Photocatalytic oxidation mechanism of alkanes in contact with titanium dioxide

Isobutane was photooxidized on titanium dioxide between -16 and +180 C in tertiary butanol and acetone. The formation of tertiary butanol preceded the formation of acetone. Above 20 C the latter compound became clearly predominant. The reaction kinetics obeyed a steady state model of oxygen chemisorption with the involvement of isobutane in the physisorbed phase

Capillary breakup and electrospinning of PA6 solutions containing FeCl3: experimental findings and correlations

In several applications, ranging from electronic to chemical sensing, great interest has grown for the exploitation of conducting polymer nanofibers, whose processing is, however, not straightforward, due to polymer low solubility and presence of rigid backbones. An interesting method to overcome this issue consists in the electrospinning of a spinnable polymer to obtain a template for the successive in situ polymerization of the conducting polymer monomers. Considering PANI nanofibers, a suitable template can be electrospun from PA6 solutions in formic acid containing FeCl3. In this system, the ionic salt may perturb or prevent H-bonds formation between amide groups of PA6 backbones: this could modify solution viscoelasticity, and thus affect fibres morphology. The aim of the present work is to identify the effect of FeCl3 on the solution rheological behaviour and to correlate it to electrospun fibres morphology. To this aim, solutions at several salt content underwent electrospinning and were characterized both in shear, by rotational rheometry, and extension, by capillary breakup rheometry, while fibres morphology and crystallinity were evaluated through SEM and DSC. The rheological analysis enlightens that a critical FeCl3 content exists above which the viscous component of the viscoelastic response becomes predominant. At the same concentration, the SEM observations of the electrospun fibres show the formation of severely inhomogeneous structures. A correlation between these results is proposed through the adimensional analysis of competing viscoelastic stabilization and surface tension-driven instability phenomena. Besides the aforementioned effects, the FeCl3 content affects also fibre crystallinity, as above a critical concentration fibres turn out to be completely amorphous. Interestingly, this concentration coincides with the one at which a transition is observed in the rheological behaviour

Chemical characterisation of iron in dust and biomass burning aerosols during AMMA-SOP0/DABEX: implication for iron solubility

The chemical composition and the soluble fraction were determined in aerosol samples collected during flights of AMMA-SOP0/DABEX campaign, which were conducted in the West African Sahel during dry season (2006). Two aerosol types are encountered in this period: dust particles (DUST) and biomass burning aerosol (BB). Chemical analysis and microscope observations showed that the iron (Fe) found in BB samples mainly originates from dust particles mostly internally mixed in the biomass burning layer. Chemical analyses of samples showed that the Fe solubility is lower in African dust samples than in biomass burning aerosols. Our data provide a first idea of the variability of iron dust solubility in the source region (0.1% and 3.4%). We found a relationship between iron solubility/clay content/source which partly confirms that the variability of iron solubility in this source region is related to the character and origin of the aerosols themselves. In the biomass burning samples, no relationship were found between Fe solubility and either the concentrations of acidic species (SO<sub>4</sub><sup>2−</sup>, NO<sub>3</sub><sup>−</sup> or oxalate) or the content of carbon (TC, OC, BC). Therefore, we were unable to determine what processes are involved in this increase of iron solubility. In terms of supply of soluble Fe to oceanic ecosystems on a global scale, the higher solubility observed for Fe in biomass burning could imply an indirect source of Fe to marine ecosystems. But these aerosols are probably not significant because the Sahara is easily the dominant source of Fe to the Atlantic Ocean

On the Parity Problem in One-Dimensional Cellular Automata

We consider the parity problem in one-dimensional, binary, circular cellular automata: if the initial configuration contains an odd number of 1s, the lattice should converge to all 1s; otherwise, it should converge to all 0s. It is easy to see that the problem is ill-defined for even-sized lattices (which, by definition, would never be able to converge to 1). We then consider only odd lattices. We are interested in determining the minimal neighbourhood that allows the problem to be solvable for any initial configuration. On the one hand, we show that radius 2 is not sufficient, proving that there exists no radius 2 rule that can possibly solve the parity problem from arbitrary initial configurations. On the other hand, we design a radius 4 rule that converges correctly for any initial configuration and we formally prove its correctness. Whether or not there exists a radius 3 rule that solves the parity problem remains an open problem.Comment: In Proceedings AUTOMATA&JAC 2012, arXiv:1208.249

Conservation Laws in Cellular Automata

If X is a discrete abelian group and B a finite set, then a cellular automaton (CA) is a continuous map F:B^X-->B^X that commutes with all X-shifts. If g is a real-valued function on B, then, for any b in B^X, we define G(b) to be the sum over all x in X of g(b_x) (if finite). We say g is `conserved' by F if G is constant under the action of F. We characterize such `conservation laws' in several ways, deriving both theoretical consequences and practical tests, and provide a method for constructing all one-dimensional CA exhibiting a given conservation law.Comment: 19 pages, LaTeX 2E with one (1) Encapsulated PostScript figure. To appear in Nonlinearity. (v2) minor changes/corrections; new references added to bibliograph

Atmospheric aerosols at the Pierre Auger Observatory and environmental implications

The Pierre Auger Observatory detects the highest energy cosmic rays. Calorimetric measurements of extensive air showers induced by cosmic rays are performed with a fluorescence detector. Thus, one of the main challenges is the atmospheric monitoring, especially for aerosols in suspension in the atmosphere. Several methods are described which have been developed to measure the aerosol optical depth profile and aerosol phase function, using lasers and other light sources as recorded by the fluorescence detector. The origin of atmospheric aerosols traveling through the Auger site is also presented, highlighting the effect of surrounding areas to atmospheric properties. In the aim to extend the Pierre Auger Observatory to an atmospheric research platform, a discussion about a collaborative project is presented.Comment: Regular Article, 16 pages, 12 figure

Aerosol-Radiation-Cloud Interactions in the South-East Atlantic: First Results from the ORACLES-2016 Deployment and Plans for Future Activities

Southern Africa produces almost a third of the Earths biomass burning (BB) aerosol particles. Particles lofted into the mid-troposphere are transported westward over the South-East (SE) Atlantic, home to one of the three permanent subtropical stratocumulus (Sc) cloud decks in the world. The SE Atlantic stratocumulus deck interacts with the dense layers of BB aerosols that initially overlay the cloud deck, but later subside and may mix into the clouds. These interactions include adjustments to aerosol-induced solar heating and microphysical effects, and their global representation in climate models remains one of the largest uncertainties in estimates of future climate. Hence, new observations over the SE Atlantic have significant implications for regional and global climate change predictions.Our understanding of aerosol-cloud interactions in the SE Atlantic is severely limited. Most notably, we are missing knowledge on the absorptive and cloud nucleating properties of aerosols, including their vertical distribution relative to clouds, on the locations and degree of aerosol mixing into clouds, on the processes that govern cloud property adjustments, and on the importance of aerosol effects on clouds relative to co-varying synoptic scale meteorology.We describe first results from various synergistic, international research activities aimed at studying aerosol-cloud interactions in the region:NASAs airborne ORACLES (ObseRvations of Aerosols Above Clouds and Their IntEractionS) deployment in AugustSeptember of 2016,the DoEs LASIC (Layered Atlantic Smoke Interactions with Clouds) deployment of the ARM Mobile Facility to Ascension Island (June 2016 October 2017), the ground-based components of CNRS AEROCLO-sA (Aerosols Clouds and Fog over the west coast of southern Africa), and ongoing regional-scale integrative, process-oriented science efforts as part of SEALS-sA (Sea Earth Atmosphere Linkages Study in southern Africa).We expect to describe experimental setups as well as showcase initial aerosol and cloud property distributions. Furthermore, we discuss the implementation of future activities in these programs in coordination with the UK Met Offices CLARIFY (CLoud-Aerosol-Radiation Interactions and Forcing) experiment in 2017

Iron/N-doped graphene nano-structured catalysts for general cyclopropanation of olefins

The first examples of heterogeneous Fe-catalysed cyclopropanation reactions are presented. Pyrolysis of in situ-generated iron/phenanthroline complexes in the presence of a carbonaceous material leads to specific supported nanosized iron particles, which are effective catalysts for carbene transfer reactions. Using olefins as substrates, cyclopropanes are obtained in high yields and moderate diastereoselectivities. The developed protocol is scalable and the activity of the recycled catalyst after deactivation can be effectively restored using an oxidative reactivation protocol under mild conditions

Change of direction asymmetry across different age categories in youth soccer

Background In youth, the development of change of direction (COD) and sprint performance is a key component for successfully competing in soccer across age. During a COD, the presence of directional asymmetries may be detrimental due to the unpredictable nature of the sport. Therefore, the aims of the study were to investigate asymmetries in COD ability and to examine the differences in COD and sprint performance across age in young soccer players. Methods Sixty-eight sub-elite soccer players of different age categories (U18, U17, U16, U15) were tested on a 10-m linear sprint test and 90°COD (5-m entry and exit) test in both directions. Asymmetric index (AI) of COD deficit was obtained for dominant (fastest) and non-dominant directions (slowest). Results The results showed that U16 were more asymmetrical than U18, U17, and U15 from large to moderate effects. The sprint time improved linearly across age with U18 and U15 displaying the fastest and slowest 10-m sprint performance (p 0.05). Conclusion Given the results of this study, practitioners are encouraged to assess asymmetries between dominant and non-dominant directions rather than solely players’ COD ability in young soccer players