An insight into alkali promotion: a density functional theory study of CO dissociation on K/Rh(111)

The important role of alkali additives in heterogeneous catalysis is, to a large extent, related to the high promotion effect they have on many fundamental reactions. The wide application of alkali additives in industry does not, however, reflect a thorough understanding of the mechanism of their promotional abilities. To investigate the physical origin of the alkali promotion effect, we have studied CO dissociation on clean Rh(111) and K-covered Rh(111) surfaces using density functional theory. By varying the position of potassium atoms relative to a dissociating CO, we have mapped out the importance of different K effects on the CO dissociation reactions. The K-induced changes in the reaction pathways and reaction barriers have been determined; in particular, a large reduction of the CO dissociation barrier has been identified. A thorough analysis of this promotion effect allows us to rationalize both the electronic and the geometrical factors that govern alkali promotion effect: (i) The extent of barrier reductions depends strongly on how close K is to the dissociating CO. (ii) Direct K-O bonding that is in a very short range plays a crucial role in reducing the barrier. (iii) K can have a rather long-range effect on the TS structure, which could reduce slightly the barriers.

Identification of an unknown b-agonist in feed by liquid chromatography/bioassay/quadrupole time-of-flight tandem mass spectrometry with accurate mass measurement.

A new approach to the search for residues of unknown growth promoting agents such as anabolic steroids and -agonists in feed is presented. Following primary extraction and clean-up, samples are separated using gradient liquid chromatography (LC). The effluent is split towards two identical 96-well fraction collectors and an optional electrospray quadrupole time-of-flight mass spectrometry (QTOFMS) system for accurate mass measurement. One 96-well plate is used for a bioassay (enzyme-immuno assay, receptor assay) and will detect the bioactivity and position of the relevant peak in the chromatogram. The positive well in the second 96-well plate is used for identification by LC/QTOFMS/MS. The value of this LC/bioassay/QTOFMS/MS methodology is highlighted by the finding and structure elucidation of a new -agonist in a feed extract.

Predicting physical properties of ionic liquids

A simple method to predict the densities of a range of ionic liquids from their surface tensions, and vice versa, using a surface-tension-weighted molar volume, the parachor, is reported. The parachors of ionic liquids containing 1-alkyl-3-methylimidazolium cations were determined experimentally, but were also calculated directly from their structural compositions using existing parachor contribution data for neutral compounds. The calculated and experimentally determined parachors were remarkably similar, and the latter data were subsequently employed to predict the densities and surface tensions of the investigated ionic liquids. Using a similar approach, the molar refractions of ionic liquids were determined experimentally, as well as calculated using existing molar refraction contribution data for uncharged compounds. The calculated molar refraction data were employed to predict the refractive indices of the ionic liquids from their surface tensions. The errors involved in the refractive index predictions were much higher than the analogous predictions employing the parachor, but nevertheless demonstrated the potential for developing parachor and molar refraction contribution data for ions as tools to predict ionic liquid physical properties.

Speech Recognition with unknown partial feature corruption - a review of the union model

This paper provides a summary of our studies on robust speech recognition based on a new statistical approach – the probabilistic union model. We consider speech recognition given that part of the acoustic features may be corrupted by noise. The union model is a method for basing the recognition on the clean part of the features, thereby reducing the effect of the noise on recognition. To this end, the union model is similar to the missing feature method. However, the two methods achieve this end through different routes. The missing feature method usually requires the identity of the noisy data for noise removal, while the union model combines the local features based on the union of random events, to reduce the dependence of the model on information about the noise. We previously investigated the applications of the union model to speech recognition involving unknown partial corruption in frequency band, in time duration, and in feature streams. Additionally, a combination of the union model with conventional noise-reduction techniques was studied, as a means of dealing with a mixture of known or trainable noise and unknown unexpected noise. In this paper, a unified review, in the context of dealing with unknown partial feature corruption, is provided into each of these applications, giving the appropriate theory and implementation algorithms, along with an experimental evaluation.

Towards Improving the Utilisation of University Teaching Space

There is a perception that teaching space in universities is a rather scarce resource. However, some studies have revealed that in many institutions it is actually chronically under-used. Often, rooms are occupied only half the time, and even when in use they are often only half full. This is usually measured by the ‘utilization’ which is defined as the percentage of available ‘seat-hours’ that are employed. Within real institutions, studies have shown that this utilization can often take values as low as 20–40%. One consequence of such a low level of utilization is that space managers are under pressure to make more efficient use of the available teaching space. However, better management is hampered because there does not appear to be a good understanding within space management (near-term planning) of why this happens. This is accompanied, within space planning (long-term planning) by a lack of experise on how best to accommodate the expected low utilizations. This motivates our two main goals: (i) To understand the factors that drive down utilizations, (ii) To set up methods to provide better space planning. Here, we provide quantitative evidence that constraints arising from timetabling and location requirements easily have the potential to explain the low utilizations seen in reality. Furthermore, on considering the decision question ‘Can this given set of courses all be allocated in the available teaching space?’ we find that the answer depends on the associated utilization in a way that exhibits threshold behaviour: There is a sharp division between regions in which the answer is ‘almost always yes’ and those of ‘almost always no’. Through analysis and understanding of the space of potential solutions, our work suggests that better use of space within universities will come about through an understanding of the effects of timetabling constraints and when it is statistically likely that it will be possible for a set of courses to be allocated to a particular space. The results presented here provide a firm foundation for university managers to take decisions on how space should be managed and planned for more effectively. Our multi-criteria approach and new methodology together provide new insight into the interaction between the course timetabling problem and the crucial issue of space planning.

The Teaching Space Allocation Problem with splitting

A standard problem within universities is that of teaching space allocation which can be thought of as the assignment of rooms and times to various teaching activities. The focus is usually on courses that are expected to fit into one room. However, it can also happen that the course will need to be broken up, or ‘split’, into multiple sections. A lecture might be too large to fit into any one room. Another common example is that of seminars or tutorials. Although hundreds of students may be enrolled on a course, it is often subdivided into particular types and sizes of events dependent on the pedagogic requirements of that particular course. Typically, decisions as to how to split courses need to be made within the context of limited space requirements. Institutions do not have an unlimited number of teaching rooms, and need to effectively use those that they do have. The efficiency of space usage is usually measured by the overall ‘utilisation’ which is basically the fraction of the available seat-hours that are actually used. A multi-objective optimisation problem naturally arises; with a trade-off between satisfying preferences on splitting, a desire to increase utilisation, and also to satisfy other constraints such as those based on event location and timetabling conflicts. In this paper, we explore such trade-offs. The explorations themselves are based on a local search method that attempts to optimise the space utilisation by means of a ‘dynamic splitting’ strategy. The local moves are designed to improve utilisation and satisfy the other constraints, but are also allowed to split, and un-split, courses so as to simultaneously meet the splitting objectives.

An Extended Implementation of the Great Deluge Algorithm for Course Timetabling

Course Scheduling consists of assigning lecture events to a limited set of specific timeslots and rooms. The objective is to satisfy as many soft constraints as possible, while maintaining a feasible solution timetable. The most successful techniques to date require a compute-intensive examination of the solution neighbourhood to direct searches to an optimum solution. Although they may require fewer neighbourhood moves than more exhaustive techniques to gain comparable results, they can take considerably longer to achieve success. This paper introduces an extended version of the Great Deluge Algorithm for the Course Timetabling problem which, while avoiding the problem of getting trapped in local optima, uses simple Neighbourhood search heuristics to obtain solutions in a relatively short amount of time. The paper presents results based on a standard set of benchmark datasets, beating over half of the currently published best results with in some cases up to 60% of an improvement.

Latin American migration in the central area of Iquique: New fronts of residential location and unequal forms of access to housing

Historically the central area of the city of Iquique has been established as residential space migrants choosing from different backgrounds , however since the late 2000s migration flows are diversified being mostly Latin American immigrants who live in precarious conditions , accessing tugurizados properties , deteriorated in an increasingly growing informal market. The results presented here are derived from quantitative residential location of migrants , as well as the implementation of 13 in-depth interviews . From these results emerge that Latin American migrants access to the same places where once lived internal migrants, however they inhabit a restrictive market , uneven and inadequate living conditions lease, but allows them to articulate residence and proximity to industrial networks , social and popular trade.

Detection of synthetic glucocorticoid residues in cattle tissue and hair samples after a single dose administration using LC-MS/MS

A sensitive and specific liquid chromatography-tandem mass spectrometry (LC-MS/MS) assay for the detection of several synthetic glucocorticoids in kidney, muscle and hair samples of cattle after a single intramuscular injection is described. After a dichloromethane wash of the hair samples, analytes were released from the hair matrix by enzymatic digestion. Muscle samples were also digested enzymatically using proteinase, while kidney samples were deconjugated by Helix pomatia juice. These preliminary steps were followed by a methanol extraction and a solid phase extraction (SPE) clean up step for all matrices. Chromatographic separation was achieved on a Hypersil Hypercarb column and MS/MS data were obtained in the multiple reaction monitoring mode using negative electrospray ionization. The developed protocols were evaluated by assessing residue concentrations in muscle, kidney and hair samples of thirteen calves, treated with a particular intramuscular injection of glucocorticoid. The lowest residue levels were found in muscle samples (approximately 5% of the residue levels in kidney), while high residue levels were obtained in hair samples. Hair is an interesting matrix since the sampling is non-invasive and the drugs may stay incorporated for a longer period of time. (C) 2004 Elsevier B.V. All rights reserved.

Atomic layer deposition of hafnium oxide dielectrics on silicon and germanium substrates

Hafnium oxide films have been deposited at 250 °C on silicon and germanium substrates by atomic layer deposition (ALD), using tetrakis-ethylmethylamino hafnium (TEMAH) and water vapour as precursors in a modified Oxford Instruments PECVD system. Self-limiting monolayer growth has been verified, characterised by a growth rate of 0.082 nm/ cycle. Layer uniformity is approximately within ±1% of the mean value. MOS capacitors have been fabricated by evaporating aluminium electrodes. CV analysis has been used to determine the bulk and interface properties of the HfO 2, and their dependence on pre-clean schedule, deposition conditions and post-deposition annealing. The dielectric constant of the HfO 2 is typically 18. On silicon, best results are obtained when the HfO 2 is deposited on a chemically oxidised hydrophilic surface. On germanium, best results are obtained when the substrate is nitrided before HfO 2 deposition, using an in-situ nitrogen plasma treatment. © Springer Science+Business Media, LLC 2007.

Improving the utilisation of University teaching space

There is a perception that teaching space in universities is a rather scarce resource. However, some studies have revealed that in many institutions it is actually chronically under-used. Often, rooms are occupied only half the time, and even when in use they are often only half full. This is usually measured by the “utilisation” which is basically the percentage of available ’seat-hours’ that are employed. In real institutions, this utilisation can often takes values as low as 20-40%. One consequence of such low utilisation is that space managers are under pressure to make a more efficient use of the available teaching space. However, better management is hampered because there does not appear to be a good understanding within space management (near-term planning) of why this happens. Nor, a good basis within space planning (long-term planning) of how best to accommodate the expected low utilisations. This motivates our two main goals: (i) To understand the factors that drive down utilisations, (ii) To set up methods to provide better space planning. Here, we provide quantitative evidence that constraints arising from timetabling and location requirements easily have the potential to explain the low utilisations seen in reality. Furthermore, on considering the decision question “Can this given set of courses all be allocated in the available teaching space?” we find that the answer depends on the associated utilisation in a way that exhibits threshold behaviour: There is a sharp division between regions in which the answer is “almost always yes” and those of “almost always no”. Our work suggests that progress in space management and planning will arise from an integrated approach; combining purely space issues with restrictions representing an aggregated or abstracted version of key constraints such as timetabling or location, and

The design and performance of a 2.5-GHz telecommand link for wireless biomedical monitoring

This paper details the implementation and operational performance of a minimum-power 2.45-GHz pulse receiver and a companion on-off keyed transmitter for use in a semi-active duplex RF biomedical transponder. A 50-Ohm microstrip stub-matched zero-bias diode detector forms the heart of a body-worn receiver that has a CMOS baseband amplifier consuming 20 microamps from +3 V and achieves a tangential sensitivity of -53 dBm. The base transmitter generates 0.5 W of peak RF output power into 50 Ohms. Both linear and right-hand circularly polarized Tx-Rx antenna sets were employed in system reliability trials carried out in a hospital Coronary Care Unit, For transmitting antenna heights between 0.3 and 2.2 m above floor level, transponder interrogations were 95% reliable within the 67-m-sq area of the ward, falling to an average of 46 % in the surrounding rooms and corridors. Overall, the circular antenna set gave the higher reliability and lower propagation power decay index.

University space planning and space-type profiles

Universities planning the provision of space for their teaching requirements need to do so in a fashion that reduces capital and maintenance costs whilst still providing a high-quality level of service. Space plans should aim to provide sufficient capacity without incurring excessive costs due to over-capacity. A simple measure used to estimate over-provision is utilisation. Essentially, the utilisation is the fraction of seats that are used in practice, or the ratio of demand to supply. However, studies usually find that utilisation is low, often only 20–40%, and this is suggestive of significant over-capacity.

Our previous work has provided methods to improve such space planning. They identify a critical level of utilisation as the highest level that can be achieved whilst still reliably satisfying the demand for places to allocate teaching events. In this paper, we extend this body of work to incorporate the notions of event-types and space-types. Teaching events have multiple ‘event-types’, such as lecture, tutorial, workshop, etc., and there are generally corresponding space-types. Matching the type of an event to a room of a corresponding space-type is generally desirable. However, realistically, allocation happens in a mixed space-type environment where teaching events of a given type are allocated to rooms of another space-type; e.g., tutorials will borrow lecture theatres or workshop rooms.

We propose a model and methodology to quantify the effects of space-type mixing and establish methods to search for better space-type profiles; where the term “space-type profile” refers to the relative numbers of each type of space. We give evidence that these methods have the potential to improve utilisation levels. Hence, the contribution of this paper is twofold. Firstly, we present informative studies of the effects of space-type mixing on utilisation, and critical utilisations. Secondly, we present straightforward though novel methods to determine better space-type profiles, and give an example in which the resulting profiles are indeed significantly improved.