Comparison of soluble manganese(IV) and acidic potassium permanganate chemiluminescence detection using flow injection and sequential injection analysis for the determination of ascorbic acid in vitamin C tablets

The limits of detection (3s) for ascorbic acid were 5×10⁻⁸ M with acidic potassium permanganate using both flow injection analysis (FIA) and sequential injection analysis (SIA) whereas the soluble manganese(IV) afforded 1×10⁻⁸ M and 5×10⁻⁹ M for FIA and SIA, respectively. Determinations of ascorbic acid in Vitamin C tablets were achieved with minimal sample pretreatment using a standard additions calibration and gave good agreement with those of iodimetric titration.

The influence of housing size, style and location on energy and greenhouse gas emissions

Concern about the growth of greenhouse gas emissions in Victoria has prompted the introduction of legislation to improve the thermal performance of the residential building envelope. Unfortunately, the size of the house is not considered in the rating tool that underpins the legislation. The energy embodied in the constructional materials is also not considered although it too is directly related to the size of the house. Another intrinsic factor relating residential housing energy and greenhouse gas emissions is the location of the residence and the travel preferences of the homeowner. The relationship between the operational, embodied and travel energy associated with a typical residential scenario in Melbourne over the last 50 years is examined in this paper. The analysis found that by the year 2000, the energy associated with work-related travel (44%) now exceeds the operational energy (37%). In terms of greenhouse gas emissions, the contribution from travel energy is almost double that from operational energy (28%).

Improving on- and off-campus student performance in structural mechanics

This paper investigates the performance of 329 (173 on- and 186  off-campus) students enrolled in two structural mechanics units at Deakin University, a leader in engineering distance-education in Australia. The two units experience unacceptably high rates of failure. An analysis of the assignment, laboratory and examination marks is presented. Consideration is also given to the total marks. The results show that on-campus students perform better in structural mechanics than their off-campus counterparts. Plots of the student performance distributions for the three assessment methods are provided (for each unit) and high failure rates are linked to low examination marks. Students tend to perform best in assignments and worst in examinations. Parametric statistical tests show a correlation between the continuous assessment and examination marks. To motivate students to fully participate in continuous assessment tasks the authors therefore propose several changes to the assessment criteria and marking schemes.

Delivery and assessment strategies to improve on- and off-campus student performance in structural mechanics

This paper considers the delivery and assessment strategies used in two structural mechanics units at Deakin University, a leader in distance education in Australia. The two units have had unacceptably high rates of student failure. Student perceptions of the delivery method were analysed and an investigation was carried out of the performance of 329 (173 on- and 156 off-campus) students enrolled in the two units. An analysis of the assignment, laboratory and examination marks is presented. Consideration is also given to the total marks. The results show that on-campus students performed better in structural mechanics than their off-campus counterparts. Plots of the distributions of student performance for the three assessment methods are provided (for each unit) and high failure rates are linked to low examination marks. Students tended to perform best in assignments and worst in examinations. Parametric statistical tests show a correlation between the marks obtained in continuous assessment and in examinations, and it is therefore proposed that, in order to improve performance, the students must be encouraged to participate fully in all aspects of the course. Many students were unenthusiastic about laboratory practical sessions and did not think they aided their understanding of the theoretical material. Motivation to participate is often dependent on the perceived relevance of a given task and its contribution to the total mark and, thus, to help motivate students to participate fully in the continuous assessment tasks, the authors propose several changes to the delivery methods, as well as to assessment criteria and marking schemes.

Energy and greenhouse gas emissions implications of alternative housing types for Australia

Many cities around the world are looking for ways to reduce their per capita greenhouse gas emissions. The outward growth of cities from a central business district, typical of many cities around the world, is often seen as working against this goal and as unsustainable. This is especially the case in circumstances where this growth is not supported by the necessary infrastructure, often resulting in an increase in the use of private transport. However, alternative scenarios to contain the outward growth are being proposed. This paper provides a comparison of the energy demand and greenhouse gas emissions between typical detached outer-suburban housing currently being built in Australia's major cities and inner-city and -suburban apartments, which are increasingly seen as a legitimate alternative to the housing that is currently being built on our outer city fringes. By analysing the energy demand associated with the construction and operation of each housing type and for occupant travel it was found that the location of the housing and its size are the dominant factors determining energy use and greenhouse gas emissions. The findings from this analysis provide useful information for policy-makers in planning the development of our cities into the future, when faced with a growing population and an increasing need to minimise greenhouse gas emissions.

Rapid discrimination and determination of polyunsaturated fatty acid composition in marine oils by FTIR Spectroscopy and Multivariate Data Analysis

A rapid analytical approach for discrimination and quantitative determination of polyunsaturated fatty acid (PUFA) contents, particularly eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), in a range of oils extracted from marine resources has been developed by using attenuated total reflection Fourier transform infrared spectroscopy and multivariate data analysis. The spectral data were collected without any sample preparation; thus, no chemical preparation was involved, but data were rather processed directly using the developed spectral analysis platform, making it fast, very cost effective, and suitable for routine use in various biotechnological and food research and related industries. Unsupervised pattern recognition techniques, including principal component analysis and unsupervised hierarchical cluster analysis, discriminated the marine oils into groups by correlating similarities and differences in their fatty acid (FA) compositions that corresponded well to the FA profiles obtained from traditional lipid analysis based on gas chromatography (GC). Furthermore, quantitative determination of unsaturated fatty acids, PUFAs, EPA and DHA, by partial least square regression analysis through which calibration models were optimized specifically for each targeted FA, was performed in both known marine oils and totally independent unknown n - 3 oil samples obtained from an actual commercial product in order to provide prospective testing of the developed models towards actual applications. The resultant predicted FAs were achieved at a good accuracy compared to their reference GC values as evidenced through (1) low root mean square error of prediction, (2) good coefficient of determination close to 1 (i.e., R 2≥ 0.96), and (3) the residual predictive deviation values that indicated the predictive power at good and higher levels for all the target FAs. © 2014 Springer Science+Business Media New York.

Sol-gel synthesis of mesoporous CaCu3Ti4O12 thin films and their gas sensing response

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Energetic, ecologic and fluid-dynamic analysis of a fluidized bed gasifier operating with sugar cane bagasse

This work aims to study the thermodynamic, ecological and fluid-dynamic aspects of a circulating fluidized bed gasifier using sugar cane bagasse as biomass, in order to estimate a model of its normal operation. In the initial stage was analysed the composition of biomass selected (sugar cane bagasse) and its lower heating value (LHV) was calculated. The energy balance of the gasifier was done, being the volumetric flow of air, synthesis gas and biomass estimated. Also the power produced by this gasifier was theoretically estimated. Then the circulating fluidized bed gasifier was designed for operation with approximately 100 kg/h of processed biomass. Cross-sectional area of the reactor, feeder size, diameter of the exit zone of the gases and minimum height of the expanded bed were selected. Some bed gasifier hydrodynamic factors were also studied. The minimum fluidization velocity, fluidization terminal velocity, and average fluidizing velocity were calculated, in order to understand the fluid-dynamic behaviour of gasification of this fuel. It was obtained a theoretical model that can support a possible prototype of circulating fluidized bed gasifier biomass. Finally, there were studied the ecological aspects of the gasifier, through an overall methodology. Ecological efficiencies were estimated for two scenarios: first considering the carbon cycle and thereafter disregarding the carbon cycle. In both cases, it can be proved the ecological viability of the project. © 2013 Elsevier Ltd. All rights reserved.

Quantitative Chemical Profile and Multivariate Statistical Analysis of Alembic Distilled Sugarcane Spirit Fractions

Concentrations of 39 organic compounds were determined in three fractions (head, heart and tail) obtained from the pot still distillation of fermented sugarcane juice. The results were evaluated using analysis of variance (ANOVA), Tukey's test, principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA). According to PCA and HCA, the experimental data lead to the formation of three clusters. The head fractions give rise to a more defined group. The heart and tail fractions showed some overlap consistent with its acid composition. The predictive ability of calibration and validation of the model generated by LDA for the three fractions classification were 90.5 and 100%, respectively. This model recognized as the heart twelve of the thirteen commercial cachacas (92.3%) with good sensory characteristics, thus showing potential for guiding the process of cuts.

The implications of arterial Po2 oscillations for conventional arterial blood gas analysis

In a surfactant-depletion model of lung injury, tidal recruitment of atelectasis and changes in shunt fraction lead to large Pao2 oscillations. We investigated the effect of these oscillations on conventional arterial blood gas (ABG) results using different sampling techniques in ventilated rabbits. In each rabbit, 5 different ventilator settings were studied, 2 before saline lavage injury and 3 after lavage injury. Ventilator settings were altered according to 5 different goals for the amplitude and mean value of brachiocephalic Pao2 oscillations, as guided by a fast responding intraarterial probe. ABG collection was timed to obtain the sample at the peak or trough of the Pao2 oscillations, or over several respiratory cycles. Before lung injury, oscillations were small and sample timing did not influence Pao2. After saline lavage, when Po2 fluctuations measured by the indwelling arterial Po2 probe confirmed tidal recruitment, Pao2 by ABG was significantly higher at peak (295 +/- 130 mm Hg) compared with trough (74 +/- 15 mm Hg) or mean (125 +/- 75 mm Hg). In early, mild lung injury after saline lavage, Pao2 can vary markedly during the respiratory cycle. When atelectasis is recruited with each breath, interpretation of changes in shunt fraction, based on conventional ABG analysis, should account for potentially large respiratory variations in arterial Po2.

THERMAL CHARACTERIZATION OF A GASOLINE TURBOCHARGED DIRECT INJECTION (GTDI) ENGINE UTILIZING LEAN OPERATION AND EXHAUST GAS RECIRCULATION (EGR)

The push for improved fuel economy and reduced emissions has led to great achievements in engine performance and control. These achievements have increased the efficiency and power density of gasoline engines dramatically in the last two decades. With the added power density, thermal management of the engine has become increasingly important. Therefore it is critical to have accurate temperature and heat transfer models as well as data to validate them. With the recent adoption of the 2025 Corporate Average Fuel Economy(CAFE) standard, there has been a push to improve the thermal efficiency of internal combustion engines even further. Lean and dilute combustion regimes along with waste heat recovery systems are being explored as options for improving efficiency. In order to understand how these technologies will impact engine performance and each other, this research sought to analyze the engine from both a 1st law energy balance perspective, as well as from a 2nd law exergy analysis. This research also provided insights into the effects of various parameters on in-cylinder temperatures and heat transfer as well as provides data for validation of other models. It was found that the engine load was the dominant factor for the energy distribution, with higher loads resulting in lower coolant heat transfer and higher brake work and exhaust energy. From an exergy perspective, the exhaust system provided the best waste heat recovery potential due to its significantly higher temperatures compared to the cooling circuit. EGR and lean combustion both resulted in lower combustion chamber and exhaust temperatures; however, in most cases the increased flow rates resulted in a net increase in the energy in the exhaust. The exhaust exergy, on the other hand, was either increased or decreased depending on the location in the exhaust system and the other operating conditions. The effects of dilution from lean operation and EGR were compared using a dilution ratio, and the results showed that lean operation resulted in a larger increase in efficiency than the same amount of dilution with EGR. Finally, a method for identifying fuel spray impingement from piston surface temperature measurements was found. Note: The material contained in this section is planned for submission as part of a journal article and/or conference paper in the future.

High-resolution glacial and deglacial record of atmospheric methane by continuous-flow and laser spectrometer analysis along the NEEM ice core

The Greenland NEEM (North Greenland Eemian Ice Drilling) operation in 2010 provided the first opportunity to combine trace-gas measurements by laser spectroscopic instruments and continuous-flow analysis along a freshly drilled ice core in a field-based setting. We present the resulting atmospheric methane (CH4) record covering the time period from 107.7 to 9.5 ka b2k (thousand years before 2000 AD). Companion discrete CH4 measurements are required to transfer the laser spectroscopic data from a relative to an absolute scale. However, even on a relative scale, the high-resolution CH4 data set significantly improves our knowledge of past atmospheric methane concentration changes. New significant sub-millennial-scale features appear during interstadials and stadials, generally associated with similar changes in water isotopic ratios of the ice, a proxy for local temperature. In addition to the midpoint of Dansgaard–Oeschger (D/O) CH4 transitions usually used for cross-dating, sharp definition of the start and end of these events brings precise depth markers (with ±20 cm uncertainty) for further cross-dating with other palaeo- or ice core records, e.g. speleothems. The method also provides an estimate of CH4 rates of change. The onsets of D/O events in the methane signal show a more rapid rate of change than their endings. The rate of CH4 increase associated with the onsets of D/O events progressively declines from 1.7 to 0.6 ppbv yr−1 in the course of marine isotope stage 3. The largest observed rate of increase takes place at the onset of D/O event #21 and reaches 2.5 ppbv yr−1.

A new Time-Of-Flight Mass Spectrometer (TOF-MS) for noble gas analysis

Noble gas analysis in early solar system materials, which can provide valuable information about early solar system processes and timescales, are very challenging because of extremely low noble gas concentrations (ppt). We therefore developed a new compact sized (33 cm length, 7.2cm diameter, 1.3 L internal volume) Time-of-Flight (TOF) noble gas mass spectrometer for high sensitivity. We call it as Edel Gas Time-of-flight (EGT) mass spectrometer. The instrument uses electron impact ionization coupled to an ion trap, which allows us to ionize and measure all noble gas isotopes. Using a reflectron set-up improves the mass resolution. In addition, the reflectron set-up also enables some extra focusing. The detection is via MCPs and the signals are processed either via ADC or TDC systems. The objective of this work is to understand the newly developed Time-Of-Flight (TOF) mass spectrometer for noble gas analysis in presolar grains of the meteorites. Chapter 1 briefly introduces the basic idea and importance of the instrument. The physics relevant to time-of-flight mass spectrometry technique is discussed in the Chapter 2 and Chapter 3 will present the oxidation technique of nanodiamonds of the presolar grains by using copper oxide. Chapter 4 will present the details about EGT data analysis software. Chapter 5 and Chapter 6 will explain the details about EGT design and operation. Finally, the performance results will be presented and discussed in the Chapter 7, and whole work is summarized in Chapter 8 and also outlook of the future work is given.

VERIFICATION OF DNA PREDICTED PROTEIN SEQUENCES BY ENZYME HYDROLYSIS AND MASS SPECTROMETRIC ANALYSIS

The focus of this thesis lies in the development of a sensitive method for the analysis of protein primary structure which can be easily used to confirm the DNA sequence of a protein's gene and determine the modifications which are made after translation. This technique involves the use of dipeptidyl aminopeptidase (DAP) and dipeptidyl carboxypeptidase (DCP) to hydrolyze the protein and the mass spectrometric analysis of the dipeptide products.^ Dipeptidyl carboxypeptidase was purified from human lung tissue and characterized with respect to its proteolytic activity. The results showed that the enzyme has a relatively unrestricted specificity, making it useful for the analysis of the C-terminal of proteins. Most of the dipeptide products were identified using gas chromatography/mass spectrometry (GC/MS). In order to analyze the peptides not hydrolyzed by DCP and DAP, as well as the dipeptides not identified by GC/MS, a FAB ion source was installed on a quadrupole mass spectrometer and its performance evaluated with a variety of compounds.^ Using these techniques, the sequences of the N-terminal and C-terminal regions and seven fragments of bacteriophage P22 tail protein have been verified. All of the dipeptides identified in these analysis were in the same DNA reading frame, thus ruling out the possibility of a single base being inserted or deleted from the DNA sequence. The verification of small sequences throughout the protein sequence also indicates that no large portions of the protein have been removed after translation. ^