2-[(3,3-Dimethylindolin-2-ylidene)methyl]-4-[(3,3-dimethyl-3H-indol-1-ium-2-yl)methylidene]-3-oxocyclobut-1-en-1-olate chloroform disolvate

In the title squaraine dye solvate, C26H24N2O2·2CHCl3, the dye molecule is essentially planar, except for the methyl groups, having a maximum deviation over the 26-membered delocalized bond system of 0.060 (2) Å. It possesses crystallographic twofold rotational symmetry with the indole ring systems adopting a syn conformation. The molecular structure features intramolecular N-HO hydrogen bonds enclosing conjoint S7 ring motifs about one of the dioxocyclobutene O atoms, while the two chloroform solvent molecules are linked to the second O atom through C-HO hydrogen bonds.

Hydrogen bonding in two ammonium salts of 5-sulfosalicylic acid : ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate and triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate

The structures of two ammonium salts of 3-carboxy-4-hydroxybenzenesulfonic acid (5-sulfosalicylic acid, 5-SSA) have been determined at 200 K. In the 1:1 hydrated salt, ammonium 3-carboxy-4-hydroxybenzenesulfonate monohydrate, NH4+·C7H5O6S-·H2O, (I), the 5-SSA- monoanions give two types of head-to-tail laterally linked cyclic hydrogen-bonding associations, both with graph-set R44(20). The first involves both carboxylic acid O-HOwater and water O-HOsulfonate hydrogen bonds at one end, and ammonium N-HOsulfonate and N-HOcarboxy hydrogen bonds at the other. The second association is centrosymmetric, with end linkages through water O-HOsulfonate hydrogen bonds. These conjoined units form stacks down c and are extended into a three-dimensional framework structure through N-HO and water O-HO hydrogen bonds to sulfonate O-atom acceptors. Anhydrous triammonium 3-carboxy-4-hydroxybenzenesulfonate 3-carboxylato-4-hydroxybenzenesulfonate, 3NH4+·C7H4O6S2-·C7H5O6S-, (II), is unusual, having both dianionic 5-SSA2- and monoanionic 5-SSA- species. These are linked by a carboxylic acid O-HO hydrogen bond and, together with the three ammonium cations (two on general sites and the third comprising two independent half-cations lying on crystallographic twofold rotation axes), give a pseudo-centrosymmetric asymmetric unit. Cation-anion hydrogen bonding within this layered unit involves a cyclic R33(8) association which, together with extensive peripheral N-HO hydrogen bonding involving both sulfonate and carboxy/carboxylate acceptors, gives a three-dimensional framework structure. This work further demonstrates the utility of the 5-SSA- monoanion for the generation of stable hydrogen-bonded crystalline materials, and provides the structure of a dianionic 5-SSA2- species of which there are only a few examples in the crystallographic literature.

Blocking layer optimisation of poly(3-hexylthiopene)based solid state dye sensitized solar cells

The optimisation study of the fabrication of a compact TiO2 blocking layer (via Spray Pyrolysis Deposition) for poly (3-hexylthiopene) (P3HT) for Solid State Dye Sensitized Solar Cells (SDSCs) is reported. We used a novel spray TiO2 precursor solution composition obtained by adding acetylacetone to a conventional formulation (Diisopropoxytitanium bis (acetylacetonate) in ethanol). By Scanning Electron Microscopy a TiO2 layer with compact morphology and thickness of around 100 nmis shown. Through a Tafel plot analysis an enhancement of the device diode-like behaviour induced by the acetylacetone blocking layer respect to the conventional one is observed. Significantly, the device fabricatedwith the acetylacetone blocking layer shows an overall increment of the cell performance with respect to the cellwith the conventional one (DJsc/Jsc = +13.8%, DFF/FF = +39.7%, DPCE/PCE = +55.6%). A conversion efficiency optimumis found for 15 successive spray cycles where the diode-like behaviour of the acetylacetone blocking layer is more effective. Over three batches of cells (fabricated with P3HT and dye D35) an average conversion efficiency value of 3.9% (under a class A sun simulator with 1 sun A.M. 1.5 illumination conditions) was measured. From the best cell we fabricated a conversion efficiency value of 4.5% was extracted. This represents a significant increment with respect to previously reported values for P3HT/dye D35 based SDSCs.

Characterization of the sulphate mineral amarantite Fe3 2 3+ (SO4)O 7H2O using infrared, Raman spectroscopy and thermogravimetry

The mineral amarantite Fe23+(SO4)O∙7H2O has been studied using a combination of techniques including thermogravimetry, electron probe analyses and vibrational spectroscopy. Thermal analysis shows decomposition steps at 77.63, 192.2, 550 and 641.4°C. The Raman spectrum of amarantite is dominated by an intense band at 1017 cm-1 assigned to the SO42- ν1 symmetric stretching mode. Raman bands at 1039, 1054, 1098, 1131, 1195 and 1233 cm-1 are attributed to the SO42- ν3 antisymmetric stretching modes. Very intense Raman band is observed at 409 cm-1 with shoulder bands at 399, 451 and 491 cm-1 are assigned to the v2 bending modes. A series of low intensity Raman bands are found at 543, 602, 622 and 650 cm-1 are assigned to the v4 bending modes. A very sharp Raman band at 3529 cm-1 is assigned to the stretching vibration of OH units. A series of Raman bands observed at 3025, 3089, 3227, 3340, 3401 and 3480 cm-1 are assigned to water bands. Vibrational spectroscopy enables aspects of the molecular structure of the mineral amarantite to be ascertained.

Raman spectroscopic study of the mineral qingheiite Na2(Mn2+,Mg,Fe2+)2(Al,Fe3+)(PO4)3, a pegmatite phosphate mineral from Santa Ana pegmatite, Argentina

The pegmatite mineral qingheiite Na2(Mn2+,Mg,Fe2+)2(Al,Fe3+)(PO4)3 has been studied by a combination of SEM and EMP, Raman and infrared spectroscopy. The studied sample was collected from the Santa Ana pegmatite, Argentina. The mineral occurs as a primary mineral in lithium bearing pegmatite, in association with beausite and lithiophilite. The Raman spectrum is characterized by a very sharp intense Raman band at 980 cm�1 assigned to the PO3�4 symmetric stretching mode. Multiple Raman bands are observed in the PO3�4 antisymmetric stretching region, providing evidence for the existence of more than one phosphate unit in the structure of qingheiite and evidence for the reduction in symmetry of the phosphate units. This concept is affirmed by the number of bands in the m4 and m2 bending regions. No intensity was observed in the OH stretching region in the Raman spectrum but significant intensity is found in the infrared spectrum. Infrared bands are observed at 2917, 3195, 3414 and 3498 cm�1 are assigned to water stretching vibrations. It is suggested that some water is coordinating the metal cations in the structure of qingheiite.

The individual and interactive relationship between long chain omega-3 polyunsaturated fatty acids and physical activity as predictors of cognition in cognitively impaired and non-impaired older adults

Alterations in cognitive function are characteristic of the aging process in humans and other animals. However, the nature of these age related changes in cognition is complex and is likely to be influenced by interactions between genetic predispositions and environmental factors resulting in dynamic fluctuations within and between individuals. These inter and intra-individual fluctuations are evident in both so-called normal cognitive aging and at the onset of cognitive pathology. Mild Cognitive Impairment (MCI), thought to be a prodromal phase of dementia, represents perhaps the final opportunity to mitigate cognitive declines that may lead to terminal conditions such as dementia. The prognosis for people with MCI is mixed with the evidence suggesting that many will remain stable within 10-years of diagnosis, many will improve, and many will transition to dementia. If the characteristics of people who do not progress to dementia from MCI can be identified and replicated in others it may be possible to reduce or delay dementia onset, thus reducing a growing personal and public health burden. Furthermore, if MCI onset can be prevented or delayed, the burden of cognitive decline in aging populations worldwide may be reduced. A cognitive domain that is sensitive to the effects of advancing age, and declines in which have been shown to presage the onset of dementia in MCI patients, is executive function. Moreover, environmental factors such as diet and physical activity have been shown to affect performance on tests of executive function. For example, improvements in executive function have been demonstrated as a result of increased aerobic and anaerobic physical activity and, although the evidence is not as strong, findings from dietary interventions suggest certain nutrients may preserve or improve executive functions in old age. These encouraging findings have been demonstrated in older adults with MCI and their non-impaired peers. However, there are some gaps in the literature that need to be addressed. For example, little is known about the effect on cognition of an interaction between diet and physical activity. Both are important contributors to health and wellbeing, and a growing body of evidence attests to their importance in mental and cognitive health in aging individuals. Yet physical activity and diet are rarely considered together in the context of cognitive function. There is also little known about potential underlying biological mechanisms that might explain the physical activity/diet/cognition relationship. The first aim of this program of research was to examine the individual and interactive role of physical activity and diet, specifically long chain polyunsaturated fatty acid consumption(LCn3) as predictors of MCI status. The second aim is to examine executive function in MCI in the context of the individual and interactive effects of physical activity and LCn3.. A third aim was to explore the role of immune and endocrine system biomarkers as possible mediators in the relationship between LCn3, physical activity and cognition. Study 1a was a cross-sectional analysis of MCI status as a function of erythrocyte proportions of an interaction between physical activity and LCn3. The marine based LCn3s eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) have both received support in the literature as having cognitive benefits, although comparisons of the relative benefits of EPA or DHA, particularly in relation to the aetiology of MCI, are rare. Furthermore, a limited amount of research has examined the cognitive benefits of physical activity in terms of MCI onset. No studies have examined the potential interactive benefits of physical activity and either EPA or DHA. Eighty-four male and female adults aged 65 to 87 years, 50 with MCI and 34 without, participated in Study 1a. A logistic binary regression was conducted with MCI status as a dependent variable, and the individual and interactive relationships between physical activity and either EPA or DHA as predictors. Physical activity was measured using a questionnaire and specific physical activity categories were weighted according to the metabolic equivalents (METs) of each activity to create a physical activity intensity index (PAI). A significant relationship was identified between MCI outcome and the interaction between the PAI and EPA; participants with a higher PAI and higher erythrocyte proportions of EPA were more likely to be classified as non-MCI than their less active peers with less EPA. Study 1b was a randomised control trial using the participants from Study 1a who were identified with MCI. Given the importance of executive function as a determinant of progression to more severe forms of cognitive impairment and dementia, Study 1b aimed to examine the individual and interactive effect of physical activity and supplementation with either EPA or DHA on executive function in a sample of older adults with MCI. Fifty male and female participants were randomly allocated to supplementation groups to receive 6-months of supplementation with EPA, or DHA, or linoleic acid (LA), a long chain polyunsaturated omega-6 fatty acid not known for its cognitive enhancing properties. Physical activity was measured using the PAI from Study 1a at baseline and follow-up. Executive function was measured using five tests thought to measure different executive function domains. Erythrocyte proportions of EPA and DHA were higher at follow-up; however, PAI was not significantly different. There was also a significant improvement in three of the five executive function tests at follow-up. However, regression analyses revealed that none of the variance in executive function at follow-up was predicted by EPA, DHA, PAI, the EPA by PAI interaction, or the DHA by PAI interaction. The absence of an effect may be due to a small sample resulting in limited power to find an effect, the lack of change in physical activity over time in terms of volume and/or intensity, or a combination of both reduced power and no change in physical activity. Study 2a was a cross-sectional study using cognitively unimpaired older adults to examine the individual and interactive effects of LCn3 and PAI on executive function. Several possible explanations for the absence of an effect were identified. From this consideration of alternative explanations it was hypothesised that post-onset interventions with LCn3 either alone or in interation with self-reported physical activity may not be beneficial in MCI. Thus executive function responses to the individual and interactive effects of physical activity and LCn3 were examined in a sample of older male and female adults without cognitive impairment (n = 50). A further aim of study 2a was to operationalise executive function using principal components analysis (PCA) of several executive function tests. This approach was used firstly as a data reduction technique to overcome the task impurity problem, and secondly to examine the executive function structure of the sample for evidence of de-differentiation. Two executive function components were identified as a result of the PCA (EF 1 and EF 2). However, EPA, DHA, the PAI, or the EPA by PAI or DHA by PAI interactions did not account for any variance in the executive function components in subsequent hierarchical multiple regressions. Study 2b was an exploratory correlational study designed to explore the possibility that immune and endocrine system biomarkers may act as mediators of the relationship between LCn3, PAI, the interaction between LCn3 and PAI, and executive functions. Insulin-like growth factor-1 (IGF-1), an endocrine system growth hormone, and interleukin-6 (IL-6) an immune system cytokine involved in the acute inflammatory response, have both been shown to affect cognition including executive functions. Moreover, IGF-1 and IL-6 have been shown to be antithetical in so far as chronically increased IL-6 has been associated with reduced IGF-1 levels, a relationship that has been linked to age related morbidity. Further, physical activity and LCn3 have been shown to modulate levels of both IGF-1 and IL-6. Thus, it is possible that the cognitive enhancing effects of LCn3, physical activity or their interaction are mediated by changes in the balance between IL-6 and IGF-1. Partial and non-parametric correlations were conducted in a subsample of participants from Study 2a (n = 13) to explore these relationships. Correlations of interest did not reach significance; however, the coefficients were quite large for several relationships suggesting studies with larger samples may be warranted. In summary, the current program of research found some evidence supporting an interaction between EPA, not DHA, and higher energy expenditure via physical activity in differentiating between older adults with and without MCI. However, a RCT examining executive function in older adults with MCI found no support for increasing EPA or DHA while maintaining current levels of energy expenditure. Furthermore, a cross-sectional study examining executive function in older adults without MCI found no support for better executive function performance as a function of increased EPA or DHA consumption, greater energy expenditure via physical activity or an interaction between physical activity and either EPA or DHA. Finally, an examination of endocrine and immune system biomarkers revealed promising relationships in terms of executive function in non-MCI older adults particularly with respect to LCn3 and physical activity. Taken together, these findings demonstrate a potential benefit of increasing physical activity and LCn3 consumption, particularly EPA, in mitigating the risk of developing MCI. In contrast, no support was found for a benefit to executive function as a result of increased physical activity, LCn3 consumption or an interaction between physical activity and LCn3, in participants with and without MCI. These results are discussed with reference to previous findings in the literature including possible limitations and opportunities for future research.

The Tashi project 2004-2010 : developing methods for creating theatre works that fully engage children aged between 3 and 10

Over a seven-year period, Mark Radvan directed a suite of children’s theatre productions adapted from the original Tashi stories by Australian writers Anna and Barbara Fienberg. The Tashi Project’s repertoire of plays performed to over 40,000 children aged between 3 and 10 years old, and their carers, in seasons at the Out of the Box Festival, at Brisbane Powerhouse and in venues across Australia in two interstate tours in 2009 and 2010. The project investigated how best to combine an exploration of theatrical forms and conventions, with a performance style evolved in a specially developed training program and a deliberate positioning of young children as audiences capable of sophisticated readings of action, symbol, theme and character. The results of this project show that when brought into appropriate relationship with the theatre artists, young children aged 3-5 can engage with sophisticated narrative forms, and with the right contextual framing they enjoy heightened dramatic and emotional tension, bringing to the event sustained and highly engaged concentration. Older children aged 6-10 also bring sustained and heightened engagement to the same stories, providing that other more sophisticated dramatic elements are woven into the construction of the performances, such as character, theme and style.

The molecular structure of the phosphate mineral senegalite Al2(PO4)(OH)3⋅3H2O – A vibrational spectroscopic study

We have studied the mineral senagalite, a hydrated hydroxy phosphate of aluminium with formula Al2(PO4)(OH)3⋅3H2O using a combination of electron microscopy and vibrational spectroscopy. Senegalite crystal aggregates shows tabular to prismatic habitus and orthorhombic form. The Raman spectrum is dominated by an intense band at 1029 cm−1 assigned to the PO43- ν1 symmetric stretching mode. Intense Raman bands are found at 1071 and 1154 cm−1 with bands of lesser intensity at 1110, 1179 and 1206 cm−1 and are attributed to the PO43- ν3 antisymmetric stretching vibrations. The infrared spectrum shows complexity with a series overlapping bands. A comparison is made with spectra of other aluminium containing phosphate minerals such as augelite and turquoise. Multiple bands are observed for the phosphate bending modes giving support for the reduction of symmetry of the phosphate anion. Vibrational spectroscopy offers a means for the assessment of the structure of senagalite.

Vibrational spectroscopic characterization of the phosphate mineral kulanite Ba(Fe2+,Mn2+,Mg)2(Al,Fe3+)2(PO4)3(OH)3

The mineral kulanite BaFe2Al2(PO4)3(OH)3, a barium iron aluminum phosphate, has been studied by using a combination of electron microscopy and vibrational spectroscopy. Scanning electron microscopy with EDX shows the mineral is homogenous with no other phases present. The Raman spectrum is dominated by an intense band at 1022 cm−1 assigned to the PO43-ν1 symmetric stretching mode. Low intensity Raman bands at 1076, 1110, 1146, 1182 cm−1 are attributed to the PO43-ν3 antisymmetric stretching vibrations. The infrared spectrum shows a complex spectral profile with overlapping bands. Multiple phosphate bending vibrations supports the concept of a reduction in symmetry of the phosphate anion. Raman spectrum at 3211, 3513 and 3533 cm−1 are assigned to the stretching vibrations of the OH units. Vibrational spectroscopy enables aspects on the molecular structure of kulanite to be assessed.

Youth Alcohol and Drug Practice Guide 3 : Practice Strategies and Interventions

This guide canvasses a range of practice strategies and interventions utilised by workers and services who engage with young people experiencing problematic AOD use whilst also exploring the many and varied challenges associated with this type of work.

Integration-segregation decisions under general value functions: "create your own bundle - choose 1, 2, or all 3!",

Whether to keep products segregated (e.g., unbundled) or integrate some or all of them (e.g., bundle) has been a problem of profound interest in areas such as portfolio theory in finance, risk capital allocations in insurance and marketing of consumer products. Such decisions are inherently complex and depend on factors such as the underlying product values and consumer preferences, the latter being frequently described using value functions, also known as utility functions in economics. In this paper, we develop decision rules for multiple products, which we generally call ‘exposure units’ to naturally cover manifold scenarios spanning well beyond ‘products’. Our findings show, e.g. that the celebrated Thaler's principles of mental accounting hold as originally postulated when the values of all exposure units are positive (i.e. all are gains) or all negative (i.e. all are losses). In the case of exposure units with mixed-sign values, decision rules are much more complex and rely on cataloging the Bell number of cases that grow very fast depending on the number of exposure units. Consequently, in the present paper, we provide detailed rules for the integration and segregation decisions in the case up to three exposure units, and partial rules for the arbitrary number of units.

The relationship between children's emotional and cognitive self-regulation at 2 to 3 years and prosocial behavior in the early years of school

This study used data from Growing Up in Australia: The Longitudinal Study of Australian Children (LSAC) to investigate how parent report of children’s emotional and cognitive regulation at age 2-3 years was associated with teacher ratings of children’s prosocial behaviors in the early years of school. A sample of 2,392 children was drawn from the LSAC Birth Cohort for the analyses. The analyses used structural equation modeling to estimate parameters of the relationships between key variables. Within the model, estimates of mother-reported emotional and cognitive regulation at age 2 to 3 years were significantly associated with teacher-reported prosocial behavior at 6 to 7 years. Emotional regulation was a slightly stronger indicator of prosocial behavior than cognitive regulation. Being female and from a family with a higher socioeconomic position were also associated with higher levels of prosocial behavior. Results are discussed in relation to the role of early childhood teachers in fostering children’s self-regulatory behaviors and in providing environments in which empathic and prosocial behaviors are modeled, guided, and scaffolded so that foundations are laid for caring behaviors to be understood and internalized by children.

Editor 3.0: Redesigining the YAWL user interface

It has long been a concern that the wider uptake of the YAWL environment may have been hindered by the usability issues identified in the current Process Editor. As a consequence, it was decided that the Editor be completely rewritten to address those usability limitations. The result has been the implementation of a new YAWL Process Editor architecture that creates a clear separation between the User Interface component layer and the core processing back end, facilitating the redesign of the default user interface. This new architecture also supports the development of multiple User Interface front ends for specific contexts that take advantage of the core capabilities the new Editor architecture has to offer.

Evidence for the adsorption of molecules at special sites located at copper/zinc oxide interfaces. Part 3. -- Fourier-transform infrared study of methyl formate adsorption on reduced and oxidised Cu/ZnO/SiO2 catalysts

FTIR spectra are reported of methyl formate adsorbed at 295 K on ZnO/SiO2, reduced Cu/ZnO/SiO2 and on Cu/ZnO/SiO2 which had been preoxidised by exposure to nitrous oxide. Methyl formate on ZnO/SiO2 gave adsorbed zinc formate species and strongly physisorbed molecular methanol on silica. The comparable reaction of methyl formate with reduced Cu/ZnO/SiO2 catalyst produced bridging formate species on copper and a diminished quantity of zinc formate relative to that formed on ZnO/SiO2 catalyst. This effect is explained in terms of site blockage on the ZnO surface by small copper clusters. Addition of methyl formate to a reoxidised Cu/ZnO/SiO2 catalyst produced a considerably greater amount of formate species on zinc oxide and methoxy groups on copper were detected. The increase in concentration of zinc formate species was rationalised in terms of rearrangement of unidentate copper formate species to become bonded to copper and zinc oxide sites located at the interface between these two components.

Molecular cocrystals of 5-(4-bromophenyl)-1,3,4-thiadiazol-2-amine: hydrogen bonding in the structures of the 1:1 adduct with 2-(naphthalen-2-yloxy)acetic acid and the salt with 3,5-dinitrobenzoic acid

The structures of the anhydrous products from the interaction of 2-amino-5-(4-bromophenyl)-1,3,4-thiadiazole with (2-naphthoxy)acetic acid, the 1:1 adduct C8H6BrN3S . C12H10O3 (I) and 3,5-dinitrobenzoic acid, the salt C8H7BrN3S+ C7H3N2O6- (II) have been determined. In the adduct (I), a heterodimer is formed through a cyclic hydrogen-bonding motif [graph set R2/2(8)], involving carboxylic acid O-H...N(hetero)and amine N-H...O(carboxyl) interactions. The heterodimers are essentially planar with a thiadiazole to naphthyl ring dihedral angle of 15.9(2)deg. and the intramolecular thiadiazole to phenyl ring angle of 4.7(2)deg. An amine N-H...N(hetero) hydrogen bond between the heterodimers generates a one-dimensional chain structure extending down [001]. Also present are weak benzene-benzene and naphthalene-naphthalene pi-pi stacking interactions down the b axis [minimum ring centroid separation, 3.936(3) Ang.]. With the salt (II), the cation-anion association is also through a cyclic R2/2(8) motif but involving duplex N-H...O(carboxyl) hydrogen bonds, giving a heterodimer which is close to planar [dihedral angles between the thiadiazole ring and the two benzene rings, 5.00(16)deg. (intra) and 7.23(15)deg. (inter)]. A secondary centrosymmetric cyclic N-H...O(carboxyl) hydrogen-bonding association involving the second amino H-atom generates a heterotetramer. Also present in the crystal are weak pi-pi i-\p interactions between thiadiazolium rings [minimum ring centroid separation, 3.936(3)Ang.], as well as a short Br...O(nitro) interaction [3.314(4)Ang.]. The two structures reported here now provide a total of three crystallographically characterized examples of co-crystalline products from the interaction of 2-amino-5-(4-bromophenyl)-1,3,4-thiadiazole with carboxylic acids, of which only one involves proton-transfer.