Alkylation of isopropanol with ethanol over heterogeneous catalysts

The importance of synthesis of carbon-carbon bonds is reflected by the fact that Nobel Prizes in Chemistry have been given to this area: The Grignard reaction (1912), the Diels-Alder reaction (1950), the Witting reaction (1979), the olefin metathesis Y. Chauvin, R.H. Grubbs and R.R. Schrock (2005), the palladiumcatalyzed cross-coupling reactions to R. F. Heck, A. Suzuki, E. Negishi (2010). For the first time ever alkylation of isopropanol with ethanol was carried out over heterogeneous 0.2-1 wt.% Au and/or 0.02-0.3 wt. %Ni - containing catalysts without any sacrificial agents and/or presence of acidic/base additives. The catalyst containing 0.2 wt.% Au and 0.18 wt.% Ni supported on γ-Al2O3 was found to be the most selective in the cross-coupling route. Total selectivity of coupling products reached up to 70 %, conversion of the both initial alcohols was 50 %. Structural investigations of the Au, Ni - containing catalysts permitted to determine probable active sites peculiarities that provide effective one-pot alkylation of isopropanol with ethanol

Real-Time UAV Trajectory Prediction for Safety Monitoring in Low-Altitude Airspace

The rising number of small unmanned aerial vehicles (UAVs) expected in the next decade will enable a new series of commercial, service, and military operations in low altitude airspace as well as above densely populated areas. These operations may include on-demand delivery, medical transportation services, law enforcement operations, traffic surveillance and many more. Such unprecedented scenarios create the need for robust, efficient ways to monitor the UAV state in time to guarantee safety and mitigate contingencies throughout the operations. This work proposes a generalized monitoring and prediction methodology that utilizes realtime measurements of an autonomous UAV following a series of way-points. Two different methods, based on sinusoidal acceleration profiles and high-order splines, are utilized to generate the predicted path. The monitoring approach includes dynamic trajectory re-planning in the event of unexpected detour or hovering of the UAV during flight. It can be further extended to different vehicle types, to quantify uncertainty affecting the state variables, e.g., aerodynamic and other environmental effects, and can also be implemented to prognosticate safety-critical metrics which depend on the estimated flight path and required thrust. The proposed framework is implemented on a simplified, scalable UAV modeling and control system traversing 3D trajectories. Results presented include examples of real-time predictions of the UAV trajectories during flight and a critical analysis of the proposed scenarios under uncertainty constraints

The role of the right temporoparietal junction in perceptual conflict: detection or resolution?

The right temporoparietal junction (rTPJ) is a polysensory cortical area that plays a key role in perception and awareness. Neuroimaging evidence shows activation of rTPJ in intersensory and sensorimotor conflict situations, but it remains unclear whether this activity reflects detection or resolution of such conflicts. To address this question, we manipulated the relationship between touch and vision using the so-called mirror-box illusion. Participants' hands lay on either side of a mirror, which occluded their left hand and reflected their right hand, but created the illusion that they were looking directly at their left hand. The experimenter simultaneously touched either the middle (D3) or the ring finger (D4) of each hand. Participants judged, which finger was touched on their occluded left hand. The visual stimulus corresponding to the touch on the right hand was therefore either congruent (same finger as touch) or incongruent (different finger from touch) with the task-relevant touch on the left hand. Single-pulse transcranial magnetic stimulation (TMS) was delivered to the rTPJ immediately after touch. Accuracy in localizing the left touch was worse for D4 than for D3, particularly when visual stimulation was incongruent. However, following TMS, accuracy improved selectively for D4 in incongruent trials, suggesting that the effects of the conflicting visual information were reduced. These findings suggest a role of rTPJ in detecting, rather than resolving, intersensory conflict

Anatomic dissociation of selective and suppressive processes in visual attention

Visual spatial attention is associated with activation in parietal regions as well as with modulation of visual activity in ventral occipital cortex. Within the parietal lobe, localisation of activity has been hampered by variation in individual anatomy. Using fMRI within regions of interest derived from individual functional maps, we examined the response of superior parietal lobule, intraparietal sulcus, and ventral occipital cortex in 11 normal adults as attention was directed to the left and right visual hemifields during bilateral visual stimulation. Activation in ventral occipital cortex was augmented contralateral to the attended hemifield (p < 0.006), while intraparietal activation was augmented ipsilaterally (p < 0.009), and superior parietal lobule showed no modulation of activity as a function of attended hemifield. These findings suggest that spatial enhancement of relevant stimuli in ventral occipital cortex is complemented by an intraparietal response associated with suppression of, or preparation of a reflexive shift of attention towards, irrelevant stimuli. The spatial attention system in superior parietal cortex, in contrast, may be driven to equal degrees by currently attended stimuli and by stimuli that are potential targets of attention

Beliefs about the Minds of Others Influence How We Process Sensory Information

Attending where others gaze is one of the most fundamental mechanisms of social cognition. The present study is the first to examine the impact of the attribution of mind to others on gaze-guided attentional orienting and its ERP correlates. Using a paradigm in which attention was guided to a location by the gaze of a centrally presented face, we manipulated participants' beliefs about the gazer: gaze behavior was believed to result either from operations of a mind or from a machine. In Experiment 1, beliefs were manipulated by cue identity (human or robot), while in Experiment 2, cue identity (robot) remained identical across conditions and beliefs were manipulated solely via instruction, which was irrelevant to the task. ERP results and behavior showed that participants' attention was guided by gaze only when gaze was believed to be controlled by a human. Specifically, the P1 was more enhanced for validly, relative to invalidly, cued targets only when participants believed the gaze behavior was the result of a mind, rather than of a machine. This shows that sensory gain control can be influenced by higher-order (task-irrelevant) beliefs about the observed scene. We propose a new interdisciplinary model of social attention, which integrates ideas from cognitive and social neuroscience, as well as philosophy in order to provide a framework for understanding a crucial aspect of how humans' beliefs about the observed scene influence sensory processing

The challenges facing public libraries in the Big Society: The role of volunteers, and the issues that surround their use in England

The use of volunteers in English public libraries is nothing new, however their use is becoming ever greater and one may argue that we are increasingly seeing a mixed economy of public library provision, in the wider arena of the Big Society. This paper presents the findings of a Delphi Study of 15 library managers undertaken as part of a Professional Doctorate exploring the challenges facing public libraries in England today, particularly focusing on volunteer use. An overview of relevant supporting literature is provided to help contextualize the research, particularly focusing on concepts such as the political background surrounding policy development, community engagement, the Big Society, and volunteering. Explanation of how the Delphi Study was conducted is given, together with a discussion of the key findings. Results show that opinions of library managers cover a broad spectrum. Although volunteer use is generally viewed by the respondents as a good thing, with potential to further enhance a service and aid community engagement, there are also a number of concerns. These concerns particularly relate to the idea of the volunteer as a replacement to paid staff rather than an enhancement to the service. Other key concerns relate to the quality of service provision, the rationale behind volunteer use, and the capacity of communities to deliver. Volunteer use in public libraries on this scale is a new phenomenon, and the longevity of such a development is largely unknown. This raises the question as to whether this is simply a large scale ideological experiment, or a move to even greater community engagement

Common Blood Flow Changes Across Visual Tasks: I. Increases in Subcortical Structures and Cerebellum but Not in Nonvisual Cortex

Nine positron emission tomography (PET) studies of human visual information processing were reanalyzed to determine the consistency across experiments of blood flow increases during active tasks relative to passive viewing of the same stimulus array. No consistent blood flow increases were found in cerebral cortex outside of the visual system, but increases were seen in the thalamus and cerebellum. Although most tasks involve increases in arousal, establishing an intention or behavioral goal, setting up control structures for sequencing task operations, detecting targets, etc., these operations do not produce blood flow increases, detectable with the present methods, in localized cortical regions that are common across tasks. Common subcortical regions, however, may be involved. A left cerebellar and a medial cerebellar focus reflected motor-related processes. Blood flow increases in these regions only occurred in experiments in which the subject made an overt response and were largest when the response was made in the active but not passive condition. These motor-related processes were more complex than simple motor execution, however, since increases were still present when the response was made in both the active and passive conditions. These cerebellar increases may reflect processes related to response selection.Blood flow increases in a right cerebellar region were not motor-related. Increases were not modulated by the presence or absence of motor responses during either the active or passive conditions, and increases were sensitive to within-experiment variables that held the motor response constant. Increases occurred in both language and nonlanguage tasks and appeared to involve a general nonmotor process, but the nature of that process was difficult to specify. A right thalamic focus was sensitive to variables related to focal attention, suggesting that this region was involved in attentional engagement. Right thalamic increases were also correlated over conditions with increases in the left and medial cerebellum, perhaps reflecting additional contributions from motor-related nuclei receiving cerebellar projections. Blood flow increases in a left thalamic focus were completely uncorrelated over conditions with increases in the right thalamus, indicating that it was involved in different functions. Both the left thalamus and right cerebellum yielded larger blood flow increases when subjects performed a complex rather than simple language task, possibly reflecting a language-related pathway. Blood flow increases in the left thalamus were also observed, however, during nonlanguage tasks.Psycholog

Effects of Multimodal Load on Spatial Monitoring as Revealed by ERPs

While the role of selective attention in filtering out irrelevant information has been extensively studied, its characteristics and neural underpinnings when multiple environmental stimuli have to be processed in parallel are much less known. Building upon a dual-task paradigm that induced spatial awareness deficits for contralesional hemispace in right hemisphere-damaged patients, we investigated the electrophysiological correlates of multimodal load during spatial monitoring in healthy participants. The position of appearance of briefly presented, lateralized targets had to be reported either in isolation (single task) or together with a concurrent task, visual or auditory, which recruited additional attentional resources (dual-task). This top-down manipulation of attentional load, without any change of the sensory stimulation, modulated the amplitude of the first positive ERP response (P1) and shifted its neural generators, with a suppression of the signal in the early visual areas during both visual and auditory dual tasks. Furthermore, later N2 contralateral components elicited by left targets were particularly influenced by the concurrent visual task and were related to increased activation of the supramarginal gyrus. These results suggest that the right hemisphere is particularly affected by load manipulations, and confirm its crucial role in subtending automatic orienting of spatial attention and in monitoring both hemispaces

The prognosis of allocentric and egocentric neglect : evidence from clinical scans

We contrasted the neuroanatomical substrates of sub-acute and chronic visuospatial deficits associated with different aspects of unilateral neglect using computed tomography scans acquired as part of routine clinical diagnosis. Voxel-wise statistical analyses were conducted on a group of 160 stroke patients scanned at a sub-acute stage. Lesion-deficit relationships were assessed across the whole brain, separately for grey and white matter. We assessed lesions that were associated with behavioural performance (i) at a sub-acute stage (within 3 months of the stroke) and (ii) at a chronic stage (after 9 months post stroke). Allocentric and egocentric neglect symptoms at the sub-acute stage were associated with lesions to dissociated regions within the frontal lobe, amongst other regions. However the frontal lesions were not associated with neglect at the chronic stage. On the other hand, lesions in the angular gyrus were associated with persistent allocentric neglect. In contrast, lesions within the superior temporal gyrus extending into the supramarginal gyrus, as well as lesions within the basal ganglia and insula, were associated with persistent egocentric neglect. Damage within the temporo-parietal junction was associated with both types of neglect at the sub-acute stage and 9 months later. Furthermore, white matter disconnections resulting from damage along the superior longitudinal fasciculus were associated with both types of neglect and critically related to both sub-acute and chronic deficits. Finally, there was a significant difference in the lesion volume between patients who recovered from neglect and patients with chronic deficits. The findings presented provide evidence that (i) the lesion location and lesion size can be used to successfully predict the outcome of neglect based on clinical CT scans, (ii) lesion location alone can serve as a critical predictor for persistent neglect symptoms, (iii) wide spread lesions are associated with neglect symptoms at the sub-acute stage but only some of these are critical for predicting whether neglect will become a chronic disorder and (iv) the severity of behavioural symptoms can be a useful predictor of recovery in the absence of neuroimaging findings on clinical scans. We discuss the implications for understanding the symptoms of the neglect syndrome, the recovery of function and the use of clinical scans to predict outcome