Chemoenzymatic routes to enantiopure hydroxytetrahydrofurans: muscarine and its analogues

Muscarine was identified as an active principle of the poisonous mushroom Amanita muscaria over 170 years ago and has been identified as an agonist of acetylcholine. The synthesis of all stereoisomers of muscarine have been accomplished at this stage by chemical methods and the biological activity of these compounds tested. A number of synthetic routes to enantiomerically pure muscarine and its analogues have been published. In this work, we are focussed on the use of a novel biotransformation strategy to access these compounds. Asymmetric synthesis involves targeting a synthetic pathway leading to one enantiomer of a compound and biocatalysis is one strategy used in asymmetric synthesis. Chapter 1 consists of a review of the relevant literature pertaining to the synthesis and stereoselective transformations of 3-hydroxytetrahydrofuranss. A review of synthetic routes to these compounds is presented, with a particular focus on routes to the natural product muscarine and its analogues. Chapter 2 discusses the preparative routes to the 3-hydroxytetrahydrofurans via 3(2H)- furanones. Steps amongst which include Rh(II) mediate cyclisation and kinetic resolution via baker’s yeast mediated carbonyl reduction, resulting in enantioenriched 3- hydroxytetrahydrofuran derivatives. Finally, application of this methodology to the preparation of all four enantiomers of an analogue of desmethylmuscarine and the synthesis of epimuscarine is described. Chapter 3 consists of a detailed experimental section outlining the synthetic procedures employed.

An investigation of routes to cancer diagnosis in 10 international jurisdictions, as part of the International Cancer Benchmarking Partnership: survey development and implementation

Objectives This paper describes the methods used in the International Cancer Benchmarking Partnership Module 4 Survey (ICBPM4) which examines time intervals and routes to cancer diagnosis in 10 jurisdictions. We present the study design with defining and measuring time intervals, identifying patients with cancer, questionnaire development, data management and analyses.
Design and setting Recruitment of participants to the ICBPM4 survey is based on cancer registries in each jurisdiction. Questionnaires draw on previous instruments and have been through a process of cognitive testing and piloting in three jurisdictions followed by standardised translation and adaptation. Data analysis focuses on comparing differences in time intervals and routes to diagnosis in the jurisdictions.
Participants Our target is 200 patients with symptomatic breast, lung, colorectal and ovarian cancer in each jurisdiction. Patients are approached directly or via their primary care physician (PCP). Patients’ PCPs and cancer treatment specialists (CTSs) are surveyed, and ‘data rules’ are applied to combine and reconcile conflicting information. Where CTS information is unavailable, audit information is sought from treatment records and databases.
Main outcomes Reliability testing of the patient questionnaire showed that agreement was complete (κ=1) in four items and substantial (κ=0.8, 95% CI 0.333 to 1) in one item. The identification of eligible patients is sufficient to meet the targets for breast, lung and colorectal cancer. Initial patient and PCP survey response rates from the UK and Sweden are comparable with similar published surveys. Data collection was completed in early 2016 for all cancer types.
Conclusion An international questionnaire-based survey of patients with cancer, PCPs and CTSs has been developed and launched in 10 jurisdictions. ICBPM4 will help to further understand international differences in cancer survival by comparing time intervals and routes to cancer diagnosis.

Origin and dispersal routes of foreign green and Kemp's ridley turtles in Spanish Atlantic and Mediterranean waters

[EN] The presence of the green and Kemp's ridley turtles is rare at Atlantic and Mediterranean Spanish waters, but the records have increased during the last decades. We reported a new set of records and reviewed all the historical observations of these species. The analysis of a mitochondrial DNA fragment of the newest records provided insights about the origin of the individuals. The Kemp's ridley turtles arrived from the western Atlantic nesting beaches, although the discovering of a new haplotype suggested the existence of an unknown or low sampled nesting area of origin.

Estimates of Total Fuel Consumption in Transporting Grain from Iowa to Major Grain-Importing Countries by Alternative Modes and Routes, 1985

This study measured fuel consumption in transporting grain from Iowa origins to Japan and Amsterdam by alternative routes and modes of transport and applied these data to construct equations for fuel consumption from Iowa origins to alternative final destinations. Some of the results are as follows: (1) The metered tractor-trailer truck averaged 186.6 gross ton-miles per gallon and 90.5 net ton-miles per gallon when loaded 50% of total miles. (2) The 1983 fuel consumption of seven trucks taken from company records was 82.4 net ton-miles per gallon at 67.5% loaded miles and 68.6 net ton-miles per gallon at 50% loaded miles. (3) Unit grain trains from Iowa to West Coast ports averaged 437.0 net ton-miles per gallon whereas unit grain trains from Iowa to New Orleans averaged 640.1 net ton-miles per gallon--a 46% advantage for the New Orleans trips. (4) Average barge fuel consumption on the Mississippi River from Iowa to New Orleans export grain elevators was 544.5 net ton-miles per gallon, with a 35% backhaul rate. (5) Ocean vessel net ton-miles per gallon varies widely by size of ship and backhaul percentage. With no backhaul, the average net ton-miles per gallon were as follows: for 30,000 dwt ship, 574.8 net ton-miles per gallon; for 50,000 dwt ship, 701.9; for 70,000 dwt ship, 835.1; and for 100,000 dwt ship, 1,043.4. (6) The most fuel efficient route and modal combination to transport grain from Iowa to Japan depends on the size of ocean vessel, the percentage of backhaul, and the origin of the grain. Alternative routes and modal combinations in shipping grain to Japan are ranked in descending order of fuel efficiencies.

Investigating routes toward atomic layer deposition of silicon carbide: Ab initio screening of potential silicon and carbon precursors

Silicon carbide (SiC) is a promising material for electronics due to its hardness, and ability to carry high currents and high operating temperature. SiC films are currently deposited using chemical vapor deposition (CVD) at high temperatures 1500–1600 °C. However, there is a need to deposit SiC-based films on the surface of high aspect ratio features at low temperatures. One of the most precise thin film deposition techniques on high-aspect-ratio surfaces that operates at low temperatures is atomic layer deposition (ALD). However, there are currently no known methods for ALD of SiC. Herein, the authors present a first-principles thermodynamic analysis so as to screen different precursor combinations for SiC thin films. The authors do this by calculating the Gibbs energy ΔGΔG of the reaction using density functional theory and including the effects of pressure and temperature. This theoretical model was validated for existing chemical reactions in CVD of SiC at 1000 °C. The precursors disilane (Si2H6), silane (SiH4), or monochlorosilane (SiH3Cl) with ethyne (C2H2), carbontetrachloride (CCl4), or trichloromethane (CHCl3) were predicted to be the most promising for ALD of SiC at 400 °C.

Spanish monarchy and the Portuguese Republic: two routes to democratization

From 1974 to 1986 the Iberian Peninsula was the arena of major political changes. The process then undertaken was characterized by the transition from two Iberian authoritarian regimes to two democracies, which enabled both countries to join the European Economic Community (EEC) on 1 January 1986. However, the political vicissitudes until full membership of what became the European Union (EU) was achieved were very different and were decisively, although not exclusively, influenced by the fact Portugal was a republic and Spain a monarchy. In Portugal the 1974 revolution took place with consequent shift of the head of state while in Spain the engine of change was precisely the head of state: King Juan Carlos I. It is also true that despite the dangers to democracy (terrorism in Spain and some radicalism in Portugal) both societies supported the political parties committed to the democratic process in elections, which helped avoid tensions that could have defeated the process. Likewise, it is possible to argue that in Spain a plan to achieve democracy within the rule of law (an archetypal transition) was designed by the head of state, while in Portugal there was no pre-established plan – the programme of the Armed Forces Movement (Movimento das Forças Armadas [MFA]) was a weak and precarious compromise between different visions of the road to follow, enabling an intense political struggle that almost led to civil war and a dangerous state of crisis.

Risk of African swine fever introduction into the European Union through transport-associated routes: returning trucks and waste from international ships and planes

BACKGROUND The uncontrolled presence of African swine fever (ASF) in Russian Federation (RF) poses a serious risk to the whole European Union (EU) pig industry. Although trade of pigs and their products is banned since the official notification in June 2007, the potential introduction of ASF virus (ASFV) may occur by other routes, which are very frequent in ASF, and more difficult to control, such as contaminated waste or infected vehicles. This study was intended to estimate the risk of ASFV introduction into the EU through three types of transport routes: returning trucks, waste from international ships and waste from international planes, which will be referred here as transport-associated routes (TAR). Since no detailed and official information was available for these routes, a semi-quantitative model based on the weighted combination of risk factors was developed to estimate the risk of ASFV introduction by TAR. Relative weights for combination of different risk factors as well as validation of the model results were obtained by an expert opinion elicitation. RESULTS Model results indicate that the relative risk for ASFV introduction through TAR in most of the EU countries (16) is low, although some countries, specifically Poland and Lithuania, concentrate high levels of risk, the returning trucks route being the analyzed TAR that currently poses the highest risk for ASFV introduction into the EU. The spatial distribution of the risk of ASFV introduction varies importantly between the analyzed introduction routes. Results also highlight the need to increase the awareness and precautions for ASF prevention, particularly ensuring truck disinfection, to minimize the potential risk of entrance into the EU. CONCLUSIONS This study presents the first assessment of ASF introduction into the EU through TAR. The innovative model developed here could be used in data scarce situations for estimating the relative risk associated to each EU country. This simple methodology provides a rapid and easy to interpret results on risk that may be used for a target and cost-effective allocation of resources to prevent disease introduction.

Developing self-guided scuba dive routes in the Algarve (Portugal) and analysing visitors' perceptions

Scuba diving allows for underwater visitation of cultural and natural resources. Underwater routes can be used as a tool for guided and supervised underwater visits. Two scuba diving routes were implemented in the Algarve (South of Portugal), the "B24" and "Poco" diving sites. The perceptions of scuba divers regarding several aspects of the routes and the existing support infrastructures were studied following a survey carried out through face-to-face interviews from 2008 to 2012. Divers profile and their perceptions were analysed using 246 valid questionnaires. Divers were mainly Portuguese, over 30 years old and with more than 12 years of formal education. Some of the support infrastructures did not achieve a "good" or "acceptable" grade. This should be carefully considered by diving operators and managers, because perceptions tend to circulate throughout the diving tourists. All features of interpretative slates were graded as highly satisfactory. Overall, diver satisfaction increased slightly after route implementation, with an average ranking of "good". These findings support the implementation of underwater routes as a way to promote diving activity, and to increase divers' environmental education and awareness. (C) 2013 Elsevier Ltd. All rights reserved.

Ecotourism snorkelling routes at Marinha Beach (Algarve)

Coastal ecotourism is one of the fastest growing leisure industries in the world and snorkelling is emerging as an important beach-based activity. Snorkelling has the potential to enhance biodiversity conservation when developed within environmental education framework. The aim of this study was to implement and evaluate snorkelling routes, in the Algarve (South Portugal), as a sustainable ecotourism offer. To achieve these objectives, three snorkelling routes were established at the pristine Marinha beach. After the diving experience, a face-to-face questionnaire survey was conducted to collect information about individuals' opinions regarding the underwater routes, their social demographic characteristics, ecological appreciation, opinions about beach facilities and trip expenditures. The survey was undertaken during the summer months of 2008 and 2009, and 202 people were interviewed. Data was analysed using univariate and multivariate statistic methods. Most respondents perceived the existence of routes to be good for the preservation of the local biodiversity and reported this experience as "good" or "excellent". The only difference in perceptions was observed by visitor snorkelling in groups of more than two people. Interviewers consider that emergency support and sanitary facilities are the most important beach support infrastructures. Overall, these routes seem to be an effective tool for developing ecological awareness in tourists, as they enhance the preservation and the understanding of the marine coastal environment.

Eco-touristic snorkelling routes at Marinha beach (Algarve): Environmental education and human impacts

The use of natural areas for underwater coastal marine activities such as snorkelling is growing, but the amount of ecological and socioeconomic data on these activities is scarce and relates mainly to coral reef areas. Three underwater self-guided routes were designed at Marinha Beach (Algarve, Portugal), based on scientific information, with in situ interpretation and guidance, as a way to enhance biodiversity awareness and, hence, reduce the probability of human impacts. The routes were implemented in two consecutive summer seasons and after each season, visual census techniques were used to describe flora composition and cover area (seaweeds and seagrasses) in order to understand patterns and evaluate human impacts. Snorkelers' opinions and perceptions about several issues related to the routes' environmental education role (e.g. role in enhancing biocliversity awareness) were investigated by questionnaire after the snorkelling activity. An inter-annual difference inflora assemblages was found, probably associated to natural variability, rather than snorkelers' impacts. Results indicate that, in fact, in situ education and interpretation can raise environmental awareness if properly addressed, resulting in a satisfactory way of engaging snorkelers in the protection and in the conservation of the visited environments, thereby preventing negative ecological impacts. (C) 2015 Elsevier Ltd. All rights reserved.

Airborne particulate matter at a bus station : concentration levels and governing parameters

Traffic emissions are an important contributor to ambient air pollution, especially in large cities featuring extensive and high density traffic networks. Bus fleets represent a significant part of inner city traffic causing an increase in exposure to general public, passengers and drivers along bus routes and at bus stations. Limited information is available on quantification of the levels, and governing parameters affecting the air pollution exposure at bus stations. The presented study investigated the bus emissions-dominated ambient air in a large, inner city bus station, with a specific focus on submicrometer particles. The study’s objectives were (i) quantification of the concentration levels; (ii) characterisation of the spatio-temporal variation; (iii) identification of the parameters governing the emissions levels at the bus station and (iv) assessment of the relationship between particle concentrations measured at the street level (background) and within the bus station. The results show that up to 90% of the emissions at the station are ultrafine particles (smaller than 100 nm), with the concentration levels up to 10 times the value of urban ambient air background (annual) and up to 4 times the local ambient air background. The governing parameters affecting particle concentration at the station were bus flow rate and meteorological conditions (wind velocity). Particle concentration followed a diurnal trend, with an increase in the morning and evening, associated with traffic rush hours. Passengers’ exposure could be significant compared to the average outdoor and indoor exposure levels.

Procurement Case Study and Decision-making Strategies

Objectives The procurement research of Sydney Opera House FM Exemplar Project aims to develop innovative methods and guidelines for the procurement of FM services, applicable to iconic and / or performing arts centre facilities, or facilities with similar FM functions. The initial procurement report in June 2005 analysed the strategic objectives and operational requirements that provide ‘demand statements’ as evaluation criteria in the service procurement process. The subsequent interim procurement report in September 2005 discussed the elements contributing to the criteria for decision-making in the service procurement process. This procurement report concentrates on the research on procurement strategies and innovative methods using a case study approach. The objectives of this report are: • to investigate service procurement methods and process in iconic and/or performing arts centre facilities; • to showcase FM innovation in Sydney Opera House through a case study; • to establish a preliminary decision-making framework and guidelines for selection of appropriate FM procurement routes to provide a useful model for FM community. Findings Findings from this procurement research are presented as follows. • FM innovation and experience of Sydney Opera House • Innovative procurement methods and processes, drawn from a case study of Sydney Opera House as exemplar • An integrated performance framework to link maintenance service functions to high level organisational objective and strategies • Procurement methods and contract outcomes, focusing on building maintenance and cleaning services of Sydney Opera House • Multi-dimensional assessment of Service Providers • General decision-making strategies and guidelines for selection of appropriate FM procurement routes Further Research Whilst the Sydney Opera House case study emphasises the experience of Sydney Opera House, a study of procurement strategies and methods from published research and FM good practice will supply facilities managers with alternative procurement routes. Further research on the procurement theme will develop a final decision-making model for the procurement of FM services, drawn from the evaluation of the case study outcomes, as well as FM good practice and findings from current published research.

Services Procurement

This Services Procurement Report incorporates the previous benchmarking research and aims to develop innovative methods and guidelines for the procurement of FM services, applicable to iconic and / or performing arts centre facilities, or facilities with similar FM functions. The FM Exemplar Project utilising the Sydney Opera House produced its initial procurement report in June 2005 which analysed the strategic objectives and operational requirements that provide ‘demand statements’ as evaluation criteria in the service procurement process. The subsequent interim procurement report in September 2005 discussed the elements contributing to the criteria for decision-making in the service procurement process. This procurement report concentrates on the research on procurement strategies and innovative methods using a case study approach. The objectives of this report are to: Investigate service procurement methods and process in iconic and/or performing arts centre facilities; Showcase FM innovation in Sydney Opera House through a case study; Establish a preliminary decision-making framework and guidelines for selection of appropriate FM procurement routes to provide a useful model for FM community