Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.

Increased body temperature following subarachnoid haemorrhage : a retrospective correlational study

Introduction: Nursing clinicians are primarily responsible for the monitoring and treatment of increased body temperature. The body temperature of patients during their acute care hospital stay is measured at regular repeated intervals. In the event a patient is assessed with an elevated temperature, a multitude of decisions are required. The action of instigating temperature reducing strategies is based upon the assumption that elevated temperature is harmful and that the strategy employed will have some beneficial effect. Background and Significance: The potential harmful effects of increased body temperature (fever, hyperthermia) following neurological insult are well recognised. Although few studies have investigated this phenomenon in the diagnostic population of non-traumatic subarachnoid haemorrhage, it has been demonstrated that increased body temperature occurs in 41 to 72% of patients with poor clinical outcome. However, in the Australian context the frequency, or other characteristics of increased body temperature, as well as the association between increased body temperature with poor clinical outcome has not been established. Design: This study used a correlational study design to: describe the frequency, duration and timing of increased body temperature; determine the association between increased body temperature and clinical outcome; and describe the clinical interventions used to manage increased body temperature in patients with non-traumatic subarachnoid haemorrhage. A retrospective clinical chart audit was conducted on 43 patients who met the inclusion criteria. Findings: The major findings of this study were: increased body temperature occurred frequently; persisted for a long time; and onset did not occur until 20 hours after primary insult; increased body temperature was associated with death or dependent outcome; and no intervention was recorded in many instances. Conclusion: This study has quantified in a non-traumatic subarachnoid haemorrhage patient population the characteristics of increased body temperature, established an association between increased body temperature with death or dependent outcome and described the current management of elevated temperatures in the Australian context to improve nursing practice, education and research.

Bringing the internet down to earth : emerging spaces of locative media

Web 1.0 referred to the early, read-only internet; Web 2.0 refers to the ‘read-write web’ in which users actively contribute to as well as consume online content; Web 3.0 is now being used to refer to the convergence of mobile and Web 2.0 technologies and applications. One of the most important developments in mobile 3.0 is geography: with many mobile phones now equipped with GPS, mobiles promise to “bring the internet down to earth” through geographically-aware, or locative media. The internet was earlier heralded as “the death of geography” with predictions that with anyone able to access information from anywhere, geography would no longer matter. But mobiles are disproving this. GPS allows the location of the user to be pinpointed, and the mobile internet allows the user to access locally-relevant information, or to upload content which is geotagged to the specific location. It also allows locally-specific content to be sent to the user when the user enters a specific space. Location-based services are one of the fastest-growing segments of the mobile internet market: the 2008 AIMIA report indicates that user access of local maps increased by 347% over the previous 12 months, and restaurant guides/reviews increased by 174%. The central tenet of cultural geography is that places are culturally-constructed, comprised of the physical space itself, culturally-inflected perceptions of that space, and people’s experiences of the space (LeFebvre 1991). This paper takes a cultural geographical approach to locative media, anatomising the various spaces which have emerged through locative media, or “the geoweb” (Lake 2004). The geoweb is such a new concept that to date, critical discourse has treated it as a somewhat homogenous spatial formation. In order to counter this, and in order to demonstrate the dynamic complexity of the emerging spaces of the geoweb, the paper provides a topography of different types of locative media space: including the personal/aesthetic in which individual users geotag specific physical sites with their own content and meanings; the commercial, like the billboards which speak to individuals as they pass in Minority Report; and the social, in which one’s location is defined by the proximity of friends rather than by geography.

In search of a hidden long-term isolated sub-chondritic 142Nd/144Nd reservoir in the deep mantle : implications for the Nd isotope systematics of the Earth

Here we search for evidence of the existence of a sub-chondritic 142Nd/144Nd reservoir that balances the Nd isotope chemistry of the Earth relative to chondrites. If present, it may reside in the source region of deeply sourced mantle plume material. We suggest that lavas from Hawai’i with coupled elevations in 186Os/188Os and 187Os/188Os, from Iceland that represent mixing of upper mantle and lower mantle components, and from Gough with sub-chondritic 143Nd/144Nd and high 207Pb/206Pb, are favorable samples that could reflect mantle sources that have interacted with an Early-Enriched Reservoir (EER) with sub-chondritic 142Nd/144Nd. High-precision Nd isotope analyses of basalts from Hawai’i, Iceland and Gough demonstrate no discernable 142Nd/144Nd deviation from terrestrial standards. These data are consistent with previous high-precision Nd isotope analysis of recent mantle-derived samples and demonstrate that no mantle-derived material to date provides evidence for the existence of an EER in the mantle. We then evaluate mass balance in the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd. The Nd isotope systematics of EERs are modeled for different sizes and timing of formation relative to ε143Nd estimates of the reservoirs in the μ142Nd = 0 Earth, where μ142Nd is ((measured 142Nd/144Nd/terrestrial standard 142Nd/144Nd)−1 * 10−6) and the μ142Nd = 0 Earth is the proportion of the silicate Earth with 142Nd/144Nd indistinguishable from the terrestrial standard. The models indicate that it is not possible to balance the Earth with respect to both 142Nd/144Nd and 143Nd/144Nd unless the μ142Nd = 0 Earth has a ε143Nd within error of the present-day Depleted Mid-ocean ridge basalt Mantle source (DMM). The 4567 Myr age 142Nd–143Nd isochron for the Earth intersects μ142Nd = 0 at ε143Nd of +8 ± 2 providing a minimum ε143Nd for the μ142Nd = 0 Earth. The high ε143Nd of the μ142Nd = 0 Earth is confirmed by the Nd isotope systematics of Archean mantle-derived rocks that consistently have positive ε143Nd. If the EER formed early after solar system formation (0–70 Ma) continental crust and DMM can be complementary reservoirs with respect to Nd isotopes, with no requirement for significant additional reservoirs. If the EER formed after 70 Ma then the μ142Nd = 0 Earth must have a bulk ε143Nd more radiogenic than DMM and additional high ε143Nd material is required to balance the Nd isotope systematics of the Earth.

Temperature enhanced effects of ozone on cardiovascular mortality in 95 large US communities, 1987-2000 - assessment using the NMMAPS data

A few studies examined interactive effects between air pollution and temperature on health outcomes. This study is to examine if temperature modified effects of ozone and cardiovascular mortality in 95 large US cities. A nonparametric and a parametric regression models were separately used to explore interactive effects of temperature and ozone on cardiovascular mortality during May and October, 1987-2000. A Bayesian meta-analysis was used to pool estimates. Both models illustrate that temperature enhanced the ozone effects on mortality in the northern region, but obviously in the southern region. A 10-ppb increment in ozone was associated with 0.41 % (95% posterior interval (PI): -0.19 %, 0.93 %), 0.27 % (95% PI: -0.44 %, 0.87 %) and 1.68 % (95% PI: 0.07 %, 3.26 %) increases in daily cardiovascular mortality corresponding to low, moderate and high levels of temperature, respectively. We concluded that temperature modified effects of ozone, particularly in the northern region.