Organic photosensitizers and nanostructured semiconductors for photoredox catalysis and artificial photosynthesis

Over the course of evolution, Nature has elegantly learned to use light to drive chemical reactions. On the other hand, humans have only recently started learning how to play with this powerful tool to carry out chemical transformations. In particular, a step forward was possible thanks to molecules and materials that can absorb light and trigger a series of processes that can drive chemical reactions. However, scarce elements are extensively employed in the design of most of these compounds and considerations on their scarcity and toxicity have sparked interest on alternatives based on earth-abundant elements. In this framework, the focus of this thesis has been the development and employment of heavy-metal free chromophores and of earth-abundant oxides. The first chapter regards the functionalization of boron-dipyrromethenes (BODIPYs) so as to allow access to their triplet excited state and tune their redox potentials, which was achieved thanks to the design of orthogonal donor-acceptor dyads. The BODIPY dyads were used to promote a photoredox reaction, and the mechanism of the reaction was clarified. In the second chapter, organic chromophores that display thermally-activated delayed fluorescence (TADF) were studied. These were used to perform enantioselective photoredox reactions, and a mechanistic investigation allowed to elucidate the fate of these photosensitizers in the reaction. Thanks to their stronger reducing power, it was possible to demonstrate the employability of TADF dyes in artificial photosynthesis, as well. Last, the oxidation of biomass-derived compounds was studied in a photoelectrochemical cell. For this purpose, hematite photoanodes were synthesized in collaboration with Prof. Caramori’s group at the University of Ferrara (Italy) and they were tested in the presence of a redox mediator. In addition to this, the possibility of repurposing a copper(II) water oxidation catalyst for the oxidation of biomass was investigated in collaboration with Prof. Llobet’s group at ICIQ (Tarragona, Spain).

Investigations on the Distribution Characteristics of Heavy Metals in Squid (Loligo spp.) in Relation to Levels in Food Fishes from the West Coast of India with a Perspective on Seafood Safety

The present study entitled "Investigations on the Distribution Characteristics of Heavy Metals in Squid (Loligo spp.) in Relation to Levels in Food Fishes from the West Coast of India with a Perspective on Seafood Safety"attempts to establish the base line data on metal levels in squids along the west coast of India. The study is of great relevance in the present context when utmost importance is being given for producing wholesome seafoods especially in the export market with a perspective on seafood safety.The thesis presents a comprehensive account of the base line data on important heavy metals, viz., Hg, Cd, Pb, Cu, Zn, Fe, Mn Cr and Ni in the edible and non-edible body components of the most abundant Loligo species, viz., L. duvauceli caught along the west coast of India.

Distribution of selected heavy metals in sediments of the Agueda river (Central Portugal)

The state of river water deterioration in the Agueda hydrographic basin, mostly in the western part, partly reflects the high rate of housing and industrial development in this area in recent years. The streams have acted as a sink for organic and inorganic loads from several origins: domestic and industrial sewage and agricultural waste. The contents of the heavy metals Cr, Cd, Ni, Cu, Pb, and Zn were studied by sequential chemical extraction of the principal geochemical phases of streambed sediments, in the <63 mum fraction, in order to assess their potential availability to the environment, investigating, the metal concentrations, assemblages, and trends. The granulometric and mineralogical characteristics of this sediment fraction were also studied. This study revealed clear pollution by Cr, Cd, Ni, Cu, Zn, and Pb, as a result from both natural and anthropogenic origins. The chemical transport of metals appears to be essentially by the following geochemical phases, in decreasing order of significance: (exchangeable + carbonates) much greater than (organics) much greater than (Mn and Fe oxides and hydroxides). The (exchangeable + carbonate) phase plays an important part in the fixation of Cu, Ni, Zn, and Cd. The organic phase is important in the fixation of Cr, Pb, and also Cu and Ni. Analyzing the metal contents in the residual fraction, we conclude that Zn and Cd are the most mobile, and Cr and Pb are less mobile than Cu and Ni. The proximity of the pollutant sources and the timing of the influx of contaminated material control the distribution of the contaminant-related sediments locally and on the network scale.

Sediment grain size distribution and heavy metals determination in a dam on the Parana River at Ilha Solteira, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Distribution of major, minor, and trace metals in lake environments of Antarctica

The concentrations of major, minor and trace metals were measured in water samples collected from five shallow Antarctic lakes (Carezza, Edmonson Point (No 14 and 15a), Inexpressible Island and Tarn Flat) found in Terra Nova Bay (northern Victoria Land, Antarctica) during the Italian Expeditions of 1993-2001. The total concentrations of a large suite of elements (Al, As, Ba, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Gd, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, Pb, Pr, Rb, Sc, Si, Sr, Ta, Ti, U, V, Y, W, Zn and Zr) were determined using spectroscopic techniques (ICP-AES, GF-AAS and ICP-MS). The results are similar to those obtained for the freshwater lakes of the Larsemann Hills, East Antarctica, and for the McMurdo Dry Valleys. Principal Component Analysis (PCA) and Cluster Analysis (CA) were performed to identify groups of samples with similar characteristics and to find correlations between the variables. The variability observed within the water samples is closely connected to the sea spray input; hence, it is primarily a consequence of geographical and meteorological factors, such as distance from the ocean and time of year. The trace element levels, in particular those of heavy metals, are very low, suggesting an origin from natural sources rather than from anthropogenic contamination.

Metal concentrations in soils around the copper smelter and surrounding industrial complex of Port Kembla, NSW, Australia

Anthropogenic emissions of metals from sources such as smelters are an international problem, but there is limited published information on emissions from Australian smelters. The objective of this study was to investigate the regional distribution of heavy metals in soils in the vicinity of the industrial complex of Port Kembla, NSW, Australia, which comprises a copper smelter, steelworks and associated industries. Soil samples (n=25) were collected at the depths of 0-5 and 5-20 cm, air dried and sieved to < 2 mm. Aqua regia extractable amounts of As, Cr, Cu, Ph and Zn were analysed by inductively coupled plasma mass spectrometry (lCP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES). Outliers were identified from background levels by statistical methods. Mean background levels at a depth of 0-5 cm were estimated at 3.2 mg/kg As, 12 mg/kg Cr, 49 mg/kg Cu, 20 mg/kg Ph and 42 mg/kg Zn. Outliers for elevated As and Cu values were mainly present within 4 km from the Port Kembla industrial complex, but high Ph at two sites and high Zn concentrations were found at six sites up to 23 km from Port Kembla. Chromium concentrations were not anomalous close to the industrial complex. There was no significant difference of metal concentrations at depths of 0-5 and 5-20 cm, except for Ph and Zn. Copper and As concentrations in the soils are probably related to the concentrations in the parent rock. From this investigation, the extent of the contamination emanating from the Port Kembla industrial complex is limited to 1-13 km, but most likely <4 km, depending on the element; the contamination at the greater distance may not originate from the industrial complex. (C) 2003 Elsevier B.V. All rights reserved.

Investlgations On The Chemical Constituents And Trace Metal Interactions In Some Bivalve Moll.USCS Of The Cochin Backwaters

The subsequent chapters of the Thesis deal with the toxic effects of mercury, copper, zinc und~1ead on these bivalve molluecs, their accumulation and distribution among various organs of the animals and also the motel retention winstica by the three species. Static biousauy tests have been conducted in these studies. It was found that the concentrations of the various metals studied in these organism are well below the permitted level given far ease ahellfienes (crab and ehrimgi and that these maliuscs are very good integrators ef trace metals from their environment and may be used as an indicator organism sf metal pallutaute. The present investigutionsemphaeie the need for a clean coastal water and gives a serious warning regarding the possiblc route of heavy metals in ta human body thraugh marine food chain.

Biennial Metal Discrepancy In The Surface Sediment Of Cochin Estuarine System

This study gave the first report on the biennial metal divergence in the sediments of Cochin Estuarine system (CES). Surface sediments from 6 prominent regions of CES were sampled in 2009 and 2011 for the geochemical and environmental assessment of trace metals (Cd, Co, Cr, Cu, Pb Fe, Mg, Mn, Ni and Zn).Besides texture, total organic carbon (TOC) and CHNS were also done. The contamination and risk assessment were performed by determining geochemical indices. Comparison with sediment quality guidelines were done to assess the probability for ecotoxicological threat to the estuary. Results showed that the measured heavy metals had varied spatial distribution patterns, indicating that they had complex origins and controlling factors

Effect of Metal-Ceramic or All-Ceramic Superstructure Materials on Stress Distribution in a Single Implant-Supported Prosthesis: Three-Dimensional Finite Element Analysis

Purpose: This three-dimensional finite element analysis study evaluated the effect of different material combinations on stress distribution within metal-ceramic and all-ceramic single implant-supported prostheses. Materials and Methods: Three-dimensional finite element models reproducing a segment of the maxilla with a missing left first premolar were created. Five groups were established to represent different superstructure materials: GP, porcelain fused to gold alloy; GR, modified composite resin fused to gold alloy; TP, porcelain fused to titanium; TR, modified composite resin fused to titanium; and ZP, porcelain fused to zirconia. A 100-N vertical force was applied to the contact points of the crowns. All models were fixed in the superior region of bone tissue and in the mesial and distal faces of the maxilla section. Stress maps were generated by processing with finite element software. Results: Stress distribution and stress values of supporting bone were similar for the GP, GR, TP, and ZP models (1,574.3 MPa, 1,574.3 MPa, 1,574.3 MPa, and 1,574.2 MPa, respectively) and different for the TR model (1,838.3 MPa). The ZP model transferred less stress to the retention screw (785 MPa) than the other groups (939 MPa for GP, 961 MPa for GR, 1,010 MPa for TP, and 1,037 MPa for TR). Conclusion: The use of different materials to fabricate a superstructure for a single implant-supported prosthesis did not affect the stress distribution in the supporting bone. The retention screw received less stress when a combination of porcelain and zirconia was used. Int J Oral Maxillofac Implants 2011;26:1202-1209

Arsenic and trace metal contents in sediment profiles from the Admiralty Bay, King George Island, Antarctica

Admiralty Bay (Antarctica) hosts three scientific stations (Ferraz, Arctowski and Macchu Picchu), which require the use of fossil fuel as an energy source. Fossil fuels are also considered the main source of pollution in the area, representing important inputs of major pollutants (organic compounds) and trace metals and metalloids of environmental interest. Accordingly, this work presents the results of As, Cd, Cr, Cu, Ni, Pb and Zn in sediment profiles from Admiralty Bay. The sediment results from Ferraz station were slightly higher than the other sampling sites. The highest contents were observed for Cu and Zn (from 44 to 89 mg kg(-1)). Otherwise, by using enrichment factors and geochronology analysis, the most relevant enrichment was observed for As in the samples collected close to the Ferraz station, indicating that increasing As content may be associated with the activities associated with this site. Published by Elsevier Ltd.

Mechanistic changes observed in heavy water for nitrate reduction reaction on palladium-modified Pt(hkl) electrodes

Reduction of nitrate on palladium-modified platinum single-crystal electrodes has been investigated both voltammetrically and spectroscopically in acidic media (pH = 1). Results obtained in H2O and D2O solvents are compared for the three crystallographic orientations. FTIR and differential electrochemical mass spectrometry (DEMS) results clearly indicate that the isotopic substitution of the solvent has a large effect in the mechanism of the reaction, changing the nature of the detected products. For Pt(111)/Pd and Pt(100)/Pd, N2O is detected as the main product of nitrate reduction when D2O is used as solvent, while no N2O is detected when the reaction is performed in H2O. For Pt(110)/Pd, N2O is detected in both solvents, although the use of D2O clearly favours the preferential formation of this product. The magnitude of voltammetric currents is also affected by the nature of the solvent. This has been analysed considering, in addition to the different product distribution, the existence of different transport numbers and optical constants of the solvent.

Heavy minerals, grain size distribution, and ice-rafted debris in the Greenland Sea during 44 to 30 Ma

The widely accepted age estimate for the onset of glaciation in the Northern Hemisphere ranges between 2 and 15 million years ago (Ma). However, recent studies indicate the date for glacial onset may be significantly older. We report the presence of ice-rafted debris (IRD) in ~44 to 30 Ma sediments from the Greenland Sea, evidence for glaciation in the North Atlantic during the Middle Eocene to Early Oligocene. Detailed sedimentological evidence indicates that glaciers extended to sea level in the region, allowing icebergs to be produced. IRD may have been sourced from tidewater glaciers, small ice caps, and/or a continental ice sheet.

Distribution of marine litter at bathyal and abyssal depths in the Mediterranean Sea

The distribution, type and quantity of marine litter accumulated on the bathyal and abyssal Mediterranean seafloor has been studied in the framework of the Spanish national projects PROMETEO and DOS MARES and the ESF-EuroDEEP project BIOFUN. Litter was collected with an otter trawl and Agassiz trawl while sampling for megafauna on the Blanes canyon and adjacent slope (Catalan margin, north-western Mediterranean) between 900 and 2700 m depth, and on the western, central and eastern Mediterranean basins at 1200, 2000 and 3000 m depth. All litter was sorted into 8 categories (hard plastic, soft plastic, glass, metal, clinker, fabric, longlines and fishing nets) and weighed. The distribution of litter was analysed in relation to depth, geographic area and natural (bathymetry, currents and rivers) and anthropogenic (population density and shipping routes) processes. The most abundant litter types were plastic, glass, metal and clinker. Lost or discarded fishing gear was also commonly found. On the Catalan margin, although the data indicated an accumulation of litter with increasing depth, mean weight was not significantly different between depths or between the open slope and the canyon. We propose that litter accumulated in the canyon, with high proportions of plastics, has predominantly a coastal origin, while litter collected on the open slope, dominated by heavy litter, is mostly ship-originated, especially at sites under major shipping routes. Along the trans-Mediterranean transect, although a higher amount of litter seemed to be found on the Western Mediterranean, differences of mean weight were not significant between the 3 geographic areas and the 3 depths. Here, the shallower sites, also closer to the coast, had a higher proportion of plastics than the deeper sites, which had a higher proportion of heavy litter and were often affected by shipping routes. The weight of litter was also compared to biomass of megafauna from the same samples. On the Blanes slope, the biomass of megafauna was significantly higher than the weight of litter between 900 and 2000 m depth and no significant differences were found at 2250 and 2700 m depth. Along the trans-Mediterranean transect, no significant differences were found between biomass and litter weight at all sites except in two sites: the Central Mediterranean at 1200 m depth, where biomass was higher than litter weight, and the Eastern Mediterranean at 1200 m depth, where litter weight was higher than biomass. The results are discussed in the framework of knowledge on marine litter accumulation, its potential impact on the habitat and fauna and the legislation addressing these issues.

Distribution of heavy minerals in sediment cores MSSTS-1 and DVDP-12

This study encompasses an investigation of the heavy mineral composition of early Oligocene-Quaternary glacial and glaciomarine sediment sequences from the Victoria Land Basin and the fjords of the South Victoria Land, Ross Sea, Antarctica. The sediment cores used were recovered during different international drilling campaigns (DVDP- 12, CIROS-2, MSSTS-l, CRP-l, CRP-212A). The main objectives were to identify possible source rocks and to unravel the provenance regions of different heavy minerals and mineral groups. Moreover, with the available data an attempt to reconstruct the general development and codiguration of the Antarctic ice sheets during the Cenozoic was also made