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.

Characterization of particle number concentrations and PM2.5 in a school : influence of outdoor air pollution on indoor air

Background, Aim and Scope The impact of air pollution on school children’s health is currently one of the key foci of international and national agencies. Of particular concern are ultrafine particles which are emitted in large quantities, contain large concentrations of toxins and are deposited deeply in the respiratory tract. Materials and methods In this study, an intensive sampling campaign of indoor and outdoor airborne particulate matter was carried out in a primary school in February 2006 to investigate indoor and outdoor particle number (PN) and mass concentrations (PM2.5), and particle size distribution, and to evaluate the influence of outdoor air pollution on the indoor air. Results For outdoor PN and PM2.5, early morning and late afternoon peaks were observed on weekdays, which are consistent with traffic rush hours, indicating the predominant effect of vehicular emissions. However, the temporal variations of outdoor PM2.5 and PN concentrations occasionally showed extremely high peaks, mainly due to human activities such as cigarette smoking and the operation of mower near the sampling site. The indoor PM2.5 level was mainly affected by the outdoor PM2.5 (r = 0.68, p<0.01), whereas the indoor PN concentration had some association with outdoor PN values (r = 0.66, p<0.01) even though the indoor PN concentration was occasionally influenced by indoor sources, such as cooking, cleaning and floor polishing activities. Correlation analysis indicated that the outdoor PM2.5 was inversely correlated with the indoor to outdoor PM2.5 ratio (I/O ratio) (r = -0.49, p<0.01), while the indoor PN had a weak correlation with the I/O ratio for PN (r = 0.34, p<0.01). Discussion and Conclusions The results showed that occupancy did not cause any major changes to the modal structure of particle number and size distribution, even though the I/O ratio was different for different size classes. The I/O curves had a maximum value for particles with diameters of 100 – 400 nm under both occupied and unoccupied scenarios, whereas no significant difference in I/O ratio for PM2.5 was observed between occupied and unoccupied conditions. Inspection of the size-resolved I/O ratios in the preschool centre and the classroom suggested that the I/O ratio in the preschool centre was the highest for accumulation mode particles at 600 nm after school hours, whereas the average I/O ratios of both nucleation mode and accumulation mode particles in the classroom were much lower than those of Aitken mode particles. Recommendations and Perspectives The findings obtained in this study are useful for epidemiological studies to estimate the total personal exposure of children, and to develop appropriate control strategies for minimizing the adverse health effects on school children.

Modulation of in vitro platelet 5-HT release by species of Erythrina and Cymbopogon

Extracts of Australian plants were screened to detect constituents affecting adenosine di-phosphate (ADP) induced platelet aggregation and [14C]5-hydroxytryptamine (5-HT) release. Extracts of four tested plants including, Eremophila gilesii, Erythrina vespertilio, Cymbopogon ambiguus, and Santalum acuminatum, were found to cause significant inhibition of platelet 5-HT release. Inhibition levels ranged from 56-98%, and was not due to the non-specific effects of protein binding tannins. These extracts, and those we have previously identified as being active, were examined further to determine if they affect epinephrine (EPN), arachidonic acid (A.A) or collagen stimulated platelet aggregation and 5-HT release. Among those extracts investigated, we found that both the methanolic extract of E. vespertilio and the dichloromethane (DCM) extract of C. ambiguus were most potent and caused significant inhibition of platelet activation induced by EPN, A.A and to a lesser extent by collagen. Inhibition of ADP induced platelet 5-HT release by both of these extracts, was dose-dependent, with IC50 values for E. vespertilio and C. ambiguus estimated to be 20.4 microl (1.855 mg/ml) and 8.34 microl (0.758 mg/ml), respectively. Overall, C. ambiguus exhibited most activity and also caused dose-dependent inhibition of A.A induced platelet activation. These results indicate that inhibition may occur specifically at a site within the A.A pathway, and suggest the presence of a cyclo-oxygenase inhibitor. Both E. vespertilio and C. ambiguus are reported to be traditional headache treatments, with the present study providing evidence that they affect 5-HT release.

Maternal pregravid body mass index and child hospital admissions in the first 5 years of life: results from an Australian birth cohort

Objectives: To examine the association of maternal pregravid body mass index (BMI) and child offspring, all-cause hospitalisations in the first 5 years of life. Methods: Prospective birth cohort study. From 2006 to 2011, 2779 pregnant women (2807 children) were enrolled in the Environments for Healthy Living: Griffith birth cohort study in South-East Queensland, Australia. Hospital delivery record and self-report baseline survey of maternal, household and demographic factors during pregnancy were linked to the Queensland Hospital Admitted Patients Data Collection from 1 November 2006 to 30 June 2012, for child admissions. Maternal pregravid BMI was classified as underweight (<18.5 kg m−2), normal weight (18.5–24.9 kg m−2), overweight (25.0–29.9 kg m−2) or obese (30 kg m−2). Main outcomes were the total number of child hospital admissions and ICD-10-AM diagnostic groupings in the first 5 years of life. Negative binomial regression models were calculated, adjusting for follow-up duration, demographic and health factors. The cohort comprised 8397.9 person years (PYs) follow-up. Results: Children of mothers who were classified as obese had an increased risk of all-cause hospital admissions in the first 5 years of life than the children of mothers with a normal BMI (adjusted rate ratio (RR) =1.48, 95% confidence interval 1.10–1.98). Conditions of the nervous system, infections, metabolic conditions, perinatal conditions, injuries and respiratory conditions were excessive, in both absolute and relative terms, for children of obese mothers, with RRs ranging from 1.3–4.0 (PYs adjusted). Children of mothers who were underweight were 1.8 times more likely to sustain an injury or poisoning than children of normal-weight mothers (PYs adjusted). Conclusion: Results suggest that if the intergenerational impact of maternal obesity (and similarly issues related to underweight) could be addressed, a significant reduction in child health care use, costs and public health burden would be likely.