111 resultados para Precursors


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A time-resolved inverse spatially offset Raman spectrometer was constructed for depth profiling of Raman-active substances under both the lab and the field environments. The system operating principles and performance are discussed along with its advantages relative to traditional continuous wave spatially offset Raman spectrometer. The developed spectrometer uses a combination of space- and time-resolved detection in order to obtain high-quality Raman spectra from substances hidden behind coloured opaque surface layers, such as plastic and garments, with a single measurement. The time-gated spatially offset Raman spectrometer was successfully used to detect concealed explosives and drug precursors under incandescent and fluorescent background light as well as under daylight. The average screening time was 50 s per measurement. The excitation energy requirements were relatively low (20 mW) which makes the probe safe for screening hazardous substances. The unit has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than previous picosecond-based systems, to provide a functional platform for in-line or in-field sensing of chemical substances.

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Chronic venous leg ulcers are a detrimental health issue plaguing our society, resulting in long term pain, immobility and decreased quality of life for a large proportion of sufferers. The frequency of these chronic wounds has led current research to focus on the wound environment to provide important information regarding the prolonged, fluctuated or static healing patterns of these wounds. Disruption to the normal wound healing process results in release of multiple factors in the wound environment that could correlate to wound chronicity. These biochemical factors can often be detected through non-invasively sampling chronic wound fluid (CWF) from the site of injury. Of note, whilst there are numerous studies comparing acute and chronic wound fluids, there have not been any reports in the literature employing a longitudinal study in order to track biochemical changes in wound fluid as patients transition from a non-healing to healed state. Initially the objective of this study was to identify biochemical changes in CWF associated with wound healing using a proteomic approach. The proteomic approach incorporated a multi-dimensional liquid chromatography fractionation technique coupled with mass spectrometry (MS) to enable identification of proteins present in lower concentrations in CWF. Not surprisingly, many of the proteins identified in wound fluid were acute phase proteins normally expressed during the inflammatory phase of healing. However, the number of proteins positively identified by MS was quite low. This was attributed to the diverse range in concentration of protein species in CWF making it challenging to detect the diagnostically relevant low molecular weight proteins. In view of this, SELDI-TOF MS was also explored as a means to target low molecular weight proteins in sequential patient CWF samples during the course of healing. Unfortunately, the results generated did not yield any peaks of interest that were altered as wounds transitioned to a healed state. During the course of proteomic assessment of CWF, it became evident that a fraction of non-proteinaceous compounds strongly absorbed at 280 nm. Subsequent analyses confirmed that most of these compounds were in fact part of the purine catabolic pathway, possessing distinctive aromatic rings and which results in high absorbance at 254 nm. The accumulation of these purinogenic compounds in CWF suggests that the wound bed is poorly oxygenated resulting in a switch to anaerobic metabolism and consequently ATP breakdown. In addition, the presence of the terminal purine catabolite, uric acid (UA), indicates that the enzyme xanthine oxidoreductase (XOR) catalyses the reaction of hypoxanthine to xanthine and finally to UA. More importantly, the studies provide evidence for the first time of the exogenous presence of XOR in CWF. XOR is the only enzyme in humans capable of catalysing the production of UA in conjunction with a burst of the highly reactive superoxide radical and other oxidants like H2O2. Excessive release of these free radicals in the wound environment can cause cellular damage disrupting the normal wound healing process. In view of this, a sensitive and specific assay was established for monitoring low concentrations of these catabolites in CWF. This procedure involved combining high performance liquid chromatography (HPLC) with tandem mass spectrometry and multiple reaction monitoring (MRM). This application was selective, using specific MRM transitions and HPLC separations for each analyte, making it ideal for the detection and quantitation of purine catabolites in CWF. The results demonstrated that elevated levels of UA were detected in wound fluid obtained from patients with clinically worse ulcers. This suggests that XOR is active in the wound site generating significant amounts of reactive oxygen species (ROS). In addition, analysis of the amount of purine precursors in wound fluid revealed elevated levels of purine precursors in wound fluid from patients with less severe ulcers. Taken together, the results generated in this thesis suggest that monitoring changes of purine catabolites in CWF is likely to provide valuable information regarding the healing patterns of chronic venous leg ulcers. XOR catalysis of purine precursors not only provides a method for monitoring the onset, prognosis and progress of chronic venous leg ulcers, but also provides a potential therapeutic target by inhibiting XOR, thus blocking UA and ROS production. Targeting a combination of these purinogenic compounds and XOR could lead to the development of novel point of care diagnostic tests. Therefore, further investigation of these processes during wound healing will be worthwhile and may assist in elucidating the pathogenesis of this disease state, which in turn may lead to the development of new diagnostics and therapies that target these processes.

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Deep Raman spectroscopy has been utilized for the standoff detection of concealed chemical threat agents from a distance of 15 meters under real life background illumination conditions. By using combined time and space resolved measurements, various explosive precursors hidden in opaque plastic containers were identified non-invasively. Our results confirm that combined time and space resolved Raman spectroscopy leads to higher selectivity towards the sub-layer over the surface layer as well as enhanced rejection of fluorescence from the container surface when compared to standoff spatially offset Raman spectroscopy. Raman spectra that have minimal interference from the packaging material and good signal-to-noise ratio were acquired within 5 seconds of measurement time. A new combined time and space resolved Raman spectrometer has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than picosecond-based laboratory systems.

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Raman spectroscopy, when used in spatially offset mode, has become a potential tool for the identification of explosives and other hazardous substances concealed in opaque containers. The molecular fingerprinting capability of Raman spectroscopy makes it an attractive tool for the unambiguous identification of hazardous substances in the field. Additionally, minimal sample preparation is required compared with other techniques. We report a field portable time resolved Raman sensor for the detection of concealed chemical hazards in opaque containers. The new sensor uses a pulsed nanosecond laser source in conjunction with an intensified CCD detector. The new sensor employs a combination of time and space resolved Raman spectroscopy to enhance the detection capability. The new sensor can identify concealed hazards by a single measurement without any chemometric data treatments.

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A 4-cylinder Ford 2701C test engine was used in this study to explore the impact of ethanol fumigation on gaseous and particle emission concentrations. The fumigation technique delivered vaporised ethanol into the intake manifold of the engine, using an injector, a pump and pressure regulator, a heat exchanger for vaporising ethanol and a separate fuel tank and lines. Gaseous (Nitric oxide (NO), Carbon monoxide (CO) and hydrocarbons (HC)) and particulate emissions (particle mass (PM2.5) and particle number) testing was conducted at intermediate speed (1700 rpm) using 4 load settings with ethanol substitution percentages ranging from 10-40 % (by energy). With ethanol fumigation, NO and PM2.5 emissions were reduced, whereas CO and HC emissions increased considerably and particle number emissions increased at most test settings. It was found that ethanol fumigation reduced the excess air factor for the engine and this led to increased emissions of CO and HC, but decreased emissions of NO. PM2.5 emissions were reduced with ethanol fumigation, as ethanol has a very low “sooting” tendency. This is due to the higher hydrogen-to-carbon ratio of this fuel, and also because ethanol does not contain aromatics, both of which are known soot precursors. The use of a diesel oxidation catalyst (as an after-treatment device) is recommended to achieve a reduction in the four pollutants that are currently regulated for compression ignition engines. The increase in particle number emissions with ethanol fumigation was due to the formation of volatile (organic) particles; consequently, using a diesel oxidation catalyst will also assist in reducing particle number emissions.

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The presence of colour in raw sugar plays a key role in the marketing strategy of the Australian raw sugar industry. Some sugars are relatively difficult to decolourise during refining and develop colour during storage. A new approach that might result in efficient and cost-effective colour removal during the sugar manufacturing process is the use of an advanced oxidation process (AOP), known as Fenton oxidation, that is, catalytic production of hydroxyl radicals from the decomposition of hydrogen peroxide using ferrous iron. As a first step towards developing this technology, this study determined the composition of colour precursors present in the juice of cane harvested by three different methods. The methods were harvesting cane after burning, harvesting the whole crop with half of the trash extracted and harvesting the whole crop with no trash extracted. The study also investigated the degradation at pH 3, 4 and 5 of a phenolic compound, caffeic acid (3,4–dihydroxycinnamic acid), which is present in sugar cane juice, using both hydrogen peroxide and Fenton’s reagent. The results show that juice expressed from whole crop cane has significantly higher colour than juices expressed from burnt cane. However, the concentrations of phenolic acids were lower in the juices expressed from whole crop cane. The main phenolic acids present in these juices were p-coumaric, vanillic, 2,3–dihydroxybenzoic, gallic and 3,4–dihydroxybenzoic acids. The degradation of caffeic acid significantly improved using Fenton’s reagent in comparison to hydrogen peroxide alone. The Fenton oxidation was optimum at pH 5 when up to ~86 % of caffeic acid degraded within 5 min.

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Colour is one of the most important parameters in sugar quality and its presence in raw sugar plays a key role in the marketing strategy of sugar industries worldwide. This study investigated the degradation of a mixture of colour precursors using the Fenton oxidation process. These colour precursors are caffeic acid, p–coumaric acid and ferulic acid, which are present in cane juice. Results showed that with a Fe(II) to H2O2 molar ratio of 1:15 in an aqueous system at 25 °C, 77% of the total phenolic acid content was removed at pH 4.72. However, in a synthetic juice solution which contained 13 mass % sucrose (35 °C, pH 5.4), only 60% of the total phenolic acid content was removed.

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The presence of colour in raw sugar plays a key role in the marketing strategy of the Australian raw sugar industry. Some sugars are relatively difficult to decolourise during refining and develop colour during storage. A new approach that might result in efficient and cost-effective colour removal during the sugar manufacturing process is the use of an advanced oxidation process (AOP), known as Fenton oxidation, that is, catalytic production of hydroxyl radicals from the decomposition of hydrogen peroxide using ferrous iron. As a first step towards developing this technology, this study determined the composition of colour precursors present in the juice of cane harvested by three different methods. The methods were harvesting cane after burning, harvesting the whole crop with half of the trash extracted and harvesting the whole crop with no trash extracted. The study also investigated the degradation at pH 3, 4 and 5 of a phenolic compound, caffeic acid (3,4–dihydroxycinnamic acid), which is present in sugar cane juice, using both hydrogen peroxide and Fenton’s reagent. The results show that juice expressed from whole crop cane has significantly higher colour than juices expressed from burnt cane. However, the concentrations of phenolic acids were lower in the juices expressed from whole crop cane. The main phenolic acids present in these juices were p-coumaric, vanillic, 2,3–dihydroxybenzoic, gallic and 3,4–dihydroxybenzoic acids. The degradation of caffeic acid significantly improved using Fenton’s reagent in comparison to hydrogen peroxide alone. The Fenton oxidation was optimum at pH 5 when up to ~86% of caffeic acid degraded within 5 min.

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Current concerns regarding terrorism and international crime highlight the need for new techniques for detecting unknown and hazardous substances. A novel Raman spectroscopy-based technique, spatially offset Raman spectroscopy (SORS), was recently devised for non-invasively probing the contents of diffusely scattering and opaque containers. Here, we demonstrate a modified portable SORS sensor for detecting concealed substances in-field under different background lighting conditions. Samples including explosive precursors, drugs and an organophosphate insecticide (chemical warfare agent surrogate) were concealed inside diffusely scattering packaging including plastic, paper and cloth. Measurements were carried out under incandescent and fluorescent light as well as under daylight to assess the suitability of the probe for different real-life conditions. In each case, it was possible to identify the substances against their reference Raman spectra in less than one minute. The developed sensor has potential for rapid detection of concealed hazardous substances in airports, mail distribution centers and customs checkpoints.

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Objective: Preclinical and clinical data suggest that lipid biology is integral to brain development and neurodegeneration. Both aspects are proposed as being important in the pathogenesis of schizophrenia. The purpose of this paper is to examine the implications of lipid biology, in particular the role of essential fatty acids (EFA), for schizophrenia. Methods: Medline databases were searched from 1966 to 2001 followed by the crosschecking of references. Results: Most studies investigating lipids in schizophrenia described reduced EFA, altered glycerophospholipids and an increased activity of a calcium-independent phospholipase A2 in blood cells and in post-mortem brain tissue. Additionally, in vivo brain phosphorus-31 Magnetic Resonance Spectroscopy (31P-MRS) demonstrated lower phosphomonoesters (implying reduced membrane precursors) in first- and multi-episode patients. In contrast, phosphodiesters were elevated mainly in first-episode patients (implying increased membrane breakdown products), whereas inconclusive results were found in chronic patients. EFA supplementation trials in chronic patient populations with residual symptoms have demonstrated conflicting results. More consistent results were observed in the early and symptomatic stages of illness, especially if EFA with a high proportion of eicosapentaenoic acid was used. Conclusion: Peripheral blood cell, brain necropsy and 31P-MRS analysis reveal a disturbed lipid biology, suggesting generalized membrane alterations in schizophrenia. 31P-MRS data suggest increased membrane turnover at illness onset and persisting membrane abnormalities in established schizophrenia. Cellular processes regulating membrane lipid metabolism are potential new targets for antipsychotic drugs and might explain the mechanism of action of treatments such as eicosapentaenoic acid.

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Outdoor workers are exposed to high levels of ultraviolet radiation (UVR) and may thus be at greater risk to experience UVR-related health effects such as skin cancer, sun burn, and cataracts. A number of intervention trials (n=14) have aimed to improve outdoor workers’ work-related sun protection cognitions and behaviours. Only one study however has reported the use of UV-photography as part of a multi-component intervention. This study was performed in the USA and showed long-term (12 months) improvements in work-related sun protection behaviours. Intervention effects of the other studies have varied greatly, depending on the population studied, intervention applied, and measurement of effect. Previous studies have not assessed whether: - Interventions are similarly effective for workers in stringent and less stringent policy organisations; - Policy effect is translated into workers’ leisure time protection; - Implemented interventions are effective in the long-term; - The facial UV-photograph technique is effective in Australian male outdoor workers without a large additional intervention package, and; - Such interventions will also affect workers’ leisure time sun-related cognitions and behaviours. Therefore, the present Protection of Outdoor Workers from Environmental Radiation [POWER]-study aimed to fill these gaps and had the objectives of: a) assessing outdoor workers’ sun-related cognitions and behaviours at work and during leisure time in stringent and less stringent sun protection policy environments; b) assessing the effect of an appearance-based intervention on workers’ risk perceptions, intentions and behaviours over time; c) assessing whether the intervention was equally effective within the two policy settings; and d) assessing the immediate post-intervention effect. Effectiveness was described in terms of changes in sun-related risk perceptions and intentions (as these factors were shown to be main precursors of behaviour change in many health promotion theories) and behaviour. The study purposefully selected and recruited two organisations with a large outdoor worker contingent in Queensland, Australia within a 40 kilometre radius of Brisbane. The two organisations differed in the stringency of implementation and reinforcement of their organisational sun protection policy. Data were collected from 154 male predominantly Australian born outdoor workers with an average age of 37 years and predominantly medium to fair skin (83%). Sun-related cognitions and behaviours of workers were assessed using self-report questionnaires at baseline and six to twelve months later. Variation in follow-up time was due to a time difference in the recruitment of the two organisations. Participants within each organisation were assigned to an intervention or control group. The intervention group participants received a one-off personalised Skin Cancer Risk Assessment Tool [SCRAT]-letter and a facial UV-photograph with detailed verbal information. This was followed by an immediate post-intervention questionnaire within three months of the start of the study. The control group only received the baseline and follow-up questionnaire. Data were analysed using a variety of techniques including: descriptive analyses, parametric and non-parametric tests, and generalised estimating equations. A 15% proportional difference observed was deemed of clinical significance, with the addition of reported statistical significance (p<0.05) where applicable. Objective 1: Assess and compare the current sun-related risk perceptions, intentions, behaviours, and policy awareness of outdoor workers in stringent and less stringent sun protection policy settings. Workers within the two organisations (stringent n=89 and less stringent n=65) were similar in their knowledge about skin cancer, self efficacy, attitudes, and social norms regarding sun protection at work and during leisure time. Participants were predominantly in favour of sun protection. Results highlighted that compared to workers in a less stringent policy organisation working for an organisation with stringent sun protection policies and practices resulted in more desirable sun protection intentions (less willing to tan p=0.03) ; actual behaviours at work (sufficient use of upper and lower body protection, headgear, and sunglasses (p<0.001 for all comparisons), and greater policy awareness (awareness of repercussions if Personal Protective Equipment (PPE) was not used, p<0.001)). However the effect of the work-related sun protection policy was found not to extend to leisure time sun protection. Objective 2: Compare changes in sun-related risk perceptions, intentions, and behaviours between the intervention and control group. The effect of the intervention was minimal and mainly resulted in a clinically significant reduction in work-related self-perceived risk of developing skin cancer in the intervention compared to the control group (16% and 32% for intervention and control group, respectively estimated their risk higher compared to other outdoor workers: , p=0.11). No other clinical significant effects were observed at 12 months follow-up. Objective 3: Assess whether the intervention was equally effective in the stringent sun protection policy organisation and the less stringent sun protection policy organisation. The appearance-based intervention resulted in a clinically significant improvement in the stringent policy intervention group participants’ intention to protect from the sun at work (workplace*time interaction, p=0.01). In addition to a reduction in their willingness to tan both at work (will tan at baseline: 17% and 61%, p=0.06, at follow-up: 54% and 33%, p=0.07, stringent and less stringent policy intervention group respectively. The workplace*time interaction was significant p<0.001) and during leisure time (will tan at baseline: 42% and 78%, p=0.01, at follow-up: 50% and 63%, p=0.43, stringent and less stringent policy intervention group respectively. The workplace*time interaction was significant p=0.01) over the course of the study compared to the less stringent policy intervention group. However, no changes in actual sun protection behaviours were found. Objective 4: Examine the effect of the intervention on level of alarm and concern regarding the health of the skin as well as sun protection behaviours in both organisations. The immediate post-intervention results showed that the stringent policy organisation participants indicated to be less alarmed (p=0.04) and concerned (p<0.01) about the health of their skin and less likely to show the facial UV-photograph to others (family p=0.03) compared to the less stringent policy participants. A clinically significantly larger proportion of participants from the stringent policy organisation reported they worried more about skin cancer (65%) and skin freckling (43%) compared to those in the less stringent policy organisation (46%,and 23% respectively , after seeing the UV-photograph). In summary the results of this study suggest that the having a stringent work-related sun protection policy was significantly related to for work-time sun protection practices, but did not extend to leisure time sun protection. This could reflect the insufficient level of sun protection found in the general Australian population during leisure time. Alternatively, reactance caused by being restricted in personal decisions through work-time policy could have contributed to lower leisure time sun protection. Finally, other factors could have also contributed to the less than optimal leisure time sun protection behaviours reported, such as unmeasured personal or cultural barriers. All these factors combined may have lead to reduced willingness to take proper preventive action during leisure time exposure. The intervention did not result in any measurable difference between the intervention and control groups in sun protection behaviours in this population, potentially due to the long lag time between the implementation of the intervention and assessment at 12-months follow-up. In addition, high levels of sun protection behaviours were found at baseline (ceiling effect) which left little room for improvement. Further, this study did not assess sunscreen use, which was the predominant behaviour assessed in previous effective appearance-based interventions trials. Additionally, previous trials were mainly conducted in female populations, whilst the POWER-study’s population was all male. The observed immediate post-intervention result could be due to more emphasis being placed on sun protection and risks related to sun exposure in the stringent policy organisation. Therefore participants from the stringent policy organisation could have been more aware of harmful effects of UVR and hence, by knowing that they usually protect adequately, not be as alarmed or concerned as the participants from the less stringent policy organisation. In conclusion, a facial UV-photograph and SCRAT-letter information alone may not achieve large changes in sun-related cognitions and behaviour, especially of assessed 6-12 months after the intervention was implemented and in workers who are already quite well protected. Differences found between workers in the present study appear to be more attributable to organisational policy. However, against a background of organisational policy, this intervention may be a useful addition to sun-related workplace health and safety programs. The study findings have been interpreted while respecting a number of limitations. These have included non-random allocation of participants due to pre-organised allocation of participants to study group in one organisation and difficulty in separating participants from either study group. Due to the transient nature of the outdoor worker population, only 105 of 154 workers available at baseline could be reached for follow-up. (attrition rate=32%). In addition the discrepancy in the time to follow-up assessment between the two organisations was a limitation of the current study. Given the caveats of this research, the following recommendations were made for future research: - Consensus should be reached to define "outdoor worker" in terms of time spent outside at work as well as in the way sun protection behaviours are measured and reported. - Future studies should implement and assess the value of the facial UV-photographs in a wide range of outdoor worker organisations and countries. - More timely and frequent follow-up assessments should be implemented in intervention studies to determine the intervention effect and to identify the best timing of booster sessions to optimise results. - Future research should continue to aim to target outdoor workers’ leisure time cognitions and behaviours and improve these if possible. Overall, policy appears to be an important factor in workers’ compliance with work-time use of sun protection. Given the evidence generated by this research, organisations employing outdoor workers should consider stringent implementation and reinforcement of a sun protection policy. Finally, more research is needed to improve ways to generate desirable behaviour in this population during leisure time.

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Chronic venous leg ulcers are a major health issue and represent an often overlooked area of biomedical research. Nevertheless, it is becoming increasingly evident that new approaches to enhance healing outcomes may arise through better understanding the processes involved in the formation of chronic wounds. We have for the first time shown that the terminal purine catabolite uric acid (UA) is elevated in wound fluid (WF) from chronic venous leg ulcers with relative concentrations correlating with wound chronicity. We have also shown a corresponding depletion in UA precursors, including adenosine, with increased wound severity. Further, we have shown that xanthine oxidase, the only enzyme in humans that catalyses the production of UA in conjunction with a burst of free radicals, is active in chronic WF. Taken together, this provides compelling evidence that xanthine oxidase may play a critical role in the formation of chronic wounds by prolonging the inflammatory process.

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The structure of Cu-ZSM-5 catalysts that show activity for direct NO decomposition and selective catalytic reduction of NOx by hydrocarbons has been investigated by a multitude of modern surface analysis and spectroscopy techniques including X-ray photoelectron spectroscopy, thermogravimetric analysis, and in situ Fourier transform infrared spectroscopy. A series of four catalysts were prepared by exchange of Na-ZSM-5 with dilute copper acetate, and the copper loading was controlled by variation of the solution pH. Underexchanged catalysts contained isolated Cu2+OH-(H2O) species and as the copper loading was increased Cu2+ ions incorporated into the zeolite lattice appeared. The sites at which the latter two copper species were located were fundamentally different. The Cu2+OH-(H2O) moieties were bound to two lattice oxygen ions and associated with one aluminum framework species. In contrast, the Cu2+ ions were probably bound to four lattice oxygen ions and associated with two framework aluminum ions. Once the Cu-ZSM-5 samples attained high levels of exchange, the development of [Cu(μ-OH)2Cu]n2+OH-(H2O) species along with a small concentration of Cu(OH)2 was observed. On activation in helium to 500°C the Cu2+OH-(H2O) species transformed into Cu2+O- and Cu+ moieties, whereas the Cu2+ ions were apparently unaffected by this treatment (apart from the loss of ligated water molecules). Calcination of the precursors resulted in the formation of Cu2+O2- and a one-dimensional CuO species. Temperature-programmed desorption studies revealed that oxygen was removed from the latter two species at 407 and 575°C, respectively. © 1999 Academic Press.

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Raman spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM) have been used to compare samples of YBa2Cu3O7 (YBCO) synthesised by the solid-state method and a novel co-precipitation technique. XRD results indicate that YBCO prepared by these two methods are phase pure, however the Raman and SEM results show marked differences between these samples.

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A co-precipitation process for large-scale manufacture of bismuth-based HTSC powders has been demonstrated. Powders manufactured by this process have a high phase purity and precisely reproducible stoichiometry. Controlled time and temperature variations are used to convert precursors to HTSC compounds and to obtain specific particle-size distributions. The process has been demonstrated for a variety of compositions in the BSCCO system. Electron microscopy X-ray diffraction, inductively coupled plasma spectroscopy and magnetic-susceptibility measurements are used to characterize the powders.