Photochemistry and chemometrics : an overview

Photochemistry has made significant contributions to our understanding of many important natural processes as well as the scientific discoveries of the man-made world. The measurements from such studies are often complex and may require advanced data interpretation with the use of multivariate or chemometrics methods. In general, such methods have been applied successfully for data display, classification, multivariate curve resolution and prediction in analytical chemistry, environmental chemistry, engineering, medical research and industry. However, in photochemistry, by comparison, applications of such multivariate approaches were found to be less frequent although a variety of methods have been used, especially with spectroscopic photochemical applications. The methods include Principal Component Analysis (PCA; data display), Partial Least Squares (PLS; prediction), Artificial Neural Networks (ANN; prediction) and several models for multivariate curve resolution related to Parallel Factor Analysis (PARAFAC; decomposition of complex responses). Applications of such methods are discussed in this overview and typical examples include photodegradation of herbicides, prediction of antibiotics in human fluids (fluorescence spectroscopy), non-destructive in- and on-line monitoring (near infrared spectroscopy) and fast-time resolution of spectroscopic signals from photochemical reactions. It is also quite clear from the literature that the scope of spectroscopic photochemistry was enhanced by the application of chemometrics. To highlight and encourage further applications of chemometrics in photochemistry, several additional chemometrics approaches are discussed using data collected by the authors. The use of a PCA biplot is illustrated with an analysis of a matrix containing data on the performance of photocatalysts developed for water splitting and hydrogen production. In addition, the applications of the Multi-Criteria Decision Making (MCDM) ranking methods and Fuzzy Clustering are demonstrated with an analysis of water quality data matrix. Other examples of topics include the application of simultaneous kinetic spectroscopic methods for prediction of pesticides, and the use of response fingerprinting approach for classification of medicinal preparations. In general, the overview endeavours to emphasise the advantages of chemometrics' interpretation of multivariate photochemical data, and an Appendix of references and summaries of common and less usual chemometrics methods noted in this work, is provided. Crown Copyright © 2010.

The role of anxiety and perspective-taking strategy on affective empathic responses

Empathy is an important pro-social behaviour critical to a positive clientetherapist relationship. Therapist anxiety has been linked to reduced ability to empathise and lower client satisfaction with therapy. However, the nature of the relationship between anxiety and empathy is currently unclear. The current study investigated the effect of experimentally-induced anxiety on empathic responses elicited during three different perspective-taking tasks. Perspective-taking was manipulated within-subjects with all participants (N¼ 52) completing imagine-self, imagine-other and objective conditions. A threat of shock manipulation was used to vary anxiety between-subjects. Participants in the threat of shock condition reported higher levels of anxiety during the experiment and lower levels of empathyrelated distress for the targets than participants in the control condition. Perspective-taking was associated with higher levels of empathy-related distress and concern compared to the objective condition. The present results suggest that perspective-taking can to a large extent mitigate the influence of heightened anxiety on an individual’s ability to empathise.

Source characterisation of road dust based on chemical and mineralogical composition

Road dust contain potentially toxic pollutants originating from a range of anthropogenic sources common to urban land uses and soil inputs from surrounding areas. The research study analysed the mineralogy and morphology of dust samples from road surfaces from different land uses and background soil samples to characterise the relative source contributions to road dust. The road dust consist primarily of soil derived minerals (60%) with quartz averaging 40-50% and remainder being clay forming minerals of albite, microcline, chlorite and muscovite originating from surrounding soils. About 2% was organic matter primarily originating from plant matter. Potentially toxic pollutants represented about 30% of the build-up. These pollutants consist of brake and tire wear, combustion emissions and fly ash from asphalt. Heavy metals such as Zn, Cu, Pb, Ni, Cr and Cd primarily originate from vehicular traffic while Fe, Al and Mn primarily originate from surrounding soils. The research study confirmed the significant contribution of vehicular traffic to dust deposited on urban road surfaces.

Genetic evidence for the vital function of osterix in cementogenesis

To date, attempts to regenerate a complete tooth, including the critical periodontal tissues associated with the tooth root, have not been successful. Controversy still exists regarding the origin of the cell source for cellular cementum (epithelial or mesenchymal). This disagreement may be partially due to a lack of understanding of the events leading to the initiation and development of the tooth roots and supportive tissues, such as the cementum. Osterix (OSX) is a transcriptional factor essential for osteogenesis, but its role in cementogenesis has not been addressed. In the present study, we first documented a close relationship between the temporal- and spatial-expression pattern of OSX and the formation of cellular cementum. We then generated 3.6 Col 1-OSX transgenic mice, which displayed accelerated cementum formation vs. WT controls. Importantly, the conditional deletion of OSX in the mesenchymal cells with two different Cre systems (the 2.3 kb Col 1 and an inducible CAG-CreER) led to a sharp reduction in cellular cementum formation (including the cementum mass and mineral deposition rate) and gene expression of dentin matrix protein 1 (DMP1) by cementocytes. However, the deletion of the OSX gene after cellular cementum formed did not alter the properties of the mature cementum as evaluated by backscattered SEM and resin-cast SEM. Transient transfection of Osx in the cementoblasts in vitro significantly inhibited cell proliferation and increased cell differentiation and mineralization. Taken together, these data support 1) the mesenchymal origin of cellular cementum (from PDL progenitor cells); 2) the vital role of OSX in controlling the formation of cellular cementum; and 3) the limited remodeling of cellular cementum in adult mice.

'Nothing exists for one cause' : putting biology back into evolution

The opening phrase of the title is from Charles Darwin’s notebooks (Schweber 1977). It is a double reminder, firstly that mainstream evolutionary theory is not just about describing nature but is particularly looking for mechanisms or ‘causes’, and secondly, that there will usually be several causes affecting any particular outcome. The second part of the title is our concern at the almost universal rejection of the idea that biological mechanisms are sufficient for macroevolutionary changes, thus rejecting a cornerstone of Darwinian evolutionary theory. Our primary aim here is to consider ways of making it easier to develop and to test hypotheses about evolution. Formalizing hypotheses can help generate tests. In an absolute sense, some of the discussion by scientists about evolution is little better than the lack of reasoning used by those advocating intelligent design. Our discussion here is in a Popperian framework where science is defined by that area of study where it is possible, in principle, to find evidence against hypotheses – they are in principle falsifiable. However, with time, the boundaries of science keep expanding. In the past, some aspects of evolution were outside the current boundaries of falsifiable science, but increasingly new techniques and ideas are expanding the boundaries of science and it is appropriate to re-examine some topics. It often appears that over the last few decades there has been an increasingly strong assumption to look first (and only) for a physical cause. This decision is virtually never formally discussed, just an assumption is made that some physical factor ‘drives’ evolution. It is necessary to examine our assumptions much more carefully. What is meant by physical factors ‘driving’ evolution, or what is an ‘explosive radiation’. Our discussion focuses on two of the six mass extinctions, the fifth being events in the Late Cretaceous, and the sixth starting at least 50,000 years ago (and is ongoing). Cretaceous/Tertiary boundary; the rise of birds and mammals. We have had a long-term interest (Cooper and Penny 1997) in designing tests to help evaluate whether the processes of microevolution are sufficient to explain macroevolution. The real challenge is to formulate hypotheses in a testable way. For example the numbers of lineages of birds and mammals that survive from the Cretaceous to the present is one test. Our first estimate was 22 for birds, and current work is tending to increase this value. This still does not consider lineages that survived into the Tertiary, and then went extinct later. Our initial suggestion was probably too narrow in that it lumped four models from Penny and Phillips (2004) into one model. This reduction is too simplistic in that we need to know about survival and ecological and morphological divergences during the Late Cretaceous, and whether Crown groups of avian or mammalian orders may have existed back into the Cretaceous. More recently (Penny and Phillips 2004) we have formalized hypotheses about dinosaurs and pterosaurs, with the prediction that interactions between mammals (and groundfeeding birds) and dinosaurs would be most likely to affect the smallest dinosaurs, and similarly interactions between birds and pterosaurs would particularly affect the smaller pterosaurs. There is now evidence for both classes of interactions, with the smallest dinosaurs and pterosaurs declining first, as predicted. Thus, testable models are now possible. Mass extinction number six: human impacts. On a broad scale, there is a good correlation between time of human arrival, and increased extinctions (Hurles et al. 2003; Martin 2005; Figure 1). However, it is necessary to distinguish different time scales (Penny 2005) and on a finer scale there are still large numbers of possibilities. In Hurles et al. (2003) we mentioned habitat modification (including the use of Geogenes III July 2006 31 fire), introduced plants and animals (including kiore) in addition to direct predation (the ‘overkill’ hypothesis). We need also to consider prey switching that occurs in early human societies, as evidenced by the results of Wragg (1995) on the middens of different ages on Henderson Island in the Pitcairn group. In addition, the presence of human-wary or humanadapted animals will affect the distribution in the subfossil record. A better understanding of human impacts world-wide, in conjunction with pre-scientific knowledge will make it easier to discuss the issues by removing ‘blame’. While continued spontaneous generation was accepted universally, there was the expectation that animals continued to reappear. New Zealand is one of the very best locations in the world to study many of these issues. Apart from the marine fossil record, some human impact events are extremely recent and the remains less disrupted by time.

Visualising the 48 hour game making challenge

We have always felt that “something very special” was happening in the 48hr and other similar game jams. This “something” is more than the intensity and challenge of the experience, although this certainly has appeal for the participants. We had an intuition that these intense 48 hour game jams exposed something pertinent to the changing shape of the Australian games industry where we see the demise of the late 20th century large studio - the “Night Elf” model and the growth of the small independent model. There are a large number of wider economic and cultural factors around this evolution but our interest is specifically in the change from “industry” to “creative industry” and the growth of games as a cultural media and art practice. If we are correct in our intuition, then illuminating this something also has important ramifications for those courses which teach game and interaction design and development. Rather than undertake a formal ethno-methodological approach, we decided to track as many of the actors in the event as possible. We documented the experience (Keith Novak’s beautiful B&W photography), the individual and their technology (IOGraph mouse tracking), the teams as a group (Time lapse photography) and movement tracking throughout the whole space (Blue tooth phone tracking). The raw data collected has given us opportunity to start a commentary on the “something special” happening in the 48hr.

Floods and human health : a systematic review

Floods are the most common type of disaster globally, responsible for almost 53,000 deaths in the last decade alone (23:1 low- versus high-income countries). This review assessed recent epidemiological evidence on the impacts of floods on human health. Published articles (2004–2011) on the quantitative relationship between floods and health were systematically reviewed. 35 relevant epidemiological studies were identified. Health outcomes were categorized into short- and long-term and were found to depend on the flood characteristics and people's vulnerability. It was found that long-term health effects are currently not well understood. Mortality rates were found to increase by up to 50% in the first year post-flood. After floods, it was found there is an increased risk of disease outbreaks such as hepatitis E, gastrointestinal disease and leptospirosis, particularly in areas with poor hygiene and displaced populations. Psychological distress in survivors (prevalence 8.6% to 53% two years post-flood) can also exacerbate their physical illness. There is a need for effective policies to reduce and prevent flood-related morbidity and mortality. Such steps are contingent upon the improved understanding of potential health impacts of floods. Global trends in urbanization, burden of disease, malnutrition and maternal and child health must be better reflected in flood preparedness and mitigation programs.

Numerical techniques for the variable order time fractional diffusion equation

In this paper we consider the variable order time fractional diffusion equation. We adopt the Coimbra variable order (VO) time fractional operator, which defines a consistent method for VO differentiation of physical variables. The Coimbra variable order fractional operator also can be viewed as a Caputo-type definition. Although this definition is the most appropriate definition having fundamental characteristics that are desirable for physical modeling, numerical methods for fractional partial differential equations using this definition have not yet appeared in the literature. Here an approximate scheme is first proposed. The stability, convergence and solvability of this numerical scheme are discussed via the technique of Fourier analysis. Numerical examples are provided to show that the numerical method is computationally efficient. Crown Copyright © 2012 Published by Elsevier Inc. All rights reserved.

Numerical methods and analysis for a class of fractional advection-dispersion models

In this paper, a class of fractional advection–dispersion models (FADMs) is considered. These models include five fractional advection–dispersion models, i.e., the time FADM, the mobile/immobile time FADM with a time Caputo fractional derivative 0 < γ < 1, the space FADM with two sides Riemann–Liouville derivatives, the time–space FADM and the time fractional advection–diffusion-wave model with damping with index 1 < γ < 2. These equations can be used to simulate the regional-scale anomalous dispersion with heavy tails. We propose computationally effective implicit numerical methods for these FADMs. The stability and convergence of the implicit numerical methods are analysed and compared systematically. Finally, some results are given to demonstrate the effectiveness of theoretical analysis.

Analytical solutions for the multi-term time-fractional diffusion-wave/diffusion equations in a finite domain

Multi-term time-fractional differential equations have been used for describing important physical phenomena. However, studies of the multi-term time-fractional partial differential equations with three kinds of nonhomogeneous boundary conditions are still limited. In this paper, a method of separating variables is used to solve the multi-term time-fractional diffusion-wave equation and the multi-term time-fractional diffusion equation in a finite domain. In the two equations, the time-fractional derivative is defined in the Caputo sense. We discuss and derive the analytical solutions of the two equations with three kinds of nonhomogeneous boundary conditions, namely, Dirichlet, Neumann and Robin conditions, respectively.

UK Design as a Global Industry : International Trade and Intellectual Property

The importance of design to the UK economy is widely recognised. It is one of the key pillars of the knowledge economy, it plays an important role in the innovation process, and it is one of a number of specialisms that help to set the UK apart from global competition. But despite this importance, the nature of design-intensive industries – the businesses that practice and sell design – is remarkably hard to pin down. This uncertainty renders it hard to analyse, and makes it difficult to develop clear, consistent policies to support the designers. The Hargreaves Review recommended that more research was needed to develop a clear evidence base for improving the intellectual property system for design. This report forms part of that evidence base. It examines how UK design figures in the global economy, and considers how the intellectual property system can best support its growth.

UK Design as a global industry : international trade and intellectual property Executive Summary

This is an independent report comissioned by the Intellectual Property Office (IPO) and supported by the Design Council.

Growth-hormone-stimulated dentinogenesis in Lewis dwarf rat molars

In dentinogenesis, certain growth factors, matrix proteoglycans, and proteins are directly or indirectly dependent on growth hormone. The hypothesis that growth hormone up-regulates the expression of enzymes, sialoproteins, and other extracellular matrix proteins implicated in the formation and mineralization of tooth and bone matrices was tested by the treatment of Lewis dwarf rats with growth hormone over 5 days. The molar teeth were processed for immunohistochemical demonstration of bone-alkaline phosphatase, bone morphogenetic proteins-2 and -4, osteocalcin, osteopontin, bone sialoprotein, and E11 protein. Odontoblasts responded to growth hormone by more cells expressing bone morphogenetic protein, alkaline phosphatase, osteocalcin, and osteopontin. No changes were found in bone sialoprotein or E11 protein expression. Thus, growth hormone may stimulate odontoblasts to express several growth factors and matrix proteins associated with dentin matrix biosynthesis in mature rat molars.

Quantile regression without the curse of unsmoothness

We consider quantile regression models and investigate the induced smoothing method for obtaining the covariance matrix of the regression parameter estimates. We show that the difference between the smoothed and unsmoothed estimating functions in quantile regression is negligible. The detailed and simple computational algorithms for calculating the asymptotic covariance are provided. Intensive simulation studies indicate that the proposed method performs very well. We also illustrate the algorithm by analyzing the rainfall–runoff data from Murray Upland, Australia.

The use of computerised simulators for training of transthoracic and transoesophageal echocardiography. The future of echocardiographic training?

Echocardiography is the commonest form of non-invasive cardiac imaging and is fundamental to patient management. However, due to its methodology, it is also operator dependent. There are well defined pathways in training and ongoing accreditation to achieve and maintain competency. To satisfy these requirements, significant time has to be dedicated to scanning patients, often in the time pressured clinical environment. Alternative, computer based training methods are being considered to augment echocardiographic training. Numerous advances in technology have resulted in the development of interactive programmes and simulators to teach trainees the skills to perform particular procedures, including transthoracic and transoesophageal echocardiography. 82 sonographers and TOE proceduralists utilised an echocardiographic simulator and assessed its utility using defined criteria. 40 trainee sonographers assessed the simulator and were taught how to obtain an apical 2 chamber (A2C) view and image the superior vena cava (SVC). 100% and 88% found the simulator useful in obtaining the SVC or A2C view respectively. All users found it easy to use and the majority found it helped with image acquisition and interpretation. 42 attendees of a TOE training day utilising the simulator assessed the simulator with 100% finding it easy to use, as well as the augmented reality graphics benefiting image acquisition. 90% felt that it was realistic. This study revealed that both trainee sonographers and TOE proceduralists found the simulation process was realistic, helped in image acquisition and improved assessment of spatial relationships. Echocardiographic simulators may play an important role in the future training of echocardiographic skills.