Spectrophotometric determination of zinc in pharmaceutical and biological samples with di-2-pyridyl ketone benzoylhydrazone: A simple, fast, accurate and sensitive method

A simple, fast, accurate, and sensitive spectrophotometric method was developed to determine zinc(II). This method is based on the reaction of Zn(II) with di-2-pyridyl ketone benzoylhydrazone (DPKBH), at pH=5.5 and 50% (v/v) ethanol. Beers law was obeyed in the range 0.020-1.82 mu g mL(-1) with a molar apsorptivity of 3.64 x 10(4) L mol(-1) cm(-1), and a detection limit (3) of 2.29 mu g L-1. The action of some interfering ions was verified and the developed method applied to pharmaceutical and biological samples. The results were then compared with those obtained by using a flame atomic absorption technique.

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Oxorhenium(V) Complexes with 2,3-Dihydroxynaphthalene

2,3-Dihydroxynaphthalene (H(2)dhn) reacts with [ReOCl(3)-(PPh(3))(2)] or [ReOBr(3)(PPh(3))(2)] in a 1:1 molar ratio with formation of the isostructural complexes [ReOCl(2)(PPh(3))(2)(Hdhn)] (4) and [ReOBr(2)-(PPh(3))(2)(Hdhn)] (5). They have distorted octahedral coordination spheres with the halide and the triphenylphosphine ligands arranged in equatorial trans positions to each other. The Hdhn-ligand coordinates monodentately in trans position to the oxo ligand. Intramolecular hydrogen bonds between the Hdhn and the halogeno ligands stabilize this coordination mode. The products represent the first examples of oxorhenium(V) complexes with monodentate catecholate-type ligands.

Analysis of response to enteral infusion of levodopa in patients with Parkinson's disease

Objective: We present a new evaluation of levodopa plasma concentrations and clinical effects during duodenal infusion of a levodopa/carbidopa gel (Duodopa ) in 12 patients with advanced Parkinson s disease (PD), from a study reported previously (Nyholm et al, Clin Neuropharmacol 2003; 26(3): 156-163). One objective was to investigate in what state of PD we can see the greatest benefits with infusion compared with corresponding oral treatment (Sinemet CR). Another objective was to identify fluctuating response to levodopa and correlate to variables related to disease progression. Methods: We have computed mean absolute error (MAE) and mean squared error (MSE) for the clinical rating from -3 (severe parkinsonism) to +3 (severe dyskinesia) as measures of the clinical state over the treatment periods of the study. Standard deviation (SD) of the rating was used as a measure of response fluctuations. Linear regression and visual inspection of graphs were used to estimate relationships between these measures and variables related to disease progression such as years on levodopa (YLD) or unified PD rating scale part II (UPDRS II).Results: We found that MAE for infusion had a strong linear correlation to YLD (r2=0.80) while the corresponding relation for oral treatment looked more sigmoid, particularly for the more advanced patients (YLD>18).

The importance of body-mass exponent optimization for evaluation of performance capability in cross-country skiing

Introduction Performance in cross-country skiing is influenced by the skier’s ability to continuously produce propelling forces and force magnitude in relation to the net external forces. A surrogate indicator of the “power supply” in cross-country skiing would be a physiological variable that reflects an important performance-related capability, whereas the body mass itself is an indicator of the “power demand” experienced by the skier. To adequately evaluate an elite skier’s performance capability, it is essential to establish the optimal ratio between the physiological variable and body mass. The overall aim of this doctoral thesis was to investigate the importance of body-mass exponent optimization for the evaluation of performance capability in cross-country skiing. Methods In total, 83 elite cross-country skiers (56 men and 27 women) volunteered to participate in the four studies. The physiological variables of maximal oxygen uptake (V̇O2max) and oxygen uptake corresponding to a blood-lactate concentration of 4 mmol∙l-1 (V̇O2obla) were determined while treadmill roller skiing using the diagonal-stride technique; mean oxygen uptake (V̇O2dp) and upper-body power output (Ẇ) were determined during double-poling tests using a ski-ergometer. Competitive performance data for elite male skiers were collected from two 15-km classical-technique skiing competitions and a 1.25-km sprint prologue; additionally, a 2-km double-poling roller-skiing time trial using the double-poling technique was used as an indicator of upper-body performance capability among elite male and female junior skiers. Power-function modelling was used to explain the race and time-trial speeds based on the physiological variables and body mass. Results The optimal V̇O2max-to-mass ratios to explain 15-km race speed were V̇O2max divided by body mass raised to the 0.48 and 0.53 power, and these models explained 68% and 69% of the variance in mean skiing speed, respectively; moreover, the 95% confidence intervals (CI) for the body-mass exponents did not include either 0 or 1. For the modelling of race speed in the sprint prologue, body mass failed to contribute to the models based on V̇O2max, V̇O2obla, and V̇O2dp. The upper-body power output-to-body mass ratio that optimally explained time-trial speed was Ẇ ∙ m-0.57 and the model explained 63% of the variance in speed. Conclusions The results in this thesis suggest that V̇O2max divided by the square root of body mass should be used as an indicator of performance in 15-km classical-technique races among elite male skiers rather than the absolute or simple ratio-standard scaled expression. To optimally explain an elite male skier’s performance capability in sprint prologues, power-function models based on oxygen-uptake variables expressed absolutely are recommended. Moreover, to evaluate elite junior skiers’ performance capabilities in 2-km double-poling roller-skiing time trials, it is recommended that Ẇ divided by the square root of body mass should be used rather than absolute or simple ratio-standard scaled expression of power output.

Feudalism in the service of the revolution Reclaiming heritage in hue

This article discusses the way the past is being reexamined in modern-day Vietnam, particularly through the medium of heritage. Hue, the old royal capital of Vietnam, provides the case study, as this city reflects the great themes and events of Vietnamese history over the last two hundred years, from the establishment of a unified nation under the Nguyen, through the imposition of colonial control, the devastation of war, reunification, and the establishment of communism, to the consolidation of an independent postcolonial nation. The importance of Hue's heritage is recognized in its status as a “world heritage” site. The author argues that Hue's heritage is, nevertheless, problematic for Vietnam's ruling communists, because to them it largely represents a regime—the Nguyen Dynasty—that was “reactionary” and that had sold out the country to the French. The apparent contradiction between the standard communist view of the Nguyen past and the value accorded to Nguyen heritage in Hue is resolved, the author contends, by recourse to the depoliticized practices of heritage preservation and tourist promotion.

Modelling of porosity defects in high pressure die casting with a neural network

High Pressure Die Casting (HPDC) is a complex process that results in casting defects if configured improperly. However, finding out the optimal configuration is a non-trivial task as eliminating one of the casting defects (for example, porosity) can result in occurrence of other casting defects. The industry generally tries to eliminate the defects by trial and error which is an expensive and error -prone process. This paper aims to improve current modelling and understanding of defects formation in HPDC machines. We have conducted conventional die casting tests with a neural network model of HPDC machine and compared the obtained results with the current understanding of formation of porosity. While most of our findings correspond well to established knowledge in the field, some of our findings are in conflict with the previous studies of die casting.

The use of scoring rubrics to determine clinical performance in the operating suite

Summary : This research evolved out of the need to examine the validity and inter-rater reliability of a set of performance-based scoring rubrics designed to measure competencies within the operating suite.

Method : Both holistic and analytical rubrics were developed aligned to the ACORN Standard [Australian College of Operating Room Nurses Standard NR4, 2004. ACORN Competency Standards for Perioperative Nurses: Standard NR4: The Instrument Nurse in the Perioperative Environment. Australian College of Operating Room Nurses Ltd, Adelaide] and underpinned by the Dreyfus model (1981). Three video clips that captured varying performance of nurses performing as instrument nurses in the operating suite were recorded and used as prompts by expert raters, who judged the performance using the rubrics.

Results : The study found that the holistic rubrics led to more consistent judgments than the analytical rubrics, yet the latter provided more diagnostic information for intervention purposes. Despite less consistency, the Analytical Observation Form had sufficient construct validity to satisfy the requirements of criterion referencing as determined by the Item Separation Index (Rasch, 1960), including high internal consistency and greater inter-rater reliability when average ratings were used.

Conclusion : The study was an empirical investigation of the use of concomitant Analytical and Holistic Rubrics to determine various levels of performance in the operating suite including inter-rater reliability. The methodology chosen was theoretically sound and sufficiently flexible to be used to develop other competencies within the operating suite.

Preliminary evaluation of monolithic column high-performance liquid chromatography with tris(2,2’-bipyridyl)ruthenium(II) chemiluminescence detection for the determination of quetiapine in human body fluids

High-performance liquid chromatography (HPLC) with tris(2,2-bipyridyl)ruthenium(II) chemiluminescence detection methodology is reported for the determination of the atypical antipsychotic drug quetiapine and the observation of its major active and inactive metabolites in human urine and serum. The method uses a monolithic chromatographic column allowing high flow rates of 3mL min−1 enabling rapid quantification. Flow injection analysis (FIA) with tris(2,2-bipyridyl)ruthenium(II) chemiluminescence detection and HPLC time of flight mass spectrometry (TOF-MS) were used for the determination of quetiapine in a pharmaceutical preparation to establish its suitability as a calibration standard. The limit of detection achieved with FIA was 2×10−11 mol L−1 in simple aqueous solution. The limits of detection achieved with HPLC were 7×10−8 and 2×10−10 mol L−1 in urine and serum, respectively. The calibration range for FIA was between 5×10−9 and 1×10−6 mol L−1. The calibration ranges for HPLC were between 1×10−7–1×10−4 and 1×10−8–1×10−4 mol L−1 in urine and serum, respectively. The quetiapine concentrations in patient samples were found to be 3×10−6 mol L−1 in urine and 7×10−7 mol L−1 in serum. Without the need for preconcentration, the HPLC detection limits compared favourably with those in previously published methodologies. The metabolites were identified using HPLC-TOF-MS.

A boarding school outbreak of pertussis in adolescents : value of laboratory diagnostic methods

Culture for Bordetella pertussis (B. pertussis) is the traditional gold standard for laboratory diagnosis of pertussis but is insensitive, especially later in the course of illness and in vaccinated persons. Interpretation of serology is limited by the lack of an appropriate reference standard. An outbreak of pertussis in a crowded boarding-school dormitory allowed evaluation of laboratory correlates of infection. Questionnaires, serum samples and throat swabs were collected from members of the exposed group. Serum samples from unexposed controls of a similar age group were used for comparison. B. pertussis PCR was performed on throat swabs, and sera were tested for IgA antibodies against whole-cell (WC) B. pertussis antigen and IgG antibodies to pertussis toxin (PT). The Centers for Disease Control and Prevention definition for pertussis was used to define clinical cases. We evaluated the use of a previously published cut-off for PT IgG of 125 EIA units (EU)/ml. Completed questionnaires were obtained from 115 students, of whom 85 (74%) reported coughing symptoms, including 32 (28%) who met the clinical case definition for pertussis. B. pertussis was detected by PCR in 17 (15%) and WC IgA in 22 (19%) students; neither correlated with symptoms, but dormitory of residence strongly predicted PCR status. The mean PT IgG geometric mean concentration, in this situation of high pertussis exposure, correlated with severity of symptoms and was significantly higher in both symptomatic and asymptomatic children exposed during the outbreak (P<0·001) than in control children. A cut-off for PT IgG of 125 EU/ml was too high in an outbreak situation to be sensitive enough to identify pertussis cases. A case of pertussis in a crowded boarding-school dormitory resulted rapidly in an outbreak. Serology and PCR were useful in identifying the outbreak and commencing disease control measures. The use of serology has mostly been evaluated in community serosurveys, where it is not possible to determine if immunity reflects vaccination, asymptomatic disease or symptomatic disease. This outbreak gave us the opportunity to evaluate the value of serology and PCR in the presence of confirmed exposure to pertussis.

Inverse opal nanoassemblies : novel architectures for gas sensors the SnO2:Zn case

A novel technique is here presented, based on inverse opal metal oxide structures for the production of high quality macro and meso-porous structures for gas sensing. Taking advantage of a sol-gel templated approach. different mixed semiconducting oxides with high surface area, commonly used in chemical sensing application, were synthesized. In this work we report the
comparison between SnO₂ and SnO₂:Zn. As witnessed by Scanning and Transmission Electron Microscopy (SEM and TEM) analyses and by Powder x-ray Diffraction (PX RD), highly ordered meso-porous structures were formed with oxide crystalline size never exceeding 20 nm . The filled templates. in form of thick films, were bound to allumina substrate with Pt interdigitated contacts
and Pt heater, through in situ calcination, in order to perform standard electrical characterization. Pollutant gases like CO and NO₂ and methanol. as interfering gas, were used for the targeted electrical gas tests. All samples showed low detection limits towards both reducing and oxidizing species in low temperature measurements. Moreover, the addition of high molar percentages of Zn( II) affected the beha viour of electrical response improv ing the se lecti vity of the proposed system.

Provision of meals on wheels to the elderly : case studies in the era of local government reform

Australia’s ageing population is on the increase. It is predicted that by 2021 one quarter of Victoria’s elderly population will be aged 60 and over. Not only are people living longer, but they also wish to remain living in the community. The Home and Community Care (HACC) Program was established in 1985 to facilitate and assist the elderly and disabled to remain in their home. In Victoria around 51% of HACC funds are managed by local governments, a level of government that has recently undergone major reforms, which ultimately impacted on the manner in which services were provided. The HACC program funds Meals on Wheels, a service that provides meals for those elderly who no longer can prepare their own meals. The aim of this study was to assess the Meals on Wheels service provided by two Melbourne councils with different service philosophies. The study has four main components: (1) Menu analysis by food and variety; (2) Analysis of actual meals; (3) Clients assessment of Food Services; and (4) Client assessment of the organoleptic qualities of Meals on Wheels. Two Melbourne councils were chosen for their different approaches to service delivery. The City of South tendered out both meal production and delivery, while the City of North maintained its MOW service in-house. The case study method of research allowed for each council’s service to be assessed objectively and without comparison. Several methodologies were used for collecting data in this study. Menu analysis was carried out by comparing the MOW menus with the HACC menu planning guidelines together with general menu planning principles. Analysis of actual meals was in two stages. The weights of the meals were recorded and compared with the HACC recommended food serving portions and meal combinations over a five-day period were analysed for their nutrient contents. Face to face interviews were conducted with clients for their assessment of MOW and the assessment of the organoleptic qualities of the meals was carried out over a five-day period. The results concluded that both councils menus were based on sound menu planning principles, but did not conform with Home and Community Care menu planning guidelines fully and did not include a serve of bread, fruit and milk. The weight analysis of the meal combinations revealed some discrepancies between actual meals and Home and Community Care guidelines by not meeting the recommended serving sizes. Meal combinations generally met Home and Community Care standard for kilojoule and protein, but other nutrients, such as thiamin, riboflavin, magnesium, calcium and zinc were generally below the recommended levels for Meals On Wheels. The majority of study group lived alone and received four to five meals per week. Delivery times of meals, selective menus and food quality were issues raised by clients. Whilst the quality and variety of vegetables was raised by clients they generally rated the organoleptic qualities of the meals as satisfactory. This study examined the four components of the service. A simple method of evaluation the service was developed, which highlight discrepancies with HACC standards and encouraged the councils to set a customer satisfaction standard. A number of recommendations are made to ensure that meals are aesthetically pleasing, including a list of different methods for preparing vegetables. The provision of additional foods, such as a “snack pack” is recommended to improve the supply of essential nutrients that were below the Home and Community Care standards. Meals on Wheels is a vital support service for the elderly living in the community and as such should aim to provide a high quality service that meets the needs of its clients.

Narrativization of actuality : convergence of form and genre in film and television

The thesis concerns the treatment of actuality in film and television, particularly the narrativization of actuality images, and the context of their placement within audio/visual texts. Several instances of the convergence of media form and genre are analyzed, and the conventions of classificatory systems and boundaries that pertain to film and television representations are reconsidered in light of changes in the conventions of genre. The distinction between, and convergence of fictional and non-fictional conventions of narrative are therefore central to the thesis, as are the related issues of viewer response, the nature of subjectivity in the viewer, the connectivity of text and culture, and the relations of actuality to the text. The thesis traces the narrativization of actuality through textual, formal and genre boundaries, adopting a ‘line of flight or deterritorialization’ that enables the thesis to ‘change in nature and connect with other multiplicities.’This line of flight passes through the conventional separation of genre groupings and texts, and, similarly, has been applied in the thesis as a rationale for the diminution of theoretical boundaries. A multiperpectival approach is applied to the permeability of, or transcendent relations of the analysis to the boundaries between genres, between texts and culture, and between actuality and virtual representation. In the thesis there is also a theoretical deterritorialization that consents to a pluralism of theory, which is an approach demonstrated by Deleuze and Guattari in A Thousand Plateaus. The model of multi-perspectivalism adopted in the thesis engages in establishing connections and similarities between theories, rather than emphasizing contradictory and exclusive practices. The Foucauldian notion of the rules of formation in discourse, Nichols’ theories of documentary representation of reality, Bordwell’s schematic interpretation, and several other positions are critiqued, as the line of flight embarked upon in the thesis intersects with, and passes through both textual and theoretical boundaries. The thesis consists of two parts: firstly, a location of theoretical perspective, in which the issues of theory pertaining to actuality and narrative are explicated, and the methodological approach of the thesis is defined. The second part commences with an analysis of the most familiar instances of actuality in film and television, with particular attention to documentary forms. It then engages in the analysis of films that represent actuality but which, in the process of narrativization, display a convergence of genre conventions. The films selected for analysis include Steven Speilberg's Schindler's List, (1993) Oliver Stone's JFK, (1991) and Robert Zemeckis' Forrest Gump, (1994) and Contact, (1996). Hence the thesis is concerned with the application of a pluralist theoretical approach, with, however, an emphasis on the Deleuzo-Guattarian notions of rhizome and assemblage. Within this theoretical frame, the connections between actuality and the audio/visual text are explicated, and the formation of text as ‘a rhizome with the world’, is analyzed across a range of examples.

Cashmere production and fleece attributes associated with farm of origin, age and sex of goat in Australia

Differences in cashmere production and fleece attributes associated with farm of origin, age and sex were quantified for commercial Australian cashmere goat enterprises. From 11 farms in four states, 1147 does and 97 wethers were monitored, representing 1- to 13-year-old goats. Individual clean cashmere production ranged from 21 to 389 g, with a mean ± standard deviation value of 134 ± 62 g. The mean cashmere production of 2-year-old does from different farms varied from 69 to 225 g and averaged 141 g. Mean ± s.d. greasy fleece weight was 394 ± 123 g, clean washing yield was 90.8 ± 4.1%, clean cashmere yield 33.4 ± 9.4%, cashmere fibre diameter 16.4 ± 1.6 µm, fibre curvature 48 ± 8.7 degrees/mm and staple length 8.7 ± 2.1 cm. There were large, commercially significant differences between farms for clean cashmere weight, mean fibre diameter and other attributes of cashmere. These were much larger than the effects of age and sex. Farm and age accounted for 42 to 67% of the variation in clean cashmere production, mean fibre diameter, fibre curvature, staple length and clean washing yield. Farm of origin affected clean cashmere yield, accounting for 24% of the variation. Sex of the goats had only a minor effect on the staple length of cashmere. The responses to age of clean cashmere weight, mean fibre diameter and the inverse of fibre curvature are very similar. Generally, cashmere production and mean fibre diameter increased with age. For the majority of farms, cashmere fibre curvature declined in a curvilinear manner with increases in age of goat. There were large differences in cashmere staple length from different farms, with means ranging from 7 to 12 cm. Between 1 and 2 years of age, the staple length of cashmere demonstrated a constant proportional increase. At ages older than 2 years, staple length either declined or increased by less than 1 cm with age, depending on the farm of origin. This study demonstrates that there are large gains in productivity that can be achieved from Australian cashmere goats. A better understanding of on-farm factors that influence cashmere production would enable all producers to optimise their production systems.

Investigation of nonisothermal crystallization behaviors of poly and silica nanocomposites using differential scanning calorimetry

Nonisothermal crystallization behaviors of PVA and poly (vinyl alcohol) and Silica (PVA/SiO2) nanocomposites prepared via a self-assembly monolayer (SAM) technique are investigated in this study. Differential scanning calorimetry (DSC) is used to measure the crystallization temperature and enthalpy of PVA and nanocomposites in nitrogen at various cooling rate. The results show that the degree of crystallinity of PVA and nanocomposites decreases when the SiO₂ content increases but increases with an increasing cooling rate. The peak crystallization temperature decreases with an increasing cooling rate.