Studies on Agriculturally Important Plant Metabolites

This thesis deals mainly with the carbohydrate metabolism of plants, and in particular with that of bracken and of potatoes. Four main projects are described: a) An investigation into the seasonal and other variations in carbohydrate levels in bracken rhizomes, which is relevant to the behaviour of herbicides in the plant and to its ability to withstand herbicide treatment. b) Examination of the glycolipid and phospholipid composition of bracken, initially to determine whether any glycolipids which could act as intermediates in polysaccharide biosynthesis might be present. None were found, but the results have implications for the composition of plastid membranes and the turnover of carbohydrates in photosynthetic tissue. c) A parallel investigation on carbohydrates and lipids in potato tubers during low-temperature storage, with a twofold objective: firstly to investigate the mechanism of low-temperature sweetening and the role of membrane lipids therein, and secondly to compare commonly-grown varieties in their tendency to accumulate sugars at low temperatures. d) The partial characterisation of a complex mucilaginous polysaccharide found in bracken. The significance of the results for carbohydrate metabolism in bracken and other plants; the storage of potatoes for processing; and bracken eradication techniques is discussed, and some observations on the ecology of bracken and its effects on the soil are presented in two appendices

Possible High-Redshift, Low-Luminosity AGN Activity in the Hubble Deep Field

In the Hubble Deep Field (HDF), twelve candidate sources of high-redshift (z > 3.5) AGN activity have been identified. The color selection criteria were established by passing spectra of selected quasars and Seyfert galaxies (appropriately redshifted and modified for "Lyman forest" absorption), as well as stars, observed normal and starburst galaxies, and galaxy models for various redshifts through the filters used for the HDF observations. The actual identification of AGN candidates also involved convolving a Laplacian-of-Gaussian filter with the HDF images, thereby removing relatively flat galactic backgrounds and leaving only the point-like components in the centers. Along with positions and colors, estimated redshifts and absolute magnitudes are reported, with the candidates falling toward the faint end of the AGN luminosity function. One candidate has been previously observed spectroscopically, with a measured redshift of 4.02. The number of sources reported here is consistent with a simple extrapolation of the observed quasar luminosity function to magnitude 30 in B_Johnson. Implications for ionization of the intergalactic medium and for gravitational lensing are discussed.Comment: 10 pages LaTex plus 2 separate files (Table 1 which is a two-page landscape LaTex file; and Figure 6 which is a large (0.7 MB) non-encapsulated postscript file). Accepted for publication in the Astronomical Journa

Structure of native cellulose microfibrils, the starting point for nanocellulose manufacture

There is an emerging consensus that higher plants synthesize cellulose microfibrils that initially comprise 18 chains. However, the mean number of chains per microfibril in situ is usually greater than 18, sometimes much greater. Microfibrils from woody tissues of conifers, grasses and dicotyledonous plants, and from organs like cotton hairs, all differ in detailed structure and mean diameter. Diameters increase further when aggregated microfibrils are isolated. Because surface chains differ, the tensile properties of the cellulose may be augmented by increasing microfibril diameter. Association of microfibrils with anionic polysaccharides in primary cell walls and mucilages leads to in vivo mechanisms of disaggregation that may be relevant to the preparation of nanofibrillar cellulose products. For the preparation of nanocrystalline celluloses, the key issue is the nature and axial spacing of disordered domains at which axial scission can be initiated. These disordered domains do not, as has often been suggested, take the form of large blocks occupying much of the length of the microfibril. They are more likely to be located at chain ends or at places where the microfibril has been mechanically damaged, but their structure and the reasons for their sensitivity to acid hydrolysis need better characterization

Organosolv pretreatment of Sitka spruce wood: conversion of hemicelluloses to ethyl glycosides

A range of organosolv pretreatments, using ethanol:water mixtures with dilute sulphuric acid, were applied to Sitka spruce sawdust with the aim of generating useful co-products as well as improving saccharification yield. The most efficient of the pretreatment conditions, resulting in subsequent saccharification yields of up to 86%, converted a large part of the hemicellulose sugars to their ethyl glycosides as identified by GC/MS. These conditions also reduced conversion of pentoses to furfural, the ethyl glycosides being more stable to dehydration than the parent pentoses. Through comparison with the behaviour of model compounds under the same reaction conditions it was shown that the anomeric composition of the products was consistent with a predominant transglycosylation reaction mechanism, rather than hydrolysis followed by glycosylation. The ethyl glycosides have potential as intermediates in the sustainable production of high-value chemicals

Isolation of high quality lignin as a by-product from ammonia percolation pretreatment of poplar wood

A two-step process combining percolation-mode ammonia pretreatment of poplar sawdust with mild organosolv purification of the extracted lignin produced high quality, high purity lignin in up to 31% yield and 50% recovery. The uncondensed fraction of the isolated lignin was up to 34%, close to that the native lignin (40%). Less lignin was recovered after pretreatment in batch mode, apparently due to condensation during the longer residence time of the solubilised lignin at elevated temperature. The lignin recovery was directly correlated with its molecular weight and its nitrogen content. Low nitrogen incorporation, observed at high ammonia concentration, may be explained by limited homolytic cleavage of -O-4 bonds. Ammonia concentrations from 15% to 25% (w/w) gave similar results in terms of lignin structure, yield and recovery

Structure and spacing of cellulose microfibrils in woody cell walls of dicots

The structure of cellulose microfibrils in situ in wood from the dicotyledonous (hardwood) species cherry and birch, and the vascular tissue from sunflower stems, was examined by wide-angle X-ray and neutron scattering (WAXS and WANS) and small-angle neutron scattering (SANS). Deuteration of accessible cellulose chains followed by WANS showed that these chains were packed at similar spacings to crystalline cellulose, consistent with their inclusion in the microfibril dimensions and with a location at the surface of the microfibrils. Using the Scherrer equation and correcting for considerable lateral disorder, the microfibril dimensions of cherry, birch and sunflower microfibrils perpendicular to the [200] crystal plane were estimated as 3.0, 3.4 and 3.3 nm respectively. The lateral dimensions in other directions were more difficult to correct for disorder but appeared to be 3 nm or less. However for cherry and sunflower, the microfibril spacing estimated by SANS was about 4 nm and was insensitive to the presence of moisture. If the microfibril width was 3 nm as estimated by WAXS, the SANS spacing suggests that a non-cellulosic polymer segment might in places separate the aggregated cellulose microfibrils

A note on monopole moduli spaces

We discuss the structure of the framed moduli space of Bogomolny monopoles for arbitrary symmetry breaking and extend the definition of its stratification to the case of arbitrary compact Lie groups. We show that each stratum is a union of submanifolds for which we conjecture that the natural $L^2$ metric is hyperKahler. The dimensions of the strata and of these submanifolds are calculated, and it is found that for the latter, the dimension is always a multiple of four.Comment: 17 pages, LaTe

FTIR measurement of cellulose microfibril angle in historic Scots pine wood and its use to detect fungal decay

Microfibril angle (MFA) – the orientation of cellulose fibres in the S2 layer of the secondary cell wall – is a key determinant of the stiffness and strength of timber. The microfibril angle depends on the way in which the timber was grown and its position within the tree. Microfibril angle can be measured by X-ray diffraction and other methods, but the methods in current use are slow or require advanced instrumentation. The aim of this study was to explore the use of polarised Fourier transform infrared (FTIR) microscopy as a relatively fast and inexpensive method for measuring MFA in historic Scots pine (Pinus sylvestris L.). The FTIR measurements were calibrated against X-ray measurements of MFA in modern Scots pine. We observed a wide range in MFA values and a radial pattern of MFA similar to modern Scots pine in undecayed Scots pine heartwood from sixteenth and seventeenth century beams in Scottish secular buildings. The density of the heartwood was also similar to modern plantation-grown Scots pine despite the much slower growth rate recorded in the ring widths of the historic timber. The sapwood, which had been attacked by both insect pests and fungi, showed an erratic reduction in density and a large increase in MFA compared to the modern material. The increased sapwood MFA was attributed to selective destruction of the S2 layer of the wood cell walls by fungal decay. Using MFA measurements in conjunction with density offers the possibility to estimate the mechanical properties of sound historic pine timber, to detect fungal decay more sensitively than by density alone, and to distinguish between pest and fungal attack in a way that relates directly to the remaining mechanical performance of the timber

Aerosol transmission of SARS-CoV-2: physical principles and implications

Evidence has recently emerged that SARS-CoV-2, the coronavirus that causes COVID-19, can be transmitted airborne in aerosol particles as well as in droplets of larger size or in surface deposits. This minireview outlines the underlying aerosol science, making links to meteorological aerosol research where some of the processes governing the size of aerosol and larger droplets are better understood. SARS-CoV-2 in aerosol form is emitted during normal breathing and speech by both asymptomatic and symptomatic people, remaining viable with a half-life of up to about an hour during which air movement can carry it considerable distances, although it simultaneously disperses. Evaporation reduces the size of the droplets, whereas coalescence increases the mean droplet size. Aerosol particles containing SARS-CoV-2 can also coalesce with pollution particulates, and pollution increases infection rates. The operation of ventilation systems in public buildings and transportation can create infection hazards via aerosols, but provides opportunities for reducing the risk of transmission in ways as simple as switching from recirculated to outside air. There are also opportunities to reduce the viability of SARS-CoV-2 in aerosol form with sunlight or UV lamps. The efficiency of masks for blocking aerosol transmission depends strongly on how well they fit. Research areas that urgently need further experimentation include the basis for variation in droplet size distribution, including droplets emitted by ‘superspreader’ individuals; the evolution of droplet sizes after emission and their dispersal by turbulence, which gives a different basis for social distancing

Chemical and Mechanical Differences between Historic and Modern Scots Pine Wood

Timber is one of the most common historic building materials, but relatively little is known about how it ages in situ. Here we investigate historic and modern Scots pine to determine any chemical or mechanical differences between them. Fourier-transform infrared (FTIR) microscopy was used to investigate differences in the chemical composition of Scots pine (Pinus sylvestris L.) timber, comparing small samples from historic beams about 500 years old with modern timber. The hemicellulosic acetyl content was reduced by about half in the historic samples, uniformly across the thickness of the beams. A chemical mechanism was therefore suggested for the loss of acetyl groups, as has been observed in paper. In paper, deacetylation and the resulting release of acetic acid are accompanied by loss of strength. Mechanical testing of the historic timber was difficult because the available length of the samples along the grain was only 20 mm. After developing a miniaturized compression test developed for the purpose, it was shown that the relative stiffness of the historic Scots pine samples was reduced by about half compared to modern material