Gas-phase rate coefficients for the reactions of nitrate radicals with (Z)-pent-2-ene, (E)-pent-2-ene, (Z)-hex-2-ene, (E)-hex-2-ene, (Z)-hex-3-ene, (E)-hex-3-ene and (E)-3-methylpent-2-ene at room temperature

Rate coefficients for reactions of nitrate radicals (NO3) with (Z)-pent-2-ene, (E)-pent-2-ene, (Z)-hex-2-ene, (E)-hex-2-ene, (Z)-hex-3-ene, (E)-hex-3-ene and (E)-3-methylpent-2-ene were determined to be (6.55 +/- 0.78) x 10(-13) cm(3) molecule(-1) s(-1), (3.78 +/- 0.45) x 10(-13) cm(3) molecule(-1) s(-1), (5.30 +/- 0.73) x 10(-13) cm(3) molecule(-1) s(-1), (3.83 +/- 0.47) x 10(-13) cm(3) molecule(-1) s(-1), (4.37 +/- 0.49) x 10(-13) cm(3) molecule(-1) s(-1), (3.61 +/- 0.40) x 10(-13) cm(3) molecule(-1) s(-1) and (8.9 +/- 1.5) x 10(-12) cm(3) molecule(-1) s(-1), respectively. We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC-FID analysis. The experimental results demonstrate a surprisingly large cis-trans (Z-E) effect, particularly in the case of the pent-2-enes, where the ratio of rate coefficients is ca. 1.7. Rate coefficients are discussed in terms of electronic and steric influences, and our results give some insight into the effects of chain length and position of the double bond on the reaction of NO3 with unsaturated hydrocarbons. Atmospheric lifetimes were calculated with respect to important oxidants in the troposphere for the alkenes studied, and NO3-initiated oxidation is found to be the dominant degradation route for (Z)-pent-2-ene, (Z)-hex-3-ene and (E)-3-methylpent-2-ene.

Constancy in the perception of speech when the level of room-reflections varies

A speech message played several metres from the listener in a room is usually heard to have much the same phonetic content as it does when played nearby, even though the different amounts of reflected sound make the temporal envelopes of these signals very different. To study this ‘constancy’ effect, listeners heard speech messages and speech-like sounds comprising 8 auditory-filter shaped noise-bands that had temporal envelopes corresponding to those in these filters when the speech message is played. The ‘contexts’ were “next you’ll get _to click on”, into which a “sir” or “stir” test word was inserted. These test words were from an 11-step continuum, formed by amplitude modulation. Listeners identified the test words appropriately, even in the 8-band conditions where the speech had a ‘robotic’ quality. Constancy was assessed by comparing the influence of room reflections on the test word across conditions where the context had either the same level of room reflections (i.e. from the same, far distance), or where it had a much lower level (i.e. from nearby). Constancy effects were obtained with both the natural- and the 8-band speech. Results are considered in terms of the degree of ‘matching’ between the context’s and test-word’s bands.

Variable selection algorithm for the construction of MIMO operating point dependent neurofuzzy networks

An input variable selection procedure is introduced for the identification and construction of multi-input multi-output (MIMO) neurofuzzy operating point dependent models. The algorithm is an extension of a forward modified Gram-Schmidt orthogonal least squares procedure for a linear model structure which is modified to accommodate nonlinear system modeling by incorporating piecewise locally linear model fitting. The proposed input nodes selection procedure effectively tackles the problem of the curse of dimensionality associated with lattice-based modeling algorithms such as radial basis function neurofuzzy networks, enabling the resulting neurofuzzy operating point dependent model to be widely applied in control and estimation. Some numerical examples are given to demonstrate the effectiveness of the proposed construction algorithm.

Room temperature synthesis of tri-, tetrasubstituted imidazoles and bis-analogues by mercaptopropylsilica (MPS) in aqueous methanol: application to the synthesis of the drug trifenagrel

The heterogeneous solid catalyst, mercaptopropylsilica (MPS), has been prepared by a modified procedure in water and its structure confirmed by solid state carbon-13 CP-MAS NMR spectrum. This catalyst has been efficiently utilized for the synthesis of a wide variety of tri-, tetrasubstituted imidazoles and their bis-analogues at room temperature. The protocol was further explored for the synthesis of the drug trifenagrel.

Distributed fuzzy logic for building management systems using local operating networks

This paper describes the development of an experimental distributed fuzzy control system for heating and ventilation (HVAC) systems within a building. Each local control loop is affected by a number of local variables, as well as information from neighboring controllers. By including this additional information it is hoped that a more equal allocation of resources can be achieved.

`Tactical' living: a situated study of teenagers' negotiations around and interactions with living room media

This paper examines everyday living room interactions in which teenage household members conduct `tactical' play in order to temporarily gain access to, and disrupt, the dominant, domestic codes of living room media. The practices of individuals are interpreted, through Michel de Certeau's language of `tactics', as struggles or a series of opportunistic actions which can often reforge these codes of living, precisely because the house `rules' are not fixed or deterministic in practice. In these tactical performances of self, the use of media is enmeshed in a host of situated and symbolic action, reaffirming how media and face-to-face interactions are multiply and closely entwined in everyday living room life. This video ethnographic work examines such instances of teenagers appealing to `house' rules and demonstrating domestic helpfulness in order to gain access to media, and the tethering of media to objects through the routine practice of `markers' and `stalls'.

Where the interaction is: collisions of the situated and mediated in living room interactions

This article presents three ethnographic tales of interactions with living room media to help recreate the experience of significant moments in time, of affective encounters at the interface in which there is a collision or confusion of situated and virtual worlds. It draws on a year-long video ethnography of the practice and performance of everyday interactions with living room media. By studying situated activity and the lived practice of (new) media, rather than taking an exclusive focus on the virtual as a detached space, this ethnographic work demonstrates how the situated and mediated clash, or are crafted into complex emotional encounters during everyday living room life.

Addressing animal health knowledge gaps in Southern Countries: the creation of a 2D animal health resource room

Livestock are a key asset for the global poor. However, access to relevant information is a critical issue for both livestock development practitioners and the poor themselves. Therefore, the following paper details the creation of an on-line Animal Health Resource Room. The aim was to create an immersive environment, which mimics the benefits of a 3D Virtual Learning Environment without the constraints on download times. Therefore, in the following paper key issues in the dissemination of such a platform such as connectivity and speed are explored within the wider context of the development of the tool itself.

Preventing carbon contamination of optical devices for X-rays: the effect of oxygen on photon-induced dissociation of CO on platinum

Platinum is one of the most common coatings used to optimize mirror reflectivity in soft X-ray beamlines. Normal operation results in optics contamination by carbon-based molecules present in the residual vacuum of the beamlines. The reflectivity reduction induced by a carbon layer at the mirror surface is a major problem in synchrotron radiation sources. A time-dependent photoelectron spectroscopy study of the chemical reactions which take place at the Pt(111) surface under operating conditions is presented. It is shown that the carbon contamination layer growth can be stopped and reversed by low partial pressures of oxygen for optics operated in intense photon beams at liquidnitrogen temperature. For mirrors operated at room temperature the carbon contamination observed for equivalent partial pressures of CO is reduced and the effects of oxygen are observed on a long time scale.

Near-infrared water vapour self-continuum at close to room temperature

The gaseous absorption of solar radiation within near-infrared atmospheric windows in the Earth's atmosphere is dominated by the water vapour continuum. Recent measurements by Baranov et al. (2011) [17] in 2500 cm−1 (4 μm) window and by Ptashnik et al. (2011) [18] in a few near-infrared windows revealed that the self-continuum absorption is typically an order of magnitude stronger than given by the MT_CKD continuum model prior to version 2.5. Most of these measurements, however, were made at elevated temperatures, which makes their application to atmospheric conditions difficult. Here we report new laboratory measurements of the self-continuum absorption at 289 and 318 K in the near-infrared spectral region 1300–8000 cm−1, using a multipass 30 m base cell with total optical path 612 m. Our results confirm the main conclusions of the previous measurements both within bands and in windows. Of particular note is that we present what we believe to be the first near-room temperature measurement using Fourier Transform Spectrometry of the self-continuum in the 6200 cm−1 (1.6 μm) window, which provides tentative evidence that, at such temperatures, the water vapour continuum absorption may be as strong as it is in 2.1 μm and 4 μm windows and up to 2 orders of magnitude stronger than the MT_CKD-2.5 continuum. We note that alternative methods of measuring the continuum in this window have yielded widely differing assessment of its strength, which emphasises the need for further measurements.