Thermal decomposition of hydrotalcite with hexacyanoferrite(II) and hexacyanoferrate(III) anions in the interlayer : a controlled rate thermal analysis study

The mechanism for the decomposition of hydrotalcite remains unsolved. Controlled rate thermal analysis enables this decomposition pathway to be explored. The thermal decomposition of hydrotalcites with hexacyanoferrite(II) and hexacyanoferrate(III) in the interlayer has been studied using controlled rate thermal analysis technology. X-ray diffraction shows the hydrotalcites studied have a d(003) spacing of 11.1 and 10.9 Å which compares with a d-spacing of 7.9 and 7.98 Å for the hydrotalcite with carbonate or sulphate in the interlayer. Calculations based upon CRTA measurements show that 7 moles of water is lost, proving the formula of hexacyanoferrite(II) intercalated hydrotalcite is Mg6Al2(OH)16[Fe(CN)6]0.5 .7 H2O and for the hexacyanoferrate(III) intercalated hydrotalcite is Mg6Al2(OH)16[Fe(CN)6]0.66 * 9 H2O. Dehydroxylation combined with CN unit loss occurs in three steps between a) 310 and 367°C b) 367 and 390°C and c) between 390 and 428°C for both the hexacyanoferrite(II) and hexacyanoferrate(III) intercalated hydrotalcite.

Dynamic axial ligand-site exchange in facially discriminated ruthenium(II) carbonyl and rhodium(III) halide metalloporphyrins

For a series of six-coordinate Ru(II)(CO)L or Rh(III)(X–)L porphyrins which are facially differentiated by having a naphthoquinol- or hydroquinol-containing strap across one face, we show that ligand migration from one face to the other can occur under mild conditions, and that ligand site preference is dependent on the nature of L and X–. For bulky nitrogen-based ligands, the strap can be displaced sideways to accommodate the ligand on the same side as the strap. For the ligand pyrazine, we show 1 H NMR evidence for monodentate and bidentate binding modes on both faces, dependent on ligand concentration and metalloporphyrin structure, and that inter-facial migration is rapid under normal conditions. For monodentate substituted pyridine ligands there is a site dependence on structure, and we show clear evidence of dynamic ligand migration through a series of ligand exchange reactions.

Least-squares congealing for large numbers of images

In this paper we pursue the task of aligning an ensemble of images in an unsupervised manner. This task has been commonly referred to as “congealing” in literature. A form of congealing, using a least-squares criteria, has been recently demonstrated to have desirable properties over conventional congealing. Least-squares congealing can be viewed as an extension of the Lucas & Kanade (LK)image alignment algorithm. It is well understood that the alignment performance for the LK algorithm, when aligning a single image with another, is theoretically and empirically equivalent for additive and compositional warps. In this paper we: (i) demonstrate that this equivalence does not hold for the extended case of congealing, (ii) characterize the inherent drawbacks associated with least-squares congealing when dealing with large numbers of images, and (iii) propose a novel method for circumventing these limitations through the application of an inverse-compositional strategy that maintains the attractive properties of the original method while being able to handle very large numbers of images.

High speed rail and regional competitiveness

The presence of High Speed Rail (HSR) systems influences market shares of road and air transport, and the development of cities and regions they serve. With the deployment of HSR infrastructure, changes in accessibility have occurred. These changes have lead researchers to investigate effects on the economic and spatial derived variables. Contention exists when managing the trade off between efficiency, and access points which are usually in the range of hundreds of kilometres apart. In short, it is argued that intermediate cities, bypassed by HSR services, suffer a decline in their accessibility and developmental opportunities. The present Chapter will analyse possible impacts derived from the presence of HSR infrastructure. In particular, it will consider small and medium agglomerations in the vicinity of HSR corridors, not always served by HSR stations. Thus, a methodology is developed to quantify accessibility benefits and their distribution. These benefits will be investigated in relation to different rail transit strategies integrating HSR infrastructure where a HSR station cannot be positioned. These strategies are selected principally for the type of service offered: (i) cadenced, (ii) express, (iii) frequent or (iv) non-stopping. Furthermore, to ground the theoretical approach linking accessibility and competitiveness, a case study in the North-Eastern Italian regions will be used for the application of the accessibility distributive patterns between the HSR infrastructure and the selected strategies. Results indicate that benefits derive from well informed decisions on HSR station positioning and the appropriate blend of complementary services in the whole region to interface HSR infrastructure. The results are significant for all countries in Europe and worldwide, not only for investing in HSR infrastructure, but mostly in terms of building territorial cohesion, while seeking international recognition for developing successful new technology and systems.

Polymer self assembly on carbon nanotubes

This chapter analyses the poly(3-hexylthiophene) self-assembly on carbon nanotubes and the interaction between the two materials forming a new hybrid nanostructure. The chapter starts with a review of the several studies investigating polymers and biomolecules self-assembled on nanotubes. Then conducting polymers and polythiophenes are briefly introduced. Accordingly, carbon nanotube structure and properties are reported in Sect. 3. The experimental section starts with the bulk characterisation of polymer thin films with the inclusion of uniformly distributed carbon nanotubes. By using volume film analysis techniques (AFM, TEM, UV–Vis and Raman), we show how the polymer’s higher degree of order is a direct consequence of interaction with carbon nanotubes. Nevertheless, it is through the use of nanoscale analysis and molecular dynamic simulations that the self-assembly of the polymer on the nanotube surface can be clearly evidenced and characterised. In Sect. 6, the effect of the carbon templating structure on the P3HT organisation on the surface is investigated, showing the chirality-driven polymer assembly on the carbon nanotube surface. The interaction between P3HT and CNTs brings also to charge transfer, with the modification of physical properties for both species. In particular, the alteration of the polymer electronic properties and the modification of the nanotube mechanical structure are a direct consequence of the P3HT p-p stacking on the nanotube surface. Finally, some considerations based on molecular dynamics studies are reported in order to confirm and support the experimental results discussed.

Introductory Chapter to The Economics of Nonprofit Enterprises

Nonprofit organizations present the analyst with a slew of puzzles. To an economist conditioned to think in terms of objectives and constraints, even the mathematical definition of the beast is a problem. What is a nonprofit organization? How does this definition shape the elaboration of objectives and constraints?

Reproductive health : findings from the Australian Longitudinal Study on Women’s Health. Chapter 3: Use of contraception

Chapter 3: Use of contraception. p15-32 Key findings: This section examines trends in the use of contraception between 1996 and 2006 by women who participated in the surveys for the 1973-1978 cohort of the Australian Longitudinal Study on Women’s Health. 1. The oral contraceptive pill was the most commonly used method of contraception at each survey, but its use decreased over time. 2.Of women who consistently used contraception, 40% used the oral contraceptive pill as their only method of contraception in at least three out of four surveys. 3. The proportion of women using condoms as their only method of contraception remained steady over time (15-18%) but only 3% of all women used condoms only at every survey. 4. The proportion of women using both condoms and the oral contraceptive pill remained steady at 13-14% of all women from Survey 1 to 3, but decreased to 8% of all women at Survey 4. 5. The use of methods other than the oral contraceptive pill and/or condoms increased at Survey 4. 6. The proportion of women using an implant (e.g. Implanon) remained steady between Surveys 3 and 4, with 3% of women using an implant only. Around one third of implant users at Survey 3 continued to use this method at Survey 4. 7. The main reasons for not using contraception at Surveys 3 and 4 were pregnancy, trying to conceive, or no male sexual partners. 8. Women who used contraception were more likely to be in de facto relationships or single, be up to date with Pap tests and have had two or more births. 9. Women who did not use contraception were more likely to be non-drinkers and/or do low levels of exercise, have had one birth and have experienced miscarriage. 10. Contraception changed in expected ways according to reproductive events: women who reported only miscarriages between surveys also stopped using contraception in the same period; most women who did not report reproductive events continued to use the same method of contraception; and women who had a termination tended to switch methods.

Reproductive health: findings from the Australian Longitudinal Study on Women’s Health. Chapter 5: fertility and infertility

Chapter 5: Fertility and infertility. p52-70. This section describes patterns of fertility across Surveys 1 to 4 among the cohort of women who were born in 1973-1978. This section includes the examination of pregnancy outcomes including both live births and pregnancy losses (stillbirths, miscarriages, terminations and ectopic pregnancies). This section also examines the prevalence of self-reported problems with fertility and whether these women sought advice and/or treatment. As women age they are more likely to experience infertility and, with little other data available, the ALSWH provides an important opportunity to examine this problem and the related use of health services. 1. Pregnancy losses are common. Half of the women who report a pregnancy outcome at Survey 4 have experienced a pregnancy loss. 2. More than one third (39%) of women who have experienced a live birth by Survey 4 have also experienced a pregnancy loss. 3. For every ten women aged 28-33 years in 2006: four women had not had been pregnant, five women had a live birth (with or without a recognised pregnancy loss), and one woman had a recognised pregnancy loss only. 4. Among women who had tried to conceive or had been pregnant, one-in-six had experienced infertility. (i.e. tried unsuccessfully to get pregnant for 12 months or more) 5. The most significant factors associated with having infertility, seeking advice and using treatment were: polycystic ovary syndrome, endometriosis and miscarriage. 6. Of the women who reported infertility, two-thirds sought advice but only half used treatment. 7. Most of the women who used fertility treatment had used low cost and non-invasive methods.

Association and linkage analyses of restriction fragment length polymorphisms for the human renin and antithrombin III genes in essential hypertension

Essential hypertension is a highly hereditable disorder in which genetic influences predominate over environmental factors. The molecular genetic profiles which predispose to essential hypertension are not known. In rats with genetic hypertension, there is some recent evidence pointing to linkage of renin gene alleles with blood pressure. The genes for renin and antithrombin III belong to a conserved synteny group which, in humans, spans the q21.3-32.3 region of chromosome I and, in rats, is linkage group X on chromosome 13. The present study examined the association of particular human renin gene (REN) and antithrombin III gene (AT3) polymorphisms with essential hypertension by comparing the frequency of specific alleles for each of these genes in 50 hypertensive offspring of hypertensive parents and 91 normotensive offspring of normotensive parents. In addition, linkage relationships were examined in hypertensive pedigrees with multiple affected individuals. Alleles of a REN HindIII restriction fragment length polymorphism (RFLP) were detected using a genomic clone, λHR5, to probe Southern blots of HindIII-cut leucocyte DNA, and those for an AT3 Pstl RFLP were detected by phATIII 113 complementary DNA probe. The frequencies of each REN allele in the hypertensive group were 0.76 and 0.24 compared with 0.74 and 0.26 in the normotensive group. For AT3, hypertensive allele frequencies were 0.49 and 0.51 compared with normotensive values of 0.54 and 0.46. These differences were not significant by χ2 analysis (P > 0.2). Linkage analysis of a family (data from 16 family members, 10 of whom were hypertensive), informative for both markers, without an age-of-onset correction, and assuming dominant inheritance of hypertension, complete penetrance and a disease frequency of 20%, did not indicate linkage of REN with hypertension, but gave a positive, although not significant, logarithm of the odds for linkage score of 0.784 at a recombination fraction of 0 for AT3 linkage to hypertension. In conclusion, the present study could find no evidence for an association of a REN HindIII RFLP with essential hypertension or for a linkage of the locus defined by this RFLP in a family segregating for hypertension. In the case of an AT3 Pstl RFLP, although association analysis was negative, linkage analysis suggested possible involvement (odds of 6:1 in favour) of a gene located near the 1q23 locus with hypertension in one informative family.

An examination of learning design in elite springboard diving

The overarching aim of this programme of work was to evaluate the effectiveness of the existing learning environment within the Australian Institute of Sport (AIS) elite springboard diving programme. Unique to the current research programme, is the application of ideas from an established theory of motor learning, specifically ecological dynamics, to an applied high performance training environment. In this research programme springboard diving is examined as a complex system, where individual, task, and environmental constraints are continually interacting to shape performance. As a consequence, this thesis presents some necessary and unique insights into representative learning design and movement adaptations in a sample of elite athletes. The questions examined in this programme of work relate to how best to structure practice, which is central to developing an effective learning environment in a high performance setting. Specifically, the series of studies reported in the chapters of this doctoral thesis: (i) provide evidence for the importance of designing representative practice tasks in training; (ii) establish that completed and baulked (prematurely terminated) take-offs are not different enough to justify the abortion of a planned dive; and (iii), confirm that elite athletes performing complex skills are able to adapt their movement patterns to achieve consistent performance outcomes from variable dive take-off conditions. Chapters One and Two of the thesis provide an overview of the theoretical ideas framing the programme of work, and include a review of literature pertinent to the research aims and subsequent empirical chapters. Chapter Three examined the representativeness of take-off tasks completed in the two AIS diving training facilities routinely used in springboard diving. Results highlighted differences in the preparatory phase of reverse dive take-offs completed by elite divers during normal training tasks in the dry-land and aquatic training environments. The most noticeable differences in dive take-off between environments began during the hurdle (step, jump, height and flight) where the diver generates the necessary momentum to complete the dive. Consequently, greater step lengths, jump heights and flight times, resulted in greater board depression prior to take-off in the aquatic environment where the dives required greater amounts of rotation. The differences observed between the preparatory phases of reverse dive take-offs completed in the dry-land and aquatic training environments are arguably a consequence of the constraints of the training environment. Specifically, differences in the environmental information available to the athletes, and the need to alter the landing (feet first vs. wrist first landing) from the take-off, resulted in a decoupling of important perception and action information and a decomposition of the dive take-off task. In attempting to only practise high quality dives, many athletes have followed a traditional motor learning approach (Schmidt, 1975) and tried to eliminate take-off variations during training. Chapter Four examined whether observable differences existed between the movement kinematics of elite divers in the preparation phases of baulked (prematurely terminated) and completed take-offs that might justify this approach to training. Qualitative and quantitative analyses of variability within conditions revealed greater consistency and less variability when dives were completed, and greater variability amongst baulked take-offs for all participants. Based on these findings, it is probable that athletes choose to abort a planned take-off when they detect small variations from the movement patterns (e.g., step lengths, jump height, springboard depression) of highly practiced comfortable dives. However, with no major differences in coordination patterns (topology of the angle-angle plots), and the potential for negative performance outcomes in competition, there appears to be no training advantage in baulking on unsatisfactory take-offs during training, except when a threat of injury is perceived by the athlete. Instead, it was considered that enhancing the athletes' movement adaptability would be a more functional motor learning strategy. In Chapter Five, a twelve-week training programme was conducted to determine whether a sample of elite divers were able to adapt their movement patterns and complete dives successfully, regardless of the perceived quality of their preparatory movements on the springboard. The data indeed suggested that elite divers were able to adapt their movements during the preparatory phase of the take-off and complete good quality dives under more varied take-off conditions; displaying greater consistency and stability in the key performance outcome (dive entry). These findings are in line with previous research findings from other sports (e.g., shooting, triple jump and basketball) and demonstrate how functional or compensatory movement variability can afford greater flexibility in task execution. By previously only practising dives with good quality take-offs, it can be argued that divers only developed strong couplings between information and movement under very specific performance circumstances. As a result, this sample was sometimes characterised by poor performance in competition when the athletes experienced a suboptimal take-off. Throughout this training programme, where divers were encouraged to minimise baulking and attempt to complete every dive, they demonstrated that it was possible to strengthen the information and movement coupling in a variety of performance circumstances, widening of the basin of performance solutions and providing alternative couplings to solve a performance problem even when the take-off was not ideal. The results of this programme of research provide theoretical and experimental implications for understanding representative learning design and movement pattern variability in applied sports science research. Theoretically, this PhD programme contributes empirical evidence to demonstrate the importance of representative design in the training environments of high performance sports programmes. Specifically, this thesis advocates for the design of learning environments that effectively capture and enhance functional and flexible movement responses representative of performance contexts. Further, data from this thesis showed that elite athletes performing complex tasks were able to adapt their movements in the preparatory phase and complete good quality dives under more varied take-off conditions. This finding signals some significant practical implications for athletes, coaches and sports scientists. As such, it is recommended that care should be taken by coaches when designing practice tasks since the clear implication is that athletes need to practice adapting movement patterns during ongoing regulation of multi-articular coordination tasks. For example, volleyball servers can adapt to small variations in the ball toss phase, long jumpers can visually regulate gait as they prepare for the take-off, and springboard divers need to continue to practice adapting their take-off from the hurdle step. In summary, the studies of this programme of work have confirmed that the task constraints of training environments in elite sport performance programmes need to provide a faithful simulation of a competitive performance environment in order that performance outcomes may be stabilised with practice. Further, it is apparent that training environments can be enhanced by ensuring the representative design of task constraints, which have high action fidelity with the performance context. Ultimately, this study recommends that the traditional coaching adage 'perfect practice makes perfect", be reconsidered; instead advocating that practice should be, as Bernstein (1967) suggested, "repetition without repetition".