NMR spectroscopy in the presence of ultrasound and other perturbations

The work described in this thesis has been concerned with exploring the potential uses of ultrasound in Nuclear Magnetic Resonance (NMR) spectroscopy, The NMR spectra of liquids provide detailed structural information that may be deduced from the chemical shifts and spin-spin coupling, that are evident in the narrow resonances, arising from some of the nuclear broadening interactions being reduced to zero. In the solid state, all of the nuclear broadening interactions are present and broad lines in the NMR spectrum are observed. Current techniques employed to reduce the line widths in solids are based on coherent averaging techniques such as MAS NMR1,2 which can remove first order interactions. Recently DOR3 and DAS4 have become available to remove higher order interactions. SINNMR (Sonically Induced Narrowing of the NMR spectra of solids) has been reported by Homer et al5 and developed by Homer and Howard6 to reduce the line widths of solids. The basis of their work is the proposal that a colloidal suspension of solid particles can be made to move like large molecules by using ultrasonic agitation. The advantage of the technique is that the particles move incoherently removing all of the nuclear interactions responsible for broad lines. This thesis describes work on the extension of SINNMR by showing that the line width of 27AI and 11B for the glass Na20/B203/AI203 can be reduced by placing solid particles in a colloidal suspension. Further line width reduction is possible by applying ultrasound, at 2 MHz, of sufficient intensity. It is proposed that a cavitation field is responsible for imparting sufficient rotational motion to the solid particles to partially average the nuclear interactions responsible for broad lines. Rapid stirring of the colloidal suspension generates turbulent flow, however, the motion is insufficient to narrow the line widths for 27AI in the glass. Investigations of sonochemical reactions for in situ rate measurements by NMR have been made. 8y using the Weissler reaction7, it has been shown that ultrasonic cavitation is possible up to 10MHz. Preliminary studies have been carried out into the rate of ultrasonic polymerisation of methylmethacrylate by NMR. Long range order in liquid crystals can imposed when they are aligned in the presence a magnetic field. The degree of alignment can be monitored by NMR using, for example a deuterated solute added to the liquid crystal8. Ultrasonic streaming can then be employed to deflect the directors of the liquid crystal from their equilibrium position, resulting in a change In the NMR spectrum. The angle of deflection has been found for the thermotropic liquid crystal (I35) to be ca, 35° and for the lyotropic (ZLI-1167) to be ca, 20°, Mechanical stirring can used to re- orientate the liquid crystal but was found to give a smaller deflection, In a separate study, that did not use ultrasound, it has been found that the signal to noise ratio of 13C NMR signals can be enhanced by rapidly stirring a Iiquid. Accelerating the diffusion of nuclei out of the coil region enables M0 to be re-established more rapidly than the normal relaxation process. This allows the pulse repetition rate to be reduced without saturating the spin system. The influence of varying the relaxation delay, acquisition time and inter-pulse delay have been studied and parameters optimised. By studying cholesterol the technique was found to be most effective for nuclei with long relaxation times, such as quaternary carbon sites. Key Worde: NMR, Ulf.rasciund, 1,.lqi.fi!:l cryllltalt!h SCll1C1otlemlstryl I!r1hano~d algnflllf

Fast algorithms for automatic mapping with space-limited covariance functions

In this paper we discuss a fast Bayesian extension to kriging algorithms which has been used successfully for fast, automatic mapping in emergency conditions in the Spatial Interpolation Comparison 2004 (SIC2004) exercise. The application of kriging to automatic mapping raises several issues such as robustness, scalability, speed and parameter estimation. Various ad-hoc solutions have been proposed and used extensively but they lack a sound theoretical basis. In this paper we show how observations can be projected onto a representative subset of the data, without losing significant information. This allows the complexity of the algorithm to grow as O(n m 2), where n is the total number of observations and m is the size of the subset of the observations retained for prediction. The main contribution of this paper is to further extend this projective method through the application of space-limited covariance functions, which can be used as an alternative to the commonly used covariance models. In many real world applications the correlation between observations essentially vanishes beyond a certain separation distance. Thus it makes sense to use a covariance model that encompasses this belief since this leads to sparse covariance matrices for which optimised sparse matrix techniques can be used. In the presence of extreme values we show that space-limited covariance functions offer an additional benefit, they maintain the smoothness locally but at the same time lead to a more robust, and compact, global model. We show the performance of this technique coupled with the sparse extension to the kriging algorithm on synthetic data and outline a number of computational benefits such an approach brings. To test the relevance to automatic mapping we apply the method to the data used in a recent comparison of interpolation techniques (SIC2004) to map the levels of background ambient gamma radiation. © Springer-Verlag 2007.

The isolation and identification of dermatologically active constituents of coal tar

The production and uses of coal tar are reviewed as are the uses of steroids and cytotoxic agents in the treatment of psoriasis with a review of the condition also. An attempt was made to improve the efficaciousness and cosmetic acceptability of a low temperature tar, by screening fractions of this tar, derived from a variety of separation procedures. The most efficacious fraction was the highest boiling acid fraction, which is believed to consist mainly of mono- and di-hydric phenols. A time and concentration study showed that the optimum regime was the application of a 10% concentration in 5% wool fat in soft, yellow paraffin daily for 21 days. The mouse tail skin was selected as an experimental model, to ascertain the efficaciousness of fractions, because of the similarities between this skin and the psoriatic lesion. The activity of a fraction was monitored by the inducement of a granular layer in the mouse tail epidermis. Because coal tar is not an easy medium to work with, and the active fractions showed no increase in cosmetic acceptability over the parent coal tar, likely coal tar constituents were selected for screening on the basis of phenolic character, and the molecular weight range elucidated by mass spectroscopy. 32 potential anti-psoriatic agents were screened on mouse tail. Two catechols, 3,5-di-t-butyl and 4-t-butyl catechols were active. Other structures showed little or no activity. 24 catechols were screened and two extremely active catechols were discovered, 3-methyl-5-t-octyl and 5-methyl-3-t-octyl catechols. The screening of catechol-rich coal tar fractions and a coal tar fraction which had had the catechols removed by oxidation, showed that some anti-psoriatic activity was contained in the catechol fraction of coal tar. Attempts to elucidate the mode of action of these two compounds met with little success, but two modes of action are suggested.

Designing a model for a corpus-driven dictionary of academic English

University students encounter difficulties with academic English because of its vocabulary, phraseology, and variability, and also because academic English differs in many respects from general English, the language which they have experienced before starting their university studies. Although students have been provided with many dictionaries that contain some helpful information on words used in academic English, these dictionaries remain focused on the uses of words in general English. There is therefore a gap in the dictionary market for a dictionary for university students, and this thesis provides a proposal for such a dictionary (called the Dictionary of Academic English; DOAE) in the form of a model which depicts how the dictionary should be designed, compiled, and offered to students. The model draws on state-of-the-art techniques in lexicography, dictionary-use research, and corpus linguistics. The model demanded the creation of a completely new corpus of academic language (Corpus of Academic Journal Articles; CAJA). The main advantages of the corpus are its large size (83.5 million words) and balance. Having access to a large corpus of academic language was essential for a corpus-driven approach to data analysis. A good corpus balance in terms of domains enabled a detailed domain-labelling of senses, patterns, collocates, etc. in the dictionary database, which was then used to tailor the output according to the needs of different types of student. The model proposes an online dictionary that is designed as an online dictionary from the outset. The proposed dictionary is revolutionary in the way it addresses the needs of different types of student. It presents students with a dynamic dictionary whose contents can be customised according to the user's native language, subject of study, variant spelling preferences, and/or visual preferences (e.g. black and white).

Can incident reporting improve safety? Healthcare practitioners' views of the effectiveness of incident reporting

OBJECTIVE: Recent critiques of incident reporting suggest that its role in managing safety has been over emphasized. The objective of this study was to examine the perceived effectiveness of incident reporting in improving safety in mental health and acute hospital settings by asking staff about their perceptions and experiences. DESIGN: /st>Qualitative research design using documentary analysis and semi-structured interviews. SETTING: /st>Two large teaching hospitals in London; one providing acute and the other mental healthcare. PARTICIPANTS: /st>Sixty-two healthcare practitioners with experience of reporting and analysing incidents. RESULTS: /st>Incident reporting was perceived as having a positive effect on safety, not only by leading to changes in care processes but also by changing staff attitudes and knowledge. Staff discussed examples of both instrumental and conceptual uses of the knowledge generated by incident reports. There are difficulties in using incident reports to improve safety in healthcare at all stages of the incident reporting process. Differences in the risks encountered and the organizational systems developed in the two hospitals to review reported incidents could be linked to the differences we found in attitudes to incident reporting between the two hospitals. CONCLUSION: /st>Incident reporting can be a powerful tool for developing and maintaining an awareness of risks in healthcare practice. Using incident reports to improve care is challenging and the study highlighted the complexities involved and the difficulties faced by staff in learning from incident data.

Shared action spaces:a basis function framework for social re-calibration of sensorimotor representations supporting joint action

The article explores the possibilities of formalizing and explaining the mechanisms that support spatial and social perspective alignment sustained over the duration of a social interaction. The basic proposed principle is that in social contexts the mechanisms for sensorimotor transformations and multisensory integration (learn to) incorporate information relative to the other actor(s), similar to the "re-calibration" of visual receptive fields in response to repeated tool use. This process aligns or merges the co-actors' spatial representations and creates a "Shared Action Space" (SAS) supporting key computations of social interactions and joint actions; for example, the remapping between the coordinate systems and frames of reference of the co-actors, including perspective taking, the sensorimotor transformations required for lifting jointly an object, and the predictions of the sensory effects of such joint action. The social re-calibration is proposed to be based on common basis function maps (BFMs) and could constitute an optimal solution to sensorimotor transformation and multisensory integration in joint action or more in general social interaction contexts. However, certain situations such as discrepant postural and viewpoint alignment and associated differences in perspectives between the co-actors could constrain the process quite differently. We discuss how alignment is achieved in the first place, and how it is maintained over time, providing a taxonomy of various forms and mechanisms of space alignment and overlap based, for instance, on automaticity vs. control of the transformations between the two agents. Finally, we discuss the link between low-level mechanisms for the sharing of space and high-level mechanisms for the sharing of cognitive representations. © 2013 Pezzulo, Iodice, Ferraina and Kessler.

A tale of two analyses: the use of archived qualitative data

This article provides a unique contribution to the debates about archived qualitative data by drawing on two uses of the same data - British Migrants in Spain: the Extent and Nature of Social Integration, 2003-2005 - by Jones (2009) and Oliver and O'Reilly (2010), both of which utilise Bourdieu's concepts analytically and produce broadly similar findings. We argue that whilst the insights and experiences of those researchers directly involved in data collection are important resources for developing contextual knowledge used in data analysis, other kinds of critical distance can also facilitate credible data use. We therefore challenge the assumption that the idiosyncratic relationship between context, reflexivity and interpretation limits the future use of data. Moreover, regardless of the complex genealogy of the data itself, given the number of contingencies shaping the qualitative research process and thus the potential for partial or inaccurate interpretation, contextual familiarity need not be privileged over other aspects of qualitative praxis such as sustained theoretical insight, sociological imagination and methodological rigour. © Sociological Research Online, 1996-2012.

Visualising and controlling the flow in biomolecular systems at and between multiple scales:from atoms to hydrodynamics at different locations in time and space

A novel framework for modelling biomolecular systems at multiple scales in space and time simultaneously is described. The atomistic molecular dynamics representation is smoothly connected with a statistical continuum hydrodynamics description. The system behaves correctly at the limits of pure molecular dynamics (hydrodynamics) and at the intermediate regimes when the atoms move partly as atomistic particles, and at the same time follow the hydrodynamic flows. The corresponding contributions are controlled by a parameter, which is defined as an arbitrary function of space and time, thus, allowing an effective separation of the atomistic 'core' and continuum 'environment'. To fill the scale gap between the atomistic and the continuum representations our special purpose computer for molecular dynamics, MDGRAPE-4, as well as GPU-based computing were used for developing the framework. These hardware developments also include interactive molecular dynamics simulations that allow intervention of the modelling through force-feedback devices.

A corpus-assisted study of the discourse marker well as an indicator of judges' institutional roles in court cases with litigants in person

In this paper, I concentrate on court cases with litigants in person (lay people who act on their own behalf in legal proceedings without a counsel or solicitor) and discuss the challenges of building a corpus of courtroom discourse where it is crucial to distinguish between speakers due to their distinct institutional roles. The corpus incorporates seven sub-corpora of verbatim transcripts from different court cases with litigants in person and comprises over eleven-million tokens. The focus of this paper is on the interplay between the legal and lay discourse types and how judges project their institutional roles through well-initiated turns directed at litigants in person and counsels. As a versatile discourse marker, well provides a good opportunity to explore how judges have to adapt their roles to ensure lay litigants in person receive the necessary support and that their lack of competence does not impede on the fairness of the proceedings. Given the breadth and importance of the topic of litigation in person, I discuss how the tools and approaches of corpus linguistics can be helpful in this multi-disciplinary area where multiple functions and uses of individual linguistic features need to be explored in depth.

Analysis and identification of spamming behaviors in Sina Weibo microblog

Spamming has been a widespread problem for social networks. In recent years there is an increasing interest in the analysis of anti-spamming for microblogs, such as Twitter. In this paper we present a systematic research on the analysis of spamming in Sina Weibo platform, which is currently a dominant microblogging service provider in China. Our research objectives are to understand the specific spamming behaviors in Sina Weibo and find approaches to identify and block spammers in Sina Weibo based on spamming behavior classifiers. To start with the analysis of spamming behaviors we devise several effective methods to collect a large set of spammer samples, including uses of proactive honeypots and crawlers, keywords based searching and buying spammer samples directly from online merchants. We processed the database associated with these spammer samples and interestingly we found three representative spamming behaviors: Aggressive advertising, repeated duplicate reposting and aggressive following. We extract various features and compare the behaviors of spammers and legitimate users with regard to these features. It is found that spamming behaviors and normal behaviors have distinct characteristics. Based on these findings we design an automatic online spammer identification system. Through tests with real data it is demonstrated that the system can effectively detect the spamming behaviors and identify spammers in Sina Weibo.