Probing the chemical environment of 3-hydroxyflavone doped ormosils by a spectroscopic study of excited state intramolecular proton transfer

Abstract The spectroscopic properties of 3-hydroxyflavone (3-HF) molecules entrapped in films and in monoliths of sol–gel derived organically modified silicates (Ormosils) xerogels are studied by excitation and fluorescence spectroscopy as a function of the sol–gel precursors used for the synthesis. Different molar ratios of tetraethoxysilane (TEOS), methyltriethoxysilane (MTES) and phenyltriethoxysilane (PTES) as precursors are used for the sol preparation. Emission and excitation spectra in the ultraviolet–visible range and photo-degradation curves as a function of time are collected with a spectrofluorimeter. The 3-hydroxyflavone optical properties change in the different networks, owing to the effects of the chemical environment on the excited state intramolecular proton transfer and to the solubility of the dye molecules in the different sol–gel systems. It turns out that the spectroscopic features can be used to probe the chemical state of the dye molecules microenvironment

Factors affecting the Faradaic efficiency of Fe(0) electrocoagulation

Electrocoagulation (EC) using Fe(0) electrodes is a low cost water treatment technology that relies on efficient production of Fe(II) from the electrolytic dissolution of Fe(0) electrodes (i.e. a high Faradaic efficiency). However, the (electro)chemical factors that favor Fe(0) oxidation rather than O2 evolution during Fe(0) EC have not been identified. In this study, we combined electrochemical methods, electron microscopy and Fe measurements to systematically examine the interdependent effects of current density (i), anodic interface potential (EA) and solution chemistry on the Faradaic efficiency. We found that Fe(0) oxidation was favored (Faradaic efficiency >0.85) in chloride and bromide solutions at all i, whereas carbonate, phosphate, citrate, and nitrate solutions lead to Faradaic efficiencies <0.1. The anodic reaction (i.e. Fe(0) oxidation or O2 evolution) only depended on i in the sulfate and formate solutions. Experiments in binary-anion solutions revealed that molar ratios of [HCO3−]/[Cl−] near 100 and [NO3−]/[Cl−] near 20 separated the electrochemical domains of Fe(0) oxidation and O2 evolution in the EC system. These molar ratios were supported by experiments in synthetic groundwater solutions. We also found that the EA vs i curves for solutions with poor Faradaic efficiency overlapped but were situated 2–4 V vs Ag/AgCl higher than those of solutions with high Faradaic efficiency. Therefore, the position of the EA vs i curve, rather than the EA alone, can be used to determine unambiguously the reaction occurring on the Fe(0) anode during EC treatment

Comparing home and parcel lockers’ delivery systems: a math-heuristic approach

E-commerce is a continuously growing sector worldwide, with important repercussions on the delivery system in urban area and especially in the Business to Consumer (B2C) sector. The delivery of a package to a consumer's address involves not only high costs for couriers (greater number of kilometres travelled), but also increased congestion and greater environmental pollution (greater volume of pollutants released into the air). To rationalize deliveries in urban areas the use of collection points, equipped with lockers, to store the goods that users have ordered has been considered in literature. This work compares two alternative delivery options: deliveries to the consumer's home versus to Lockers. To make this comparison we used a cluster first route second math-heuristic approach. In the clustering phase, we experimented a new clustering function, while the routing phase consists in solving an instance of the Traveling Salesman Problem for each generated cluster. Finally, we applied the math-heuristic to a real case (the Italian municipality of Dolo near Venice) and compared the two delivery alternatives. We evaluate the performance considering two different fleets of vehicles, with small and medium capacity. In addition, since additional trips might be performed by consumers to pick up parcels at Lockers, a sensitivity analysis was carried out to analyse the sustainability of the proposed city logistics scheme

Does EO NDVI seasonal metrics capture variations in species composition and biomass due to grazing in semi-arid grassland savannas?

Most regional scale studies of vegetation in the Sahel have been based on Earth observation (EO) imagery due to the limited number of sites providing continuous and long term in situ meteorological and vegetation measurements. From a long time series of coarse resolution normalized difference vegetation index (NDVI) data a greening of the Sahel since the 1980s has been identified. However, it is poorly understood how commonly applied remote sensing techniques reflect the influence of extensive grazing (and changes in grazing pressure) on natural rangeland vegetation. This paper analyses the time series of Moderate Resolution Imaging Spectroradiometer (MODIS) NDVI metrics by comparing it with data from the Widou Thiengoly test site in northern Senegal. Field data include grazing intensity, end of season standing biomass (ESSB) and species composition from sizeable areas suitable for comparison with moderate – coarse resolution satellite imagery. It is shown that sampling plots excluded from grazing have a different species composition characterized by a longer growth cycle as compared to plots under controlled grazing or communal grazing. Also substantially higher ESSB is observed for grazing exclosures as compared to grazed areas, substantially exceeding the amount of biomass expected to be ingested by livestock for this area. The seasonal integrated NDVI (NDVI small integral; capturing only the signal inherent to the growing season recurrent vegetation), derived using absolute thresholds to estimate start and end of growing seasons, is identified as the metric most strongly related to ESSB for all grazing regimes. However plot-pixel comparisons demonstrate how the NDVI/ESSB relationship changes due to grazing-induced variation in annual plant species composition and the NDVI values for grazed plots are only slightly lower than the values observed for the ungrazed plots. Hence, average ESSB in ungrazed plots since 2000 was 0.93 t ha−1, compared to 0.51 t ha−1 for plots subjected to controlled grazing and 0.49 t ha−1 for communally grazed plots, but the average integrated NDVI values for the same period were 1.56, 1.49, and 1.45 for ungrazed, controlled and communal, respectively, i.e. a much smaller difference. This indicates that a grazing-induced development towards less ESSB and shorter-cycled annual plants with reduced ability to turn additional water in wet years into biomass is not adequately captured by seasonal NDVI metrics

Editorial: crime patterns in time and space: the dynamics of crime opportunities in urban areas

The routine activity approach and associated crime pattern theory emphasise how crime emerges from spatio-temporal routines. In order to understand this crime should be studied in both space and time. However, the bulk of research into crime patterns and related activities has investigated the spatial distributions of crime, neglecting the temporal dimension. Specifically, disaggregation of crime by place and by time, for example hour of day, day of week, month of year, season, or school day versus none school day, is extremely relevant to theory. Modern data make such spatio-temporal disaggregation increasingly feasible, as exemplified in this special issue. First, much larger data files allow disaggregation of crime data into temporal and spatial slices. Second, new forms of data are generated by modern technologies, allowing innovative and new forms of analyses. Crime pattern analyses and routine activity inquiries are now able to explore avenues not previously available. The unique collection of nine papers in this thematic issue specifically examine spatio-temporal patterns of crime to; demonstrate the value of this approach for advancing knowledge in the field; consider how this informs our theoretical understanding of the manifestations of crime in time and space; to consider the prevention implications of this; and to raise awareness of the need for further spatio-temporal research into crime event

Crime at the intersection of rail and retail

This chapter examines shoplifting at rail station shops over a 12 month period in England and Wales. Key findings were: shoplifting is concentrated at particular stations; the top 20 stations account for 85% of shoplifting. Clear temporal patterns were evident; shoplifting was higher on weekdays and during holidays with higher levels of travel; shoplifting is lower when there is a reduced rail service. There was no clear relationship between shoplifting rates outside of a station at shops nearby, and shoplifting within a rail station. It is suggested a correlation may occur for medium and smaller size stations. Large stations may attract offenders in their own right without other shops being nearby. The similarities observed between shoplifting patterns at rail stations and those at non-rail station shops suggest the learning from successful crime prevention measures applied outside of the rail environment could successfully transferred to rail stations