Free-radical bulk polymerization of styrene: ESR and near-infrared spectroscopic study of the entire conversion range

The free radical polymerization of styrene in bulk was monitored by ESR and FT near-infrared spectroscopy at 70°C for a series of concentrations of the initiator, dimethyl 2,2′-azobis(isobutyrate). In order to obtain detailed kinetic information over the intire conversion range, and the gel effect range in particular, conversion and free radical concentration data points were accumulated with exceptionally short time intervals. The polystyrene radical concentration ([St•]) went through a sharp maximum at the gel effect, a feature that has hitherto escaped observation due to the rapid concentration changes in the gel effect range relative to the data point time intervals of previous studies. Temperature measurements throughout the polymerization were employed to calculate that a temperature increase was not the cause of the [St•] maximum, which thus appeares to be a genuine feature of the gel effect of this system under isothermal conditions. The propagation rate constant (kp) as a function of monomer conversion exhibited a marked dependence on initiator concentration at high monomer conversion; the sharp decrease in kp with increasing conversion was shifted to higher conversions with increasing initiator concentration.

Teledermatology: a review

Teledermatology holds great potential for revolutionizing the delivery of dermatology services, providing equitable service to remote areas and allowing primary care physicians to refer patients to dermatology centres of excellence at a distance. However, before its routine application asa service tool, its reliability, accuracy and cost-effectiveness need to be verified by rigorous evaluation. Teledermatology can be applied in one of two ways: it may be conducted in real-time, utilizing videoconferencing equipment, or by store-and-forward methods, when transmitted digital images or photographs are submitted with a clinical history. While there is a considerable range of reported accuracy and reliability, evidence suggests that teledermatology will become increasingly utilized and incorporated into more conventional dermatology service delivery systems. Studies to date have generally found that real-time dermatology is likely to allow greater clinical information to be obtained from the patient. This may result in fewer patients requiring conventional consultations, but it is generally more time-consuming and costly to the health service provider It is often favoured by the patient because of the instantaneous nature of the diagnosis and management regimen for the condition, and it has educational value to the primary care physician. Store-and-forward systems of teledermatology often give high levels of diagnostic accuracy, and are cheaper and more convenient for the health care provider, but lack the immediacy of patient contact with the dermatologist, and involve a delay in obtaining the diagnosis and advice on management. It is increasingly likely that teledermatology will prove to be a significant tool in the provision of dermatology services in the future. These services will probably be provided by store-and-forward digital image systems, with real-time videoconferencing being used for case conferences and education. However, much more research is needed into the outcomes and Limitations of such a service and its effect on waiting lists, as well as possible cost benefits for patients, primary health care professionals and dermatology departments.

Dynamic assessment of tongue function in children with dysarthria associated with acquired brain injury using electromagnetic articulography

The study to be presented is the first to use a new physiological device, the electromagnetic articulograph, to assess articulatory dysfunction in children with acquired brain injury. Two children with dysarthria subsequent to acquired brain injury participated in the study. One child, a female aged 12 years 9 months exhibited a mild-moderate ataxic dysarthria following traumatic head injury while the other, a male aged 13 years 10 months, demonstrated a moderate-severe flaccid-ataxic dysarthria also following traumatic head injury. The speed and accuracy of their tongue movements was assessed using the Carstens AG100 electromagnetic articulograph. Movement trajectories together with a range of quantitative kinematic parameters were estimated during performance of ten repetitions of the lingual consonants /t, s, k/ and consonant cluster /kl/ in the word initial position of single syllable words. A group of ten non-neurologically impaired children served as controls. Examination of the kinematic parameters, including movement trajectories, velocity, acceleration, deceleration, distance travelled and duration of movement, revealed differences in the speed and accuracy of the tongue movements in both children with acquired brain injury compared to those produced by the non-neurologically impaired controls. The results are discussed in relation to contemporary theories of the effects of acquired brain injury on neuromuscular function. The implications of the findings for the treatment of articulatory dysfunction in children with motor speech disorders associated with acquired brain injury are highlighted.

A new diffusion and flow theory for activated carbon from low pressure to capillary condensation range

In this paper, we develop a theory for diffusion and flow of pure sub-critical adsorbates in microporous activated carbon over a wide range of pressure, ranging from very low to high pressure, where capillary condensation is occurring. This theory does not require any fitting parameter. The only information needed for the prediction is the complete pore size distribution of activated carbon. The various interesting behaviors of permeability versus loading are observed such as the maximum permeability at high loading (occurred at about 0.8-0.9 relative pressure). The theory is tested with diffusion and flow of benzene through a commercial activated carbon, and the agreement is found to be very good in the light that there is no fitting parameter in the model. (C) 2001 Elsevier Science B.V. All rights reserved.

Growth regime map for liquid-bound granules: further development and experimental validation

An attempt was made to quantify the boundaries and validate the granule growth regime map for liquid-bound granules recently proposed by Iveson and Litster (AlChE J. 44 (1998) 1510). This regime map postulates that the type of granule growth behaviour is a function of only two dimensionless groups: the amount of granule deformation during collision (characterised by a Stokes deformation number, St(def)) and the maximum granule pore saturation, s(max). The results of experiments performed with a range of materials (glass ballotini, iron ore fines, copper chalcopyrite powder and a sodium sulphate and cellulose mixture) using both drum and high shear mixer granulators were examined. The drum granulation results gave good agreement with the proposed regime map. The boundary between crumb and steady growth occurs at St(def) of order 0.1 and the boundary between steady and induction growth occurs at St(def) of order 0.001. The nucleation only boundary occurs at pore saturations that increase from 70% to 80% with decreasing St(def). However, the high shear mixer results all had St(def) numbers which were too large. This is most likely to be because the chopper tip-speed is an over-estimate of the average impact velocity granules experience and possibly also due to the dynamic yield strength of the materials being significantly greater than the yield strengths measured at low strain rates. Hence, the map is only a useful tool for comparing the granulation behaviour of different materials in the same device. Until we have a better understanding of the flow patterns and impact velocities in granulators, it cannot be used to compare different types of equipment. Theoretical considerations also revealed that several of the regime boundaries are also functions of additional parameters not explicitly contained on the map, such as binder viscosity. (C) 2001 Elsevier Science B.V. All rights reserved.

Nucleation, growth and breakage phenomena in agitated wet granulation processes: a review

Wet agglomeration processes have traditionally been considered an empirical art, with great difficulties in predicting and explaining observed behaviour. Industry has faced a range of problems including large recycle ratios, poor product quality control, surging and even the total failure of scale up from laboratory to full scale production. However, in recent years there has been a rapid advancement in our understanding of the fundamental processes that control granulation behaviour and product properties. This review critically evaluates the current understanding of the three key areas of wet granulation processes: wetting and nucleation, consolidation and growth, and breakage and attrition. Particular emphasis is placed on the fact that there now exist theoretical models which predict or explain the majority of experimentally observed behaviour. Provided that the correct material properties and operating parameters are known, it is now possible to make useful predictions about how a material will granulate. The challenge that now faces us is to transfer these theoretical developments into industrial practice. Standard, reliable methods need to be developed to measure the formulation properties that control granulation behaviour, such as contact angle and dynamic yield strength. There also needs to be a better understanding of the flow patterns, mixing behaviour and impact velocities in different types of granulation equipment. (C) 2001 Elsevier Science B.V. All rights reserved.

Stability of nest range, home range and movement of the northern bettong (Bettongia tropica) following moderate-intensity fire in a tropical woodland, north-eastern Queensland

Nest use, home-range characteristics and nightly movements by the northern bettong (Bettongia tropica) were examined before and after a low- to moderate-intensity fire in sclerophyll woodland in north-eastern Australia using radio-telemetry. In all, 23 animals were radio-tracked at three-month intervals between February 1995 and May 1996. During November 1995 a low- intensity experimental fire burned the entire home range of most animals. The northern bettong appeared fairly catholic in choice of nest site, with a variety of nest locations and nesting materials used. Prior to the fire, nests were generally located in areas of dense cover, such as the skirts of grass trees (46%) or grass close to a log (29%). After fire removed most ground cover in the nesting areas of most animals, bettongs used remaining shelter such as boulder piles (45%), recently fallen trees (8%) and patches of unburnt vegetation (21%). Nest areas (10.1 ha) of males were significantly larger than those of females (5.4 ha). Home ranges of both sexes were large (59 ha) and most ranges lacked distinct core areas, suggesting that bettongs used all parts of their home ranges equally. High mean rates of nightly movement by the northern bettong indicated that large distances were moved within home ranges during nightly foraging. No significant fire-related changes were detected in home-range size, home-range location, nest-area location or mean rates of nightly movement, suggesting that the northern bettong is well adapted to the low- and medium-intensity fires that characterise its habitat.

Relationship of high energy expenditure and variation in dietary intake with reporting accuracy on 7 day food records and diet histories in a group of healthy adult volunteers

Objectives: To assess the accuracy of reporting from both a diet history and food record and identify some of the characteristics of more accurate reporters in a group of healthy adult volunteers for an energy balance study. Design: Prospective measurements in free-living people. Setting: Wollongong, Australia. Subjects: Fifteen healthy volunteers (seven male, eight female; aged 22 -59 y; body mass index (BMI) 19 - 33 kg/m(2)) from the local community in the city of Wollongong, Australia. Interventions: Measurement of energy intake via diet history interview and 7 day food records, total energy expenditure by the doubly labelled water technique over 14 days, physical activity by questionnaire, and body fat by dual-energy X-ray absorptiometry. Results: Increased misreporting of energy intake was associated with increased energy expenditure (r = 0.90, P < 0.0001, diet history; r(s)=0.79, P=0.0005, food records) but was not associated with age, sex, BMI or body fat. Range in number of recorded dinner foods correlated positively with energy expenditure (r(s)=0.63, P=0.01) and degree of misreporting (r(s)=0.71, P=0.003, diet history; r(s)=0.63, P=0.01, food records). Variation in energy intake at dinner and over the whole day identified by the food records correlated positively with energy expenditure (r=0.58, P = 0.02) and misreporting on the diet history (r=0.62, P=0.01). Conclusions: Subjects who are highly active or who have variable dietary and exercise behaviour may be less accurate in reporting dietary intake. Our findings indicate that it may be necessary to screen for these characteristics in studies where accuracy of reporting at an individual level is critical. Sponsorship: The study was supported in part by Australian Research Council funds made available through the University of Wollongong.

High-speed MAS F-19 NMR analysis of an irradiated fluoropolymer

The effect of gamma-radiation on a perfluoroalkoxy (PFA) resin was examined using solid-state high-speed magic angle spinning (MAS) F-19 NMR spectroscopy. Samples were prepared for analysis by subjecting them to gamma-radiation in the dose range 0.5-3 MGy at either 303, 473, or 573 K. New structures identified include new saturated chain ends, short and long branches, and unsaturated groups. The formation of branched structures was found to increase with increasing irradiation temperature; however, at all temperatures the radiation chemical yield (G value) of new chain ends was greater than the G value of long branch points, suggesting that chain scission is the net process.

High resolution 3-D imaging via multi-pass SAR

Spaceborne/airborne synthetic aperture radar (SAR) systems provide high resolution two-dimensional terrain imagery. The paper proposes a technique for combining multiple SAR images, acquired on flight paths slightly separated in the elevation direction, to generate high resolution three-dimensional imagery. The technique could be viewed as an extension to interferometric SAR (InSAR) in that it generates topographic imagery with an additional dimension of resolution. The 3-D multi-pass SAR imaging system is typically characterised by a relatively short ambiguity length in the elevation direction. To minimise the associated ambiguities we exploit the relative phase information within the set of images to track the terrain landscape. The SAR images are then coherently combined, via a nonuniform DFT, over a narrow (in elevation) volume centred on the 'dominant' terrain ground plane. The paper includes a detailed description of the technique, background theory, including achievable resolution, and the results of an experimental study.

Quantification and stability of everolimus (SDZ RAD) in human blood by high-performance liquid chromatography-electrospray tandem mass spectrometry

We report here a validated method for the quantification of a new immunosuppressant drug, everolimus (SDZ RAD), using HPLC-tandem mass spectrometry. Whole blood samples (500 mul) were prepared by protein precipitation, followed by C-18 solid-phase extraction. Mass spectrometric detection was by selected reaction monitoring with an electrospray interface operating in positive ionization mode. The assay was linear from 0.5 to 100 mug/l (r(2) > 0.996, n = 9). The analytical recovery and inter-day imprecision, determined using whole blood quality control samples (n = 5) at 0.5, 1.2, 20.0, and 75.0 mug/l, was 100.3-105.4% and less than or equal to7.6%, respectively. The assay had a mean relative recovery of 94.8 +/- 3.8%. Extracted samples were stable for up to 24 h. Fortified everolimus blood samples were stable at -80 degreesC for at least 8 months and everolimus was found to be stable in blood when taken through at least three freeze-thaw cycles. The reported method provides accurate, precise and specific measurement of everolimus in blood over a wide analytical range and is currently supporting phase 11 and III clinical trials. (C) 2002 Elsevier Science B.V. All rights reserved.

Enriched behavioral prediction equation and its impact on structured learning and the dynamic calculus

This theoretical note describes an expansion of the behavioral prediction equation, in line with the greater complexity encountered in models of structured learning theory (R. B. Cattell, 1996a). This presents learning theory with a vector substitute for the simpler scalar quantities by which traditional Pavlovian-Skinnerian models have hitherto been represented. Structured learning can be demonstrated by vector changes across a range of intrapersonal psychological variables (ability, personality, motivation, and state constructs). Its use with motivational dynamic trait measures (R. B. Cattell, 1985) should reveal new theoretical possibilities for scientifically monitoring change processes (dynamic calculus model; R. B. Cattell, 1996b), such as encountered within psycho therapeutic settings (R. B. Cattell, 1987). The enhanced behavioral prediction equation suggests that static conceptualizations of personality structure such as the Big Five model are less than optimal.

Ultra-high-temperature (UHT) treatment of milk: comparison of direct and indirect modes of heating

UHT processing of milk and its subsequent storage causes several changes which affect the shelf-life of UHT milk although it remains 'commercially sterile'. These changes include whey protein denaturation, protein-protein interaction, lactose-protein interaction, isomerisation of lactose, Maillard browning, sulphydryl compound formation, formation of a range of carbonyl and other flavoursome compounds, and formation of insoluble substances. They ultimately reduce the quality and limit the shelf life of UHT milk through development of off-flavours, fat separation, age gelation and sedimentation. The extent of these changes depends on many factors, a major one being the type of UHT heating. This review compares the effect heating milk by direct and indirect modes on various aspects of processing and quality of UHT milk.

Modeling of gas adsorption equilibrium over a wide range of pressure: A thermodynamic approach based on equation of state

A thermodynamic approach based on the Bender equation of state is suggested for the analysis of supercritical gas adsorption on activated carbons at high pressure. The approach accounts for the equality of the chemical potential in the adsorbed phase and that in the corresponding bulk phase and the distribution of elements of the adsorption volume (EAV) over the potential energy for gas-solid interaction. This scheme is extended to subcritical fluid adsorption and takes into account the phase transition in EAV The method is adapted to gravimetric measurements of mass excess adsorption and has been applied to the adsorption of argon, nitrogen, methane, ethane, carbon dioxide, and helium on activated carbon Norit R I in the temperature range from 25 to 70 C. The distribution function of adsorption volume elements over potentials exhibits overlapping peaks and is consistently reproduced for different gases. It was found that the distribution function changes weakly with temperature, which was confirmed by its comparison with the distribution function obtained by the same method using nitrogen adsorption isotherm at 77 K. It was shown that parameters such as pore volume and skeleton density can be determined directly from adsorption measurements, while the conventional approach of helium expansion at room temperature can lead to erroneous results due to the adsorption of helium in small pores of activated carbon. The approach is a convenient tool for analysis and correlation of excess adsorption isotherms over a wide range of pressure and temperature. This approach can be readily extended to the analysis of multicomponent adsorption systems. (C) 2002 Elsevier Science (USA).

Measuring range of active cervical rotation in a position of full head flexion using the 3D Fastrak measurement system: an intra-tester reliability study

Most external assessments of cervical range of motion assess the upper and lower cervical regions simultaneously. This study investigated the within and between days reliability of the clinical method used to bias this movement to the upper cervical region, namely measuring rotation of the head and neck in a position of full cervical flexion. Measurements were made using the Fastrak measurement system and were conducted by one operator. Results indicated high levels of within and between days repeatability (range of ICC2,1 values: 0.85-0.95). The ranges of axial rotation to right and left, measured with the neck positioned in full flexion, were approximately 56% and 50%, respectively of total cervical rotation, which relates well to the proportional division of rotation in the upper and lower cervical regions. These results suggest that this method of measuring rotation would be appropriate for use in subject studies where movement dysfunction is present in the upper cervical region, such as those with cervicogenic headache. (C) 2003 Elsevier Science Ltd. All rights reserved.