Synthesis and characterisation of heterometallic molecular triangles using ambidentate linker: self-selection of a single linkage isomer

The coordination driven self-assembly of discrete molecular triangles from a non-symmetric ambidentate linker 5-pyrimidinecarboxylate (5-pmc) and Pd(II)/Pt(II) based 90◦ acceptors is presented. Despite the possibility of formation of a mixture of isomeric macrocycles (linkage isomers) due to different connectivity of the ambidentate linker, formation of a single and symmetrical linkage somer in both the cases is an interesting observation. Moreover, the reported macrocycles represent the first example of discrete metallamacrocycles of bridging 5-pmc. While solution composition in both the cases was characterised by multinuclear NMR study and electrospray ionization mass spectrometry (ESI-MS), the identity of the assemblies in the solid state was established by X-ray single crystals structure analysis. Variable temperature NMR study clearly ruled out the formation of any other macrocycles by [4 + 4] or [2 + 2] self-assembly of the reacting components.

A comparative study of side-band Fresnel holograms recorded with self-imaging and general objects

This paper deals with new results obtained in regard to the reconstruction properties of side-band Fresnel holograms (SBFH) of self-imaging type objects (for example, gratings) as compared with those of general objects. The major finding is that a distribution I2, which appears on the real-image plane along with the conventional real-image I1, remains a 2Z distribution (where 2Z is the axial distance between the object and its self-imaging plane) under a variety of situations, while its nature and focusing properties differ from one situation to another. It is demonstrated that the two distributions I1 and I2 can be used in the development of a novel technique for image subtraction.

“We live in in a house of blo- in a block of flats.” – Self-repair in EFL Spoken Language

Tämä tutkielma on osa Helsingin yliopiston rahoittamaa HY-talk -tutkimusprojektia, jonka tavoite on vankentaa puheviestinnän, erityisesti vieraiden kielten suullisen taidon opetusta ja arviointia yleissivistävässä koulutuksessa ja korkeakouluasteella. Tämän tutkielman tavoite on selvittää millaisia korjauksia englantia vieraana kielenä puhuvat ihmiset tekevät puheeseensa ja tutkia itsekorjauksen ja sujuvuuden välistä suhdetta. Korjausjäsennystä ja itsekorjausta on aiemmin tutkittu sekä keskustelunanalyysin että psykolingvistiikan aloilla, ja vaikka tämä tutkielma onkin lähempänä aiempaa keskustelunanalyyttistä kuin psykolingvististä tutkimusta, siinä hyödynnetään molempia suuntauksia. Itsekorjausta on yleisesti pidetty merkkinä erityisesti ei-natiivien kielenpuhujien sujuvuuden puutteesta. Tämän tutkielman tarkoitus on selvittää, kuinka läheisesti itsekorjaus todella liittyy sujuvuuteen tai sen puutteeseen. Tutkielman materiaali koostuu HY-talk -projektia varten kerätyistä puhenäytteistä ja niiden pohjalta tehdyistä taitotasoarvioinneista. Puhenäytteet kerättiin vuonna 2007 projektia varten järjestettyjen puhekielen testaustilanteiden yhteydessä kolmessa eteläsuomalaisessa koulussa. Koska projektin tavoitteena on tutkia ja parantaa kielten suullisen taidon arviointia, projektissa mukana olleet kieliammattilaiset arvioivat puhujien taitotasot projektia varten (Eurooppalaisen Viitekehyksen taitotasokuvainten pohjalta) koottujen arviointiasteikoiden perusteella, ja nämä arvioinnit tallennettiin osaksi projektin materiaalia. Tutkielmassa analysoidaan itsekorjauksia aiemman psykolingvistisen tutkimuksen pohjalta kootun korjaustyyppiluokituksen sekä tätä tutkielmaa varten luodun korjausten oikeellisuutta vertailevan luokituksen avulla. Lisäksi siinä vertaillaan kahden korkeamman ja kahden matalamman taitotasoarvioinnin saaneen puhujan itsekorjauksia. Tulokset osoittavat, että ei-natiivien puheessa esiintyy monenlaisia eri korjaustyyppejä, ja että yleisimpiä korjauksia ovat alkuperäisen lausuman toistot. Yleisiä ovat myös korjaukset, joissa puhuja korjaa virheen tai keskeyttää puheensa ja aloittaa kokonaan uuden lausuman. Lisäksi tuloksista käy ilmi, ettei suurin osa korjauksista todennäköisesti johdu puhujien sujuvuuden puutteesta. Yleisimmät korjaustyypit voivat johtua suurimmaksi osaksi yksilön puhetyylistä, siitä, että puhuja hakee jotain tiettyä sanaa tai ilmausta mielessään tai siitä, että puhuja korjaa puheessaan huomaamansa kieliopillisen, sanastollisen tai äänteellisen virheen. Vertailu korkeammalle ja matalammalle taitotasolle arvioitujen puhujien välillä osoittaa selkeimmin, ettei suurin osa itsekorjauksista ole yhteydessä puhujan sujuvuuteen. Vertailusta käy ilmi, ettei pelkkä itsekorjausten määrä kerro kuinka sujuvasti puhuja käyttää kieltä, sillä toinen korkeammalle taitotasolle arvioiduista puhujista korjaa puhettaan lähes yhtä monesti kuin matalammalle tasolle arvioidut puhujat. Lisäksi korjausten oikeellisuutta vertailevan luokituksen tulokset viittaavat siihen, etteivät niin korkeammalle kuin matalammallekaan tasolle arvioidut puhujat useimmiten korjaa puhettaan siksi, etteivät pystyisi ilmaisemaan viestiään oikein ja ymmärrettävästi.

'Work it out': Evaluation of a chronic condition self-management program for urban Aboriginal and Torres Strait Islander people with or at risk of cardiovascular disease

This thesis evaluates a chronic condition self-management program for Aboriginal and Torres Strait Islander people in urban south-east Queensland who have or are at risk of cardiovascular disease. Outcomes showed short-term improvements for some anthropometry measures which could be a trend for improvement in other anthropometry indicators over the longer term. The program was of particular benefit for participants who had several social and emotional wellbeing conditions. The use of an Aboriginal and Torres Strait Islander conceptual framework was critical in undertaking culturally competent quantitative research in this project.

Self-love and self-liking in the moral and political philosophy of Bernard Mandeville and David Hume

This work offers a novel interpretation of David Hume’s (1711–1776) conception of the conjectural development of civil society and artificial moral institutions. It focuses on the social elements of Hume’s Treatise of human nature (1739–40) and the necessary connection between science of man and politeness, civilised monarchies, social distance and hierarchical structure of civil society. The study incorporates aspects of intellectual history, history of philosophy and book history. In order to understand David Hume’s thinking, the intellectual development of Bernard Mandeville (1670–1733) needs to be accounted for. When put into a historical perspective, the moral, political and social components of Treatise of human nature can be read in the context of a philosophical tradition, in which Mandeville plays a pivotal role. A distinctive character of Mandeville and Hume’s account of human nature and moral institutions was the introduction of a simple distinction between self-love and self-liking. The symmetric passions of self-interest and pride can only be controlled by the corresponding moral institutions. This is also the way in which we can say that moral institutions are drawn from human nature. In the case of self-love or self-interest, the corresponding moral institution is justice. Respectively, concerning self-liking or pride the moral institution is politeness. There is an explicit analogy between these moral institutions. If we do not understand this analogy, we do not understand the nature of either justice or politeness. The present work is divided into two parts. In the first part, ‘Intellectual development of Bernard Mandeville’, it is argued that the relevance of the paradigmatic change in Mandeville’s thinking has been missed. It draws a picture of Mandeville turning from the Hobbism of The Fable of the Bees to an original theory of civil society put forward in his later works. In order to make this change more apparent, Mandeville’s career and the publishing history of The Fable of the Bees are examined comprehensively. This interpretation, based partly on previously unknown sources, challenges F. B. Kaye’s influential decision to publish the two parts of The Fable of the Bees as a uniform work of two volumes. The main relevance, however, of the ‘Intellectual development of Mandeville’ is to function as the context for the young Hume. The second part of the work, ‘David Hume and Greatness of mind’, explores in philosophical detail the social theory of the Treatise and politics and the science of man in his Essays. This part will also reveal the relevance of Greatness of mind as a general concept for David Hume’s moral and political philosophy.

Long-term ambient air pollution exposure and self-reported morbidity in the Australian Longitudinal Study on Women's Health: A cross-sectional study

- Objective We sought to assess the effect of long-term exposure to ambient air pollution on the prevalence of self-reported health outcomes in Australian women. - Design Cross-sectional study - Setting and participants The geocoded residential addresses of 26 991 women across 3 age cohorts in the Australian Longitudinal Study on Women's Health between 2006 and 2011 were linked to nitrogen dioxide (NO2) exposure estimates from a land-use regression model. Annual average NO2 concentrations and residential proximity to roads were used as proxies of exposure to ambient air pollution. - Outcome measures Self-reported disease presence for diabetes mellitus, heart disease, hypertension, stroke, asthma, chronic obstructive pulmonary disease and self-reported symptoms of allergies, breathing difficulties, chest pain and palpitations. - Methods Disease prevalence was modelled by population-averaged Poisson regression models estimated by generalised estimating equations. Associations between symptoms and ambient air pollution were modelled by multilevel mixed logistic regression. Spatial clustering was accounted for at the postcode level. - Results No associations were observed between any of the outcome and exposure variables considered at the 1% significance level after adjusting for known risk factors and confounders. - Conclusions Long-term exposure to ambient air pollution was not associated with self-reported disease prevalence in Australian women. The observed results may have been due to exposure and outcome misclassification, lack of power to detect weak associations or an actual absence of associations with self-reported outcomes at the relatively low annual average air pollution exposure levels across Australia.

Adipocytes promote prostate cancer stem cell self-renewal through amplification of the cholecystokinin autocrine loop

Obesity has long been linked with prostate cancer progression, although the underlying mechanism is still largely unknown. Here, we report that adipocytes promote the enrichment of prostate cancer stem cells (CSCs) through a vicious cycle of autocrine amplification. In the presence of adipocytes, prostate cancer cells actively secrete the peptide hormone cholecystokinin (CCK), which not only stimulates prostate CSC self-renewal, but also induces cathepsin B (CTSB) production of the adipocytes. In return, CTSB facilitates further CCK secretion by the cancer cells. More importantly, inactivation of CCK receptor not only suppresses CTSB secretion by the adipocytes, but also synergizes the inhibitory effect of CTSB inhibitor on adipocyte-promoted prostate CSC self-renewal. In summary, we have uncovered a novel mechanism underlying the mutual interplay between adipocytes and prostate CSCs, which may help explaining the role of adipocytes in prostate cancer progression and provide opportunities for effective intervention.

Novel Self-Supported Natural and Synthetic Polymer Membranes for Air Humidification

Novel self-supported natural and synthetic polymer membranes of chitosan-hydroxy ethyl Cellulose-montmorillonite (CS-HEC-MMT) and polyvinyl alcohol (PVA)-polystyrene sulfonic acid (PSSA) are prepared by solution casting method followed by crosslinking. These membranes are employed for air humidification at varying temperatures between 30 degrees C and 70 degrees C and their performances are compared with commercial Nafion membranes. High hater fluxes with desired humidified-air output have been achieved for CS-HEC-MMT and PVA-PSSA hybrid membranes at air-flow rates of 1-10 slpm. Variation in the air/water mixing ratio, dew point, and relative humidity that ultimately results in desired water flux With respect to air-flow rates are also quantified for all the membranes. Water flux values for CS-HEC-MMT are less than those for Nafion (R) and PVA-PSSA membranes, but the operational Stability of CS-HEC-MMT membrane is higher than PVA-PSSA and comparable with Nafion (R) both of which can operate up to 70 degrees C at repetitive cycles of humidification.

Motorcycle riders' self-reported aggression when riding compared with car driving

Aggressive driving has been shown to be related to increased crash risk for car driving. However, less is known about aggressive behaviour and motorcycle riding and whether there are differences in on-road aggression as a function of vehicle type. If such differences exist, these could relate to differences in perceptions of relative vulnerability associated with characteristics of the type of vehicle such as level of protection and performance. Specifically, the relative lack of protection offered by motorcycles may cause riders to feel more vulnerable and therefore to be less aggressive when they are riding compared to when they are driving. This study examined differences in self-reported aggression as a function of two vehicle types: passenger cars and motorcycles. Respondents (n = 247) were all motorcyclists who also drove a car. Results were that scores for the composite driving aggression scale were significantly higher than on the composite riding aggression scale. Regression analyses identified different patterns of predictors for driving aggression from those for riding aggression. Safety attitudes followed by thrill seeking tendencies were the strongest predictors for driving aggression, with more positive safety attitudes being protective while greater thrill seeking was associated with greater self-reported aggressive driving behaviour. For riding aggression, thrill seeking was the strongest predictor (positive relationship), followed by self-rated skill, such that higher self rated skill was protective against riding aggression. Participants who scored at the 85th percentile or above for the aggressive driving and aggressive riding indices had significantly higher scores on thrill seeking, greater intentions to engage in future risk taking, and lower safety attitude scores than other participants. In addition participants with the highest aggressive driving scores also had higher levels of self-reported past traffic offences than other participants. Collectively, these findings suggest that people are less likely to act aggressively when riding a motorcycle than when driving a car, and that those who are the most aggressive drivers are different from those who are the most aggressive riders. However, aggressive riders and drivers appear to present a risk to themselves and others on road. Importantly, the underlying influences for aggressive riding or driving that were identified in this study may be amenable to education and training interventions.

Fusion of worlds?: Consumers' self-narrative in a hybrid digital/physical world

As the Internet becomes deeply embedded in consumers' life and continuously accessed through mobile devices, the boundary between the digital and the physical becomes less defined. This thesis investigates how this blurring boundary impacts on consumers' construction of their self-narrative and found that consumers' narrative is paradoxically coherent and fragmented and depicts a heroic story of the self. Prior studies show consumers achieve their desired life story through meaningful consumption, however, the notion of fragmented lives are challenged. Further, extensive digital leisure consumption is often viewed in a less positive light. Nevertheless, consumers, who significantly consume digital leisure, do not disregard their physical world or favour one space over the other. Rather, they negotiate key aspects from their digital and physical lives and fluidly move between these two worlds, creating a hybrid narrative that saves their self and others.

Self-similar solution of unsteady compressible three-dimensional stagnation-point boundary layers

The self-similar solution of the unsteady laminar compressible boundary-layer flow with variable properties at a three-dimensional stagnation point with mass transfer has been obtained when the free-stream velocity varies inversely as a linear function of time. The resulting ordinary differential equations have been solved numerically using an implicit finite-difference scheme. The results are found to be strongly dependent on the parameter characterizing the unsteadiness in the free-stream velocity. The velocity profiles show some features not encountered in steady flows.

Self-Assembly of Bile Steroid Analogues: Molecules, Fibers, and Networks

Structural and rheological features of a series of molecular hydrogels formed by synthetic bile salt analogues have been scrutinized. Among seven gelators, two are neutral compounds, while the others are cationic systems among which one is a tripodal steroid derivative. Despite the fact that the chemical structures are closely related, the variety of physical characteristics is extremely large in the structures of the connected fibers (either plain cylinders or ribbons), in the dynamical modes for stress relaxation of the associated SAFINs, in the scaling laws of the shear elasticity (typical of either cellular solids or fractal floc-like assemblies), in the micron-scale texture and the distribution of ordered domains (spherulites, crystallites) embedded in a random mesh, in the type of nodal zones (either crystalline-like, fiber entanglements, or bundles), in the evolution of the distribution and morphology of fibers and nodes, and in the sensitivity to added salt. SANS appears to be a suitable technique to infer all geometrical parameters defining the fibers, their interaction modes, and the volume fraction of nodes in a SAFIN. The tripodal system is particularly singular in the series and exhibits viscosity overshoots at the startup of shear flows, an “umbrella-like” molecular packing mode involving three molecules per cross section of fiber, and scattering correlation peaks revealing the ordering and overlap of 1d self-assembled polyelectrolyte species.

Self-rating scales in the assessment of current and childhood symptoms of attention deficit hyperactivity disorder in adults

Objective: Attention deficit hyperactivity disorder (ADHD) is a life-long condition, but because of its historical status as a self-remitting disorder of childhood, empirically validated and reliable methods for the assessment of adults are scarce. In this study, the validity and reliability of the Wender Utah Rating Scale (WURS) and the Adult Problem Questionnaire (APQ), which survey childhood and current symptoms of ADHD, respectively, were studied in a Finnish sample. Methods: The self-rating scales were administered to adults with an ADHD diagnosis (n = 38), healthy control participants (n = 41), and adults diagnosed with dyslexia (n = 37). Items of the self-rating scales were subjected to factor analyses, after which the reliability and discriminatory power of the subscales, derived from the factors, were examined. The effects of group and gender on the subscales of both rating scales were studied. Additionally, the effect of age on the subscales of the WURS was investigated. Finally, the diagnostic accuracy of the total scores was studied. Results: On the basis of the factor analyses, a four-factor structure for the WURS and five-factor structure for the APQ had the best fit to the data. All of the subscales of the APQ and three of the WURS achieved sufficient reliability. The ADHD group had the highest scores on all of the subscales of the APQ, whereas two of the subscales of the WURS did not statistically differ between the ADHD and the Dyslexia group. None of the subscales of the WURS or the APQ was associated with the participant's gender. However, one subscale of the WURS describing dysthymia was positively correlated with the participant's age. With the WURS, the probability of a correct positive classification was .59 in the current sample and .21 when the relatively low prevalence of adult ADHD was taken into account. The probabilities of correct positive classifications with the APQ were .71 and .23, respectively. Conclusions: The WURS and the APQ can provide accurate and reliable information of childhood and adult ADHD symptoms, given some important constraints. Classifications made on the basis of the total scores are reliable predictors of ADHD diagnosis only in populations with a high proportion of ADHD and a low proportion of other similar disorders. The subscale scores can provide detailed information of an individual's symptoms if the characteristics and limitations of each domain are taken into account. Improvements are suggested for two subscales of the WURS.

The effect of a self-development coaching program on the psychological health and the academic performance among medical and dental students in Saudi Arabia

Observational studies have shown that medical and dental students have poor psychological health worldwide; however, few interventional studies have been used to test approaches to help students. This thesis used a randomised control trial study design to evaluate the effect of a self-development coaching program on psychological health and the academic performance among medical and dental students in Saudi Arabia. The outcomes indicated that these medical and dental students in Saudi Arabia experienced high levels of depression, anxiety and stress, and that the self-development coaching program was a promising intervention to improve students' psychological health.

Self-Organization of n-Alkane Chains in Water: Length Dependent Crossover from Helix and Toroid to Molten Globule

We demonstrate a chain length dependent crossover in the structural properties of linear hydrocarbon (n-alkane) chains using detailed atomistic simulations in explicit water. We identify a number of exotic structures of the polymer chain through energy minimization of representative snapshots collected from molecular dynamics trajectory. While the collapsed state is ring-like (circular) for small chains (CnH2n+2; n <= 20) and spherical for very long ones (n = 100), we find the emergence of ordered helical structures at intermediate lengths (n similar to 40). We find different types of disordered helices and toroid-like structures at n = 60. We also report a sharp transition in the stability of the collapsed state as a function of the chain length through relevant free energy calculations. While the collapsed state is only marginally metastable for C20H42, a clear bistable free energy surface emerges only when the chain is about 30 monomers long. For n = 30, the polymer exhibits an intermittent oscillation between the collapsed and the coil structures, characteristic of two stable states separated by a small barrier.