1-Naphthyl- and mesityltellurium(IV,II) derivatives of small bite chelating organic ligands: effect of steric bulk and intramolecular secondary bonding interaction on molecular geometry and supramolecular association

The synthesis and characterization of unsymmetric diorganotellurium compounds containing a sterically demanding I-naphthyl or
mesitylligand and a small bite chelating organic ligand capable of 1,4-Te···N(O) intramolecular interaction is described. The reaction
of ArTeCl₃ (Ar = I-C_lOH₇, Np; 2,4,6-Me₃C₆H_2' Mes) with (SB)HgCI [SB = the Schiff base, 2-(4,4'-N0₂C₆H₄CH=NC₆H₃-Me)] or a methyl ketone (RCOCH₃) afforded the corresponding dichlorides (SB)ArTeCI₂ (Ar = Np, 1Aa; Mes, 1Ba) or (RCOCH₂)ArTeCl₂ (Ar = Np; R = Ph (2Aa), Me (3Aa), Np (4Aa); Ar = Mes, R = Ph (2Ba)). Reduction of 1Aa and 1Ba by Na₂S₂0₅ readily gave the tellurides (SB)ArTe (Ar = Np (1A), Mes, (1B) but that of dichlorides derived from methylketones was complicated due to partial decomposition to tellurium powder and diarylditelluride (Ar₂Te₂), resulting in poor yields of the corresponding tellurides 2A, 2B and 3A. Oxidation of the isolated tellurides with S0₂Cl₂, Br₂ and I₂ yielded the corresponding dihalides. All the synthesized compounds have been characterized with the help of IR, ¹H, ^l3C, and ¹²⁵Te NMR and in the case of 2Aa, and 2Ba by X-ray crystallography. Appearance of only one ¹²⁵Te signal indicated that the unsymmetric derivatives were stable to disproportionation to symmetric species. Intramolecular 1,4-Te· . ·0 secondary bonding interactions (SBIs) are exhibited in the crystal structures of both the tellurium(IV) dichlorides, 2Aa, and 2Ba. Steric repulsion of the mesityl group in the latter dominates over lone pair-bond pair repulsion, resulting in significant widening of the equatorial C-Te-C angle. This appears to be responsible for the lack of Te· . ·CI involved supramolecular associations in the crystal structure of 2Ba.

Parent-reported health status of overweight and obese Australian primary school children: a cross-sectional population survey

Introduction: Childhood overweight/obesity is associated with poor physical and psychosocial health in clinical samples. However, there is little information on the health status of overweight and obese children in the community, who now represent a large proportion of the child population. We examined parent-reported child health and well-being and parent concern about child weight by body mass index (BMI) category in a population sample of primary school children.

Design: A stratified two-stage random cluster sample of 24 primary schools representative of the state of Victoria, Australia.

Measures: BMI (weight/height2) transformed to normalised Z-scores using the 1990 UK Growth Reference; the Child Health Questionnaire (CHQ), a 13-scale 50-item parent-completed measure of health and well-being; parent self-reported height and weight; parent concern about child's weight.

Results: Data were available for 2863 children aged 5-13 y (50.5% male), of whom 17% were overweight and 5.7% obese. Using logistic regression analyses with 'normal weight' as the referent category, obese boys were at greater risk of poor health (ie <15th centile) on seven of the 12 CHQ scales: Physical Functioning (odds ratio (OR) 2.8), Bodily Pain (OR 1.8), General Health (OR 3.5), Mental Health (OR 2.8), Self Esteem (OR 1.8), Parent Impact¾Emotional (OR 1.7) and Parent Impact¾Time (OR 1.9). Obese girls were at greater risk of poor health on only two scales: General Health (OR 2.1) and Self Esteem (OR 1.8). Forty-two percent of parents with obese children and 81% with overweight children did not report concern about their child's weight. Parents were more likely to report concern if the child was obese (OR 21.3), overweight (OR 3.5) or underweight (OR 5.4) than normal weight (P<0.05). Concern was not related to child gender, parental BMI or parental education after controlling for child BMI. Perceived health and well-being of overweight/obese children varied little by weight category of the reporting parent (overweight vs non-overweight).

Conclusions: Parents were more likely to report poorer health and well-being for overweight and obese children (particularly obese boys). Parental concern about their child's weight was strongly associated with their child's actual BMI. Despite this, most parents of overweight and obese children did not report poor health or well-being, and a high proportion did not report concern. This has implications for the early identification of such children and the success of prevention and intervention efforts.

Melding: a new alternative to adhesive bonding

Melding, a novel method for joining composites is examined in this paper. The method uses Quickstep ™ technology to retain partially cured areas of a composite laminate, enabling subsequent bonding operations. The effect of melding on the mechanical properties of the composite has been investigated. Flexural testing of HexPly 914 indicates consistent properties throughout a melded section. Flexural strength values of 1.36±O.03 GPa compared to 1.35±O.03 GPa for a standard laminate were recorded. In order to achieve sufficient bond strength, the portion of the composite to be joined must have a significant proportion of uncured matrix. The ability of Hexply 914 prepreg to retain sufficient bonding potential to form a strong joint was also investigated. HexPly 914 Lap Shear results indicated no significant variation in strength values between co-cured and melded joins, with a recorded
strength value of 15.0±0. 7 MPa.

Including the siblings of youth substance abusers in a parent-focused intervention : a pilot test of the best plus program

Substance use is common among young people and can escalate into significant problems for affected individuals and their families. Family responses can influence the course of youth substance use and its consequences for family members, including parents and siblings. Family-level interventions developed to date have neglected the important role that siblings can play. This article describes a pilot test of an intervention designed to assist parents and siblings affected by youth substance use and related problems. The BEST Plus intervention consisting of professionally-led, multifamily groups sequenced over eight sessions is described with reference to the intended therapeutic processes. Professionally observed and self-reported changes for family participants including siblings suggested that the program had a beneficial therapeutic impact. This evaluation of early impacts suggests the BEST Plus program
offers a promising means of assisting families to respond to substance use problems in young people.

Selective hydrogen bonding and hierarchical nanostructures in poly(hydroxyether of bisphenol A)/poly(ε-caprolactone)-block-poly(2-vinyl pyridine) blends

The phase behavior, hydrogen bonding interactions and morphology of poly(hydroxyether of bisphenol A) (phenoxy) and poly(var epsilon-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP) were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy and atomic force microscopy (AFM). In this A-b-B/C type block copolymer/homopolymer system, both P2VP and PCL blocks have favorable intermolecular interaction towards phenoxy via hydrogen bonding. However, the hydrogen bonding between P2VP and phenoxy is significantly stronger than that between PCL and phenoxy. Selective hydrogen bonding between phenoxy/P2VP pair at lower phenoxy contents and co-existence of two competitive hydrogen bonding interactions between phenoxy/P2VP and phenoxy/PCL pairs at higher phenoxy contents were observed in the blends. This leads to the formation of a variety of composition dependent nanostructures including wormlike, hierarchical and core–shell morphologies. The blends became homogeneous at 95 wt% phenoxy where both blocks of the PCL-b-P2VP were miscible with phenoxy due to hydrogen bonding. In the end, a model was proposed to explain the microphase morphology of blends based on the experimental results obtained. The swelling of the PCL-b-P2VP block copolymer by phenoxy due to selective hydrogen bonding causes formation of different microphases

Self-assembled complexes of poly(4-vinylphenol) and poly(ε-caprolactone)-block-poly(2-vinylpyridine) via competitive hydrogen bonding

Nanostructured complexes were prepared from poly(ε-caprolactone)-block-poly(2-vinylpyridine) (PCL-b-P2VP) and poly(4-vinylphenol) (PVPh) in tetrahydrofuran (THF). The phase behavior, specific interactions, and morphology were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). In this A-b-B/C type block copolymer/homopolymer system, both blocks of the PCL-b-P2VP block copolymer have favorable intermolecular interaction toward PVPh via hydrogen bonding, but the interaction between P2VP block and PVPh is significantly stronger than that between PCL block and PVPh. It was found that the disparity in competitive intermolecular interactions, specifically PVPh and P2VP block interact strongly whereas PVPh and PCL block interact weakly, leads to the formation of a variety of nanostructures depending on PVPh concentration. Spherical micelles of 30−40 nm in diameter were obtained in the complex with 10 wt % PVPh, followed by wormlike micelles with size in the order of 40−50 nm in the complexes with 30−60 wt % PVPh. At low PVPh concentrations, PCL interacts weakly with PVPh, whereas in the complexes containing more than 20 wt % PVPh, the PCL block began to interact considerably with PVPh, leading to the formation of composition-dependent nanostructures. The complex becomes homogeneous with PVPh content beyond 60 wt %, since a sufficient amount of PVPh is available to form hydrogen bonds with both PCL and P2VP. Finally, a model was proposed to explain the self-assembly and microphase morphology of these complexes based on the experimental results obtained. The competitive hydrogen-bonding interactions cause the self-assembly and formation of different microphase morphologies.

Nanostructure and hydrogen bonding in interpolyelectrolyte complexes of poly(ε-caprolactone)-block-poly(2-vinyl pyridine) and poly(acrylic acid)

Nanostructured poly(ε-caprolactone)-block-poly(2-vinyl pyridine) (PCL-b-P2VP)/poly(acrylic acid) (PAA) interpolyelectrolyte complexes (IPECs) were prepared by casting from THF/ethanol solution. The morphological behaviour of this amphiphilic block copolymer/polyelectrolyte complexes with respect to the composition was investigated in a solvent mixture. The phase behaviour, specific interactions and morphology were investigated using differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, optical microscopy (OM), dynamic light scattering (DLS) and atomic force microscopy (AFM). Micelle formation occurred due to the aggregation of hydrogen bonded P2VP block and polyelectrolyte (PAA) from non-interacted PCL blocks. It was observed that the hydrodynamic diameter (D_h) of the micelles in solution decreased with increasing PAA content up to 40 wt%. After 50 wt% PAA content, D_h again increased. The micelle formation in PCL-b-P2VP/PAA IPECs was due to the strong intermolecular hydrogen bonding between PAA homopolymer units and P2VP blocks of the block copolymer. The penetration of PAA homopolymers into the shell of the PCL-b-P2VP block copolymer micelles resulted in the folding of the P2VP chains, which in turn reduced the hydrodynamic size of the micelles. After the saturation of the shell with PAA homopolymers, the size of the micelles increased due to the absorption of added PAA onto the surface of the micelles.

Discrepancy between expected and actual child support payments : predicting the health and health-related quality of life of children living in low-income, single-parent families

Objective Although the amount and frequency of child support payments received by single parents are often erratic and fluctuate, no study to date has quantitatively explored how the discrepancy between expected and actual payments relates to child health. This study aims to examine whether the discrepancy between expected and actual child support payments predicts a range of child health outcomes, including global health, health-related quality of life, involvement in activities and parental psychological distress.

Methods This study used results from the Longitudinal Study of Australian Children, which included a sample of parents of children aged 4–5 years (n = 4983). The questionnaire was completed by the parent who spent the most time with the child and knew the child best. From the 4983 families, 332 low-income single parents reliant on welfare with a formal or informal child support order in place were identified.

Results After controlling for income, the discrepancy between expected and actual child support predicted school functioning, conduct problems, total mental health problems and involvement in activities. Discrepancy between expected and actual child support payments did not predict the remaining health-related quality of life domains, mental health domains, global child health or parental psychosocial distress.

Conclusion This was the first study to examine how the discrepancy between expected and actual child support payments relates to child health, providing important data on the effectiveness of the child support system for children's well-being. These findings highlight the potential impact of the discrepancy on school functioning, conduct problems, total mental health problems and involvement in activities.

Parent's views of the importance of making changes in settings where children spend time to prevent obesity

Aim : To examine the kinds of changes parents would like to see in those settings where children spend time (kindergartens and schools, child care centres and after-school care facilities, and the local neighbourhood) in policies and practices that impact on children’s risk of obesity, and to establish whether parents might be willing to advocate for changes in these settings.

Materials and Methods : 175 parents from five randomly selected primary schools and five randomly selected kindergartens located in suburbs of metropolitan Melbourne completed a questionnaire in which they rated the importance of a number of potential changes to promote healthy eating and increase physical activity in their children.

Results : Parents of children in kindergarten most commonly rated changes to the eating environment as important. In contrast, parents of primary school children believed changes related to both eating and physical activity in school were important. Ninety-five per cent of parents of kindergarten children and 89% of parents of primary school children believed it was possible for parents to bring about change to provide more opportunities for their child to eat more healthily and be more physically active. One in four parents reported that they had thought about or had tried to bring about changes in their community.

Conclusions : The findings suggest that mobilising parents to take an active role in advocating for change in those settings that have the potential to shape their children’s physical activity and eating behaviours may be feasible.

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

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

The reactivity of diorganotellurium oxides towards phenol and o-nitrophenol. Hypervalent and secondary bonding of four different product classes

The reaction of the diorganotellurium oxides R2TeO (R = Ph, p-MeOC6H4, p-Me2NC6H4) with phenol and o-nitrophenol produces diorganotellurium hydroxy phenolates, R2Te(OH)OPh (1, R = Ph; 2, R = p-MeOC6H4; 3, R = p-Me2NC6H4), diorganotellurium bis(phenolates) R2Te(OPh)2 (4, R = Ph; 5, R = p-MeOC6H4; 6, R = p-Me2NC6H4), tetraorganoditelluroxane bis(o-nitrophenolates), (R′O)R2TeOTeR2(OR′) (7, R = p-MeOC6H4; 8, R = p-Me2NC6H4; R′ = o-NO2C6H4), and a hexaphenyltritelluroxane bis(o-nitrophenolate) (R′O)Ph2TeOTePh2OTePh2(OR′) (9, R′ = o-NO2C6H4), respectively. The redistribution reactions of R2Te(OPh)2 (4, R = Ph; 5, R = p-MeOC6H4; 6, R = p-Me2NC6H4) with the corresponding diorganotellurium oxides R2TeO and diorganotellurium dichlorides R2TeCl2 (R = Ph, p-MeOC6H4, p-Me2NC6H4) give rise to the formation of moisture sensitive tetraorganoditelluroxane bis(phenolates) (PhO)R2TeOTeR2(OPh) (10, R = Ph; 11, R = p-MeOC6H4; 12, R = p-Me2NC6H4) and diorganotellurium chloro phenolates, R2Te(Cl)OPh (13, R = Ph; 14, R = p-MeOC6H4; 15, R = p-Me2NC6H4), respectively. The reaction of the diorganotellurium oxides R2TeO with the corresponding diorganotellurium dichlorides R2TeCl2 (R = Ph, p-MeOC6H4, p-Me2NC6H4) affords tetraorganoditelluroxane dichlorides ClR2TeOTeR2Cl (16, R = Ph; 17, R = p-MeOC6H4; 18, R = p-Me2NC6H4) as air-stable solid materials. The reactivity of 1–18 can be rationalized by the kinetic lability of the Te–O and Te–Cl bonds. Compounds 1–18 have been characterized by solution and solid-state 125Te NMR spectroscopy and 2, 4, 6, 7, 9, 17, and 18 have also been analyzed by X-ray crystallography.

Female labour force participation, fertility and infant mortality in Australia : some empirical evidence from Granger causality tests

This study applies Granger causality tests within a multivariate error correction framework to examine the relationship between female participation rates, infant mortality rates and fertility rates for Australia using annual data from 1960 to 2000. Decomposition of variance and impulse response functions are also considered. The main findings are twofold. First, in the short run there is unidirectional Granger causality running from the fertility rate to female labour force participation and from the infant mortality rate to female labour force participation while there is neutrality between the fertility rate and infant mortality rate. Second, in the long run both the fertility rate and infant mortality rate Granger cause female labour participation.