Climbing Combinatorial Fitness Landscapes

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Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Humanistic science education : moves from within and challenges from without

For a number of years now it has been evident that the major issue facing science educators in the more developed countries of the world is the quantitative decline in enrolments in the senior secondary sciences, particularly the physical sciences, and in the number of higher achieving students applying for places in universities to undertake further studies in science. The deep malaise in school science to which these quantitative measures point has been elucidated by more qualitative studies of the students’ experience of studying science in secondary school in several of these countries (Sweden, Lindahl (2003); England, Simon and Osborne (2002); and Australia, Lyons (2005)). Remarkably concordant descriptions of these experiences can be summarized as: School science is: • transmission of knowledge from the teacher or the textbook to the students. • about content that is irrelevant and boring to our lives. • difficult to learn in comparison with other subjects Incidentally, the Australian study only involved consistently high achieving students; but even so, most of them found science more difficult than other more interesting subjects, and concluded that further science studies should be avoided unless they were needed for some career purpose. Other more representative confirmations of negative evaluations of the science curricula across Australia (and in particular states) are now available in Australia, from the large scale reviews of Goodrum, Hackling and Rennie (2001) and from the TIMSS (2002). The former reported that well under half of secondary students find the science at school relevant to my future, useful ion everyday life, deals with things I am concerned with and helps me make decisions about my health.. TIMSS found that 62 and 65 % of females and males in Year 4 agree with I like learning science, but by Year 8 only 26 and 33 % still agree. Students in Japan have been doubly notably because of (a) their high performance in international measures of science achievement like TIMSS and PISA and (b) their very low response to items in these studies which relate to interest in science. Ogura (2003) reported an intra-national study of students across Years 6-9 (upper primary through Junior High); interest in a range of their subjects (including science) that make up that country’s national curriculum. There was a steady decline in interest in all these subjects which might have indicated an adolescent reaction against schooling generally. However, this study went on to ask the students a further question that is very meaningful in the Japanese context, If you discount the importance of this subject for university entrance, is it worth studying? Science and mathematics remained in decline while all the other subjects were seen more positively. It is thus ironic, at a time when some innovations in curriculum and other research-based findings are suggesting ways that these failures of school science might be corrected, to find school science under a new demands that come from quite outside science education, and which certainly do not have the correction of this malaise as a priority. The positive curricular and research findings can be characterized as moves from within science education, whereas the new demands are moves that come from without science education. In this paper I set out these two rather contrary challenges to the teaching of science as it is currently practised, and go on to suggest a way forward that could fruitfully combine the two.

Control schemes for equalization of capacitor voltages in neutral clamped shunt compensator

Voltage imbalance in capacitors is a well-known problem in compensator topologies which use two or more capacitors. This imbalance may exist even if the load does not contain any DC component, due to practical factors. However, when the load contains a DC part, the voltage imbalance problem becomes critical. In this paper, a two-quadrant chopper has been used to regulate the capacitor voltages in a two-capacitor compensator structure. Two different control strategies for the two-quadrant chopper to equalize the voltage of the capacitors have been proposed. The strategies are validated through detailed simulation studies. Experiments have also been carried out to validate the hysteresis control of chopper.

Driving speed is altered by monocular Neutral Density filters : the Enright phenomenon

Introduction: An observer, looking sideways from a moving vehicle, while wearing a neutral density filter over one eye, can have a distorted perception of speed, known as the Enright phenomenon. The purpose of this study was to determine how the Enright phenomenon influences driving behaviour. Methods: A geometric model of the Enright phenomenon was developed. Ten young, visually normal, participants (mean age = 25.4 years) were tested on a straight section of a closed driving circuit and instructed to look out of the right side of the vehicle and drive at either 40 Km/h or 60 Km/h under the following binocular viewing conditions: with a 0.9 ND filter over the left eye (leading eye); 0.9 ND filter over the right eye (trailing eye); 0.9 ND filters over both eyes, and with no filters over either eye. The order of filter conditions was randomised and the speed driven recorded for each condition. Results: Speed judgments did not differ significantly between the two baseline conditions (no filters and both eyes filtered) for either speed tested. For the baseline conditions, when subjects were asked to drive at 60 Km/h they matched this speed well (61 ± 10.2 Km/h) but drove significantly faster than requested (51.6 ± 9.4 Km/h) when asked to drive at 40 Km/h. Subjects significantly exceeded baseline speeds by 8.7± 5.0 Km/h, when the trailing eye was filtered and travelled slower than baseline speeds by 3.7± 4.6 Km/h when the leading eye was filtered. Conclusions: This is the first quantitative study demonstrating how the Enright effect can influence perceptions of driving speed, and demonstrates that monocular filtering of an eye can significantly impact driving speeds, albeit to a lesser extent than predicted by geometric models of the phenomenon.

Digital Disruption : Cinema Moves Online

Digital Disruption: Cinema Moves On-line helps to make sense of what has happened in the short but turbulent history of on-line moving image distribution. It provides a realistic assessment of both the genuine and the not-so-promising methods that have been experimented in response to the disruptions that moving from ‘analogue dollars’ to ‘digital cents’ have provoked in the film industry. Paying close attention to how the Majors have dealt – often unsuccessfully – with the challenges it poses, it also focuses closely on the innovations and practices that have taken place beyond the mainstream, showcasing important entrepreneurial innovations such as Mubi, Jaman, Withoutabox and IMDb. Written by leading academic commentators and experts close to the fluctuating fortunes of the industry, Digital Disruption: Cinema Moves On-line is an indispensable guide to the changes currently facing film and its audiences.

Monitoring charged particles in indoor air using a neutral cluster and air ion spectrometer

While there are sources of ions both outdoors and indoors, ventilation systems can introduce as well as remove ions from the air. As a result, indoor ion concentrations are not directly related to air exchange rates in buildings. In this study, we attempt to relate these quantities with the view of understanding how charged particles may be introduced into indoor spaces.

The role of defects, or active states, in surface electrochemistry with particular reference to gold in neutral solution

Metastable, active, or nonequilibrium states due to the presence of abnormal structures and various types of defects are well known in metallurgy. The role of such states at gold surfaces in neutral aqueous media (an important electrode system in the microsensor area) was explored using cyclic voltammetry. It was demonstrated that, as postulated in earlier work from this laboratory, there is a close relationship between premonolayer oxidation, multilayer hydrous oxide reduction and electrocatalytic behaviour in the case of this and other metal electrode systems. Some of the most active, and therefore most important, entities at surfaces (e.g., metal adatoms) are not readily imageable or detectable by high resolution surface microscopy techniques. Cyclic voltammetry, however, provides significant, though not highly specific, information about such species. The main conclusion is that further practical and theoretical work on active states of metal surfaces is highly desirable as their behaviour is not simple and is of major importance in many electrocatalytic processes.

Observation of ions and particles near busy roads using a Neutral Cluster and Air Ion Spectrometer (NAIS)

Motor vehicles emit large quantities of ions in the form of both charged particles and molecular cluster ions. While, the health effects of inhalation of charged particles is largely unexplored, the concentrations near busy roads and the distance to which these particles and ions are carried have important implications for the exposure of the large percentage of the population that lives close to such roadways. We measured ion concentrations using a neutral cluster and air ion spectrometer (NAIS) near seven busy roads carrying on the average approximately 7000 vehicles hr-1 including about 15% heavy duty diesel vehicles. In this study, charged particle concentrations were measured as a function of downwind distance from the road for the first time. We show that, at a moderate wind speed of 2.0 m s-1, mean charged particle concentrations at the kerb were of the order of 2x104 cm-3 and, more importantly, decreased as d 0.6 where d is the distance from the road. While cluster ions were rapidly depleted by attachment to particles and were not carried to more than about 20 m from the road, elevated concentrations of charged particle were detected up to at least 400 m from the road. Most of the charge on the downwind side was carried on the larger particles, with no excess charge on particles smaller than about 10 nm. At 30 nm, particles carried more than double the charge they would normally carry in equilibrium. There are very few measurements of ions near road traffic and this is the first study of the spatial dispersion of charged particles from a road.