Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.

Air pollution levels measured at traffic hot spots : Brisbane urban corridor study

Air pollution levels were monitored continuously over a period of 4 weeks at four sampling sites along a busy urban corridor in Brisbane. The selected sites were representative of industrial and residential types of urban environment affected by vehicular traffic emissions. The concentration levels of submicrometer particle number, PM2.5, PM10, CO, and NOx were measured 5-10 meters from the road. Meteorological parameters and traffic flow rates were also monitored. The data were analysed in terms of the relationship between monitored pollutants and existing ambient air quality standards. The results indicate that the concentration levels of all pollutants exceeded the ambient air background levels, in certain cases by up to an order of magnitude. While the 24-hr average concentration levels did not exceed the standard, estimates for the annual averages were close to, or even higher than the annual standard levels.

How can land and urban development make houses healthier?

Traditionally, the main focus of the professional community involved with indoor air quality has been indoor pollution sources, preventing or reducing their emissions, as well as lowering the impact of the sources by replacing the polluted indoor air with "fresh" outdoor air. However, urban outdoor air cannot often be considered "fresh", as it contains high concentrations of pollutants emitted from motor vehicles - the main outdoor pollution sources in cities. Evidence from epidemiological studies conducted worldwide demonstrates that outdoor air quality has considerable effects on human health, despite the fact that people spend the majority of their time indoors. This is because pollution from outdoors penetrates indoors and becomes a major constituent of indoor pollution. Urban land and transport development has significant impact on the overall air quality of the urban airshed as well as the pollution concentration in the vicinity of high-density traffic areas. Therefore, an overall improvement in indoor air quality would be achieved by lowering urban airshed pollution, as well as by lowering the impact of the hot spots on indoor air. This paper explores the elements of urban land and vehicle transport developments, their impact on global and local air quality, and how the science of outdoor pollution generation and transport in the air could be utilized in urban development towards lowering indoor air pollution.