Kinetic Formulation and Uniqueness for Scalar Conservation Laws with Discontinuous Flux

We prove a uniqueness result for BV solutions of scalar conservation laws with discontinuous flux in several space dimensions. The proof is based on the notion of kinetic solution and on a careful analysis of the entropy dissipation along the discontinuities of the flux.     

Development of a broad spectrum method for measuring flame retardants - Overcoming the challenges of non-invasive human biomonitoring studies

Flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs) and phosphate flame retardants (PFRs), are a diverse group of compounds that are used to improve fire safety in many consumer products, such as furniture, textiles, electronics, etc. As these compounds are potentially harmful for human health, there is a need to better understand human exposure. Exposure to environmental contaminants can be monitored by the measurement of external sources of exposures and also by the determination of contaminant levels in human samples. For ethical and practical reasons, noninvasive matrices, such as hair, are preferred but, unfortunately, not widely used due to methodological limitations. A major challenge is sample availability: only small amounts can be sampled per individual. Multi-residue methods are therefore essential in order to determine multiple compounds in low sample amounts. In the framework of the FP7 project (INFLAME), an analytical method for the simultaneous determination of PBDEs and PFRs in human hair has been optimized and validated. Before extraction, hair samples (200 mg) were denaturated in nitric acid (HNO₃) for 25 min at 25 °C. Consecutively, the samples were extracted using a mixture of hexane:dichloromethane, and extracts were further fractionated on Florisil. Fraction A which contained PBDEs was additionally cleaned on acidified silica gel and measured by gas chromatography coupled with electron capture negative ionization mass spectrometry (GC-ECNI-MS), while fraction B containing PFRs was directly analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). This approach resulted in recoveries between 81–120 % for PBDEs and 75–113 % for PFRs (relative standard deviation (RSD)?n?=?9). The optimized multi-residue method has been applied to 20 human hair samples. The obtained results indicated that the levels of PBDEs in hair samples were very low (0.2–12 ng/g) in relation to PBDE levels in human hair samples from other studies and most of the time below the method limit of quantification (LOQ_m). On the contrary, the PFR levels were relatively high as they were in the range of the levels previously found in dust samples (2–5,032 ng/g hair). We would like to highlight that the contribution of air and dust cannot be neglected (especially in the case of PFRs); therefore, we suggest that hair might be a good indicator of retrospective and integral exposure (which includes atmospheric deposition as well as endogenous mechanisms). Moreover, the aim of our study is focused on exposure assessment and levels detected in hair (independently of whether they come from internal or external exposure) and will significantly contribute to the exposure assessment. Graphical abstract

Hair - an efficient way for sampling of personal cloud of exposure. Copyright ©2014 iStockphoto LP     

An exact branch-and-price algorithm for scheduling rescue units during disaster response

In disaster operations management, a challenging task for rescue organizations occurs when they have to assign and schedule their rescue units to emerging incidents under time pressure in order to reduce the overall resulting harm. Of particular importance in practical scenarios is the need to consider collaboration of rescue units. This task has hardly been addressed in the literature. We contribute to both modeling and solving this problem by (1) conceptualizing the situation as a type of scheduling problem, (2) modeling it as a binary linear minimization problem, (3) suggesting a branch-and-price algorithm, which can serve as both an exact and heuristic solution procedure, and (4) conducting computational experiments – including a sensitivity analysis of the effects of exogenous model parameters on execution times and objective value improvements over a heuristic suggested in the literature – for different practical disaster scenarios. The results of our computational experiments show that most problem instances of practically feasible size can be solved to optimality within ten minutes. Furthermore, even when our algorithm is terminated once the first feasible solution has been found, this solution is in almost all cases competitive to the optimal solution and substantially better than the solution obtained by the best known algorithm from the literature. This performance of our branch-and-price algorithm enables rescue organizations to apply our procedure in practice, even when the time for decision making is limited to a few minutes. By addressing a very general type of scheduling problem, our approach applies to various scheduling situations.     

Thermal stability and flame retardancy of polyester fabrics sol–gel treated in the presence of boehmite nanoparticles

Polyester fabrics have been treated with hybrid organic-inorganic sols containing aluminium hydroxide, namely a synthetic boehmite. The treated fabrics have been thoroughly investigated by infrared spectroscopy, scanning electron microscopy coupled to elemental analysis and thermogravimetry. Furthermore, the flammability of the coated fabrics has been assessed and compared with that achieved by applying the two components separately. More specifically, flammability tests have shown that the sol–gel treatment in the presence of boehmite nanoparticles is able to suppress the dripping phenomenon, which represents the main issue to fulfil for polyester fabrics.     

Facile Synthesis of 3-Alkyl-5-methyloxazolidine-2,4-diones and N-Lactoyl-N,N′-dialkylureas

The reaction between aliphatic amines and propylene carbonate can be performed in solventless conditions under microwave irradiation, becoming nearly complete within 15 min of irradiation. Oxidation of the formed mixture of 2-hydroxyethylcarbamates gives 3,5-methylalkyl-oxazolidine-2,4-diones. These compounds can react further with aliphatic primary amines to give N-lactoylureas.

A high selective and sensitive liquid chromatography–tandem mass spectrometry method for quantization of BPA urinary levels in children

A selective and highly sensitive liquid chromatography–tandem mass spectrometry method has been developed and validated for determination of Bisphenol A (BPA) in human urine using labeled d₆-BPA as internal standard. BPA was purified from human urine by affinity chromatography on solid extraction AFFINIMIP® Bisphenol A cartridges, based on molecularly imprinted polymers. After purification, the samples were analyzed on a Phenomenex Kinetex 100?×?4.6 mm, 2.6 μm particle PFP reversed-phase HPLC column, coupled to a triple quadrupole mass spectrometer by an electrospray ion source. Analyses were performed in the multiple reaction monitoring mode and negative ionization; the product ions at 133.2 and 212.1?m/z for BPA and at 138.2 and 215.0?m/z for d₆-BPA were monitored to assess unambiguous identification. The linearity of the detector response was verified in human urine over the concentration range 0.100–200 ng/mL. The detection limit was calculated as 0.03 ng/mL and the limit of quantification of the method is 0.10 ng/mL. This LC/ESI-MS/MS method was in-house validated evaluating specificity, trueness, within-day and between-days precision. The mean recoveries of BPA from spiked urine samples were higher than 94 % and good reproducibility (relative standard deviations?≤?8.1 %) was observed. The developed method was applied to a pilot study involving 105 children, aged from 6 to 14 years (16 normal weight and 89 obese children), from the Regione Campania (Southern Italy). The aim of this study was to determine the concentrations of BPA in urine of children and possible correlations with childhood obesity.     

Dynamic Complex‐to‐Complex Transformations of Heterobimetallic Systems Influence the Cage Structure or Spin State of Iron(II) Ions

Two new heterobimetallic cages, a trigonal‐bipyramidal and a cubic one, were assembled from the same mononuclear metalloligand by adopting the molecular library approach, using iron(II) and palladium(II) building blocks. The ligand system was designed to readily assemble through subcomponent self‐assembly. It allowed the introduction of steric strain at the iron(II) centres, which stabilizes its paramagnetic high‐spin state. This steric strain was utilized to drive dynamic complex‐to‐complex transformations with both the metalloligand and heterobimetallic cages. Addition of sterically less crowded subcomponents as a chemical stimulus transformed all complexes to their previously reported low‐spin analogues. The metalloligand and bipyramid incorporated the new building block more readily than the cubic cage, probably because the geometric structure of the sterically crowded metalloligand favours the cube formation. Furthermore it was possible to provoke structural transformations upon addition of more favourable chelating ligands, converting the cubic structures into bipyramidal ones.     

Argon cluster cleaning of Ga+ FIB-milled sections of organic and hybrid materials

Secondary ion mass spectrometry studies have been made of the removal of the degraded layer formed on polymeric materials when cleaning focused ion beam (FIB)-sectioned samples comprising both organic and inorganic materials with a 30-keV Ga⁺ FIB. The degraded layer requires a higher-than-expected Ar gas cluster ion beam (GCIB) dose for its removal, and it is shown that this arises from a significant reduction in the layer sputtering yield compared with that for the undamaged polymer. Stopping and Range of Ions in Matter calculations for many FIB angles of incidence on flat polymer surfaces show the depth of the damage and of the implantation of the Ga⁺ ions, and these are compared with the measured depth profiles for Ga⁺-implanted flat polymer surfaces at several angles of incidence using an Ar⁺ GCIB. The Stopping and Range of Ions in Matter depth and the measured dose give the sputtering yield volume for this damaged and Ga⁺-implanted layer. These, and literature yield values for Ga⁺ damaged layers, are combined on a plot showing how the changing sputtering yield is related to the implanted Ga density for several polymer materials. This plot contains data from both the model flat poly(styrene) surfaces and FIB-milled sections showing that these 2 surfaces have the same yield reduction. The results show that the damaged and Ga⁺-implanted layer's sputtering rate, after FIB sectioning, is 50 to 100 times lower than for undamaged polymers and that it is this reduction in sputtering rate, rather than any development of microtopography, that causes the high Ar⁺ GCIB dose required for cleaning these organic surfaces.     

Influence of dielectric barrier plasma treatment of ZnMgAl alloy-coated steel on the adsorption of organophosphonic acid monolayers

The adsorption of octadecyl phosphonic acid (ODPA) on oxide-covered surfaces of ZnMgAl alloy coatings is described as a function of a dielectric barrier discharge (DBD) pretreatment step. The ODPA monolayer formation enables the investigation of the influence of the DBD treatment on the resulting interfacial bond formation and surface coverage. Surface characterisation by means of surface spectroscopy (PM-IRRAS, XPS) and surface electrochemistry (cyclic voltammetry) showed that the DBD pretreatment with Ar, Ar/O₂ and Ar/H₂O gas mixtures leads to improved barrier properties of the adsorbed ODPA monolayer. Moreover, during ODPA monolayer formation from ethanolic solution, a partial etching of the surface oxide layer occurs.     

Long‐Lived Radical Cation Salts Obtained by Interaction of Monocyclic Arenes with Niobium and Tantalum Pentahalides at Room Temperature: EPR and DFT Studies

The 1:3 reactions of the alkoxy arenes 1,4‐(MeO)₂C₆H₄ and 1,4‐F₂‐2,5‐(MeO)₂C₆H₂ with TaF₅ in chloroform at 40–50 °C resulted in formation in about 35 % yield of the long‐lived radical cation salts [1,4‐(MeO)₂C₆H₄][Ta₂F₁₁] ( 2 a ) and [1,4‐F₂‐2,5‐(MeO)₂C₆H₂][Ta₂F₁₁] ( 2 b ), respectively. The non‐alkoxy‐substituted [arene][M₂X₁₁] [M=Ta, X=F: arene=C₆H₅Me ( 2 c ), 1,4‐C₆H₄Me₂ ( 2 d ), C₆H₅F ( 2 e ), C₆H₅NO₂ ( 2 f ); M=Nb, X=F: arene=C₆H₅Me ( 4 a ), 1,4‐C₆H₄Me₂ ( 4 b ), C₆H₅F ( 4 c ), C₆H₅NO₂ ( 4 d ); M=Ta, X=Cl: arene=1,4‐C₆H₄Me₂ ( 5 )] were obtained from the 3:1 reactions of MX₅ with the appropriate arene in chloroform at temperatures in the range 40–90 °C. Compounds 2 – 5 were detected by EPR spectroscopy (in CHCl₃) at room temperature, and their gas‐phase structures were optimized by DFT calculations. Formation of the M^IV species [MX₄(NCMe)₂] [M=Ta, X=F ( 3 a ); M=Nb, X=F ( 3 b ); M=Ta, X=Cl ( 3 c )] was ascertained by EPR spectroscopy on solutions obtained by treatment of the reaction mixtures with acetonitrile. Non‐selective reactions occurred upon combination of 1,4‐F₂‐2,5‐(MeO)₂C₆H₂ with AgNbF₆ (in CH₂Cl₂) and 1,4‐(MeO)₂C₆H₄ with SbF₅.