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.

Mechanochemical treatment of kaolinite

Kaolinite surfaces were modified by mechanochemical treatment for periods of time up to 10 h. X-ray diffraction shows a steady decrease in intensity of the d(001) spacing with mechanochemical treatment, resulting in the delamination of the kaolinite and a subsequent decrease in crystallite size with grinding time. Thermogravimetric analyses show the dehydroxylation patterns of kaolinite are significantly modified. Changes in the molecular structure of the kaolinite surface hydroxyls were followed by infrared spectroscopy. Hydroxyls were lost after 10 h of grinding as evidenced by a decrease in intensity of the OH stretching vibrations at 3695 and 3619 cm−1 and the deformation modes at 937 and 915 cm−1. Concomitantly an increase in the hydroxyl stretching vibrations of water is found. The water-bending mode was observed at 1650 cm−1, indicating that water is coordinating to the modified kaolinite surface. Changes in the surface structure of the OSiO units were reflected in the SiO stretching and OSiO bending vibrations. The decrease in intensity of the 1056 and 1034 cm−1 bands attributed to kaolinite SiO stretching vibrations were concomitantly matched by the increase in intensity of additional bands at 1113 and 520 cm−1 ascribed to the new mechanically synthesized kaolinite surface. Mechanochemical treatment of the kaolinite results in a new surface structure.

The effect of mechanochemical activation upon the intercalation of a high-defect kaolinite with formamide

The effect of mechanochemical activation upon the intercalation of formamide into a high-defect kaolinite has been studied using a combination of X-ray diffraction, thermal analysis, and DRIFT spectroscopy. X-ray diffraction shows that the intensity of the d(001) spacing decreases with grinding time and that the intercalated high-defect kaolinite expands to 10.2 A. The intensity of the peak of the expanded phase of the formamide-intercalated kaolinite decreases with grinding time. Thermal analysis reveals that the evolution temperature of the adsorbed formamide and loss of the inserting molecule increases with increased grinding time. The temperature of the dehydroxylation of the formamide-intercalated high-defect kaolinite decreases from 495 to 470oC with mechanochemical activation. Changes in the surface structure of the mechanochemically activated formamide-intercalated high-defect kaolinite were followed by DRIFT spectroscopy. Fundamentally the intensity of the high-defect kaolinite hydroxyl stretching bands decreases exponentially with grinding time and simultaneously the intensity of the bands attributed to the OH stretching vibrations of water increased. It is proposed that the mechanochemical activation of the high-defect kaolinite caused the conversion of the hydroxyls to water which coordinates the kaolinite surface. Significant changes in the infrared bands assigned to the hydroxyl deformation and amide stretching and bending modes were observed. The intensity decrease of these bands was exponentially related to the grinding time. The position of the amide C&unknown;O vibrational mode was found to be sensitive to grinding time. The effect of mechanochemical activation of the high-defect kaolinite reduces the capacity of the kaolinite to be intercalated with formamide.

Autoethnography : critical appreciation of an emerging art

In this article, the author discusses how she applied autoethnography in a study of the design of hypermedia educational resources and shows how she addressed problematic issues related to autoethnographic legitimacy and representation. The study covered a 6-year period during which the practitioner’s perspective on the internal and external factors influencing the creation of three hypermedia CD-ROMs contributed to an emerging theory of design. The author highlights the interrelationship between perception and reality as vital to qualitative approaches and encourages researchers to investigate their reality more fully by practicing the art of autoethnography.

Smoothing a Discrete Hazard Function for the Number of Patients Colonized with Methicillin-Resistance Staphylococcus Aureus in an Intensive Care Unit

A new method for estimating the time to colonization of Methicillin-resistant Staphylococcus Aureus (MRSA) patients is developed in this paper. The time to colonization of MRSA is modelled using a Bayesian smoothing approach for the hazard function. There are two prior models discussed in this paper: the first difference prior and the second difference prior. The second difference prior model gives smoother estimates of the hazard functions and, when applied to data from an intensive care unit (ICU), clearly shows increasing hazard up to day 13, then a decreasing hazard. The results clearly demonstrate that the hazard is not constant and provide a useful quantification of the effect of length of stay on the risk of MRSA colonization which provides useful insight.

On Ordinal VC-Dimension and Some Notions of Complexity

We generalize the classical notion of Vapnik–Chernovenkis (VC) dimension to ordinal VC-dimension, in the context of logical learning paradigms. Logical learning paradigms encompass the numerical learning paradigms commonly studied in Inductive Inference. A logical learning paradigm is defined as a set W of structures over some vocabulary, and a set D of first-order formulas that represent data. The sets of models of ϕ in W, where ϕ varies over D, generate a natural topology W over W. We show that if D is closed under boolean operators, then the notion of ordinal VC-dimension offers a perfect characterization for the problem of predicting the truth of the members of D in a member of W, with an ordinal bound on the number of mistakes. This shows that the notion of VC-dimension has a natural interpretation in Inductive Inference, when cast into a logical setting. We also study the relationships between predictive complexity, selective complexity—a variation on predictive complexity—and mind change complexity. The assumptions that D is closed under boolean operators and that W is compact often play a crucial role to establish connections between these concepts. We then consider a computable setting with effective versions of the complexity measures, and show that the equivalence between ordinal VC-dimension and predictive complexity fails. More precisely, we prove that the effective ordinal VC-dimension of a paradigm can be defined when all other effective notions of complexity are undefined. On a better note, when W is compact, all effective notions of complexity are defined, though they are not related as in the noncomputable version of the framework.

Raman spectroscopy of kaolinites using different excitation wavelengths

The Raman spectra of both low- and high-defect kaolinites in the hydroxyl stretching and low-wavenumber region were obtained with excitation at three visible wavelengths of 633, 514 and 442 nm and a UV wavelength of 325 nm. The UV-excited spectra were comparable to those excited by the visible wavelengths. The Raman spectra show hydroxyl stretching bands at 3621 cm-1 attributed to the inner hydroxyl, at 3692 and 3684 cm-1 attributed to the longitudinal and transverse optic modes of the inner surface hydroxyls and at 3668 and 3653 cm-1 assigned to the out-of phase vibrations of the inner surface hydroxyls. Two bands were observed in the spectral profile at 3695 cm-1 for the high-defect kaolinite at 3698 and 3691 cm-1 and were assigned to TO/LO splitting. An increase in relative intensity of the transverse optic mode is observed with decrease in laser wavelength. The intensity of the out-of-phase vibrations at 3668 and 3653 cm-1 of the inner surface hydroxyls shows a linear relationship with the longitudinal and transverse optic modes. In the low-wavenumber region excellent correlation was found between the experimentally determined and the calculated band positions.

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.

Tracking people in 3D using position, size and shape

This paper presents a prototype tracking system for tracking people in enclosed indoor environments where there is a high rate of occlusions. The system uses a stereo camera for acquisition, and is capable of disambiguating occlusions using a combination of depth map analysis, a two step ellipse fitting people detection process, the use of motion models and Kalman filters and a novel fit metric, based on computationally simple object statistics. Testing shows that our fit metric outperforms commonly used position based metrics and histogram based metrics, resulting in more accurate tracking of people.

Testing a framework for the quality of process models: A case study

Process modeling can be regarded as the currently most popular form of conceptual modeling. Research evidence illustrates how process modeling is applied across the different information system life cycle phases for a range of different applications, such as configuration of Enterprise Systems, workflow management, or software development. However, a detailed discussion of critical factors of the quality of process models is still missing. This paper proposes a framework consisting of six quality factors, which is derived from a comprehensive literature review. It then presents in a case study, a utility provider, who had designed various business process models for the selection of an Enterprise System. The paper summarizes potential means of conducting a successful process modeling initiative and evaluates the described modeling approach within the Guidelines of Modeling (GoM) framework. An outlook shows the potential lessons learnt, and concludes with insights to the next phases of this study.

A Method of Preparing Future Hourly Weather Data for the Study of Global Warming Impact on the Built Environment

The dynamic interaction between building systems and external climate is extremely complex, involving a large number of difficult-to-predict variables. In order to study the impact of global warming on the built environment, the use of building simulation techniques together with forecast weather data are often necessary. Since all building simulation programs require hourly meteorological input data for their thermal comfort and energy evaluation, the provision of suitable weather data becomes critical. Based on a review of the existing weather data generation models, this paper presents an effective method to generate approximate future hourly weather data suitable for the study of the impact of global warming. Depending on the level of information available for the prediction of future weather condition, it is shown that either the method of retaining to current level, constant offset method or diurnal modelling method may be used to generate the future hourly variation of an individual weather parameter. An example of the application of this method to the different global warming scenarios in Australia is presented. Since there is no reliable projection of possible change in air humidity, solar radiation or wind characters, as a first approximation, these parameters have been assumed to remain at the current level. A sensitivity test of their impact on the building energy performance shows that there is generally a good linear relationship between building cooling load and the changes of weather variables of solar radiation, relative humidity or wind speed.

Success factors in an alliancing contract : a case study in Australia

Many studies have been carried out in relation to construction procurement methods. Evidence shows that there needs to be a change of culture and attitude in the construction industry, moving away from traditional adversarial relationship into cooperative and collaborative relationship. At the same time there is also an increasing concern and discussion on alternative procurement methods, drifting away from traditional procurement systems. Relational contracting approaches have become more popular in recent years, and have appeared in common forms such as partnering, alliancing and relationship management contracts. This paper reports the findings of a survey undertaken with a private organisation based on an alliance project during its design stage, identifying the critical factors that influence the success of the alliance project. Legal aspects focusing on dispute resolution in alliancing are also highlighted.

Adaptive optical flow for person tracking

Person tracking systems are dependent on being able to locate a person accurately across a series of frames. Optical flow can be used to segment a moving object from a scene, provided the expected velocity of the moving object is known; but successful detection also relies on being able segment the background. A problem with existing optical flow techniques is that they don’t discriminate the foreground from the background, and so often detect motion (and thus the object) in the background. To overcome this problem, we propose a new optical flow technique, that is based upon an adaptive background segmentation technique, which only determines optical flow in regions of motion. This technique has been developed with a view to being used in surveillance systems, and our testing shows that for this application it is more effective than other standard optical flow techniques.

How does ‘Newstainment’ actually work? : ethnographic research methods and contemporary popular news

Much debate has taken place recently over the potential for entertainment genres and unorthodox forms of news to provide legitimate – indeed democratized – in-roads into the public sphere. Amidst these discussions, however, little thought has been paid to the audiences for programs of this sort, and (even when viewers are considered) the research can too easily treat audiences in homogenous terms and therefore replicate the very dichotomies these television shows directly challenge. This paper is a critical reflection on an audience study into the Australian morning “newstainment” program Sunrise. After examining the show and exploring how it is ‘used’ as a news source, this paper will promote the use of ethnographic study to better conceptualize how citizens integrate and connect the increasingly fragmented and multifarious forms of postmodern political communication available in their everyday lives.

From concept to embodiment : challenge and strategy

Facing with the difficulty in information propagation and synthesizing from conceptual to embodiment design, this paper introduces a function-oriented, axiom based conceptual modeling scheme. Default logic reasoning is exploited for recognition and reconstitution of conceptual product geometric and topological information. The proposed product modeling system and reasoning approach testify a methodology of "structural variation design", which is verified in the implementation of a GPAL (Green Product All Life-cycle) CAD system. The GPAL system includes major enhancement modules of a mechanism layout sketching method based on fuzzy logic, a knowledge-based function-to-form mapping mechanism and conceptual form reconstitution paradigm based on default geometric reasoning. A mechanical hand design example shows a more than 20 times increase in design efficacy with these enhancement modules in the GPAL system on a general 3D CAD platform.