Chelating carbene ligands and their metal complexes

This thesis describes the synthesis of a number of functionalised imidazolium salts as precursors to N- heterocyclic carbenes and their subsequent coordination to Ag and Pd. Further a number of the Pd complexes were tested in the Heck reaction and their activities compared to complexes with similar structural features currently within the literature. A range of imidazolium salts have been synthesised which include quinoline and octahydroacridine moieties and have been characterised by a number of methods including X-ray crystallography. A bis imidazolium salt has also been prepared as a DIOP analogue. The imidazolium salts were successfully reacted with Ag20 to form the NHCAg(I) complexes. The quinoline and octahydroacridine based NHCs were transmetallated to Pd as chelating ligands, the quinoline based systems appearing as planar, strained complexes in the X-ray structure. The activities of the quinoline and octahydroacridine based NHCPd(II) complexes in the Heck coupling of 4-bromoacetophenone and 4-chlorobenzaldehyde with n-butyl acrylate were assessed and found to be comparable to similar systems with low to satisfactory conversions.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Singlet vs Nonsinglet Perturbative Renormalization factors of Staggered Fermion Bilinears

In this paper we present the perturbative computation of the difference between the renormalization factors of flavor singlet ($\sum_f\bar\psi_f\Gamma\psi_f$, $f$: flavor index) and nonsinglet ($\bar\psi_{f_1} \Gamma \psi_{f_2}, f_1 \neq f_2$) bilinear quark operators (where $\Gamma = \mathbb{1},\,\gamma_5,\,\gamma_{\mu},\,\gamma_5\,\gamma_{\mu},\, \gamma_5\,\sigma_{\mu\,\nu}$) on the lattice. The computation is performed to two loops and to lowest order in the lattice spacing, using Symanzik improved gluons and staggered fermions with twice stout-smeared links. The stout smearing procedure is also applied to the definition of bilinear operators. A significant part of this work is the development of a method for treating some new peculiar divergent integrals stemming from the staggered formalism. Our results can be combined with precise simulation results for the renormalization factors of the nonsinglet operators, in order to obtain an estimate of the renormalization factors for the singlet operators. The results have been published in Physical Review D.Comment: 8 pages, 3 figures, 2 tables, Proceedings of the 35th International Symposium on Lattice Field Theory, 18-24 June 2017, Granada, Spai

SARS-CoV-2 concentrations and virus-laden aerosol size distributions in outdoor air in north and south of Italy

The COVID-19 disease spread at different rates in the different countries and in different regions of the same country, as happened in Italy. Transmission by contact or at close range due to large respiratory droplets is widely accepted, however, the role of airborne transmission due to small respiratory droplets emitted by infected individuals (also asymptomatic) is controversial. It was suggested that outdoor airborne transmission could play a role in determining the differences observed in the spread rate. Concentrations of virus-laden aerosol are still poorly known and contrasting results are reported, especially for outdoor environments. Here we investigated outdoor concentrations and size distributions of virus-laden aerosol simultaneously collected during the pandemic, in May 2020, in northern (Veneto) and southern (Apulia) regions of Italy. The two regions exhibited significantly different prevalence of COVID-19. Genetic material of SARS-CoV-2 (RNA) was determined, using both real time RT-PCR and ddPCR, in air samples collected using PM10 samplers and cascade impactors able to separate 12 size ranges from nanoparticles (diameter D < 0.056 µm) up to coarse particles (D > 18 µm). Air samples tested negative for the presence of SARS-CoV-2 at both sites, viral particles concentrations were <0.8 copies m−3 in PM10 and <0.4 copies m−3 in each size range investigated. Outdoor air in residential and urban areas was generally not infectious and safe for the public in both northern and southern Italy, with the possible exclusion of very crowded sites. Therefore, it is likely that outdoor airborne transmission does not explain the difference in the spread of COVID-19 observed in the two Italian regions

A new method for the evaluation of the direct effect of the ship traffic on PAHs

Emissions of exhaust gases and particles from ships can affect significantly the chemical composition of the atmosphere, local and regional air quality and climate. These emissions might have harmful effects on human health, since Mediterranean harbors are often located near or within the cities. Moreover ships and harbours emissions are currently increasing, due to the grow of tourism and trade, further amplifying this issue. International legislation and local agreements are mainly based on the use of low-sulphur fuel content, but also other chemicals, such as polycyclic aromatic hydrocarbons (PAHs), play an important role. Because of their low reactivity PAHs can persist in the environment for a long time; moreover they bioaccumulate, causing adverse effect on human health, such as reproductive and immune effects, developmental anomalies and cancer. This work is linked to the POSEIDON project (POllution monitoring of Ship Emission: an IntegrateD approach fOr harbor of the Adriatic basiN), that aims to quantify the atmospheric pollution generated by ship traffic and harbor activities in four port-cities of the Adriatic Sea (Brindisi, Venice, Rijeka, Patras). Here, a new method for the evaluation of the direct effect of ship traffic and harbour activities on polycyclic aromatic hydrocarbons is presented. In this method two high-volume samplers are operating: one of them collecting air from all directions; the other one is programmed to activate only when the wind is blowing from a specific sector (the harbour area). From the compared results, information about the effect of the harbour on the global PAHs concentration can be obtained. The method was applied in Venice in two summer sampling campaigns, in 2009 and 2012

The impact of ship traffic and harbor activities on the atmospheric pollution in two northern adriatic ports: Venice and Rijeka

The aim of the POSEIDON project is to quantify the relative contribution of maritime traffic and harbor activities to atmospheric pollutants concentration in four port-cities of the Adriatic Sea. This study focuses on the harbors of Venice and Rijeka. In order to investigate the main pollution sources, emission inventories were used as input for receptor models: PMF (positive matrix factorization) and PCA (principal components analysis); moreover source identification was also conducted using PAHs diagnostic ratios. The ship traffic impact was quantified: i) on gaseous and particulate PAHs, collected using a new method which consisted in a double simultaneous sampling, in different wind sectors; ii) applying PMF to data of metals, PAHs and ions in PM10; iii) using the vanadium concentration according to the Agrawal methodology

Piecewise Silence in Discrete Cosmological Models

20 pages, 1 figure20 pages, 1 figureWe consider a family of cosmological models in which all mass is confined to a regular lattice of identical black holes. By exploiting the reflection symmetry about planes that bisect these lattices into identical halves, we are able to consider the evolution of a number of geometrically distinguished surfaces that exist within each of them. We find that the evolution equations for the reflection symmetric surfaces can be written as a simple set of Friedmann-like equations, with source terms that behave like a set of interacting effective fluids. We then show that gravitational waves are effectively trapped within small chambers for all time, and are not free to propagate throughout the space-time. Each chamber therefore evolves as if it were in isolation from the rest of the universe. We call this phenomenon "piecewise silence"

Metamorphosis in the Cirripede Crustacean Balanus amphitrite

Stalked and acorn barnacles (Cirripedia Thoracica) have a complex life cycle that includes a free-swimming nauplius larva, a cypris larva and a permanently attached sessile juvenile and adult barnacle. The barnacle cyprid is among the most highly specialized of marine invertebrate larvae and its settlement biology has been intensively studied. By contrast, surprisingly few papers have dealt with the critical series of metamorphic events from cementation of the cyprid to the substratum until the appearance of a suspension feeding juvenile. This metamorphosis is both ontogenetically complex and critical to the survival of the barnacle. Here we use video microscopy to present a timeline and description of morphological events from settled cyprid to juvenile barnacle in the model species Balanus amphitrite, representing an important step towards both a broader understanding of the settlement ecology of this species and a platform for studying the factors that control its metamorphosis. Metamorphosis in B. amphitrite involves a complex sequence of events: cementation, epidermis separation from the cypris cuticle, degeneration of cypris musculature, rotation of the thorax inside the mantle cavity, building of the juvenile musculature, contraction of antennular muscles, raising of the body, shedding of the cypris cuticle, shell plate and basis formation and, possibly, a further moult to become a suspension feeding barnacle. We compare these events with developmental information from other barnacle species and discuss them in the framework of barnacle settlement ecology

Impact of maritime transport on particulate matter concentrations and chemical compositions in four port-cities of the Adriatic/Ionian area: an overview of the results of POSEIDON project

Pollutant emissions from ships and harbour activities constitute an important source of pollution of coastal areas with potential influences on the climate and the health of their inhabitants. A recent review (Viana et al., 2014) shows that these emissions could have an important impact on the Mediterranean and that there is a lack of data for the Eastern and South-Eastern part of this area. This work presents an analysis of the impact of ship emissions to atmospheric particle concentrations (PM) in four important port-cities (Patras Greece, Brindisi and Venice Italy, and Rijeka Croatia) of the Adriatic/Ionian area. The study was performed within the POSEIDON project (Pollution monitoring of ship emissions: an integrated approach for harbours of the Adriatic basin, funded within the MED Programme 2007-2013). The study uses an integrated approach using emission inventories, dispersion modelling and measurements taken at high temporal resolution (1 min) and low temporal resolution for chemical characterization of PM. The emission inventories of the four port-cities show that ships contribute between 11.7% and 31.0% of the total PM emissions being a source locally comparable with road traffic (ranging between 11.8% and 26.6%). The source apportionment using the receptor model PMF showed and oil combustion source (that includes ship emissions), characterized by V and Ni, in Brindisi, Venice and Rijeka with V/Ni ratio ranging between 1.4 and 4.2 indicating local differences in chemical profiles of the emissions. The V concentrations were used to evaluate the contributions of primary ship emissions to PM (Agrawal et al., 2009) that resulted between 1.3% and 2.8%. The contribution to secondary sulphate was 11% of PM2.5 in Brindisi (Cesari et al., 2014). The analysis of high-temporal resolution measurements taken near the harbour areas of Venice, Patras and Brindisi showed a contribution of ship emissions to PM2.5 varying between 3.5% and 7.4%. The relative contribution to particle number concentrations (PNC) was larger at all sites (between 6% and 26%). This demonstrates that ship particulate missions include mainly small and ultrafine particles. The trend of the impact of passenger ships primary emissions to PM2.5 concentrations in Venice between 2007 and 2012 showed a decrease from 7% (+-1%) to 3.5% (+-1%) even if the gross tonnage of ship traffic increased in the same period by 47% (Contini et al., 2015). This was a consequence of the use of low-sulphur content fuels due to the application of local mitigation strategies and of the European Directive 2005/33/EC. The WRF-CAMx modeling system was applied over the Central and Eastern Mediterranean so as to identify the air quality impact of ship emissions. The zero-out modelling method was implemented involving model simulations performed while including and omitting the ship emissions. The results for both gaseous and particulate pollutant concentrations generally show a fairly good agreement with observations at the areas under study. Agrawal et al., 2009. Environmental Science and Technology 43, 5398-5402. Cesari et al., 2014. Science of the Total Environment 497-498, 392-400. Contini et al., 2015. Atmospheric Environment 102, 183-190. Viana et al., 2014. Atmospheric Environment 90, 96-105

Impact of maritime traffic on polycyclic aromatic hydrocarbons, metals and particulate matter in Venice air

Harbours are important hubs for economic growth in both tourism and commercial activities. They are also an environmental burden being a source of atmospheric pollution often localized near cities and industrial complexes. The aim of this study is to quantify the relative contribution of maritime traffic and harbour activities to atmospheric pollutant concentration in the Venice lagoon. The impact of ship traffic was quantified on various pollutants that are not directly included in the current European legislation for shipping emission reduction: (i) gaseous and particulate PAHs; (ii) metals in PM10; and (iii) PM10 and PM2.5. All contributions were correlated with the tonnage of ships during the sampling periods and results were used to evaluate the impact of the European Directive 2005/33/EC on air quality in Venice comparing measurements taken before and after the application of the Directive (year 2010). The outcomes suggest that legislation on ship traffic, which focused on the issue of the emissions of sulphur oxides, could be an efficient method also to reduce the impact of shipping on primary particulate matter concentration; on the other hand, we did not observe a significant reduction in the contribution of ship traffic and harbour activities to particulate PAHs and metals