Acylmethyl(aryl)tellurium(IV,II) derivatives : intramolecular secondary bonding and steric rigidity

Electrophilic substitution of acylmethanes (methyl ketones), RCOCH3 (R = i-Pr, 1; Et, 2; Me, 3) with aryltellurium trichlorides, ArTeCl3 (Ar = 1-C10H7, Np, A; 2,4,6-Me3C6H2, Mes, B; 4-MeOC6H4, Anisyl, C) under mild conditions affords the corresponding acylmethyl(aryl)tellurium dichlorides (RCOCH2)ArTeCl2. Reduction of the dichlorides, gives tellurides, (i-PrCOCH2)ArTe, 1A–1C, which give the corresponding dihalides, (i-PrCOCH2)ArTeX2 (X = Cl, 1Aa–1Ca; Br, 1Ab–1Cb; I, 1Ac–1Cc) when reacted in situ with SO2Cl2, Br2 or I2. The unsymmetric tellurides are labile towards disproportionation and attempts to obtain them lead to the isolation of Ar2Te2 except in the case of (i-PrCOCH2)MesTe ( 1B), which represents an interesting example of a kinetically stable aryl(alkyl)telluride. All the dihalomesityltellurium(IV) derivatives show separate 1H and 13C NMR signals for the ortho methyls irrespective of the sizes of R and X ligands. The telluride, 1B with free rotation about Te–C(mesityl) bond shows, like the unsymmetric diorganotellurium(IV) dihalides, only one 125Te NMR signal. The 1,4-chelating behavior of the acyl ligand among diorganotellurium(IV) compounds is inferred from the X-ray diffraction data for 1Aa, 1Ac, 1Ba, 1Bb, 1Ca and 1Cc which are indicative of the presence of intramolecular TeO secondary bonding interactions (SBIs) at least in the solid state. As a consequence, steric repulsion in case of the mesityltellurium(IV) derivatives, 1Ba and 1Bb, reaches the threshold so as to cause loss of two-fold rotational symmetry of the mesityl group about the Te–C(mesityl) bond axis. Intermolecular C–HO H-bonding interactions appears to stabilize such an orientation of the aryl ligand at least in the solid state.

Returns to scale, market power, and the nature of price rigidity in new keynesian models with self-fulfilling expectations

Increasing returns to scale and firms' market power are two potential sources of sunspot expectations in neoclassical models. We show that in New Keynesian models, returns to scale and market power can have fundamentally different implications for broad macroeconomic issues, including self-fulfilling expectations, depending on the nature of price rigidity. Our findings suggest that the design of stabilization monetary policy can depend on precise knowledge about the economy's real and nominal features. Therefore, a clear understanding of the specific economic environment and its relevance to monetary policymaking for ensuring macroeconomic stability can be an integrated part of monetary policy practice.

The effect of mechanical loading on the size and shape of bone in pre-, peri-, and postpubertal girls: a study in tennis players

Exercise during growth results in biologically important increases in bone mineral content (BMC). The aim of this study was to determine whether the effects of loading were site specific and depended on the maturational stage of the region. BMC and humeral dimensions were determined using DXA and magnetic resonance imaging (MRI) of the loaded and nonloaded arms in 47 competitive female tennis players aged 8-17 years. Periosteal (external) cross-sectional area (CSA), cortical area, medullary area, and the polar second moments of area (I_p, mm⁴) were calculated at the mid and distal sites in the loaded and nonloaded arms. BMC and I _p of the humerus were 11-14% greater in the loaded arm than in the nonloaded arm in prepubertal players and did not increase further in peri- or postpubertal players despite longer duration of loading (both, _p < 0.01). The higher BMC was the result of a 7-11% greater cortical area in the prepubertal players due to greater periosteal than medullary expansion at the midhumerus and a greater periosteal expansion alone at the distal humerus. Loading late in puberty resulted in medullary contraction. Growth and the effects of loading are region and surface specific, with periosteal apposition before puberty accounting for the increase in the bone's resistance to torsion and endocortical contraction contributing late in puberty conferring little increase in resistance to torsion. Increasing the bone's rt.osistance to torsion is achieved hy modifying bone shape and mass, not necessarily bone density.

Dietary omega 3 fatty acids decrease intraocular pressure with age by increasing Aqueous outflow

Purpose: To determine whether there is an association between dietary omega-3 (ω-3) fatty acid intake, age, and intraocular pressure (IOP) caused by altered aqueous outflow. Methods: Sprague–Dawley rats were fed either ω-3–sufficient (ω-3⁺) or ω-3–deficient (ω-3^–) diets from conception. The diets had 7% lipid content. The ω-3⁺ diet contained safflower, flaxseed, and tuna oils (5.5:1.0:0.5), and the ω-3^– diet contained safflower oil only. Intraocular pressure was measured at 5 to 40 weeks of age under light anesthesia (ω-3⁺, n = 39; ω-3^–, n = 48). Aqueous outflow was determined at 45 weeks in a subgroup of animals (ω-3⁺, n = 15;ω-3^–, n = 22) using pulsed infusion. Ciliary body tissues (n = 6 per group) were assayed for fatty acid content by thin-layer and gas-liquid chromatography in both diet groups. Results: Animals raised on ω-3⁺ diets had a 13% decrease in IOP at 40 weeks of age (13.48 ± 0.32 mm Hg vs. 15.46 ± 0.29 mm Hg; P < 0.01). When considered as a change in IOP relative to 5 weeks of age, the ω-3⁺ group showed a 23% decrease (P < 0.001). This lower IOP in the ω-3⁺ diet group was associated with a significant increase (+56%; P < 0.001) in outflow facility and a decrease in ocular rigidity (–59%; P < 0.001). The ω-3⁺ group showed a 3.3 times increase in ciliary body docosahexaenoic acid (P < 0.001). Conclusions: Increasing dietary ω-3 reduces IOP with age because of increased outflow facility, likely resulting from an increase in docosanoids. This indicates that dietary manipulation may provide a modifiable factor for IOP regulation. However, further studies are needed to consider whether this can modify the risk for glaucoma and can play a role in treatment of the disease.

The Pareto plus syndrome in top marketing journals: research and journal criteria

Purpose – Pareto’s Law often refers to the theory that a small percentage of a total is responsible for a large proportion of the total outcome. It is commonly known as the 80/20 law or principle. The objective is to review and debate whether there is a “Pareto syndrome” in the distribution of crucial research and journal criteria in top marketing journals.

Design/methodology/approach – The authors provide a review and a debate based upon previous research on top marketing journals. For this purpose, the Pareto syndrome concept is introduced, based upon a set of research and journal criteria. Their distribution is examined.

Findings – The review of research and journal criteria in top marketing journals generated an extremely skewed outcome. When it comes to the criteria, the top journals in marketing tend to be governed by narrow concerns of research rather than broad ones.

Research limitations/implications – The research and journal criteria that have a skewed outcome may reinforce the rigidity and the lack of innovativeness of the marketing discipline. The evolutionary speed of the discipline may at best be reduced or it may at worst grind to a halt. The authors argue that there are a number of serious concerns to be addressed in the future review and debate of top journals in marketing.

Practical implications – Editors and editorial boards need seriously to address the concerns reviewed and debated, namely the skewed distribution of criteria, such as affiliation, data and methodology.

Originality/value – The authors debate that there is evidence that confirms the existence of a Pareto plus syndrome in key research and journal criteria of top marketing journals.

Reducing position error of cantilevered loads in motion systems

The positioning error of a large cantilevered mass that is actuated at its supported end is minimized as this mass travels at challenging high speeds and accelerations. An integrated approach is adopted to realize the task. After selecting the appropriate actuator that would provide higher rigidity, the system is viewed as a multi-degree of freedom system, and hence the concept of system-generated disturbance is introduced. This allows the use of appropriate mechanical design considerations and a proper generation of the kinematics commands to minimize such disturbance. A disturbance observer is then designed to detect and compensate the remaining disturbance, hence minimizing the positioning error.

The softness of alpaca fibres

Softness is a unique selling point for luxury fibres such as alpaca. However, there is very little objective data on the softness of animal fibres. This study first establishes that the resistance to compression (RtC) behaviour of alpaca and wool fibres is quite different, and that the RtC method can not be used to examine the softness of different animal fibres. It then reports a new method for evaluating fibre softness. This method is based on the measurement of the force required to pull a fibre bundle through a series of parallel pins. This force, reflecting the combined effect of fibre surface properties, fibre diameter and rigidity, can achieve reasonable discrimination between fibres of varying levels of softness, such as alpaca and wool. Mechanisms responsible for the superior softness of alpaca fibres are discussed also.

Exploding the stability myth : structural change in the Australian trade union movement, 1969-85

Traditional studies of long-term change in trade union structure have predominantly relied upon the aggregate number of trade unions as the principal measure, or indicator of change over time. Using the Australian trade union movement as an example, this article argues that our understanding of the long-term change in the external structure of trade unions would be better served by using Waddington's structural events approach examining the incidence of four distinct 'structural events'--union formations, dissolutions, breakaways and mergers. In doing so, this article presents new data on structural change in the Australian trade union movement between 1969 and 1985. It casts doubt on the traditional argument, which relied on the apparent lack of change in the aggregate number of unions reported by the Australian Bureau of Statistics to argue that this period was one of structural rigidity. The structural events data reveals that far from being a period of structural stability, it was in fact one of significant change, albeit in the composition of the Australian trade union movement, rather than in the aggregate number of trade unions in operation.

The dimensional and mechanical properties of wool/polyester fabrics made from vortex and ring-spun yarns

Fabric woven from wool/polyester (PES) Murata vortex spun (MVS) blend yarn is a commercially viable proposition particularly on the basis of advantageous wear-resistant properties, compared with fabric made from traditional worsted ring-spun yarn. However, in some early industrial trials with fabric made from 45/55-blend wool/PES MVS yarn, significantly greater relaxation shrinkage was found relative to comparable worsted ring-spun fabric. It was noted at the time that the amount of relaxation shrinkage in MVS fabric could be reduced to a large extent by using steamed MVS yarn.

In this study, the extent of variations in the dimensional and mechanical properties of fabric samples woven from a combination of steamed and unsteamed MVS yarn and equivalent worsted ring-spun yarn is examined. In general, greater hygral expansion and relaxation shrinkage were found in loom-state fabrics made from unsteamed MVS yarns, whereas the fabric made from steamed MVS and ring-spun yarns gave relatively low levels of relaxation shrinkage and hygral expansion. Permanent setting of fabrics, by pressure steaming, was found to be more effective than yarn pre-steaming in reducing relaxation shrinkage levels of fabrics made from unsteamed MVS yarn. After pressure steaming, all fabrics showed similar levels of relaxation shrinkage and hygral expansion.

Permanent setting of the fabrics, by pressure steaming, resulted in similar levels of relaxation shrinkage and hygral expansion, irrespective of the yarn production method; relaxation shrinkage fell to around 1% and hygral expansion increased by about 1%, relative to the loom-state samples. MVS fabrics were relatively heavier and fuller and had a firmer handle than the worsted ring-spun fabrics, reflecting the greater fabric weight, thickness and shear rigidity measured on these fabrics. These attributes are associated with different structures of the worsted ring-spun and MVS yarns used to make the fabrics.

Experimental and numerical investigation of low pressure tube hydroforming on 409 stainless steel

Tube hydroforming has been widely used to produce automotive structural components due to the superior properties of the hydroformed parts in terms of their light weight and structural rigidity. Compared to the traditional manufacturing process for a closed-section member including stamping and followed by welding, tube-hydro forming leads to cost savings due to reduced tooling and material handling. However, the high pressure pumps and high tonnage press required in hydroforming, lead to increased capital investment reducing the cost benefits. This study explores low pressure tube hydro forming which reduces the internal fluid pressure and die closing force required to produce the hydroformed part. The experimental and numerical analysis was for low pressure hydro formed stainless steel tubes. Die filling conditions and thickness distributions are measured and critically analysed.

Numerical investigation of high and low pressure tube hydroforming

Hydroforming is one option to reduce vehicle weight while increasing component stiffness and rigidity. This typically involves using a fluid to form a component with high internal pressure. Tube hydroforming has gained increasing interest in the automotive and aerospace industries because of its many advantages such as part consolidation, good quality of the formed part etc. The main advantage is that the uniform pressure can be transferred to whole part at the same time. In low pressure hydroforming, the internal pressure is significantly and the hydroformed section length of line stays almost the same as the circumference of the blank tube. This paper details the comparison between high and low pressure hydroforming. It is shown that the internal pressure and holding force required for low pressure hydroforming process is much less than that of high pressure. Also stress and thickness distribution are more uniform and the process is highly suitable for the forming of advanced high strength steels.

Benchmarking the teaching of Australian Indigenous content in undergraduate psychology

This paper discusses a teaching and learning project on incorporating Australian Indigenous content into psychology undergraduate programs. After the impetus generated by the Head of Schools meeting in Perth in 1998 and the publication of the special issue of the Australian Psychologist on Psychology and Indigenous peoples in 2000, little progress seems to have been made. The paper discusses the process of developing curriculum guidelines for psychology academics wishing to include Indigenous content. These include the need to critically examine the assumptions and history of Western psychology in relation to Indigenous peoples, the inclusion of non-conventional teaching and learning methods, staff and institutional support, and appropriate staff development. While we have been encouraged by the growing support for this process, there are also significant obstacles, including rigidity of thinking about psychology programs and the attitude that it is all too hard. It is important to get this right, since the token inclusion of Indigenous material into otherwise mainstream Western psychology courses will be ineffective in bringing about the required understanding for psychology students wishing to work with Indigenous people in their professional careers and bring about social justice.

Role of exercise in the development of bone strength during growth

Exercise during growth may increase peak bone mass; if the benefits are maintained it may reduce the risk of fracture later in life (1). It is hypothesised that exercise will preferentially enhance bone formation on the surface of cortical bone that is undergoing bone modeling at the time (2). Therefore, exercise may increase bone mass accrual on the outer periosteal surface during the pre- and peri-pubertal years, and on the inner endocortical surface during puberty (3). An increase in bone formation on the periosteal surface is, however, more effective for increasing bone strength than medullary contraction (4). While exercise may have a role in osteoporosis prevention, there is little evidential basis to support this notion. It is generally accepted that weight-bearing exercise is important, but it is not known how much, how often, what magnitude or how long children need to exercise before a clinically important increase in bone density is obtained. In this thesis, the effect of exercise on the growing skeleton is investigated in two projects. The first quantifies the magnitude and number of loads associated with and in a moderate and low impact exercise program and non-structured play. The second project examines how exercise affects bone size and shape during different stages of growth. Study One: The Assessment of the Magnitude of Exercise Loading and the Skeletal Response in Girls Questions: 1) Does moderate impact exercise lead to a greater increase in BMC than low impact exercise? 2) Does loading history influence the osteogenic response to moderate impact exercise? 3) What is the magnitude and number of loads that are associated with a moderate and low impact exercise program? Methods: Sixty-eight pre-and early-pubertal girls (aged 8.9±0.2 years) were randomised to either a moderate or low impact exercise regime for 8.5-months. In each exercise group the girls received either calcium fortified (-2000 mg/week) or non-fortified foods for the duration of the study. The magnitude and number of loads associated with the exercise programs and non-structured play were assessed using a Pedar in-sole mobile system and video footage, respectively. Findings: After adjusting for baseline BMC, change in length and calcium intake, the girls in the moderate exercise intervention showed greater increases in BMC at the tibia (2.7%) and total body (1.3%) (p ≤0.05). Girl's who participated in moderate impact sports outside of school, showed greater gains in BMC in response to the moderate impact exercise program compared to the low impact exercise program (2.5 to 4.5%, p ≤0.06 to 0.01). The moderate exercise program included -400 impacts per class, that were applied in a dynamic manner and the magnitude of impact was up to 4 times body weight. Conclusion: Moderate-impact exercise may be sufficient to enhance BMC accrual during the pre-pubertal years. However, loading history is likely to influence the osteogenic response to additional moderate impact exercise. These findings contribute towards the development of school-based exercise programs aimed at improving bone health of children. Study Two: Exercise Effect on Cortical Bone Morphology During Different Stages of Maturation in Tennis Players Questions: 1) How does exercise affect bone mass (BMC) bone geometry and bone strength during different stages of growth? 2) Is there an optimal stage during growth when exercise has the greatest affect on bone strength? Methods: MRI was used to measure average total bone, cortical and medullary areas at the mid- and distal-regions of the playing and non-playing humerii in 47 pre-, peri- and post-pubertal competitive female tennis players aged 8 to 17 years. To assess bone rigidity, each image was imported into Scion Image 4.0.2 and the maximum, minimum and polar second moments of area were calculated using a custom macro. DXA was used to measure BMC of the whole humerus. Longitudinal data was collected on 37 of the original cohort. Findings: Analysis of the entire cohort showed that exercise was associated with increased BMC and cortical area (8 to 14%), and bone rigidity (11 to 23%) (all p ≤0.05). The increase in cortical bone area was associated with periosteal expansion in the pre-pubertal years and endocortical contraction in the post-pubertal years (p ≤0.05). The exercise-related gains in bone mass that were accrued at the periosteum during the pre-pubertal years, did not increase with advanced maturation and/or additional training. Conclusion: Exercise increased cortical BMC by enhancing bone formation on the periosteal surface during the pre-pubertal years and on the endocortical surface in the post-pubertal years. However, bone strength only increased in response to bone acquisition on the periosteal surface. Therefore the pre-pubertal years appear to be the most opportune time for exercise to enhance BMC accrual and bone strength

Contribution of multi-tenure reserve networks to biodiversity conservation

A consistent and integrated approach to nature conservation across the landscape and regardless of tenure is widely recognised as essential in ensuring the effective conservation of biodiversity. 'Multi-tenure reserve networks', which incorporate public and private lands managed for conservation, are considered a means of achieving landscape scale conservation. Biosphere Reserves (BR) and Conservation Management Networks (CMN) are characteristic models in Australia. This thesis aims to evaluate the role of such networks in protecting biodiversity, specifically by: (1) analysing the spatial configuration (size, shape, connectivity) of networks and their individual components; (2) evaluating the contribution of networks (in real terms and in reporting procedures) to biodiversity conservation objectives; (3) analysing the influence of the attitudes and perceptions of land managers on the functionality of networks; and (4) evaluating the influence of coordinating bodies on network functionality. In order to account for deficiencies in existing classifications of conservation lands, a new classification system was developed for this thesis - the Conservation Lands Classification. This classification incorporates conservation mechanisms on public and private lands and forms the basis for comparing network components in three Australian case studies - the Bookmark BR located in the Murray Mallee of South Australia, the Gippsland Plains CMN on the eastern Gippsland Plains of Victoria and the Grassy Box Woodlands CMN across the inland slopes of New South Wales. The spatial configuration of individual components within networks was measured using spatial analysis techniques within a geographic information system (GIS). GIS was also used to measure the contribution that networks made to a comprehensive, adequate and representative reserve system through the ecosystems they protected. The attitudes and perceptions of landowners and managers within the networks were obtained using questionnaires. Questionnaires were also sent to network coordinators. Statistical and descriptive analysis was conducted on the results. The sizes of individual components varied markedly between the three networks, however within each network public reserves were on average larger than private conservation lands. Although levels of physical connectivity varied between networks, Bookmark BR and Gippsland Plains CMN showed greater similarity to each other than to the Grassy Box Woodlands CMN. The findings raise important questions about the real and perceived differences in the BR and CMN models. All networks, and particularly those components outside the public protected area estate, contributed to enhancing the protection of ecosystems unrepresented or under-represented in the reserve system, although the extent of this contribution varied between networks. Trade-offs between reserve design efficiency and a contribution to a comprehensive, adequate and representative reserve system were evident between networks. Bookmark BR was characterised by high connectivity, strong reserve design integrity but a lower contribution to protecting under-reserved ecosystems, whereas the opposite was evident in the Grassy Box Woodlands CMN. Over 88% of managers considered their involvement in multi-tenure reserve networks to be a positive or very positive experience. A lack of resources and time for management were considered major limitations of these networks. The majority (80%) of private land managers within networks were willing to be included in a national reserve system of conservation lands. This has important implications for the Australian National Reserve System, which currently incorporates mostly public land. The changing nature of the network coordination arrangements suggests an organic fluid evolution of network structures is likely, contrasting with the desire for legalistic and administrative rigidity promoted by government agencies. The thesis concludes that all the networks studied contribute in varying degrees to biodiversity conservation. The key factors influencing the current and potential contribution that such networks make are: (1) the aims, directions and restrictions set by or imposed upon the coordinating body; and (2) the biophysical nature of the surrounding bioregion and resultant historical land use and tenure pattern. Although the successful operation of such 'multi-tenure' networks ultimately relies on the willing participation of private landholders, ongoing institutional support is likely to be required for maintaining networks in the longer term. Considering networks are increasingly formed outside of the influence of government institutions, this presents a significant challenge for effective coordinated conservation.