Productivity, demand and the home market effect

The causality between international trade and industrialization is still ambiguous. We consider a model of international trade with the Home Market Effect - with differences in income and productivity between sectors and between countries - in order to identify additional channels for determining the effects of international trade on industrialization. Introducing non-homothetic preferences and differences in productivity aids in the interpretation of any apparent paradoxes within international trade, such as the commercial relations between more populated countries like China and India and large economies such as the U.S. Population size, demand composition and productivity levels constitute the three main channels for determining the effects of international trade. Interactions among these channels define the results obtained in terms of industrialization, while welfare levels are always higher in relation to autarky.

Rhodium(I) catalyzed [2+2+2] cycloaddition reactions: experimental and theoretical studies

The [2+2+2] cycloaddition reaction involves the formation of three carbon-carbon bonds in one single step using alkynes, alkenes, nitriles, carbonyls and other unsaturated reagents as reactants. This is one of the most elegant methods for the construction of polycyclic aromatic compounds and heteroaromatic, which have important academic and industrial uses. The thesis is divided into ten chapters including six related publications. The first study based on the Wilkinson’s catalyst, RhCl(PPh3)3, compares the reaction mechanism of the [2+2+2] cycloaddition process of acetylene with the cycloaddition obtained for the model of the complex, RhCl(PH3)3. In an attempt to reduce computational costs in DFT studies, this research project aimed to substitute PPh3 ligands for PH3, despite the electronic and steric effects produced by PPh3 ligands being significantly different to those created by PH3 ones. In this first study, detailed theoretical calculations were performed to determine the reaction mechanism of the two complexes. Despite some differences being detected, it was found that modelling PPh3 by PH3 in the catalyst helps to reduce the computational cost significantly while at the same time providing qualitatively acceptable results. Taking into account the results obtained in this earlier study, the model of the Wilkinson’s catalyst, RhCl(PH3)3, was applied to study different [2+2+2] cycloaddition reactions with unsaturated systems conducted in the laboratory. Our research group found that in the case of totally closed systems, specifically 15- and 25-membered azamacrocycles can afford benzenic compounds, except in the case of 20-membered azamacrocycle (20-MAA) which was inactive with the Wilkinson’s catalyst. In this study, theoretical calculations allowed to determine the origin of the different reactivity of the 20-MAA, where it was found that the activation barrier of the oxidative addition of two alkynes is higher than those obtained for the 15- and 25-membered macrocycles. This barrier was attributed primarily to the interaction energy, which corresponds to the energy that is released when the two deformed reagents interact in the transition state. The main factor that helped to provide an explanation to the different reactivity observed was that the 20-MAA had a more stable and delocalized HOMO orbital in the oxidative addition step. Moreover, we observed that the formation of a strained ten-membered ring during the cycloaddition of 20-MAA presents significant steric hindrance. Furthermore, in Chapter 5, an electrochemical study is presented in collaboration with Prof. Anny Jutand from Paris. This work allowed studying the main steps of the catalytic cycle of the [2+2+2] cycloaddition reaction between diynes with a monoalkyne. First kinetic data were obtained of the [2+2+2] cycloaddition process catalyzed by the Wilkinson’s catalyst, where it was observed that the rate-determining step of the reaction can change depending on the structure of the starting reagents. In the case of the [2+2+2] cycloaddition reaction involving two alkynes and one alkene in the same molecule (enediynes), it is well known that the oxidative coupling may occur between two alkynes giving the corresponding metallacyclopentadiene, or between one alkyne and the alkene affording the metallacyclopentene complex. Wilkinson’s model was used in DFT calculations to analyze the different factors that may influence in the reaction mechanism. Here it was observed that the cyclic enediynes always prefer the oxidative coupling between two alkynes moieties, while the acyclic cases have different preferences depending on the linker and the substituents used in the alkynes. Moreover, the Wilkinson’s model was used to explain the experimental results achieved in Chapter 7 where the [2+2+2] cycloaddition reaction of enediynes is studied varying the position of the double bond in the starting reagent. It was observed that enediynes type yne-ene-yne preferred the standard [2+2+2] cycloaddition reaction, while enediynes type yne-yne-ene suffered β-hydride elimination followed a reductive elimination of Wilkinson’s catalyst giving cyclohexadiene compounds, which are isomers from those that would be obtained through standard [2+2+2] cycloaddition reactions. Finally, the last chapter of this thesis is based on the use of DFT calculations to determine the reaction mechanism when the macrocycles are treated with transition metals that are inactive to the [2+2+2] cycloaddition reaction, but which are thermally active leading to new polycyclic compounds. Thus, a domino process was described combining an ene reaction and a Diels-Alder cycloaddition.

Isomerism and C-H, C-C, O-O, C-O bond activation studies by transition metals

Aquesta tesi és el reflex que de la cooperació entre grups experimentals i grups teòrics s'aconsegueix l'assoliment d'objectius inassolibles de forma individual. A partir de la DFT s'expliquen processos inorgànics i organometàl·lics de gran valor biològic i/o industrial. La tesi està enfocada especialment a l'estudi de complexos mononuclears i binuclears de coure, on té lloc l'activació d'enllaços C-H, C-C, i O-O. L'estudi de complexos octaèdrics de ruteni ha permès dur a terme extensos estudis isomèrics i racionalitzar les propietats espectroscòpiques dels mateixos. A més a més, estudis més puntuals respecte clusters de coure, l'estudi de la reacció de Pawson-Khand, l'estudi d'enllaços Pt-Pt en complexos trimèrics de platí, a més a més de l'estudi de la isomeria de complexos de Ni i Pt.

An inventory of heavy metals inputs to agricultural soils in England and Wales

An inventory of heavy metal inputs (Zn, Cu, Ni, Pb, Cd, Cr, As and Hg) to agricultural soils in England and Wales in 2000 is presented, accounting for major sources including atmospheric deposition, sewage sludge, livestock manures, inorganic fertilisers and lime, agrochemicals, irrigation water, industrial by-product 'wastes' and composts. Across the whole agricultural land area, atmospheric deposition was the main source of most metals, ranging from 25 to 85% of total inputs. Livestock manures and sewage sludge were also important sources, responsible for an estimated 37-40 and 8-17% of total Zn and Cu inputs, respectively. However, at the individual field scale sewage sludge, livestock manures and industrial wastes could be the major source of many metals where these materials are applied. This work will assist in developing strategies for reducing heavy metal inputs to agricultural land and effectively targeting policies to protect soils from long-term heavy metal accumulation. (C) 2003 Elsevier Science B.V. All rights reserved.

"Ever-growing Amman", Jordan: Urban expansion, social polarisation and contemporary urban planning issues

Amman the primate capital city of the Hashemite Kingdom of Jordan currently has a population in excess of 2 million, but in 1924 it consisted of little more than a collection of dwellings and some 2000-3000 inhabitants. The present paper sets out to document and explain the phenomenal expansion of "ever-growing Amman". The physical geography of the urban region and the early growth of the city are considered at the outset and this leads directly to consideration of the highly polarised social structuring that characterises contemporary Amman. In doing this, original data derived from the recent Greater Amman Municipality's Geographical Information System are presented. In this respect, the essential modernity of the city is exemplified. The employment and industrial bases of the city and a range of pressing contemporary issues are then considered, including transport and congestion, the provision of urban water under conditions of water stress and privatisation, and urban and regional development planning for the city. The paper concludes by emphasizing the growing regional and international geopolitical salience of the city of Amman at the start of the 21st century. (C) 2008 Elsevier Ltd. All rights reserved.

Water quality and ecology of the River Lee: mass balance and a review of temporal and spatial data

A regional overview of the water quality and ecology of the River Lee catchment is presented. Specifically, data describing the chemical, microbiological and macrobiological water quality and fisheries communities have been analysed, based on a division into river, sewage treatment works, fish-farm, lake and industrial samples. Nutrient enrichment and the highest concentrations of metals and micro-organics were found in the urbanised, lower reaches of the Lee and in the Lee Navigation. Average annual concentrations of metals were generally within environmental quality standards although, oil many occasions, concentrations of cadmium, copper, lead, mercury and zinc were in excess of the standards. Various organic substances (used as herbicides, fungicides, insecticides, chlorination by-products and industrial solvents) were widely detected in the Lee system. Concentrations of ten micro-organic substances were observed in excess of their environmental quality standards, though not in terms of annual averages. Sewage treatment works were the principal point source input of nutrients. metals and micro-organic determinands to the catchment. Diffuse nitrogen sources contributed approximately 60% and 27% of the in-stream load in the upper and lower Lee respectively, whereas approximately 60% and 20% of the in-stream phosphorus load was derived from diffuse sources in the upper and lower Lee. For metals, the most significant source was the urban runoff from North London. In reaches less affected by effluent discharges, diffuse runoff from urban and agricultural areas dominated trends. Flig-h microbiological content, observed in the River Lee particularly in urbanised reaches, was far in excess of the EC Bathing Water Directive standards. Water quality issues and degraded habitat in the lower reaches of the Lee have led to impoverished aquatic fauna but, within the mid-catchment reaches and upper agricultural tributaries, less nutrient enrichment and channel alteration has permitted more diverse aquatic fauna.

Financial protection in the UK building industry: a guide for clients and the construction supply chain.

There is a clear need for financial protection in the construction industry, both to guarantee satisfactory completion of construction projects and to guard against non-payment. However, the cost of financial protection is often felt to be disproportionately high, with unnecessary overlap between different measures. The Reading Construction Forum has commissioned and steered research which is published in this report in an effort to bring the problem out into the open and to clarify the various options open to the various parties and stakeholders in the construction process. "Financial Protection in the UK Building Industry" is the first definitive report on the subject, offering an accurate and simple guide that all levels within the construction industry can understand. This accessible new guide considers the problem of financial protection and clearly lays out the alternative solutions.It looks by turn at the client, the main contractor, and the sub-contractor, discussing which financial protection options are available to each of them, and considers the pros and cons of each option. The cost of each type of financial protection is weighed against the amount of protection provided and the risks involved. The book concludes with guidance for consultants, emphasising relevant points to consider when advising clients and contractors about which type of financial protection to choose. "Financial Protection in the UK Building Industry" was researched by a literature search, collection of statistical data, and financial data, as well as discussions with clients, contractors, sub-contractors and consultants. This investigation has shown that the direct costs of implementing financial protection measures are marginal, and that wider adoption of payment protection would create a more equitable situation between contracting parties.This guide will enable anyone in the construction industry to consider all the options, and determine what is the best solution for them. "Reading Construction Forum Financial Protection for the UK Building Industry" was complied by the University of Reading, funded by the Reading Construction Forum. The Forum has recently commissioned and steered a number of high-profile reports covering important aspects of the construction industry. Members of the Forum include major companies which are concerned with achieving high quality in the design, construction and use of commercial, retail and industrial buildings. All are committed to change and innovation in the British and European construction industries.

Efficient and cost-effective experimental determination of kinetic constants and data: the success of a Bayesian systematic approach to drug transport, receptor binding, continuous culture and cell transport kinetics

Details about the parameters of kinetic systems are crucial for progress in both medical and industrial research, including drug development, clinical diagnosis and biotechnology applications. Such details must be collected by a series of kinetic experiments and investigations. The correct design of the experiment is essential to collecting data suitable for analysis, modelling and deriving the correct information. We have developed a systematic and iterative Bayesian method and sets of rules for the design of enzyme kinetic experiments. Our method selects the optimum design to collect data suitable for accurate modelling and analysis and minimises the error in the parameters estimated. The rules select features of the design such as the substrate range and the number of measurements. We show here that this method can be directly applied to the study of other important kinetic systems, including drug transport, receptor binding, microbial culture and cell transport kinetics. It is possible to reduce the errors in the estimated parameters and, most importantly, increase the efficiency and cost-effectiveness by reducing the necessary amount of experiments and data points measured. (C) 2003 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

Conservation and sustainable use of wild species as sources of new ornamentals

While only about 1-200 species are used intensively in commercial floriculture (e.g. carnations, chrysanthemums, gerbera, narcissus, orchids, tulips, lilies, roses, pansies and violas, saintpaulias, etc.) and 4-500 as house plants, several thousand species of herbs, shrubs and trees are traded commercially by nurseries and garden centres as ornamentals or amenity species. Most of these have been introduced from the wild with little selection or breeding. In Europe alone, 12 000 species are found in cultivation in general garden collections (i.e. excluding specialist collections and botanic gardens). In addition, specialist collections (often very large) of many other species and/or cultivars of groups such as orchids, bromeliads, cacti and succulents, primulas, rhododendrons, conifers and cycads are maintained in several centres such as botanic gardens and specialist nurseries, as are 'national collections' of cultivated species and cultivars in some countries. Specialist growers, both professional and amateur, also maintain collections of plants for cultivation, including, increasingly, native plants. The trade in ornamental and amenity horticulture cannot be fully estimated but runs into many billions of dollars annually and there is considerable potential for further development and the introduction of many new species into the trade. Despite this, most of the collections are ad hoc and no co-ordinated efforts have been made to ensure that adequate germplasm samples of these species are maintained for conservation purposes and few of them are represented at all adequately in seed banks. Few countries have paid much attention to germplasm needs of ornamentals and the Ornamental Plant Germplasm Center in conjunction with the USDA National Plant Germplasm System at The Ohio State University is an exception. Generally there is a serious gap in national and international germplasm strategies, which have tended to focus primarily on food plants and some forage and industrial crops. Adequate arrangements need to be put in place to ensure the long- and medium-term conservation of representative samples of the genetic diversity of ornamental species. The problems of achieving this will be discussed. In addition, a policy for the conservation of old cultivars or 'heritage' varieties of ornamentals needs to be formulated. The considerable potential for introduction of new ornamental species needs to be assessed. Consideration needs to be given to setting up a co-ordinating structure with overall responsibility for the conservation of germplasm of ornamental and amenity plants.