Raman spectroscopic study of vivianites of different origins

Raman spectroscopy has been used to study a selection of vivianites from different origins. A band is identified at around 3480 cm-1 whose intensity is sample dependent. The band is attributed to the stretching vibration of Fe3+ OH units which are formed through the autooxidation of the vivianite minerals either by self-oxidation or by photocatalytic oxidation according to the reaction: (Fe2+)3(PO4)2·8H2O + 1/2O2 (Fe2+)3– x(Fe3+)x(PO4)2(OH)x·(8–x)H2O in which some of the water of crystallization is converted to hydroxyl anions. Complexity of the OH stretching region through the overlap of broad bands is reflected in the water HOH deformation modes at 1660 cm–1. Using the infrared bands at 3281, 3105 and 3025 cm–1, hydrogen bond distances of 2.734(5), 2.675(2) and 2.655(2) Å are calculated. Vivianites are characterised by an intense band at 950 cm–1 assigned to the PO4 symmetric stretching vibration. Low Raman intensity bands are observed at ~1077, ~1050, 1015 and ~ 985 cm–1 assigned to the phosphate PO4 antisymmetric stretching vibrations. Multiple antisymmetric stretching vibrations are due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Two bands are observed at ~ 423 and ~ 456 cm–1 assigned to the2bending modes. For the vivianites four bands are observed at ~ 584, ~ 571, ~ 545 and ~ 525 cm–1 assigned to the 4modes of vivianite.

Membership retention within the sporting industry : factors affecting relationship dissolution

Relationship dissolution has been somewhat ignored in the study of relationship marketing paradigm. While there has been an abundance of literature giving broad conceptualizations on how to master the intricacies of relationships, very little has discussed the concept of relationship dissolution. This is especially true of the sporting industry, which does not yet understand the factors that contribute to members relinquishing their membership and severing relationship ties with the club. Team performance was found to be the most powerful predictor of relationship dissolution; however, both satisfaction with the sportscape and emotional bonds had a significant influence on the decision for a member not to renew their membership. Although team performance is mostly out of the hands of sport marketers, greater focus should be given to implementing strategies that enhance the emotional aspects of the club-member relationship while also improving aspects of the service facility.

The emotional manipulation-psychopathy nexus : relationships with emotional intelligence, alexithymia, and ethical position

This research examined for the first time the relationship between emotional manipulation, emotional intelligence, and primary and secondary psychopathy. As predicted, in Study 1 (N = 73), emotional manipulation was related to both primary and secondary psychopathy. Only secondary psychopathy was related to perceived poor emotional skills. Secondary psychopathy was also related to emotional concealment. Emotional intelligence was negatively related to perceived poor emotional skills, emotional concealment, and primary and secondary psychopathy. In Study 2 (N = 275), two additional variables were included: alexithymia and ethical position. It was found that for males, primary psychopathy and emotional intelligence predicted emotional manipulation, while for females emotional intelligence acted as a suppressor, and ethical idealism and secondary psychopathy were additional predictors. For males, emotional intelligence and alexithymia were related to perceived poor emotional skills, while for females emotional intelligence, but not alexithymia, predicted perceived poor emotional skills, with ethical idealism acting as a suppressor. For both males and females, alexithymia predicted emotional concealment. These findings suggest that the mechanisms behind the emotional manipulation–psychopathy relationship differ as a function of gender. Examining the different aspects of emotional manipulation as separate but related constructs may enhance understanding of the construct of emotional manipulation.

Dussertite BaFe3+3(AsO4)2(OH)5 : a Raman spectroscopic study of a hydroxy-arsenate mineral

The mineral dussertite, a hydroxy-arsenate mineral of formula BaFe3+3(AsO4)2(OH)5, has been studied by Raman complimented with infrared spectroscopy. The spectra of three minerals from different origins were investigated and proved quite similar, although some minor differences were observed. In the Raman spectra of Czech dussertite, four bands are observed in the 800 to 950 cm-1 region. The bands are assigned as follows: the band at 902 cm-1 is assigned to the (AsO4)3- ν3 antisymmetric stretching mode, at 870 cm-1 to the (AsO4)3- ν1 symmetric stretching mode, and both at 859 cm-1 and 825 cm-1 to the As-OM2+/3+ stretching modes/and or hydroxyls bending modes. Raman bands at 372 and 409 cm-1 are attributed to the ν2 (AsO4)3- bending mode and the two bands at 429 and 474 cm-1 are assigned to the ν4 (AsO4)3- bending mode. An intense band at 3446 cm-1 in the infrared spectrum and a complex set of bands centred upon 3453 cm-1 in the Raman spectrum are attributed to the stretching vibrations of the hydrogen bonded (OH)- units and/or water units in the mineral structure. The broad infrared band at 3223 cm-1 is assigned to the vibrations of hydrogen bonded water molecules. Raman spectroscopy identified Raman bands attributable to (AsO4)3- and (AsO3OH)2- units.

Essays on irrigation development, farm production and unaccounted costs : theory and empirical evidence

A review of the literature related to issues involved in irrigation induced agricultural development (IIAD) reveals that: (1) the magnitude, sensitivity and distribution of social welfare of IIAD is not fully analysed; (2) the impacts of excessive pesticide use on farmers’ health are not adequately explained; (3) no analysis estimates the relationship between farm level efficiency and overuse of agro-chemical inputs under imperfect markets; and (4) the method of incorporating groundwater extraction costs is misleading. This PhD thesis investigates these issues by using primary data, along with secondary data from Sri Lanka. The overall findings of the thesis can be summarised as follows. First, the thesis demonstrates that Sri Lanka has gained a positive welfare change as a result of introducing new irrigation technology. The change in the consumer surplus is Rs.48,236 million, while the change in the producer surplus is Rs. 14,274 millions between 1970 and 2006. The results also show that the long run benefits and costs of IIAD depend critically on the magnitude of the expansion of the irrigated area, as well as the competition faced by traditional farmers (agricultural crowding out effects). The traditional sector’s ability to compete with the modern sector depends on productivity improvements, reducing production costs and future structural changes (spillover effects). Second, the thesis findings on pesticides used for agriculture show that, on average, a farmer incurs a cost of approximately Rs. 590 to 800 per month during a typical cultivation period due to exposure to pesticides. It is shown that the value of average loss in earnings per farmer for the ‘hospitalised’ sample is Rs. 475 per month, while it is approximately Rs. 345 per month for the ‘general’ farmers group during a typical cultivation season. However, the average willingness to pay (WTP) to avoid exposure to pesticides is approximately Rs. 950 and Rs. 620 for ‘hospitalised’ and ‘general’ farmers’ samples respectively. The estimated percentage contribution for WTP due to health costs, lost earnings, mitigating expenditure, and disutility are 29, 50, 5 and 16 per cent respectively for hospitalised farmers, while they are 32, 55, 8 and 5 per cent respectively for ‘general’ farmers. It is also shown that given market imperfections for most agricultural inputs, farmers are overusing pesticides with the expectation of higher future returns. This has led to an increase in inefficiency in farming practices which is not understood by the farmers. Third, it is found that various groundwater depletion studies in the economics literature have provided misleading optimal water extraction quantity levels. This is due to a failure to incorporate all production costs in the relevant models. It is only by incorporating quality changes to quantity deterioration, that it is possible to derive socially optimal levels. Empirical results clearly show that the benefits per hectare per month considering both the avoidance costs of deepening agro-wells by five feet from the existing average, as well as the avoidance costs of maintaining the water salinity level at 1.8 (mmhos/Cm), is approximately Rs. 4,350 for farmers in the Anuradhapura district and Rs. 5,600 for farmers in the Matale district.

Factors associated with recall of media reports about vitamin D and sun protection

Objective: To assess the recall of media reports about vitamin D and associated factors. Methods: Analysis of cross-sectional telephone interview data (2,001 Queensland adults, 18-70 years) on vitamin D and personal sun protection, recall of media reports and participant characteristics. Results: 83.7% of participants had heard of vitamin D, 47.5% through the media. Only 513 (25.6%) participants recalled the media content within four main themes: vitamin D is beneficial/comes from the sun (47.0%); some people aren’t getting enough vitamin D, need more sun (27.9%); need to balance sun exposure and skin protection (11.5%); or other (13.6%). Only 65 of the 950 participants (6.8%) reported a change to their behaviour(s) due to the media report. Conclusion: Although the media were the main source of information about vitamin D for almost 50% of participants, recall of the content and direct effect on behaviour was low. Only a small minority recalled a balanced media report of beneficial and harmful aspects of sun exposure. Implications Health professionals often supply media with background information. To achieve best public health practice for sun protection and vitamin D, information to foster balanced media reports should be provided.

Sri Lanka in global medical research: a scientific analysis of the Sri Lankan research output during 2000-2009

Background Scientific research is an essential component in guiding improvements in health systems. There are no studies examining the Sri Lankan medical research output at international level. The present study evaluated the Sri Lankan research performance in medicine as reflected by the research publications output between years 2000-2009. Methods This study was based on Sri Lankan medical research publication data, retrieved from the SciVerse Scopus® from January 2000 to December 2009. The process of article selection was as follows: Affiliation - 'Sri Lanka' or 'Ceylon', Publication year - 'January 2000 to December 2009' and Subject area - 'Life and Health Sciences'. The articles identified were classified according to disease, medical speciality, institutions, major international collaborators, authors and journals. Results Sri Lanka's cumulative medical publications output between years 2000-2009 was 1,740 articles published in 160 different journals. The average annual publication growth rate was 9.1%. Majority of the articles were published in 'International' (n = 950, 54.6%) journals. Most articles were descriptive studies (n = 611, 35.1%), letters (n-345, 19.8%) and case reports (n = 311, 17.9%). The articles were authored by 148 different Sri Lankan authors from 146 different institutions. The three most prolific local institutions were Universities of; Colombo (n = 547), Kelaniya (n = 246) and Peradeniya (n = 222). Eighty four countries were found to have published collaborative papers with Sri Lankan authors during the last decade. UK was the largest collaborating partner (n = 263, 15.1%). Malaria (n = 75), Diabetes Mellitus (n = 55), Dengue (n = 53), Accidental injuries (n = 42) and Lymphatic filariasis (n = 40) were the major diseases studied. The 1,740 publications were cited 9,708 times, with an average citation of 5.6 per paper. The most cited paper had 203 citations, while there were 597 publications with no citations. The Sri Lankan authors' contribution to the global medical research output during the last decade was only 0.086%. Conclusion The Sri Lankan medical research output during the last decade is only a small fraction of the global research output. There it is a necessity to setup an enabling environment for research, with a proper vision, support, funds and training. In addition, collaborations across the region need to be strengthened to face common regional health challenges. Keywords: Sri Lanka, Medical research, Publication, Analysis

Effect of engine backpressure on the performance and emissions of a CI engine

This study investigated the effect of engine backpressure on the performance and emissions of a CI engine under different speed and load conditions. A 4-stroke single cylinder naturally aspirated direct injection (DI) diesel engine was used for the investigation with the backpressure of 0, 40, 60 and 80 mm of Hg at engine speed of 600, 950 and 1200 rpm. Two parameters were measured during the engine operation: one is engine performance (brake thermal efficiency and brake specific fuel consumption), and the other is the exhaust emissions (NOx, CO and odor). NOx and CO emission were measured by flue gas analyzer (IMR 1400). The engine backpressure produced by the flow regulating valve in the exhaust line was measured by Hg (mercury) manometer. The result showed that, the brake thermal efficiency and brake specific fuel consumption (bsfc) are almost unchanged with increasing backpressure up to 40 mm of Hg pressure for all engine speed and load conditions. The NOx emission became constant or a little decreased with increasing backpressure. The formation of CO was slightly higher with increase of load and back pressure at low engine speed condition. However, under high speed conditions, CO reduced significantly with increasing backpressure for all load conditions. The odor level was similar or a little higher with increasing backpressure for all engine speed and load conditions. Hence, backpressure up to a certain level is not detrimental for a CI engine.

Assessment of the molecular structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O using vibrational spectroscopy

The structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O, a borate–carbonate of calcium and magnesium has been assessed using vibrational spectroscopy. Assignment of bands is undertaken by comparison with the data from other published results. Intense Raman band at 1134 cm−1 with a shoulder at 1123 cm−1 is assigned to the symmetric stretching mode. The Raman spectrum displays bands at 1479, 1524 and 1560 cm−1 which are assigned to the antisymmetric stretching vibrations. The observation of multiple carbonate stretching bands supports the concept that the carbonate units are non-equivalent. The Raman band at 968 cm−1 with a shoulder at 950 cm−1 is assigned to the symmetric stretching mode of trigonal boron. Raman bands at 627 and 651 cm−1 are assigned to the out-of-plane bending modes of trigonal and tetrahedral boron. Raman spectroscopy coupled with infrared spectroscopy enables the molecular structure of the mineral sakhaite to be assessed.

Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O – a mineral found in lithium bearing pegmatites

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O from Boa Vista mine, Galiléia, Brazil and to assess the molecular structure of the mineral. The phosphate mineral ludlamite has been characterized by EMP-WDS, Raman and infrared spectroscopic measurements. The mineral is shown to be a ferrous phosphate with some minor substitution of Mg and Mn. Raman bands at 917 and 950 cm−1 are assigned to the symmetric stretching mode of and units. Raman bands at 548, 564, 599 and 634 cm−1 are assigned to the ν4 bending modes. Raman bands at 2605, 2730, 2896 and 3190 cm−1 and infrared bands at 2623, 2838, 3136 and 3185 cm−1 are attributed to water stretching vibrations. By using a Libowitzky empirical function, hydrogen bond distances are calculated from the OH stretching wavenumbers. Strong hydrogen bonds in the structure of ludlamite are observed as determined by their hydrogen bond distances. The application of infrared and Raman spectroscopy to the study of ludlamite enables the molecular structure of the pegmatite mineral ludlamite to be assessed.

Sitting-time, physical activity and depressive symptoms in mid-aged women

Background: Associations between sitting-time and physical activity (PA) with depression are unclear. Purpose: To examine concurrent and prospective associations between both sitting-time and PA with prevalent depressive symptoms in mid-aged Australian women. Methods: Data were from 8,950 women, aged 50-55 years in 2001, who completed mail surveys in 2001, 2004, 2007 and 2010. Depressive symptoms were assessed using the Center for Epidemiological Studies Depression questionnaire. Associations between sitting-time (≤4, >4-7, >7 hrs/day) and PA (none, some, meeting guidelines) with depressive symptoms (symptoms/no symptoms) were examined in 2011 in concurrent and lagged mixed effect logistic modeling. Both main effects and interaction models were developed. Results: In main effects modeling, women who sat >7 hrs/day (OR 1.47, 95%CI 1.29-1.67) and women who did no PA (OR 1.99, 95%CI 1.75-2.27) were more likely to have depressive symptoms than women who sat ≤4 hrs/day and who met PA guidelines, respectively. In interaction modeling, the likelihood of depressive symptoms in women who sat >7 hrs/day and did no PA was triple that of women who sat ≤4 hrs/day and met PA guidelines (OR 2.96, 95%CI 2.37-3.69). In prospective main effects and interaction modeling, sitting-time was not associated with depressive symptoms, but women who did no PA were more likely than those who met PA guidelines to have future depressive symptoms (OR 1.26, 95%CI 1.08-1.47). Conclusions: Increasing PA to a level commensurate with PA guidelines can alleviate current depression symptoms and prevent future symptoms in mid-aged women. Reducing sitting-time may ameliorate current symptoms.

Furan substituted diketopyrrolopyrrole and thienylenevinylene based low band gap copolymer for high mobility organic thin film transistors

A novel solution processable donor-acceptor (D-A) based low band gap polymer semiconductor poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4- c]pyrrole-1,4-dione-alt-thienylenevinylene} (PDPPF-TVT), was designed and synthesized by a Pd-catalyzed Stille coupling route. An electron deficient furan based diketopyrrolopyrrole (DPP) block and electron rich thienylenevinylene (TVT) donor moiety were attached alternately in the polymer backbone. The polymer exhibited good solubility, film forming ability and thermal stability. The polymer exhibits wide absorption bands from 400 nm to 950 nm (UV-vis-NIR region) with absorption maximum centered at 782 nm in thin film. The optical band gap (Eoptg) calculated from the polymer film absorption onset is around 1.37 eV. The π-energy band level (ionization potential) calculated by photoelectron spectroscopy in air (PESA) for PDPPF-TVT is around 5.22 eV. AFM and TEM analyses of the polymer reveal nodular terrace morphology with optimized crystallinity after 200 °C thermal annealing. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The highest hole mobility of 0.13 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices with on/off ratios in the range of 10 6-10 7. This work reveals that the replacement of thiophene by furan in DPP copolymers exhibits such a high mobility, which makes DPP furan a promising block for making a wide range of promising polymer semiconductors for broad applications in organic electronics.

Predictors of mental health in midlife and older women : results from the Australian Healthy Aging of Women Study

Purpose: To examine the extent to which socio-demographic characteristics, modifiable lifestyle factors and health status influence the mental health of midlife and older Australian women from the Australian Healthy Aging of Women (HOW) study. Methods: Data on health status, chronic disease and modifiable lifestyle factors were collected from a random sample of 340 women aged 40-65 years, residing in Queensland, Australia in 2011. Structural equation modelling (SEM) was used to measure the effect of a range of socio-demographic characteristics (marital status, age, income), modifiable lifestyle factors (caffeine intake, alcohol consumption, exercise, physical activity, sleep), and health markers (self-reported physical health, history of chronic illness) on the latent construct, mental health. Mental health was evaluated using the Medical Outcomes Study Short Form 12 (SF-12®) and the Center for Epidemiologic Studies Depression Scale (CES-D). Results: The model was a good fit for the data (χ2 = 40.166, df =312, p 0.125, CFI = 0.976, TLI = 0.950, RMSEA = 0.030, 90% CI = 0.000-0.053); the model suggested mental health was negatively influenced by sleep disturbance (β = -0.628), sedentary lifestyle (β = -0.137), having been diagnosed with one or more chronic illnesses (β = -0.203), and poor self-reported physical health (β = - 0.161). While mental health was associated with sleep, it was not correlated with many other lifestyle factors (BMI (β = -0.050), alcohol consumption (β = 0.079), or cigarette smoking (β = 0.008)) or background socio-demographic characteristics (age (β = 0.078), or income (β = -0.039)). Conclusion: While research suggests that it is important to engage in a range health promoting behaviours to preserve good health, we found that only sleep disturbance, physical health, chronic illness and level of physical activity predicted current mental health. However, while socio-demographic characteristics and modifiable lifestyle factors seemed to have little direct impact on mental health, they probably had an indirect effect.

A multicenter study on chronic cough in children : burden and etiologies based on a standardized management pathway

Background While the burden of chronic cough in children has been documented, etiologic factors across multiple settings and age have not been described. In children with chronic cough, we aimed (1) to evaluate the burden and etiologies using a standard management pathway in various settings, and (2) to determine the influence of age and setting on disease burden and etiologies and etiology on disease burden. We hypothesized that the etiology, but not the burden, of chronic cough in children is dependent on the clinical setting and age. Methods From five major hospitals and three rural-remote clinics, 346 children (mean age 4.5 years) newly referred with chronic cough (> 4 weeks) were prospectively managed in accordance with an evidence-based cough algorithm. We used a priori definitions, timeframes, and validated outcome measures (parent-proxy cough-specific quality of life [PC-QOL], a generic QOL [pediatric quality of life (PedsQL)], and cough diary). Results The burden of chronic cough (PC-QOL, cough duration) significantly differed between settings (P = .014, 0.021, respectively), but was not influenced by age or etiology. PC-QOL and PedsQL did not correlate with age. The frequency of etiologies was significantly different in dissimilar settings (P = .0001); 17.6% of children had a serious underlying diagnosis (bronchiectasis, aspiration, cystic fibrosis). Except for protracted bacterial bronchitis, the frequency of other common diagnoses (asthma, bronchiectasis, resolved without specific-diagnosis) was similar across age categories. Conclusions The high burden of cough is independent of children’s age and etiology but dependent on clinical setting. Irrespective of setting and age, children with chronic cough should be carefully evaluated and child-specific evidence-based algorithms used.