950 resultados para Unsaturated bonds
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Executive Summary The Australian Psychological Society categorically condemns the practice of detaining child asylum seekers and their families, on the grounds that it is not commensurate with psychological best practice concerning children’s development and mental health and wellbeing. Detention of children in this fashion is also arguably a violation of the UN Convention on the Rights of the Child. A thorough review of relevant psychological theory and available research findings from international research has led the Australian Psychological Society to conclude that: • Detention is a negative socialisation experience. • Detention is accentuates developmental risks. • Detention threatens the bonds between children and significant caregivers. • Detention limits educational opportunities. • Detention has traumatic impacts on children of asylum seekers. • Detention reduces children’s potential to recover from trauma. • Detention exacerbates the impacts of other traumas. • Detention of children from these families in many respects is worse for them than being imprisoned. In the absence of any indication from the Australian Government that it intends in the near future to alter the practice of holding children in immigration detention, the Australian Psychological Society’s intermediate position is that the facilitation of short-term and long-term psychological development and wellbeing of children is the basic tenet upon which detention centres should be audited and judged. Based on that position, the Society has identified a series of questions and concerns that arise directly from the various psychological perspectives that have been brought to bear on estimating the effects of detention on child asylum seekers. The Society argues that, because these questions and concerns relate specifically to improvement and maintenance of child detainees’ educational, social and psychological wellbeing, they are legitimate matters for the Inquiry to consider and investigate. • What steps are currently being taken to monitor the psyc hological welfare of the children in detention? In particular, what steps are being taken to monitor the psychological wellbeing of children arriving from war-torn countries? • What qualifications and training do staff who care for children and their families in detention centres have? What knowledge do they have of psychological issues faced by people who have been subjected to traumatic experiences and are suffering high degrees of anxiety, stress and uncertainty? • What provisions have been made for psycho-educational assessment of children’s specific learning needs prior to their attending formal educational programmes? • who are suffering chronic and/or vicarious trauma as a result of witnessing threatening behaviour whilst in detention? • What provisions have been made for families who have been seriously affected by displacement to participate in family therapy? • What critical incident debriefing procedures are in place for children who have witnessed their parents, other family members, or social acquaintances engaging in acts of self-harm or being harmed while in detention? What psychotherapeutic support is in place for children who themselves have been harmed or have engaged in self- harmful acts while in detention? • What provisions are in place for parenting programmes that provide support for parents of children under extremely difficult psychological and physical circumstances? • What efforts are being made to provide parents with the opportunity to model traditional family roles for children, such as working to earn an income, meal preparation, other household duties, etc.? • What opportunities are in place for the assessment of safety issues such as bullying, and sexual or physical abuse of children or their mothers in detention centres? • How are resources distributed to children and families in detention centres? • What socialization opportunities are available either within detention centres or in the wider community for children to develop skills and independence, engage in social activities, participate in cultural traditions, and communicate and interaction with same-age peers and adults from similar ethnic and religious backgrounds? • What access do children and families have to videos, music and entertainment from their cultures of origin? • What provisions are in place to ensure the maintenance of privacy in a manner commensurate with usual cultural practice? • What is the Government’s rationale for continuing to implement a policy of mandatory detention of child asylum seekers that on the face of it is likely to have a pernicious impact on these children’s mental health? • In view of the evidence on the potential long-term impact of mandatory detention on children, what processes may be followed by Government to avoid such a practice and, more importantly, to develop policies and practices that will have a positive impact on these children’s psychological development and mental health?
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Boron–nitrogen containing compounds with high hydrogen contents as represented by ammonia borane (NH3BH3) have recently attracted intense interest for potential hydrogen storage applications. One such compound is [(NH3)2BH2]B3H8 with a capacity of 18.2 wt% H. Two safe and efficient synthetic routes to [(NH3)2BH2]B3H8 have been developed for the first time since it was discovered 50 years ago. The new synthetic routes avoid a dangerous starting chemical, tetraborane (B4H10), and afford a high yield. Single crystal X-ray diffraction analysis reveals N–Hδ+Hδ−–B dihydrogen interactions in the [(NH3)2BH2]B3H8·18-crown-6 adduct. Extended strong dihydrogen bonds were observed in pure [(NH3)2BH2]B3H8 through crystal structure solution based upon powder X-ray analysis. Pyrolysis of [(NH3)2BH2]B3H8 leads to the formation of hydrogen gas together with appreciable amounts of volatile boranes below 160 °C.
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Density functional theory (DFT) calculations have been carried out to explore the catalytic activation of C–H bonds in methane by the iron atom, Fe, and the iron dimer, Fe2. For methane activation on an Fe atom, the calculations suggest that the activation of the first C–H bond is mediated via the triplet excited-state potential energy surface (PES), with initial excitation of Fe to the triplet state being necessary for the reaction to be energetically feasible. Compared with the breaking of the first C–H bond, the cleavage of the second C–H bond is predicted to involve a significantly higher barrier, which could explain experimental observations of the HFeCH3 complex rather than CH2FeH2 in the activation of methane by an Fe atom. For methane activation on an iron dimer, the cleavage of the first C–H bond is quite facile with a barrier only 11.2, 15.8 and 8.4 kcal/mol on the septet state energy surface at the B3LYP/6-311+G(2df,2dp), BPW91/6-311+G(2df,2dp) and M06/B3LYP level, respectively. Cleavage of the second C–H bond from HFe2CH3 involves a barrier calculated respectively as 18.0, 10.7 and 12.4 kcal/mol at the three levels. The results suggest that the elimination of hydrogen from the dihydrogen complex is a rate-determining step. Overall, our results indicate that the iron dimer Fe2 has a stronger catalytic effect on the activation of methane than the iron atom.
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Electronic word-of-mouth (eWOM) has gained significant attention from academics and practitioners since it has become an important source of consumers’ product information, which can influence consumer purchase intentions (Cheung & Lee, 2012). eWOM exchanges exist in two types of online communities: online communities of practice and online communities of interest. A few prior studies in online communities of interest have examined members’ motivations for product knowledge exchange (Hung & Li, 2007; Ma & Agarwal, 2007). However, there is a lack of understanding of member motivations for exchanging social bonds and enjoyment in addition to exchanging knowledge pertaining to products in the community. It is important to have an initial comprehension of motivation as an antecedent of these three eWOM exchanges so as to be able to determine the driving factors that lead members to generate eWOM communication. Thus, the research problem "What are the driving factors for members to exchange eWOM in an online community?" was justified for investigation. The purpose of this study was to examine different member motivations for exchanging three types of eWOM. Resource exchange theory and theory on consumer motivation and behavior were applied to develop a conceptual framework for this study. This study focused on an online beauty community since there is an increasing trend of consumers turning to online beauty resources so as to exchange useful beauty product information (SheSpot, 2011). As this study examined consumer motivation in an online beauty community, a web-based survey was the most effective and efficient way to gain responses from beauty community members and these members were appropriate samples from which to draw a conclusion about the whole population. Multiple regression analysis was used to test the relationships between member motivations and eWOM exchanges. It was found that members have different motivations for exchanging knowledge, social bonds, and enjoyment related to products: self-development, problem solving support, and relaxation, respectively. This study makes three theoretical contributions. First, this study identifies the influence of self-development motivation on knowledge exchange in an online community of interest, just as this motivation has previously been found in online communities of practice. This study highlights that members of the two different types of online communities share similar goals of knowledge exchange, despite the two communities evincing different attributes (e.g., member characteristics and tasks’ objectives). Further, this study will assist researchers to understand other motivations identified by prior research in online communities of practice since such motivations may be applicable to online communities of interest. Second, this study offers a new perspective on member motivation for social bonding. This study indicates that in addition to social support from friends and family, consumers are motivated to build social bonds with members in an online community of interest since they are an important source of problem solving support in regard to products. Finally, this study extends the body of knowledge pertaining to member motivation for enjoyment exchange. This study provides a basis for researchers to understand that members in an online community of interest value experiential aspects of enjoyable consumption activities, and thus based on group norms, members have a mutual desire for relaxation from enjoyment exchange. The major practical contribution is that this study provides an important guideline for marketing managers to develop different marketing strategies based on member motivations for exchanging three types of eWOM in an online community of interest, such as an online beauty community. This will potentially help marketing managers increase online traffic and revenue, and thus bring success to the community. Although, this study contributes to the literature by highlighting three distinctive member motivations for eWOM exchanges in an online community of interest, there are some possible research limitations. First, this study was conducted in an online beauty community in Australia. Hence, further research should replicate this study in other industries and nations so as to give the findings greater generalisability. Next, online beauty community members are female skewed. Thus, future research should examine whether similar patterns of motivations would emerge in other online communities that tend to be populated by males (e.g., communities focused on football). Further, a web-based survey has its limitations in terms of self-selection and self-reporting (Bhatnagar & Ghose, 2004). Therefore, further studies should test the framework by employing different research methods in order to overcome these weaknesses.
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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.
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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.
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The structures of the anhydrous proton-transfer compounds of the sulfa drug sulfamethazine with 5-nitrosalicylic acid and picric acid, namely 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2-hydroxy-5-nitrobenzoate, C12H15N4O2S(+)·C7H4NO4(-), (I), and 2-(4-aminobenzenesulfonamido)-4,6-dimethylpyrimidinium 2,4,6-trinitrophenolate, C12H15N4O2S(+)·C6H2N3O7(-), (II), respectively, have been determined. In the asymmetric unit of (I), there are two independent but conformationally similar cation-anion heterodimer pairs which are formed through duplex intermolecular N(+)-H...Ocarboxylate and N-H...Ocarboxylate hydrogen-bond pairs, giving a cyclic motif [graph set R2(2)(8)]. These heterodimers form separate and different non-associated substructures through aniline N-H...O hydrogen bonds, one one-dimensional, involving carboxylate O-atom acceptors, the other two-dimensional, involving both carboxylate and hydroxy O-atom acceptors. The overall two-dimensional structure is stabilized by π-π interactions between the pyrimidinium ring and the 5-nitrosalicylate ring in both heterodimers [minimum ring-centroid separation = 3.4580 (8) Å]. For picrate (II), the cation-anion interaction involves a slightly asymmetric chelating N-H...O R2(1)(6) hydrogen-bonding association with the phenolate O atom, together with peripheral conjoint R1(2)(6) interactions between the same N-H groups and O atoms of the ortho-related nitro groups. An inter-unit amine N-H...Osulfone hydrogen bond gives one-dimensional chains which extend along a and inter-associate through π-π interactions between the pyrimidinium rings [centroid-centroid separation = 3.4752 (9) Å]. The two structures reported here now bring to a total of four the crystallographically characterized examples of proton-transfer salts of sulfamethazine with strong organic acids.
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In this work, ab initio density functional calculations were performed to explore the effect of surface lithium vacancies on the initial dehydrogenation kinetics of lithium borohydride. We found that some B−H bonds in neighboring BH4-1 complexes around the vacancy became elongated (weakened). The activation barriers for the recombination of H atoms to form H2 were decreased from 3.64 eV for the stoichiometrically complete LiBH4(010) surface to 1.53 and 0.23 eV in the presence of mono- and di-vacancies, respectively. Our results indicate that the creation of Li vacancies may play a critical role in accelerating the dehydrogenation kinetics of LiBH4.
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The sidewall additions of diazomethane to (n, n), n = 3–10 armchair single-walled carbon nanotubes (SWCNTs) on two different orientations of C–C bonds have been studied using the ONIOM(B3LYP/6-31G(d):PM3) approach. The binding energies of SWCNTs complexes with CH2N2, CH2 and their transition-state structures were computed at the B3LYP/6-31G(d) level. The effects of diameters of armchair SWCNTs on their binding energies were studied. Relative reactivities of all the SWCNTs and their complexes based on their frontier orbital energies gaps are reported.
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In this work, ab initio density functional theory (DFT) calculations are performed to study the structural and electronic properties of diazonium reagent functionalized (4, 4) single-walled carbon nanotube (SWCNT). We find the aryl group covalently bonds with SWCNT and prefers to be perpendicular to the side wall of nanotube. It has a rotational barrier of 0.35 eV around the formed aryl-tube bond axis and should be thermodynamically stable at room temperature. Additionally, new peaks appeared around the Fermi energy in the density of state (DOS) due to the weak band dispersion. Increasing of the coverage of the functional group will result in significant upshift of the Fermi level.
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In this paper, the collision of a C36, with D6h symmetry, on diamond (001)-(/2×1) surface was investigated using molecular dynamics (MD) simulation based on the semi-empirical Brenner potential. The incident kinetic energy of the C36 ranges from 20 to 150 eV per cluster. The collision dynamics was investigated as a function of impact energy Ein. The C36 cluster was first impacted towards the center of two dimers with a fixed orientation. It was found that when Ein was lower than 30 eV, C36 bounces off the surface without breaking up. Increasing Ein to 30-45 eV, bonds were formed between C36 and surface dimer atoms, and the adsorbed C36 retained its original free-cluster structure. Around 50-60 eV, the C36 rebounded from the surface with cage defects. Above 70 eV, fragmentation both in the cluster and on the surface was observed. Our simulation supported the experimental findings that during low-energy cluster beam deposition small fullerenes could keep their original structure after adsorption (i.e. the memory effect), if Ein is within a certain range. Furthermore, we found that the energy threshold for chemisorption is sensitive to the orientation of the incident C36 and its impact position on the asymmetric surface.
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Awareness to avoid losses and casualties due to rain-induced landslide is increasing in regions that routinely experience heavy rainfall. Improvements in early warning systems against rain-induced landslide such as prediction modelling using rainfall records, is urgently needed in vulnerable regions. The existing warning systems have been applied using stability chart development and real-time displacement measurement on slope surfaces. However, there are still some drawbacks such as: ignorance of rain-induced instability mechanism, mislead prediction due to the probabilistic prediction and short time for evacuation. In this research, a real-time predictive method was proposed to alleviate the drawbacks mentioned above. A case-study soil slope in Indonesia that failed in 2010 during rainfall was used to verify the proposed predictive method. Using the results from the field and laboratory characterizations, numerical analyses can be applied to develop a model of unsaturated residual soils slope with deep cracks and subject to rainwater infiltration. Real-time rainfall measurement in the slope and the prediction of future rainfall are needed. By coupling transient seepage and stability analysis, the variation of safety factor of the slope with time were provided as a basis to develop method for the real-time prediction of the rain-induced instability of slopes. This study shows the proposed prediction method has the potential to be used in an early warning system against landslide hazard, since the FOS value and the timing of the end-result of the prediction can be provided before the actual failure of the case study slope.
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Kinship care is the oldest form of alternative child care in the world. Recent years have witnessed a significant increase in the number of children being placed in kinship care across Western countries. However, in contrast to rapid knowledge advances about formal kinship care, far less is known about the needs of children in informal kinship care, especially in Asian contexts. This thesis and the study upon which it is formed sought to redress this knowledge gap. Qualitative approach was adopted to explore social constructions of children in informal kinship care in rural China. Parents in China seeking work in cities have left behind around 58 million rural children, mostly with relatives and without the involvement of the state. The present study examined caregivers’ and school personnel’s understandings of these school-age children’s needs through semi-structured interviews with 23 kin caregivers and five school personnel in Shijiapu Town, Jilin Province, China. The central question that guided the whole study is: What are the needs of children in informal kinship care in rural Jilin Province, China? Interpretative Phenomenological Analysis was used to categorise and interpret the qualitative data. Based on participants’ constructions, this study developed a need model with eight themes. They are: (1) emotional needs and mental health, (2) relationships, (3) empowerment and agency, (4) safety, (5) education, (6) basic care, (7) physical health, and (8) personal development. These needs are grounded in the Chinese context, and therefore a good understanding of Chinese culture is essential to address them. The first four needs particularly capture children’s separations from their parents, and the rest are more general, and can be applied to most Chinese children. To meet the most important need for children left behind, namely education, these caregivers determined that others needs sometimes have to be compromised. Children left behind are a vulnerable group in contemporary rural China, and their diverse needs are attended to by several groups. This study found that as children’s closest kin while their parents are away, caregivers play a vital role in salving the children’s emotional loss. Caregivers’ love and familial obligations strongly motivate them to care for these children, and sensitivity to social stigma makes them strive to show their love and care to compensate for perceived differences between these children and their peers. Caregivers’ efforts to make children happy, however, were sometimes criticised by some school personnel, who see this as spoiling. The conflicting viewpoint between caregivers and school personnel indicate their different roles and perceptions in children’s lives, and the latter influence these children in a more authoritative way. Informal kinship care has several advantages of addressing children’s needs, especially their needs for emotional bonds with family. Community-based kin networks provide children with both emotional and material support. However, these advantages sometimes are restricted by caregivers’ child rearing capacity. Having developed a model of the needs of children left behind in China, this study suggests that caregivers, school personnel and government social services work in harmony to be child-centred and meet these children’s diverse needs. The unmet needs of children left behind mainly result from unbalanced development between urban and rural China, therefore, it is imperative to enhance state policies and programs that improve wellbeing for this growing part of China’s people.
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Infrared spectra are reported of methyl formate and formaldehyde adsorbed at 300 K on silica, Cu/SiO2 reduced in hydrogen and Cu/SiO2 which had been oxidised by exposure to nitrous oxide after reduction. Silanol groups on silica form hydrogen bonds with carbonyl groups in weakly adsorbed methyl formate molecules. Methyl formate ligates via its carbonyl groups to Cu atoms in the surface of reduced copper. A low residual concentration of surface oxygen on copper promoted the slow reaction of ligated methyl formate to give a bridging formate species on copper and adsorbed methoxy groups. Methyl formate did not ligate to an oxidised copper surface but was rapidly chemisorbed to give unidentate formate and methoxy species. Formaldehyde slowly polymerises on silica to form trioxane and other oxymethylene species. The reaction is faster over Cu/SiO2 which, in the reduced state, also catalyses the formation of bridging formate anions adsorbed on copper. The reaction between formaldehyde and oxidised Cu/SiO2 leads to both unidentate and bidentate formate and adsorbed water.
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The effect of oxidation and reduction conditions upon the morphology of polycrystalline silver catalysts has been investigated by means of in situ Fourier-transform infrared (FTIR) spectroscopy. Characterization of the sample was achieved by inspection of the νas(COO) band profile of adsorbed formate, recorded after dosing with formic acid at ambient temperature. Evidence was obtained for the existence of a silver surface reconstructed by the presence of subsurface oxygen in addition to the conventional family of Ag(111) and Ag(110) crystal faces. Oxidation at 773 K facilitated the reconstruction of silver planes due to the formation of subsurface oxygen species. Prolonged oxygen treatment at 773 K also caused particle fragmentation as a consequence of excessive oxygen penetration of the silver catalyst at defect sites. It was also deduced that the presence of oxygen in the gas phase stabilized the growth of silver planes which could form stronger bonds with oxygen. In contrast, high-temperature thermal treatment in vacuum induced significant sintering of the silver catalyst. Reduction at 773 K resulted in substantial quantities of dissolved hydrogen (and probably hydroxy species) in the bulk silver structure. Furthermore, enhanced defect formation in the catalyst was also noted, as evidenced by the increased concentration of formate species associated with oxygen-reconstructed silver faces.