Metastable de-excitation spectroscopy and density functional theory study of the selective oxidation of crotyl alcohol over Pd(111)

The extremely surface sensitive technique of metastable de-excitation spectroscopy (MDS) has been utilized to probe the bonding and reactivity of crotyl alcohol over Pd(111) and provide insight into the selective oxidation pathway to crotonaldehyde. Auger de-excitation (AD) of metastable He (23S) atoms reveals distinct features associated with the molecular orbitals of the adsorbed alcohol, corresponding to emission from the hydrocarbon skeleton, the O n nonbonding, and C═C π states. The O n and C═C π states of the alcohol are reversed when compared to those of the aldehyde. Density functional theory (DFT) calculations of the alcohol show that an adsorption mode with both C═C and O bonds aligned somewhat parallel to the surface is energetically favored at a substrate temperature below 200 K. Density of states calculations for such configurations are in excellent agreement with experimental MDS measurements. MDS revealed oxidative dehydrogenation of crotyl alcohol to crotonaldehyde between 200 and 250 K, resulting in small peak shifts to higher binding energy. Intramolecular changes lead to the opposite assignment of the first two MOs in the alcohol versus the aldehyde, in accordance with DFT and UPS studies of the free molecules. Subsequent crotonaldehyde decarbonylation and associated propylidyne formation above 260 K could also be identified by MDS and complementary theoretical calculations as the origin of deactivation and selectivity loss. Combining MDS and DFT in this way represents a novel approach to elucidating surface catalyzed reaction pathways associated with a “real-world” practical chemical transformation, namely the selective oxidation of alcohols to aldehydes.

Physical and functional characterisation of apoptotic cell-derived extracellular vesicles

Damaged, aged or unwanted cells are removed from the body by an active process known as apoptosis. This highly orchestrated programme results in the exposure of 'flags' at the dying cell surface and the release of attractive signals to recruit phagocytes. Together these changes ensure efficient phagocytic removal of dying cells and prevention of inflammatory and autoimmune disorders. Extracellular vesicles (EV) are released from a variety of cells (both viable and apoptotic) and they serve as a novel means of intercellular communication. They range in size: 70-100nm ('exosomes') through 100-1000nm ('microparticles') to large vesicles released from dying cells ('apoptotic bodies'). Release of apoptotic cell-derived extracellular vesicles (acdEV) of less than 1000nm is an important mechanism by which phagocytes are attracted to sites of cell death. Using a variety of approaches we characterize the release, physical characteristics and function of acdEV. Using fluorescence microscopy we demonstrate release of ICAM-3 on acdEV from dying leukocytes and, through the use of resistive pulse technology (qNano, IZON Science), we accurately size and quantitate acdEV release. The function of acdEV is revealed through the use of both horizontal chemotaxis assays (Dunn chambers) and vertical transwell migration assays (Cell-IQ, CM Technologies). These assays reveal potent chemoattractive capacity of acdEV and associated ICAM-3. Additionally we demonstrate an additional novel function of acdEV as anti-inflammatory immune-modulators. These data support an integrated approach to the physical and functional analyses of EV.

A Semantic-Oriented Architecture of a Functional Module for Personalized and Adaptive Access to the Knowledge in a Multimedia Digital Library

This article presents the principal results of the doctoral thesis “Semantic-oriented Architecture and Models for Personalized and Adaptive Access to the Knowledge in Multimedia Digital Library” by Desislava Ivanova Paneva-Marinova (Institute of Mathematics and Informatics), successfully defended before the Specialised Academic Council for Informatics and Mathematical Modelling on 27 October, 2008.

Information Processing in a Cognitive Model of NLP

A model of the cognitive process of natural language processing has been developed using the formalism of generalized nets. Following this stage-simulating model, the treatment of information inevitably includes phases, which require joint operations in two knowledge spaces – language and semantics. In order to examine and formalize the relations between the language and the semantic levels of treatment, the language is presented as an information system, conceived on the bases of human cognitive resources, semantic primitives, semantic operators and language rules and data. This approach is applied for modeling a specific grammatical rule – the secondary predication in Russian. Grammatical rules of the language space are expressed as operators in the semantic space. Examples from the linguistics domain are treated and several conclusions for the semantics of the modeled rule are made. The results of applying the information system approach to the language turn up to be consistent with the stages of treatment modeled with the generalized net.

Functional neuroanatomy and behavioural correlates of the basal ganglia:evidence from lesion studies

Introduction: The basal ganglia are interconnected with cortical areas involved in behavioural, cognitive and emotional processes, in addition to movement regulation. Little is known about which of these functions are associated with individual basal ganglia substructures. Methods: Pubmed was searched for literature related to behavioural, cognitive and emotional symptoms associated with focal lesions to basal ganglia structures in humans. Results: Six case-control studies and two case reports were identified as relevant. Lesion sites included the caudate nucleus, putamen and globus pallidus. These were associated with a spectrum of behavioural and cognitive symptoms, including abulia, poor working memory and deficits in emotional recognition. Discussion: It is often difficult to precisely map associations between cognitive, emotional or behavioural functions and particular basal ganglia substructures, due to the non-specific nature of the lesions. However, evidence from lesion studies shows that most symptoms correspond with established non-motor frontal-subcortical circuits. © 2013-IOS Press and the authors. All rights reserved.

On a Direct Approach to the Solution of Inverse Optical Problems

The evaluation from experimental data, of physical quantities, which enter into the electromagnetic Maxwell equations, is described as inverse optical problem. The functional relations between the dependent and independent variables are of transcendental character and numeric procedures for evaluation of the unknowns are largely used. Herein, we discuss a direct approach to the solution, illustrated by a specific example of determination of thin films optical constants from spectrophotometric data. New algorithm is proposed for the parameters evaluation, which does not need an initial guess of the unknowns and does not use iterative procedures. Thus we overcome the intrinsic deficiency of minimization techniques, such as gradient search methods, Simplex methods, etc. The price of it is a need of more computing power, but our algorithm is easily implemented in structures such as grid clusters. We show the advantages of this approach and its potential for generalization to other inverse optical problems.

JSONYA/FN: Functional Computation in JSON

Functional programming has a lot to offer to the developers of global Internet-centric applications, but is often applicable only to a small part of the system or requires major architectural changes. The data model used for functional computation is often simply considered a consequence of the chosen programming style, although inappropriate choice of such model can make integration with imperative parts much harder. In this paper we do the opposite: we start from a data model based on JSON and then derive the functional approach from it. We outline the identified principles and present Jsonya/fn — a low-level functional language that is defined in and operates with the selected data model. We use several Jsonya/fn implementations and the architecture of a recently developed application to show that our approach can improve interoperability and can achieve additional reuse of representations and operations at relatively low cost. ACM Computing Classification System (1998): D.3.2, D.3.4.

An empirical examination of emotional and cognitive responses to threat appeals

Advertising and other forms of communications are often used by government bodies, non-government organisations, and other institutions to try to influence the population to either a) reduce some form of harmful behaviour (e.g. smoking, drunk- driving) or b) increase some more healthy behaviour (e.g. eating healthily). It is common for these messages to be predicated on the chances of some negative event occurring if the individual does not either a) stop the harmful behaviour, or b) start / increase the healthy behaviour. This design of communication is referred to by many names in the relevant literature, but for the purposes of this thesis, will be termed a ‘threat appeal’. Despite their widespread use in the public sphere, and concerted academic interest since the 1950s, the effectiveness of threat appeals in delivering their objective remains unclear in many ways. In a detailed, chronological and thematic examination of the literature, two assumptions are uncovered that have either been upheld despite little evidence to support them, or received limited attention at all, in the literature. Specifically, a) that threat appeal characteristics can be conflated with their intended responses, and b) that a threat appeal always and necessarily evokes a fear response in the subject. A detailed examination of these assumptions underpins this thesis. The intention is to take as a point of departure the equivocality of empirical results, and deliver a novel approach with the objective of reducing the confusion that is evident in existing work. More specifically, the present thesis frames cognitive and emotional responses to threat appeals as part of a decision about future behaviour. To further develop theory, a conceptual framework is presented that outlines the role of anticipated and anticipatory emotions, alongside subjective probabilities, elaboration and immediate visceral emotions, resultant from manipulation of the intrinsic message characteristics of a threat appeal (namely, message direction, message frame and graphic image). In doing so, the spectrum of relevant literature is surveyed, and used to develop a theoretical model which serves to integrate key strands of theory into a coherent model. In particular, the emotional and cognitive responses to the threat appeal manipulations are hypothesised to influence behaviour intentions and expectations pertaining to future behaviour. Using data from a randomised experiment with a sample of 681 participants, the conceptual model was tested using analysis of covariance. The results for the conceptual framework were encouraging overall, and also with regard to the individual hypotheses. In particular, empirical results showed clearly that emotional responses to the intrinsic message characteristics are not restricted to fear, and that different responses to threat appeals were clearly attributed to specific intrinsic message characteristics. In addition, the inclusion of anticipated emotions alongside cognitive appraisals in the framework generated interesting results. Specifically, immediate emotions did not influence key response variables related to future behaviour, in support of questioning the assumption of the prominent role of fear in the response process that is so prevalent in existing literature. The findings, theoretical and practical implications, limitations and directions for future research are discussed.

On modeling and satisfaction of non-functional requirements using cloud computing

Specification of the non-functional requirements of applications and determining the required resources for their execution are activities that demand a great deal of technical knowledge, frequently resulting in an inefficient use of resources. Cloud computing is an alternative for provisioning of resources, which can be done using either the provider's own infrastructure or the infrastructure of one or more public clouds, or even a combination of both. It enables more flexibly/elastic use of resources, but does not solve the specification problem. In this paper we present an approach that uses models at runtime to facilitate the specification of non-functional requirements and resources, aiming to facilitate dynamic support for application execution in cloud computing environments with shared resources. © 2013 IEEE.

A joint approach to treating dental phobia:a re-evaluation of a collaboration between community dental services and specialist psychotherapy services ten years on

Objective To audit the records of a group of patients who had previously benefited from cognitive behavioural therapy (CBT) for dental phobia.Aim To ascertain if they had returned to the use of intravenous (IV) sedation to facilitate dental treatment. Ten years ago these patients were routinely requiring IV sedation to facilitate dental treatment due to severe dental phobia.Method Sixty patients entered the original pilot project. Of those, 30 were offered CBT and 21 attended. Twenty of those patients (95.2%) were subsequently able to have dental treatment without IV sedation. In this follow-up study the electronic records of 19 of the 20 patients who had originally been successful with CBT were re-audited. Our purpose was to see if there was any record of subsequent IV sedation administration in the intervening ten years.Results Of the 19 successful CBT patients available to follow-up, 100% had not received IV sedation since the study ten years ago. This may suggest the initial benefit of CBT has endured over the ten-year period.Conclusion This study indicates that the use of CBT for patients with dental phobia proves beneficial not only in the initial treatment but that the benefits may endure over time. This results in a significant reduction in health risks to the patient from repeated IV sedation. It may also translate into significant financial savings for dental care providers. Our evidence for CBT as treatment for dental phobia suggests dental services should be implementing this approach now rather than pursuing further research. © 2011 Macmillan Publishers Limited. All rights reserved.

Transition from community dwelling to retirement village in older adults:cognitive functioning and psychological health outcomes

Supported living and retirement villages are becoming a significant option for older adults with impairments, with independence concerns or for forward planning in older age, but evidence as to psychological benefits for residents is sparse. This study examined the hypothesis that the multi-component advantages of moving into a supported and physically and socially accessible “extra care” independent living environment will impact on psychological and functioning measures. Using an observational longitudinal design, 161 new residents were assessed initially and three months later, in comparison to 33 older adults staying in their original homes. Initial group differences were apparent but some reduced after three months. Residents showed improvement in depression, perceived health, aspects of cognitive function, and reduced functional limitations, while controls showed increased functional limitations (worsening). Ability to recall specific autobiographical memories, known to be related to social-problem solving, depression and functioning in social relationships, predicted change in communication limitations, and cognitive change predicted changes in recreational limitations. Change in anxiety and memory predicted change in depression. Findings suggest that older adults with independent living concerns who move to an independent but supported environment can show significant benefits in psychological outcomes and reduction in perceived impact of health on functional limitations in a short period. Targets for focussed rehabilitation are indicated, but findings also validate development of untargeted general supportive environments.

A three-level RFID-based automation approach to enhance network competitiveness

Today, the question of how to successfully reduce supply chain costs whilst increasing customer satisfaction continues to be the focus of many firms. It is noted in the literature that supply chain automation can increase flexibility whilst reducing inefficiencies. However, in the dynamic and process driven environment of distribution, there is the absence of a cohesive automation approach to guide companies in improving network competitiveness. This paper aims to address the gap in the literature by developing a three-level framework automation application approach with the assistance of radio frequency identification (RFID) technology and returnable transport equipment (RTE). The first level considers the automation of data retrieval and highlights the benefits of RFID. The second level consists of automating distribution processes such as unloading and assembling orders. As the labour is reduced with the introduction of RFID enabled robots, the balance between automation and labour is discussed. Finally, the third level is an analysis of the decision-making process at network points and the application of cognitive automation to objects. A distribution network scenario is formed and used to illustrate network reconfiguration at each level. The research pinpoints that RFID enabled RTE offers a viable tool to assist supply chain automation. Further research is proposed in particular, the area of cognitive automation to aide with decision-making.

Resting state morphology predicts the effect of theta burst stimulation in false belief reasoning:ventrolateral prefrontal cortex in false belief reasoning

When required to represent a perspective that conflicts with one's own, functional magnetic resonance imaging (fMRI) suggests that the right ventrolateral prefrontal cortex (rvlPFC) supports the inhibition of that conflicting self-perspective. The present task dissociated inhibition of self-perspective from other executive control processes by contrasting belief reasoning-a cognitive state where the presence of conflicting perspectives was manipulated-with a conative desire state wherein no systematic conflict existed. Linear modeling was used to examine the effect of continuous theta burst stimulation (cTBS) to rvlPFC on participants' reaction times in belief and desire reasoning. It was anticipated that cTBS applied to rvlPFC would affect belief but not desire reasoning, by modulating activity in the Ventral Attention System (VAS). We further anticipated that this effect would be mediated by functional connectivity within this network, which was identified using resting state fMRI and an unbiased model-free approach. Simple reaction-time analysis failed to detect an effect of cTBS. However, by additionally modeling individual measures from within the stimulated network, the hypothesized effect of cTBS to belief (but, importantly, not desire) reasoning was demonstrated. Structural morphology within the stimulated region, rvlPFC, and right temporoparietal junction were demonstrated to underlie this effect. These data provide evidence that inconsistencies found with cTBS can be mediated by the composition of the functional network that is being stimulated. We suggest that the common claim that this network constitutes the VAS explains the effect of cTBS to this network on false belief reasoning. Hum Brain Mapp, 2016. © 2016 Wiley Periodicals, Inc.

Mobility changes in older age: neuropsychological, neurophysiological and cognitive predictors of successful adaptation in a real world scenario

The aims of this thesis were to investigate the neuropsychological, neurophysiological, and cognitive contributors to mobility changes with increasing age. In a series of studies with adults aged 45-88 years, unsafe pedestrian behaviour and falls were investigated in relation to i) cognitive functions (including response time variability, executive function, and visual attention tests), ii) mobility assessments (including gait and balance and using motion capture cameras), iii) motor initiation and pedestrian road crossing behavior (using a simulated pedestrian road scene), iv) neuronal and functional brain changes (using a computer based crossing task with magnetoencephalography), and v) quality of life questionnaires (including fear of falling and restricted range of travel). Older adults are more likely to be fatally injured at the far-side of the road compared to the near-side of the road, however, the underlying mobility and cognitive processes related to lane-specific (i.e. near-side or far-side) pedestrian crossing errors in older adults is currently unknown. The first study explored cognitive, motor initiation, and mobility predictors of unsafe pedestrian crossing behaviours. The purpose of the first study (Chapter 2) was to determine whether collisions at the near-side and far-side would be differentially predicted by mobility indices (such as walking speed and postural sway), motor initiation, and cognitive function (including spatial planning, visual attention, and within participant variability) with increasing age. The results suggest that near-side unsafe pedestrian crossing errors are related to processing speed, whereas far-side errors are related to spatial planning difficulties. Both near-side and far-side crossing errors were related to walking speed and motor initiation measures (specifically motor initiation variability). The salient mobility predictors of unsafe pedestrian crossings determined in the above study were examined in Chapter 3 in conjunction with the presence of a history of falls. The purpose of this study was to determine the extent to which walking speed (indicated as a salient predictor of unsafe crossings and start-up delay in Chapter 2), and previous falls can be predicted and explained by age-related changes in mobility and cognitive function changes (specifically within participant variability and spatial ability). 53.2% of walking speed variance was found to be predicted by self-rated mobility score, sit-to-stand time, motor initiation, and within participant variability. Although a significant model was not found to predict fall history variance, postural sway and attentional set shifting ability was found to be strongly related to the occurrence of falls within the last year. Next in Chapter 4, unsafe pedestrian crossing behaviour and pedestrian predictors (both mobility and cognitive measures) from Chapter 2 were explored in terms of increasing hemispheric laterality of attentional functions and inter-hemispheric oscillatory beta power changes associated with increasing age. Elevated beta (15-35 Hz) power in the motor cortex prior to movement, and reduced beta power post-movement has been linked to age-related changes in mobility. In addition, increasing recruitment of both hemispheres has been shown to occur and be beneficial to perform similarly to younger adults in cognitive tasks (Cabeza, Anderson, Locantore, & McIntosh, 2002). It has been hypothesised that changes in hemispheric neural beta power may explain the presence of more pedestrian errors at the farside of the road in older adults. The purpose of the study was to determine whether changes in age-related cortical oscillatory beta power and hemispheric laterality are linked to unsafe pedestrian behaviour in older adults. Results indicated that pedestrian errors at the near-side are linked to hemispheric bilateralisation, and neural overcompensation post-movement, 4 whereas far-side unsafe errors are linked to not employing neural compensation methods (hemispheric bilateralisation). Finally, in Chapter 5, fear of falling, life space mobility, and quality of life in old age were examined to determine their relationships with cognition, mobility (including fall history and pedestrian behaviour), and motor initiation. In addition to death and injury, mobility decline (such as pedestrian errors in Chapter 2, and falls in Chapter 3) and cognition can negatively affect quality of life and result in activity avoidance. Further, number of falls in Chapter 3 was not significantly linked to mobility and cognition alone, and may be further explained by a fear of falling. The objective of the above study (Study 2, Chapter 3) was to determine the role of mobility and cognition on fear of falling and life space mobility, and the impact on quality of life measures. Results indicated that missing safe pedestrian crossing gaps (potentially indicating crossing anxiety) and mobility decline were consistent predictors of fear of falling, reduced life space mobility, and quality of life variance. Social community (total number of close family and friends) was also linked to life space mobility and quality of life. Lower cognitive functions (particularly processing speed and reaction time) were found to predict variance in fear of falling and quality of life in old age. Overall, the findings indicated that mobility decline (particularly walking speed or walking difficulty), processing speed, and intra-individual variability in attention (including motor initiation variability) are salient predictors of participant safety (mainly pedestrian crossing errors) and wellbeing with increasing age. More research is required to produce a significant model to explain the number of falls.

Developing multidimensional metrics for evaluating paediatric neurodevelopmental disorders

Healthy brain functioning depends on efficient communication of information between brain regions, forming complex networks. By quantifying synchronisation between brain regions, a functionally connected brain network can be articulated. In neurodevelopmental disorders, where diagnosis is based on measures of behaviour and tasks, a measure of the underlying biological mechanisms holds promise as a potential clinical tool. Graph theory provides a tool for investigating the neural correlates of neuropsychiatric disorders, where there is disruption of efficient communication within and between brain networks. This research aimed to use recent conceptualisation of graph theory, along with measures of behaviour and cognitive functioning, to increase understanding of the neurobiological risk factors of atypical development. Using magnetoencephalography to investigate frequency-specific temporal dynamics at rest, the research aimed to identify potential biological markers derived from sensor-level whole-brain functional connectivity. Whilst graph theory has proved valuable for insight into network efficiency, its application is hampered by two limitations. First, its measures have hardly been validated in MEG studies, and second, graph measures have been shown to depend on methodological assumptions that restrict direct network comparisons. The first experimental study (Chapter 3) addressed the first limitation by examining the reproducibility of graph-based functional connectivity and network parameters in healthy adult volunteers. Subsequent chapters addressed the second limitation through adapted minimum spanning tree (a network analysis approach that allows for unbiased group comparisons) along with graph network tools that had been shown in Chapter 3 to be highly reproducible. Network topologies were modelled in healthy development (Chapter 4), and atypical neurodevelopment (Chapters 5 and 6). The results provided support to the proposition that measures of network organisation, derived from sensor-space MEG data, offer insights helping to unravel the biological basis of typical brain maturation and neurodevelopmental conditions, with the possibility of future clinical utility.