The River Endrick - then and now, monitoring by photography

A major survey of the River Endrick was carried out in 1959-60. This survey was repeated three decades later in 1989-90 and comparisons were made of the fauna at the two times of sampling. During both surveys, photographs were taken of all the sampling sites and the objective of the present paper is to compare some of these photographs and discuss the value of photography in studies of river ecology. The sites used for photographic comparison were not chosen originally for that purpose but as appropriate places on the river from source to mouth to study its ecology. The pairs of photos now available have proved of interest and value and some lessons have been learned in relation to the selection of sites for any future photographic studies. Ideally photos should be taken in more than one season of the year as much of the river can be obscured by riparian trees and shrubs during the vegetative season. The exact position from which each photograph is taken is also a major factor to be considered.

Falling through the cracks: are European directives and international conventions the panacea for freshwater nature conservation?

There are many ways of practising freshwater nature conservation: from strict legislative protection of individual species considered rare or threatened to protecting whole lakes or long stretches of rivers; from practical conservation management at a local scale to integrated catchment management at the river basin scale; and from the encouragement of better habitat management through codes of good practice to statutory control of pollution or abstraction. Whatever the mechanism, an essential pre-requisite is a way of choosing where to put the effort, especially when resources for nature conservation are severely limited. The aim of this article is to review the contribution from four specific international measures to the task of assigning priorities for conservation. The 1990s saw the introduction of two European directives (the Habitats Directive (HD) and the Water Framework Directive (WFD)) and one international convention (the Biodiversity Convention (CBD)) each with the potential for influencing, to a greater or lesser extent, the conservation of freshwater habitats and species. This article also discusses a much older convention – the Ramsar Convention – adopted in 1971 specifically to help tackle the conservation and management of wetlands and aquatic ecosystems. Although the authors have focused mainly on the UK, the subject is relevant to other parts of Europe and beyond. The article explores the degree to which these measures help in identifying the most important fresh waters for conservation, and asks whether or not they present the right conservation message to a wide audience.

Fish communities and fisheries in Wales's National Nature Reserves: a review

Wales is important for fish conservation in Britain. In much of Wales, atchments are small (median catchment size = 121 km2 ) and frequently eparated by areas of upland (> 600 m altitude), creating a highly agmented habitat for freshwater fish. Consequently, fish communities onsist mainly of diadromous species such as trout, eel and sticklebacks hat were able to recolonise freshwaters via the sea following the retreat of he ice sheets ca. 10 000 years BP. This review aims to (i) update the former work of Lyle and Maitland, taking into account new National Nature Reserves (NNRs)and additional data collected since 1991; (ii) assess the different fish communities represented on Welsh NNRs with respect to their naturalness; (iii) examine the use of NNRs for angling; (iv) evaluate opportunities for expanding the NNR series to conserve fish populations of conservation importance. The paper provides a table of freshwater fish occurrence by water body in Wales.

From molecules to organs : Microscopy and multi-scale nature of development

Morphogenesis is a phenomenon of intricate balance and dynamic interplay between processes occurring at a wide range of scales (spatial, temporal and energetic). During development, a variety of physical mechanisms are employed by tissues to simultaneously pattern, move, and differentiate based on information exchange between constituent cells, perhaps more than at any other time during an organism's life. To fully understand such events, a combined theoretical and experimental framework is required to assist in deciphering the correlations at both structural and functional levels at scales that include the intracellular and tissue levels as well as organs and organ systems. Microscopy, especially diffraction-limited light microscopy, has emerged as a central tool to capture the spatio-temporal context of life processes. Imaging has the unique advantage of watching biological events as they unfold over time at single-cell resolution in the intact animal. In this work I present a range of problems in morphogenesis, each unique in its requirements for novel quantitative imaging both in terms of the technique and analysis. Understanding the molecular basis for a developmental process involves investigating how genes and their products- mRNA and proteins-function in the context of a cell. Structural information holds the key to insights into mechanisms and imaging fixed specimens paves the first step towards deciphering gene function. The work presented in this thesis starts with the demonstration that the fluorescent signal from the challenging environment of whole-mount imaging, obtained by in situ hybridization chain reaction (HCR), scales linearly with the number of copies of target mRNA to provide quantitative sub-cellular mapping of mRNA expression within intact vertebrate embryos. The work then progresses to address aspects of imaging live embryonic development in a number of species. While processes such as avian cartilage growth require high spatial resolution and lower time resolution, dynamic events during zebrafish somitogenesis require higher time resolution to capture the protein localization as the somites mature. The requirements on imaging are even more stringent in case of the embryonic zebrafish heart that beats with a frequency of ~ 2-2.5 Hz, thereby requiring very fast imaging techniques based on two-photon light sheet microscope to capture its dynamics. In each of the hitherto-mentioned cases, ranging from the level of molecules to organs, an imaging framework is developed, both in terms of technique and analysis to allow quantitative assessment of the process in vivo. Overall the work presented in this thesis combines new quantitative tools with novel microscopy for the precise understanding of processes in embryonic development.

Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

I. The effect of N,N,N',N' -tetramethylethylenediamine on the Schlenk Equilibrium. II. The nature of the Di-Grignard reagent

I. The influence of N,N,N’,N’-tetramethylethylenediamine on the Schlenk equilibrium

The equilibrium between ethylmagnesium bromide, diethylmagnesium, and magnesium bromide has been studied by nuclear magnetic resonance spectroscopy. The interconversion of the species is very fast on the nmr time scale, and only an averaged spectrum is observed for the ethyl species. When N,N,N’,N’-tetramethylethylenediamine is added to solutions of these reagents in tetrahydrofuran, the rate of interconversion is reduced. At temperatures near -50°, two ethylmagnesium species have been observed. These are attributed to the different ethyl groups in ethylmagnesium bromide and diethylmagnesium, two of the species involved in the Schlenk equilibrium of Grignard reagents.

II. The nature of di-Grignard reagents

Di-Grignard reagents have been examined by nuclear magnetic resonance spectroscopy in an attempt to prove that dialkylmagnesium reagents are in equilibrium with alkylmagnesium halides. The di-Grignard reagents of compounds such as 1,4-dibromobutane have been investigated. The dialkylmagnesium form of this di-Grignard reagent can exist as an intramolecular cyclic species, tetramethylene-magnesium. This cyclic form would give an nmr spectrum different from that of the classical alkylmagnesium halide di-Grignard reagent. In dimethyl ether-tetrahydrofuran solutions of di-Grignard reagents containing N N,N,N’,N’-Tetramethylethylenediamine, evidence has been found for the existence of an intramolecular dialkylmagnesium species. This species is rapidly equilibrating with other forms, but at low temperatures, the rates of interconversion are reduced. Two species can be seen in the nmr spectrum at -50°. One is the cyclic species; the other is an open form.

Inversion of the carbon at the carbon-magnesium bond in di-Grignard reagents has also been studied. This process is much faster than in corresponding monofunctional Grignard reagents.

The microbiological quality of water: the nature of the problem

Improvements in methods for the detection and enumeration of microbes in water, particularly the application of techniques of molecular biology, have highlighted shortcomings in the ”standard methods” for assessing water quality. Higher expectations from the consumer and increased publicity associated with pollution incidents can lead to an uncoupling of the cycle which links methodological development with standard-setting and legislation. The new methodology has also highlighted problems within the water cycle, related to the introduction, growth and metabolism of microbes. A greater understanding of the true diversity of the microbial community and the ability to transmit genetic information within aquatic systems ensures that the subject of this symposium and volume provides an ideal forum to discuss the problems encountered by both researcher and practitioner.

Habitat degradation - its nature, causes and treatment

Since the latter part of the 19th century the Ribble and its tributaries have suffered habitat degradation to varying degrees. This report examims the causes for its degradation, specific problems and their treatment, progress, plans and procedures, and benefits of restoration including species identified by English Nature as threatened or declining and which are listed in the UK Biodiversity Action Plan.

Carbono: arte, ciência e as impurezas do tempo

Esta dissertação enfoca uma série de trabalhos artísticos desenvolvidos antes e durante o período do mestrado, como Sumi, Infiltração e Carbono, que utilizam a fotografia, o vídeo, a instalação, o desenho, a frotagem e a escultura como meios de produção. A partir das obras desenvolveu-se uma discussão teórica acerca de algumas das relações possíveis entre a arte e a ciência, enquanto esferas produtoras de conhecimento. O embate entre o homem e a natureza, através da filosofia, da ciência e da arte, é objeto de estudo, além das especificidades do átomo Carbono, em especial suas estruturas macroscópicas os materiais e suas transformações ao longo do tempo. A instabilidade, a entropia, o fluxo, os paradigmas e as diversas concepções de Tempo são alguns dos temas tratados nesta pesquisa, que utilizou como base os escritos e as obras de artistas, cientistas, filósofos e pesquisadores da arte e da ciência