Thermochemical characterisation of various biomass feedstock and bio-oil generated by fast pyrolysis

The projected decline in fossil fuel availability, environmental concerns, and security of supply attract increased interest in renewable energy derived from biomass. Fast pyrolysis is a possible thermochemical conversion route for the production of bio-oil, with promising advantages. The purpose of the experiments reported in this thesis was to extend our understanding of the fast pyrolysis process for straw, perennial grasses and hardwoods, and the implications of selective pyrolysis, crop harvest and storage on the thermal decomposition products. To this end, characterisation and laboratory-scale fast pyrolysis were conducted on the available feedstocks, and their products were compared. The variation in light and medium volatile decomposition products was investigated at different pyrolysis temperatures and heating rates, and a comparison of fast and slow pyrolysis products was conducted. Feedstocks from different harvests, storage durations and locations were characterised and compared in terms of their fuel and chemical properties. A range of analytical (e.g. Py-GC-MS and TGA) and processing equipment (0.3 kg/h and 1.0 kg/h fast pyrolysis reactors and 0.15 kg slow pyrolysis reactor) was used. Findings show that the high bio-oil and char heating value, and low water content of willow short rotation coppice (SRC) make this crop attractive for fast pyrolysis processing compared to the other investigated feedstocks in this project. From the analytical sequential investigation of willow SRC, it was found that the volatile product distribution can be tailored to achieve a better final product, by a variation of the heating rate and temperature. Time of harvest was most influential on the fuel properties of miscanthus; overall the late harvest produced the best fuel properties (high HHV, low moisture content, high volatile content, low ash content), and storage of the feedstock reduced the moisture and acid content.

Characterisation of staphylococci associated with atopic eczema and chronic plaque psoriasis

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Characterisation of resistance to ß-lactam antibiotics in a population of Haemophilus influenzae

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Method for characterisation of weakly guiding waveguides by measuring mode field diameter

In this paper, we described an efficient theoretical approach to determine the integral characteristics such as Mode Field Diameter (MFD) and V-parameter of the Weakly guiding waveguides. To test the described method we measured MFD for the commercially available step index single mode fibre with known parameters. The results of these measurements are presented for two different wavelengths. It is worth noting that the developed approach implies infinite cladding, thus care should be taken to avoid influence of finiteness of cladding when MFD compares to cladding diamete.

Experimental characterisation of the impact of neighbouring modulation-formats on 43Gb/s P-DPSK over SSMF and LEAF

We report an experimental characterisation examining the impact of differing 50GHz neighbouring modulation formats and bit rates on the performance of 43Gb/s P-DPSK over 1300km of SSMF and LEAF types. Performance is shown to be robust for hybrid P-DPSK and OOK systems. © VDE VERLAG GMBH.

Vitamin E-stabilised UHMWPE for orthopaedic implants:quantitative determination of vitamin E and characterisation of its transformation products

The fate of vitamin E and the formation and identification of its transformation products were investigated at different stages of the manufacturing process of commercially produced cross-linked (by γ-irradiation) UHMWPE stabilised with vitamin E (vitamin E infused-post irradiation) used for tibia-components (as articulating surfaces) in total knee arthroplasty (total knee replacement). Vitamin E (α-tocopherol) and its transformation products were extracted from microtomed Tibia films and the different products were separated, isolated, purified using high performance liquid chromatography (HPLC), and characterised by spectroscopic methods and LC-MS. The amount of vitamin E and that of the products formed in the different Tibia samples and in their extracts were also quantified using FTIR and HPLC analysis and calibration curves. Thorough analysis of the Tibia extracts has shown that a number of vitamin E transformation products were formed at different concentrations at two selected stages of the implant manufacturing process that is before and after sterilisation by γ-irradiation. The identified products were found to correspond mainly to different stereoisomeric forms of a small number of vitamin E transformation products. Most of the observed products were of dimeric and trimeric nature with their identity confirmed through a detailed study of their spectral and chromatographic characteristics. It was found that the products of vitamin E, prior to the sterilisation step but after the crosslinking and doping of vitamin E, were mainly the dihydroxydimers and trimers (Tibia samples at this stage are referred to as “Tibia-VEPE”). After sterilisation and completion of the manufacturing process, additional dimers of vitamin E were also formed (Tibia samples at this stage are referred to as ‘Tibia-VEPE-Sterile’), Furthermore, two tocopherol-derived aldehydes (aldehyde 5-formyl-γ-tocopherol and aldehyde 7-formyl-γ-tocopherol) were also formed but at very low concentrations especially in the Tibia-VEPE-Sterile samples. The question of whether vitamin E becomes chemically reacted (grafted) onto the polymer matrix during the manufacturing process of the Tibia is also addressed.

Characterisation of electrospun polystyrene scaffolds for three-dimensional in vitro biological studies

The purpose of this study was to produce a well-characterised electrospun polystyrene scaffold which could be used routinely for three-dimensional (3D) cell culture experimentation. A linear relationship (p<0.01p<0.01) between three principal process variables (applied voltage, working distance and polymer concentration) and fibre diameter was reliably established enabling a mathematical model to be developed to standardise the electrospinning process. Surface chemistry and bulk architecture were manipulated to increase wetting and handling characteristics, respectively. X-ray photoelectron spectroscopy (XPS) confirmed the presence of oxygen-containing groups after argon plasma treatment, resulting in a similar surface chemistry to treated tissue culture plastic. The bulk architecture of the scaffolds was characterised by scanning electron microscopy (SEM) to assess the alignment of both random and aligned electrospun fibres, which were calculated to be 0.15 and 0.66, respectively. This compared to 0.51 for collagen fibres associated with native tissue. Tensile strength and strain of approximately of 0.15 MPa and 2.5%, respectively, allowed the scaffolds to be routinely handled for tissue culture purposes. The efficiency of attachment of smooth muscle cells to electrospun scaffolds was assessed using a modified 3-[4,5-dimethyl(thiazol-2yl)-3,5-diphery] tetrazolium bromide assay and cell morphology was assessed by phalloidin-FITC staining of F-actin. Argon plasma treatment of electrospun polystyrene scaffold resulted in significantly increased cell attachment (p<0.05p<0.05). The alignment factors of the actin filaments were 0.19 and 0.74 for the random and aligned scaffold respectively, compared to 0.51 for the native tissue. The data suggests that electrospinning of polystyrene generates 3D scaffolds which complement polystyrene used in 2D cell culture systems.

catena-[μ-tris(1,2-bis(tetrazol-1-yl)ethane-N4,N4')iron(II)] bis(tetrafluoroborate): Synthesis, structure, spectroscopic and magnetic characterisation of a chain-type coordination polymer spin-crossover compound.

In analogy to a common synthesis of 1-substituted 5-H tetrazoles (Tetrahedron Lett. 36 (1995)1759; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 11 (1985) 1521; Beloruss. Gos. Univ., Minsk, USSR. Khim. Geterotsikl. Soedin. 1 (1991) 66; BGU, Belarus. Vestsi Akad. Navuk Belarusi, Ser. Khim. Navuk 1 (1992) 73), the new bidentate ligand 1,2-bis(tetrazol-1-yl)ethane [endi] was synthesized and characterized by X-ray diffraction, NMR, IR and UV–Vis spectroscopy. By using iron(II) tetrafluoroborate hexahydrate the complexation with this ligand yields a 1-dimensional linear coordination polymer similar to the recently published chain compound (Inorg. Chem. 39 (2000) 1891) exhibiting a thermally induced spin-crossover phenomenon. Similar to the 1,2-bis(tetrazol-1-yl)propane-bridged compound, our 1,2-bis(tetrazol-1-yl)ethane-bridged compound shows a gradual spin transition, but the spin-crossover temperature T1/2≈140 K is found to be 10 K above the other T1/2. The T1/2 was determined by temperature-dependent 57Fe-Mössbauer, far FT-IR and UV–Vis spectroscopy as well as by temperature-dependent magnetic susceptibility measurements. Single crystals of the complex were grown in situ from a solution of the ligand and iron(II) tetrafluoroborate. The X-ray structure determinations of both the high spin as well as the low spin state of the compound revealed a solid state structure, which is comparable to that of catena-[Fe(1,2-bis(tetrazole-1-yl)propane)3](ClO4)2 (Inorg. Chem. 39 (2000) 1891; 2nd TMR-TOSS Meeting, 4th Spin Crossover Family Meeting, Lufthansa Training Center, Seeheim/Germany, April 30–May 2, 1999). Both the 1,2-bis(tetrazol-1-yl)propane-bridged and our compound do not show a thermal hysteresis effect (J. Am. Chem. Soc. 115 (1993) 9810; Inorg. Chim. Acta 37 (1979) 169; Chem. Phys. Lett. 93 (1982) 567). The synthesis of the complex described in the experimental section yielded a fine powdered product being poorly soluble in most common solvents. The single crystal measurements were done with crystals obtained by various diffusion methods. Most of them yielded either thin needles or small hexagonal prism crystals depending on the specific conditions.

Fabrication and characterisation of ultra-long-period fibre gratings

We report here for the first time the fabrication and characterisation of long-period fibre gratings (LPFGs) with period size up to several millimetres. The resonant loss peaks of these ultra-long-period gratings are generated from the coupling of the forward propagating core mode to the cladding modes of fundamental and harmonic orders. The dependence of temperature sensitivity of the coupled cladding modes on the diffraction order has been investigated. The possibility of utilising resonant peaks of different diffraction orders to perform simultaneous multi-parameter measurement has been explored. © 2002 Elsevier Science B.V. All rights reserved.

Physical and functional characterisation of apoptotic cell-derived extracellular vesicles

Damaged, aged or unwanted cells are removed from the body by an active process known as apoptosis. This highly orchestrated programme results in the exposure of 'flags' at the dying cell surface and the release of attractive signals to recruit phagocytes. Together these changes ensure efficient phagocytic removal of dying cells and prevention of inflammatory and autoimmune disorders. Extracellular vesicles (EV) are released from a variety of cells (both viable and apoptotic) and they serve as a novel means of intercellular communication. They range in size: 70-100nm ('exosomes') through 100-1000nm ('microparticles') to large vesicles released from dying cells ('apoptotic bodies'). Release of apoptotic cell-derived extracellular vesicles (acdEV) of less than 1000nm is an important mechanism by which phagocytes are attracted to sites of cell death. Using a variety of approaches we characterize the release, physical characteristics and function of acdEV. Using fluorescence microscopy we demonstrate release of ICAM-3 on acdEV from dying leukocytes and, through the use of resistive pulse technology (qNano, IZON Science), we accurately size and quantitate acdEV release. The function of acdEV is revealed through the use of both horizontal chemotaxis assays (Dunn chambers) and vertical transwell migration assays (Cell-IQ, CM Technologies). These assays reveal potent chemoattractive capacity of acdEV and associated ICAM-3. Additionally we demonstrate an additional novel function of acdEV as anti-inflammatory immune-modulators. These data support an integrated approach to the physical and functional analyses of EV.

Characterisation of ICAM-3 and extracellular vesicles in the clearance of apoptotic cells

Apoptotic cell clearance by phagocytes is a vital part of programmed cell death that prevents dying cells from undergoing necrosis which may lead to inflammatory and autoimmune disorders. Apoptotic cells (AC) are removed by phagocytes, in a process that involves 'find me' and 'eat me' signals that facilitate the synapsing and engulfment of cell corpses. Extracellular vesicles (EV) are shed during apoptosis and promote phagocyte recruitment. Binding of AC is achieved by multiple ligand-receptor interactions. One interesting AC associated ligand is ICAM-3, a highly glycosylated adhesion molecule of the IgSF family, expressed on human leukocytes. On viable cells ICAM-3 participates in initiating immune responses, whereas on AC we show it attracts phagocytes through EV and aids in the binding of AC to the phagocytes. This project aims to characterize the role of ICAM-3 and EV in the clearance of AC and to identify the mechanisms that underlie their function in apoptotic cell clearance. Human B cells induced to apoptosis by UV irradiation were observed during their progression from viable to apoptotic via flow cytometry. The involvement of ICAM-3 in mediating interaction between AC and MØ was assessed. The ability of ICAM3 on EV to mediate chemoattraction was observed using chemotaxis assays. Additionally the anti-inflammatory effect was assessed using LPS-induced TNF-α production that suggested it may have anti-inflammatory effects. Future work in this project will assess the role of ICAM3 on EV from different phases of apoptosis to exert functional effects both in vitro and in vivo.

Isolation and characterisation of bacteria associated with flying insects in hospitals, with particualr emphasis on Clostridum difficile

Clostridium difficile is a bacterial healthcare-associated infection, which houseflies Musca domestica may transfer due to their synanthropic nature. The aims of this thesis were to determine the ability of M. domestica to transfer C. difficile mechanically and to collect and identify flying insects in UK hospitals and classify any associated bacteria. M. domestica exposed to independent suspensions of vegetative cells and spores of C. difficile were able to mechanically transfer the bacteria on to agar for up to 4 hours following exposure. C. difficile could be recovered from fly excreta for 96hrs and was isolated from the M. domestica alimentary canal. Also confirmed was the carriage of C. difficile by M. domestica larvae, although it was not retained in the pupae or in the adults that subsequently developed. Flying insects were collected from ultra-violet light flytraps in hospitals. Flies (order Diptera) were the most commonly identified. Chironomidae were the most common flies, Calliphora vicina were the most common synanthropic fly and ‘drain flies’ were surprisingly numerous and represent an emerging problem in hospitals. External washings and macerates of flying insects were prepared and inoculated onto a variety of agars and following incubation bacterial colonies identified by biochemical tests. A variety of flying insects, including synanthropic flies (e.g. M. domestica and C. vicina) collected from UK hospitals harboured pathogenic bacteria of different species. Enterobacteriaceae were the group of bacteria most commonly isolated, followed by Bacillus spp, Staphylococci, Clostridia, Streptococci and Micrococcus spp. This study highlights the potential for M. domestica to contribute to environmental persistence and spread of C. difficile in hospitals. Also illustrated is the potential for flying insects to contribute to environmental persistence and spread of other pathogenic bacteria in hospitals and therefore the need to implement pest control as part of infection control strategies.

Stabilisation and characterisation of peroxide-crosslinked high density polyethylene

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Characterisation of baseline oscillation in congenital nystagmus eye movement recordings

Congenital nystagmus is an ocular-motor disorder that develops in the first few months of life; its pathogenesis is still unknown. Patients affected by congenital nystagmus show continuous, involuntary, rhythmical oscillations of the eyes. Monitoring eye movements, nystagmus main features such as shape, amplitude and frequency, can be extracted and analysed. Previous studies highlighted, in some cases, a much slower and smaller oscillation, which appears added up to the ordinary nystagmus waveform. This sort of baseline oscillation, or slow nystagmus, hinder precise cycle-to-cycle image placement onto the fovea. Such variability of the position may reduce patient visual acuity. This study aims to analyse more extensively eye movements recording including the baseline oscillation and investigate possible relationships between these slow oscillations and nystagmus. Almost 100 eye movement recordings (either infrared-oculographic or electrooculographic), relative to different gaze positions, belonging to 32 congenital nystagmus patients were analysed. The baseline oscillation was assumed sinusoidal; its amplitude and frequency were computed and compared with those of the nystagmus by means of a linear regression analysis. The results showed that baseline oscillations were characterised by an average frequency of 0.36 Hz (SD 0.11 Hz) and an average amplitude of 2.1° (SD 1.6°). It also resulted in a considerable correlation (R2 scored 0.78) between nystagmus amplitude and baseline oscillation amplitude; the latter, on average, resulted to be about one-half of the correspondent nystagmus amplitude. © 2009 Elsevier Ltd. All rights reserved.