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.

Particle and gaseous emissions from compressed natural gas and ultralow sulphur diesel-fuelled buses at four steady engine loads

Exhaust emissions from thirteen compressed natural gas (CNG) and nine ultralow sulphur diesel in-service transport buses were monitored on a chassis dynamometer. Measurements were carried out at idle and at three steady engine loads of 25%, 50% and 100% of maximum power at a fixed speed of 60 kmph. Emission factors were estimated for particle mass and number, carbon dioxide and oxides of nitrogen for two types of CNG buses (Scania and MAN, compatible with Euro 2 and 3 emission standards, respectively) and two types of diesel buses (Volvo Pre-Euro/Euro1 and Mercedez OC500 Euro3). All emission factors increased with load. The median particle mass emission factor for the CNG buses was less than 1% of that from the diesel buses at all loads. However, the particle number emission factors did not show a statistically significant difference between buses operating on the two types of fuel. In this paper, for the very first time, particle number emission factors are presented at four steady state engine loads for CNG buses. Median values ranged from the order of 1012 particles min-1 at idle to 1015 particles km-1 at full power. Most of the particles observed in the CNG emissions were in the nanoparticle size range and likely to be composed of volatile organic compounds The CO2 emission factors were about 20% to 30% greater for the diesel buses over the CNG buses, while the oxides of nitrogen emission factors did not show any difference due to the large variation between buses.

1,10-phenanthrolin-1-ium 2-carboxy-4,5-dichlorobenzoate

In the structure of the 1:1 proton-transfer compound of 1,10-phenanthroline with 4,5-dichlorophthalic acid, C12H9N2+ C8H3Cl2O4-, determined at 130 K, the 1,10-phenanthroline cation and the hydrogen 4,5-dichlorophthalate anion associate through a single N-H...O(carboxyl) hydrogen bond giving discrete units which have no extension except through a number of weak cation C-H...O(anion) associations and weak cation--anion aromatic ring pi-pi interactions [minimum centroid separation, 3.6815(12)A]. The anions are essentially planar [maximum deviation 0.214(1)A (a carboxyl O)] with the syn-related H atom of the carboxyl group forming a short intramolecular O-H...O(carboxyl) hydrogen bond.

Raman spectroscopic study of the mixed anion sulphate-arsenate mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O has been studied by Raman spectroscopy. Characteristic bands associated with arsenate, sulphate, hydroxyl units are identified. Broad bands are observed and are resolved into component bands. Two intense bands at 859 and 830 cm-1 are assigned to the 1 (AsO4)3- symmetric stretching and 3 (AsO4)3- antisymmetric stretching modes. The comparatively sharp band at 976 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode and a broad spectral profile centered upon 1097 cm-1 is attributed to the ν3 (SO4)2- antisymmetric stretching mode. A comparison of the Raman spectra is made with other arsenate bearing minerals such as carminite, clinotyrolite, kankite, tilasite and pharmacosiderite.

Uncertainty budget in the measurement of typical airborne number, surface area and mass particle distributions

The effects of particulate matter on environment and public health have been widely studied in recent years. A number of studies in the medical field have tried to identify the specific effect on human health of particulate exposure, but agreement amongst these studies on the relative importance of the particles’ size and its origin with respect to health effects is still lacking. Nevertheless, air quality standards are moving, as the epidemiological attention, towards greater focus on the smaller particles. Current air quality standards only regulate the mass of particulate matter less than 10 μm in aerodynamic diameter (PM10) and less than 2.5 μm (PM2.5). The most reliable method used in measuring Total Suspended Particles (TSP), PM10, PM2.5 and PM1 is the gravimetric method since it directly measures PM concentration, guaranteeing an effective traceability to international standards. This technique however, neglects the possibility to correlate short term intra-day variations of atmospheric parameters that can influence ambient particle concentration and size distribution (emission strengths of particle sources, temperature, relative humidity, wind direction and speed and mixing height) as well as human activity patterns that may also vary over time periods considerably shorter than 24 hours. A continuous method to measure the number size distribution and total number concentration in the range 0.014 – 20 μm is the tandem system constituted by a Scanning Mobility Particle Sizer (SMPS) and an Aerodynamic Particle Sizer (APS). In this paper, an uncertainty budget model of the measurement of airborne particle number, surface area and mass size distributions is proposed and applied for several typical aerosol size distributions. The estimation of such an uncertainty budget presents several difficulties due to i) the complexity of the measurement chain, ii) the fact that SMPS and APS can properly guarantee the traceability to the International System of Measurements only in terms of number concentration. In fact, the surface area and mass concentration must be estimated on the basis of separately determined average density and particle morphology. Keywords: SMPS-APS tandem system, gravimetric reference method, uncertainty budget, ultrafine particles.

A gendered educational agenda : what's wrong with 10 Things I Hate About You?

Both William Shakespeare's play The Taming of the Shrew (1593) and the film 10 thing I hate About You (Gil Junger, 1999) contain tropes of gender and education and gendered education, and both represent and perform 'education'. That is, they depict characters undergoing a range of educational experiences and in turn educate their audience about what it means to be educated appropriately. It seems fitting then that these pairng of texts has been popular with high school teachers who, more often than not, use them as ways into teaching Shakespeare to contemporary adolescents. I suggest that the play-film pairing can be more productively introduced into the classroom as texts that offer critical readers the opportunity to contest the values of education and gender contatined within them, rather than as tools to reintroduce outdated notions of gendered agency and cultural authority. Indeed it is precisely because 10 Things is unequivocally a romantic comedy that aims to work within the audience's comfort zone that we must seriously interrogate the cultural politics of gender and education it promotes.

Analysis of phasor measurement method in tracking the power frequency of distorted signals

This paper presents an analysis of phasor measurement method for tracking the fundamental power frequency to show if it has the performance necessary to cope with the requirements of power system protection and control. In this regard, several computer simulations presenting the conditions of a typical power system signal especially those highly distorted by harmonics, noise and offset, are provided to evaluate the response of the Phasor Measurement (PM) technique. A new method, which can shorten the delay of estimation, has also been proposed for the PM method to work for signals free of even-order harmonics.

A practical approach for reliability prediction of pipeline systems

Pipelines play an important role in the modern society. Failures of pipelines can have great impacts on economy, environment and community. Preventive maintenance (PM) is often conducted to improve the reliability of pipelines. Modern asset management practice requires accurate predictability of the reliability of pipelines with multiple PM actions, especially when these PM actions involve imperfect repairs. To address this issue, a split system approach (SSA) based model is developed in this paper through an industrial case study. This new model enables maintenance personnel to predict the reliability of pipelines with different PM strategies and hence effectively assists them in making optimal PM decisions.

Year 8, 9 and 10 students’ understanding and access of percent knowledge

This paper reports on Years 8, 9 and 10 students’ knowledge of percent problem types, use of diagrams, and type of solution strategy. Non- and semi-proficient students displayed the expected inflexible formula approach to solution but proficient students used a flexible mixture of estimation, number sense and trial and error instead of expected schema based methods.

The 10% rule. Maximising learning through collaborative game design

This paper presents a retrospective view of a game design practice that recently switched from the development of complex learning games to the development of simple authoring tools for students to design their own learning games for each other. We introduce how our ‘10% Rule’, a premise that only 10% of what is learnt during a game design process is ultimately appreciated by the player, became a major contributor to the evolving practice. We use this rule primarily as an analytical and illustrative tool to discuss the learning involved in designing and playing learning games rather than as a scientifically and empirically proven rule. The 10% rule was promoted by our experience as designers and allows us to explore the often overlooked and valuable learning processes involved in designing learning games and mobile games in particular. This discussion highlights that in designing mobile learning games, students are not only reflecting on their own learning processes through setting up structures for others to enquire and investigate, they are also engaging in high-levels of independent inquiry and critical analysis in authentic learning settings. We conclude the paper with a discussion of the importance of these types of learning processes and skills of enquiry in 21st Century learning.

Quality of cause-of-death reporting using ICD-10 drowning codes : a descriptive study of 69 countries

Background: The systematic collection of high-quality mortality data is a prerequisite in designing relevant drowning prevention programmes. This descriptive study aimed to assess the quality (i.e., level of specificity) of cause-of-death reporting using ICD-10 drowning codes across 69 countries.---------- Methods: World Health Organization (WHO) mortality data were extracted for analysis. The proportion of unintentional drowning deaths coded as unspecified at the 3-character level (ICD-10 code W74) and for which the place of occurrence was unspecified at the 4th character (.9) were calculated for each country as indicators of the quality of cause-of-death reporting.---------- Results: In 32 of the 69 countries studied, the percentage of cases of unintentional drowning coded as unspecified at the 3-character level exceeded 50%, and in 19 countries, this percentage exceeded 80%; in contrast, the percentage was lower than 10% in only 10 countries. In 21 of the 56 countries that report 4-character codes, the percentage of unintentional drowning deaths for which the place of occurrence was unspecified at the 4th character exceeded 50%, and in 15 countries, exceeded 90%; in only 14 countries was this percentage lower than 10%.---------- Conclusion: Despite the introduction of more specific subcategories for drowning in the ICD-10, many countries were found to be failing to report sufficiently specific codes in drowning mortality data submitted to the WHO.