Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes : (Part 10) The infrared and Raman characteristics of phthalocyanine in heteroleptic bis(phthalocyaninato) rare earth complexes with decreased molecular symmetry

The infrared (IR) spectroscopic data for a series of eleven heteroleptic bis(phthalocyaninato) rare earth complexes MIII(Pc)[Pc(α-OC5H11)4] (M = Sm–Lu, Y) [H2Pc = unsubstituted phthalocyanine, H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected with 2 cm−1 resolution. Raman spectroscopic properties in the range of 500–1800 cm−1 for these double-decker molecules have also been comparatively studied using laser excitation sources emitting at 632.8 and 785 nm. Both the IR and Raman spectra for M(Pc)[Pc(α-OC5H11)4] are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues due to the decreased molecular symmetry of these double-decker compounds, namely C4. For this series, the IR Pc√− marker band appears as an intense absorption at 1309–1317 cm−1, attributed to the pyrrole stretching. With laser excitation at 632.8 nm, Raman vibrations derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. In contrast, when excited with laser radiation of 785 nm, the ring radial vibrations of isoindole moieties and dihedral plane deformations between 500 and 1000 cm−1 for M(Pc)[Pc(α-OC5H11)4] intensify to become the strongest scatterings. Both techniques reveal that the frequencies of pyrrole stretching, isoindole breathing, isoindole stretchings, aza stretchings and coupling of pyrrole and aza stretchings depend on the rare earth ionic size, shifting to higher energy along with the lanthanide contraction due to the increased ring-ring interaction across the series. The assignments of the vibrational bands for these compounds have been made and discussed in relation to other unsubstituted and substituted bis(phthalocyaninato) rare earth analogues, such as M(Pc)2 and M(OOPc)2 [H2OOPc = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine].

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

An infrared spectroscopic study of the some Autunite minerals

A series of selected autunites with phosphate as the anion have been studied using infrared spectroscopy. Each autunite mineral has its own characteristic spectrum. The spectra for different autunites with the same composition are different. It is proposed that this difference is due to the structure of water and hydrated cations in the interlayer region between the uranyl phosphate sheets. This structure is different for different autunites. The position of the water hydroxyl stretching bands is related to the strength of the hydrogen bonds as determined by hydrogen bond distance. The highly ordered structure of water is also observed in the water HOH bending modes where a high wavenumber bands are observed. The phosphate and uranyl stretching vibrations overlap and are obtained by curve resolution.

Thermal treatment of weddellite—a Raman and infrared emission spectroscopic study

Thermal transformations of natural calcium oxalate dihydrate known in mineralogy as weddellite have been undertaken using a combination of Raman microscopy and infrared emission spectroscopy. The vibrational spectroscopic data was complimented with high resolution thermogravimetric analysis combined with evolved gas mass spectrometry. TG–MS identified three mass loss steps at 114, 422 and 592 °C. In the first mass loss step water is evolved only, in the second and third steps carbon dioxide is evolved. The combination of Raman microscopy and a thermal stage clearly identifies the changes in the molecular structure with thermal treatment. Weddellite is the phase in the temperature range up to the pre-dehydration temperature of 97 °C. At this temperature, the phase formed is whewellite (calcium oxalate monohydrate) and above 114 °C the phase is the anhydrous calcium oxalate. Above 422 °C, calcium carbonate is formed. Infrared emission spectroscopy shows that this mineral decomposes at around 650 °C. Changes in the position and intensity of the C=O and C---C stretching vibrations in the Raman spectra indicate the temperature range at which these phase changes occur.

"Well, now I'm upset": Moral and social orders in the playground

There is much still to learn about how young children’s membership with peers shapes their constructions of moral and social obligations within everyday activities in the school playground. This paper investigates how a small group of girls, aged four to six years, account for their everyday social interactions in the playground. They were video-recorded as they participated in a pretend game of school. Several days later, a video-recorded excerpt of the interaction was shown to them and invited to comment on what was happening in the video. This conversation was audio-recorded. Drawing on a conversation analysis approach, this chapter shows that, despite their discontent and complaining about playing the game of school, the girls’ actions showed their continued orientation to the particular codes of the game, of ‘no going away’ and ‘no telling’. By making relevant these codes, jointly constructed by the girls during the interview, they managed each other’s continued participation within two arenas of action: the pretend, as a player in a pretend game of school; and the real, as a classroom member of a peer group. Through inferences to explicit and implicit codes of conduct, moral obligations were invoked as the girls attempted to socially exclude or build alliances with others, and enforce their own social position. As well, a shared history that the girls re-constructed has moral implications for present and future relationships. The girls oriented to the history as an interactional resource for accounting for their actions in the pretend game. This paper uncovers how children both participate in, and shape, their everyday social worlds through talk and interaction and the consequences a taken-for-granted activity such as playing school has for their moral and social positions in the peer group.

Infrared and infrared emission spectroscopy of gallium oxide α-GaO(OH) nanostructures

Infrared spectroscopy has been used to study nano to micro sized gallium oxyhydroxide α-GaO(OH), prepared using a low temperature hydrothermal route. Rod-like α-GaO(OH) crystals with average length of ~2.5 μm and width of 1.5 μm were prepared when the initial molar ratio of Ga to OH was 1:3. β-Ga2O3 nano and micro-rods were prepared through the calcination of α-GaO(OH) The initial morphology of α-GaO(OH) is retained in the β-Ga2O3 nanorods. The combination of infrared and infrared emission spectroscopy complimented with dynamic thermal analysis were used to characterise the α-GaO(OH) nanotubes and the formation of β-Ga2O3 nanorods. Bands at around 2903 and 2836 cm-1 are assigned to the -OH stretching vibration of α-GaO(OH) nanorods. Infrared bands at around 952 and 1026 cm-1 are assigned to the Ga-OH deformation modes of α-GaO(OH). A significant number of bands are observed in the 620 to 725 cm-1 region and are assigned to GaO stretching vibrations.

How well are Australian children doing in the first year of school : a demographic analysis

Background: The transition to school is a sensitive period for children in relation to school success. In the early school years, children need to develop positive attitudes to school and have experiences that promote academic, behavioural and social competence. When children begin school there are higher expectations of responsibility and independence and in the year one class, there are more explicit academic goals for literacy and numeracy and more formal instruction. Most importantly, children’s early attitudes to learning and learning styles have an impact on later educational outcomes. Method: Data were drawn from The Longitudinal Study of Australian Children (LSAC). LSAC is a cross-sequential cohort study funded by the Australian Government. In these analyses, Wave 2 (2006) data for 2499 children in the Kindergarten Cohort were used. Children, at Wave 2, were in the first year of formal school. They had a mean age of 6.9 years (SD= 0.26). Measures included a 6-item measure of Approaches to Learning (task persistence, independence) and the Academic Rating Scales for language and literacy and mathematical thinking. Teachers rated their relationships with children on the short form of the STRS. Results: Girls were rated by their teachers as doing better than boys on Language and literacy, Approaches to learning; and they had a better relationship with their teacher. Children from an Aboriginal or Torres Strait Island (ATSI) background were rated as doing less well on Language and Literacy and Mathematical thinking and on their Approaches to learning. Children from high Socio Economic Position families are doing better on teacher rated Language and Literacy, Mathematical thinking, Approaches to learning and they had a better relationship with their teacher. Conclusions: Findings highlight the importance of key demographic variables in understanding children’s early school success.

How the whiteness embedded in health services impacts on the health and well-being of Aboriginal peoples

Aboriginal women are treated differently by non-indigenous health care providers based on perceptions of Aboriginality and skin colour and white race privilege within health care environments. The experiences shared below are from some of the Aboriginal woman respondents in a research project undertaken within Rockhampton, a regional area in Central Queensland (Fredericks, 2003). The experiences give an insight into how the Aboriginal women interviewed felt and their observations of how other Aboriginal women were treated within health care settings based on skin colour and perceptions of Aboriginality. A number of the women demonstrated a personal in-depth analysis of the issues surrounding place, skin colour and Aboriginality. For example, one of the women, who I named Kay, identified one particular health service organisation and stated that, ‘it is a totally white designed space. There is nothing that identifies me to that place. I just won’t go there as a client because I don’t feel they cater for me as a black woman’. Kay’s words give us an understanding of the reality experienced by Aboriginal women as they move in and out of places within health environments and broader society. Some of these experiences are examples of direct racism, whilst other examples are subtle and demonstrate how whiteness manifests and plays out within places. I offer acknowledgement and honour to the Aboriginal women who shared their stories and gave me a glimpse of their realities in the research project from which the findings presented in this chapter are taken. It is to this research project that is the subject of this chapter.

Property Education : an evaluation of how well undergraduate property students are prepared for commencing their careers

The evolution of property education to adapt to the changing business environment requires changes to course content, method of delivery and assessment. Many universities have a special interest in understanding how the students transition in and transition out of the property programs. The impact of the first year student experience is often easier to assess through students’ progression in the course and performance in their intermediate and advanced units. However, the students’ success in transitioning from university student to property professional is often more difficult to determine. In an environment where many property students commence their professional careers while still completing their undergraduate property qualification, a survey of current final year students was undertaken to identify the students’ perception of their level of preparedness for entry into the professional world. This study has also been informed by feedback received from and informal discussions held with industry representative bodies, alumni and senior members of professional organisations. The QUT UD40 Bachelor of Urban Development, Property Economics course has been designed to achieve graduate capabilities in core technical skills and generic professional skills which are required by property professionals. The results of this study were that some units in the program were perceived to provide direct preparation for students commencing their professional careers whilst the impact of other units was less tangible. Valuable feedback received during the study included an assessment of the relevance of many multi-disciplinary units, the appropriateness of the programming of units within the course and the appropriateness of repetition of content during the course. The further research question arises as to how universities can better assist students in the transition to the professional environment when frequently this occurs prior to completion of the property course.

How well are Australian children doing in the first year of school?

Background: The transition to school is a sensitive period for children in relation to school success. In the early school years, children need to develop positive attitudes to school and have experiences that promote academic, behavioural and social competence. When children begin school there are higher expectations of responsibility and independence and in the year one class, there are more explicit academic goals for literacy and numeracy and more formal instruction. Most importantly, children’s early attitudes to learning and learning styles have an impact on later educational outcomes. Method: Data were drawn from The Longitudinal Study of Australian Children (LSAC). LSAC is a cross-sequential cohort study funded by the Australian Government. In these analyses, Wave 2 (2006) data for 2499 children in the Kindergarten Cohort were used. Children, at Wave 2, were in the first year of formal school. They had a mean age of 6.9 years (SD= 0.26). Measures included a 6-item measure of Approaches to Learning (task persistence, independence) and the Academic Rating Scales for language and literacy and mathematical thinking. Teachers rated their relationships with children on the short form of the STRS. Results: Girls were rated by their teachers as doing better than boys on Language and literacy, Approaches to learning; and they had a better relationship with their teacher. Children from an Aboriginal or Torres Strait Island (ATSI) background were rated as doing less well on Language and Literacy and Mathematical thinking and on their Approaches to learning. Children from high Socio Economic Position families are doing better on teacher rated Language and Literacy, Mathematical thinking, Approaches to learning and they had a better relationship with their teacher. Conclusions: Findings highlight the importance of key demographic variables in understanding children’s early school success.