Rovibrational energy levels of hydrogen peroxide, studied by MULTIMODE with a reaction path Hamiltonian

Recently. Carter and Handy [J. Chem. Phys. 113 (2000) 987] have introduced the theory of the reaction path Hamiltonian (RPH) [J. Chem. Phys. 72 (1980) 99] into the variational scheme MULTIMODE, for the calculation of the J = 0 vibrational levels of polyatomic molecules, which have a single large-amplitude motion. In this theory the reaction path coordinate s becomes the fourth dimension of the moment-of-inertia tensor, and must be treated separately from the remaining 3N - 7 normal coordinates in the MULTIMODE program. In the modified program, complete integration is performed over s, and the M-mode MULTIMODE coupling approximation for the evaluation of the matrix elements applies only to the 3N - 7 normal coordinates. In this paper the new algorithm is extended to the calculation of rotational-vibration energy levels (i.e. J > 0) with the RPH, following from our analogous implementation for rigid molecules [Theoret. Chem. Acc. 100 (1998) 191]. The full theory is given, and all extra terms have been included to give the exact kinetic energy operator. In order to validate the new code, we report studies on hydrogen peroxide (H2O2), where the reaction path is equivalent to torsional motion. H2O2 has previously been studied variationally using a valence coordinate Hamiltonian; complete agreement for calculated rovibrational levels is obtained between the previous results and those from the new code, using the identical potential surface. MULTIMODE is now able to calculate rovibrational levels for polyatomic molecules which have one large-amplitude motion. (C) 2003 Elsevier B.V. All rights reserved.

Gas-solid reactions of single crystals: a study of reactions of NH3 and NO2 with single crystalline organic substrates by infrared microspectroscopy

Reaction of single crystals of benzoic and trans-cinnamic acids with 200 Torr pressure of ammonia gas in a sealed glass bulb at 20 degrees C generates the corresponding ammonium salts; there is no sign of any 1:2 adduct as has been reported previously for related systems. Isotopic substitution using ND3 has been used to aid identification of the products. Adipic acid likewise reacts with NH3 gas to form a product in which ammonium salts are formed at both carboxylic acid groups. Reaction of 0.5 Torr pressure of NO2 gas with single crystals of 9-methylanthracene and 9-anthracenemethanol in a flow system generates nitrated products where the nitro group appears to be attached at the 10-position, i.e. the position trans to the methyl or methoxy substituent on the central ring. Isotopic substitution using (NO2)-N-15 has been used to confirm the identity of the bands arising from the coordinated NO2 group. The products formed when single crystals of hydantoin are reacted with NO2 gas under similar conditions depend on the temperature of the reaction. At 20 degrees C, a nitrated product is formed, but at 65 degrees C this gives way to a product containing no nitro groups. The findings show the general applicability of infrared microspectroscopy to a study of gas-solid reactions of organic single crystals. (c) 2005 Elsevier B.V. All rights reserved.

Mineralised organic remains from cesspits at the Roman town of Silchester: processes and preservation

Mineralised organic remains (including apple pips and cereal grains) collected during the ongoing excavations of Insula IX at the Roman town of Silchester, Hampshire have been analysed by a combination of SEM-EDX, powder XRD and IR spectroscopy. The experiments included mapping experiments using spatially resolved versions of each technique. IR and powder XRD mapping have been carried out utilising the synchrotron source at The Daresbury Laboratory oil stations 11.1 and 9.6. It is concluded that these samples are preserved by rapid mineralisation in the carbonate-substituted calcium phosphate mineral, dahllite. The rapid mineralisation leads to excellent preservation of the samples and a small crystal size. The value of IR spectroscopy in studying materials like this where the crystal size is small is demonstrated. A comparison is made between the excellent preservation seen in this context and the much poorer preservation of mineralised remains seen in Context 5276 or Cesspit 5251. Comments on the possible mechanism of mineralisation of these samples are made. (C) 2008 Elsevier B.V.. All rights reserved.

Analysis of ochres from Clearwell Caves: the role of particle size in determining colour

Three ochre samples (A (orange-red in colour), B (red) and C (purple)) from Clearwell Caves, (Gloucestershire, UK) have been examined using an integrated analytical methodology based on the techniques of IR and diffuse reflectance UV-visible-NIR spectroscopy, X-ray diffraction, elemental analysis by ICP-AES and particle size analysis. It is shown that the chromophore in each case is haematite. The differences in colour may be accounted for by (i) different mineralogical and chemical composition in the case of the orange ochre, where hi,,her levels of dolomite and copper are seen and (ii) an unusual particle size distribution in the case of the purple ochre. When the purple ochre was ground to give the same particle size distribution as the red ochre then the colours of the two samples became indistinguishable. An analysis has now been completed of a range of ochre samples with colours from yellow to purple from the important site of Clearwell Caves. (C) 2004 Elsevier B.V. All rights reserved.

Analysis of red and yellow ochre samples from Clearwell Caves and Catalhoyuk by vibrational spectroscopy and other techniques

Ochre samples excavated from the neolithic site at Qatalhoyuk, Turkey have been compared with "native" ochres from Clearwell Caves, UK using infrared spectroscopy backed up by Raman spectroscopy, scanning electron microscopy (with energy-dispersive X-rays (EDX) analysis), powder X-ray diffraction, diffuse reflection UV-Vis and atomic absorption spectroscopies. For the Clearwell Caves ochres, which range in colour from yellow-orange to red-brown, it is shown that the colour is related to the nature of the chromophore present and not to any differences in particle size. The darker red ochres contain predominantly haematite while the yellow ochre contains only goethite. The ochres from Qatalhoyuk contain only about one-twentieth of the levels of iron found in the Clearwell Caves ochres. The iron oxide pigment (haematite in all cases studied here) has been mixed with a soft lime plaster which also contains calcite and silicate (clay) minerals. (C) 2003 Elsevier B.V. All rights reserved.

Rapid characterisation of archaeological midden components using FT-IR spectroscopy, SEM-EDX and micro-XRD

Samples taken from middens at the Neolithic site of Catalhoyuk in Turkey have been analysed using IR spectroscopy backed up by powder XRD and SEM-EDX. Microcomponents studied include fossil hack-berries (providing evidence of ancient diet and seasonality), mineral nodules (providing evidence of post-depositional change) and phytoliths (mineralised plant cells, providing evidence of usage of plant species). Finely laminated ashy deposits have also been investigated allowing chemical and mineralogical variations to be explored. It is found that many layers which appear visually to be quite distinctive have, in fact, very similar mineralogy. (C) 2009 Elsevier B.V. All rights reserved.

Teachers' views on the nature of models

A semi-structured interview was used in Brazil to enquire into the 'notion of model' held by a total sample of 39 science teachers who were: employed in 'fundamental' (6-14 years) and 'medium' (15-17 years) schools; student science teachers currently doing their practicum; and university science teachers. Seven 'aspects' of their notions of a model were identified: the nature of a model, the use to which it can be put, the entities of which it consists, its relative uniqueness, the time span over which it is used, its status in the making of predictions, and the basis for the accreditation of its existence and use. Categories of meaning were identified for each of these aspects. The profiles of teachers' notions of 'model' in terms of the aspects and categories were complex, providing no support for the notion of 'Levels' in understanding. Teachers with degrees in chemistry or physics had different views about the notion of 'model' to those with degrees in biology or with teacher training certificates.

Molecular mechanisms by which dietary isoflavones potentially prevent atherosclerosis

Dietary isoflavones are currently receiving much attention because of their potential role in preventing coronary artery disease and other chronic diseases. Accumulating evidence from cell culture and laboratory animal experiments indicates that isoflavones have the potential to prevent or delay atherogenesis. Suggested mechanisms of action include: a reduction in low-density lipoprotein (LDL) cholesterol and a potential reduction in the susceptibility of the LDL particle to oxidation; (2) an improvement in vascular reactivity; (3) an inhibition of pro-inflammatory cytokines, cell adhesion proteins and nitric oxide (NO) production; and (4) an inhibition of platelet aggregation. These mechanisms are consistent with the epidemiological evidence that a high consumption of isoflavone-rich soy products is associated with a reduced incidence of coronary artery disease. Biological effects of isoflavones are dependent on many factors, including dose consumed, duration of use, protein-binding affinity, and an individual's metabolism or intrinsic oestrogenic state. Further clinical studies are necessary to determine the potential health effects of isoflavones in specific population groups as we currently know little about age-related differences in exposure to these compounds and there are few guidelines on optimal dose for cardiovascular health benefits.

Changes in nucleolar morphology and proteins during infection with the coronavirus infectious bronchitis virus

The nucleolus is a dynamic subnuclear structure involved in ribosome subunit biogenesis, cell cycle control and mediating responses to cell stress, among other functions. While many different viruses target proteins to the nucleolus and recruit nucleolar proteins to facilitate virus replication, the effect of infection on the nucleolus in terms of morphology and protein content is unknown. Previously we have shown that the coronavirus nucleocapsid protein will localize to the nucleolus. In this study, using the avian infectious bronchitis coronavirus, we have shown that virus infection results in a number of changes to the nucleolus both in terms of gross morphology and protein content. Using confocal microscopy coupled with fluorescent labelled nucleolar marker proteins we observed changes in the morphology of the nucleolus including an enlarged fibrillar centre. We found that the tumour suppressor protein, p53, which localizes normally to the nucleus and nucleolus, was redistributed predominately to the cytoplasm.

Perceptions of the risks and benefits of medicines in patients with rheumatoid arthritis and other painful musculoskeletal conditions

Objectives. To examine beliefs about medication risks and benefits in patients attending a specialist rheumatology clinic for pain-related conditions. Methods. Eighty-one patients (37 first attendees and 44 existing clinic patients) completed a written questionnaire which asked about current treatments, perceived effectiveness, main risks and benefits, and compliance. Results. Existing clinic patients perceived medications to be more effective and more risky than did the new patients, although both groups rated risks to be moderately low. The main perceived risks were adverse side-effects, although patients reported only moderately low levels of experiencing such effects. Conclusions. In contrast to some other studies, many of our patients were aware of medication risks and were prepared to accept them provided benefits were seen to be high. Existing clinic patients were more aware of risks and benefits, and reported higher compliance levels than new patients, possibly as a result of the hospital education programme. Future studies should evaluate the effects of the programme more systematically.

Information system evolvability, feedback and pattern languages

Information systems for business are frequently heavily reliant on software. Two important feedback-related effects of embedding software in a business process are identified. First, the system dynamics of the software maintenance process can become complex, particularly in the number and scope of the feedback loops. Secondly, responsiveness to feedback can have a big effect on the evolvability of the information system. Ways have been explored to provide an effective mechanism for improving the quality of feedback between stakeholders during software maintenance. Understanding can be improved by using representations of information systems that are both service-based and architectural in scope. The conflicting forces that encourage change or stability can be resolved using patterns and pattern languages. A morphology of information systems pattern languages has been described to facilitate the identification and reuse of patterns and pattern languages. The kind of planning process needed to achieve consensus on a system's evolution is also considered.

Optimal discrimination and classification of THz spectra in the wavelet domain

In rapid scan Fourier transform spectrometry, we show that the noise in the wavelet coefficients resulting from the filter bank decomposition of the complex insertion loss function is linearly related to the noise power in the sample interferogram by a noise amplification factor. By maximizing an objective function composed of the power of the wavelet coefficients divided by the noise amplification factor, optimal feature extraction in the wavelet domain is performed. The performance of a classifier based on the output of a filter bank is shown to be considerably better than that of an Euclidean distance classifier in the original spectral domain. An optimization procedure results in a further improvement of the wavelet classifier. The procedure is suitable for enhancing the contrast or classifying spectra acquired by either continuous wave or THz transient spectrometers as well as for increasing the dynamic range of THz imaging systems. (C) 2003 Optical Society of America.

MusiCam: an instrument to demonstrate chromaphonic synesthesia

Inspired by a type of synesthesia where colour typically induces musical notes the MusiCam project investigates this unusual condition, particularly the transition from colour to sound. MusiCam explores the potential benefits of this idiosyncrasy as a mode of human computer interaction (1-10), providing a host of meaningful applications spanning control, communication and composition. Colour data is interpreted by means of an off-the-shelf webcam, and music is generated in real-time through regular speakers. By making colour-based gestures users can actively control the parameters of sounds, compose melodies and motifs or mix multiple tracks on the fly. The system shows great potential as an interactive medium and as a musical controller. The trials conducted to date have produced encouraging results, and only hint at the new possibilities achievable by such a device.