins are homogeneously or heterogeneously expressed. Owing to difficulties in their purification, very few mass spectrometry studies have been performed with those proteins and even less with G-protein coupled receptors. Here we have set up a procedure that is highly compatible with MALDI-TOF mass spectrometry to analyze an intact histidine-tagged G-protein coupled, namely, the tachykinin NK-1 receptor expressed in CHO cells, solubilized and purified using cobalt or nickel chelating magnetic beads. The metal-chelating magnetic beads containing the receptor were directly spotted on the MALDI plate for analysis. SDS-PAGE, combined with in-gel digestion analyzed by mass spectrometry, Western blot ((His)6 and FLAG M2 tags), photoaffinity labeling with a radioactive agonist, and Edman sequencing, confirmed the identity of the purified protein as the human tachykinin NK-1 receptor. Mass spectrometry study of both the glycosylated and deglycosylated intact protein forms revealed the existence of several receptor species that is tempting to correlate with the unusual pharmacological behavior of the receptor.     

Design and facile production of recombinant resilin-like polypeptides: gene construction and a rapid protein purification method

Resilin is an elastic protein found in specialized regions of the cuticle of insects, which displays unique resilience and fatigue lifetime properties. As is the case with many elastomeric proteins, including elastin, gliadin and spider silks, resilin contains distinct repetitive domains that appear to confer elastic properties to the protein. Recent work within our laboratory has demonstrated that cloning and expression of exon 1 of the Drosophila melanogaster CG15920 gene, encoding a putative resilin-like protein, results in a recombinant protein that can be photochemically crosslinked to form a highly resilient, elastic biomaterial (Rec1 resilin). The current study describes a recursive cloning strategy for generating synthetic genes encoding multiple copies of consensus polypeptides, based on the repetitive domains within resilin-like genes from D. melanogaster and Anopheles gambiae. A simple non-chromatographic purification method that can be applied to these synthetic proteins and Rec1 is also reported. These methods for the design and purification of resilin-like periodic polypeptides will facilitate the future investigation of structural and functional properties of resilin, and the development of novel highly resilient biomaterials.     

Charge transport in cellular nanoparticle networks: meandering through nanoscale mazes

The transport of electrons through topologically complex two-dimensional Au nanoparticle networks has been investigated using a combination of low temperature (4.5 K) direct current I(V) measurements and numerical simulations. Intricate, spatially correlated nanostructured networks were formed via spin-casting. The topological complexity of the nanoparticle assemblies produces I(V) curves associated with nonlinearity exponents, zeta approximately 4.0. Simulations based on tunneling transport in sparse and inhomogeneous planar networks are used to elucidate the influence of topology on the value of zeta.     

Relevance of the skewness index in DTI exploration of multiple sclerosis

Object  To this day, no parameter can really monitor the progression of multiple sclerosis (MS). In this study, an index the skewness (S) derived from parameters calculated in diffusion tensor imaging (DTI) has been tested on MS patients for its ability to monitor the disease course. Materials and methods  Eighteen patients underwent two examinations within 3 months consisting of a clinical evaluation (EDSS) and DTI acquisitions on a 1.5 T imager. Tensor was calculated thanks to“home-made” software. Mean diffusivity (MD) and fractional anisotropy (FA) histograms were described for normal-appearing white matter (NAWM) and gray matter (GM) of patients with S and also with usually indices peak position (pp) and peak height (ph) for the whole group of patients and for two separate groups according to their clinical status (EDSS  ≤  3 and EDSS  > 3 at month 0). Results  Although no significant clinical evolution is observed over 3 months, S in GM showed a significant shift for both MD/FA histograms towards abnormal values for the whole group of patients (p = 0.02/p = 0.04) and for the group with EDSS  ≤  3 (p = 0.04/p = 0.007), while ph and pp do not. Conclusion  S in GM could be an alternative marker to monitor the disease course before the repercussion on the clinical score.     

Charge‐Transfer Interactions: An Efficient Tool for Recycling Bis(oxazoline)‐Copper Complexes in Asymmetric Henry Reactions

An anthracenyl‐modified chiral bis(oxazoline) copper complex has been demonstrated to efficiently promote nitroaldol reactions between structurally varying aldehydes and nitromethane or nitroethane. The catalyst was recovered through formation of a charge transfer complex between the chiral ligand and trinitrofluorenone and its subsequent precipitation with pentane. The efficiency of this procedure was proved through several consecutive catalytic cycles that allowed the sturdy formation of the expected product with a high enantioselectivity. The catalyst′s stability was also put to the test in an original multi‐substrate procedure. Following the same recovery concept, a new heterogeneous procedure was tested for which trinitrofluorenone was covalently linked to a silica support. Asymmetric heterogeneous catalysis was performed under these conditions as one of the few examples demonstrating the potential catalyst recycling in nitroaldol reactions through reversible, non‐covalent interactions.     

Impact of biofouling on diffusive gradient in thin film measurements in water

The technique of diffusive gradient in thin film (DGT) is commonly used to assess metal contamination in natural waters. In this paper, we assess the effect of biofouling on DGT measured labile concentrations in water and investigate whether an additional nuclepore polycarbonate membrane on the surface of DGT devices can limit biofilm growth. Simultaneous field deployments of DGT equipped with and without the additional membrane in a canal receiving wastewater were compared. The effect of the biofilm was also assessed in controlled laboratory experiments, completed by the experimental determination of several metals diffusion coefficients in the hydrogel and membrane systems. The biofilms effect was problematic only from the 10th day of accumulation. Accumulation of some elements is highly biased by the presence of a thick biofilm (Zn, Ni, Cd). The polycarbonate membrane improved the quantification of Cd and Ni but adversely affects the quantification of Cr and Co. A kinetic model is proposed to explain the biofilm role on the DGT measurement. Depending on the metals of interest, it is possible to limit bias due to biofilms by using an additional polycarbonate membrane.     

Risk and protection factors in fatal accidents

This paper aims at addressing the interest and appropriateness of performing accident severity analyses that are limited to fatal accident data. Two methodological issues are specifically discussed, namely the accident-size factors (the number of vehicles in the accident and their level of occupancy) and the comparability of the baseline risk. It is argued that - although these two issues are generally at play in accident severity analyses - their effects on, e.g., the estimation of survival probability, are exacerbated if the analysis is limited to fatal accident data. As a solution, it is recommended to control for these effects by (1) including accident-size indicators in the model, (2) focusing on different sub-groups of road-users while specifying the type of opponent in the model, so as to ensure that comparable baseline risks are worked with. These recommendations are applied in order to investigate risk and protection factors of car occupants involved in fatal accidents using data from a recently set up European Fatal Accident Investigation database (Reed and Morris, 2009). The results confirm that the estimated survival probability is affected by accident-size factors and by type of opponent. The car occupants’ survival chances are negatively associated with their own age and that of their vehicle. The survival chances are also lower when seatbelt is not used. Front damage, as compared to other damaged car areas, appears to be associated with increased survival probability, but mostly in the case in which the accident opponent was another car. The interest of further investigating accident-size factors and opponent effects in fatal accidents is discussed.