Defect-controlled halogenating properties of lanthanide-doped ceria nanozymes.

Marine organisms combat bacterial colonization by biohalogenation of signaling compounds that interfere with bacterial communication. These reactions are catalyzed by haloperoxidase enzymes, whose activity can be emulated by nanoceria using milli- and micromolar concentrations of Br- and H2O2. We show that the haloperoxidase-like activity of nanoceria can greatly be enhanced by Ln substitution in Ce1-xLnxO2-x/2. Non-agglomerated nanosized Ce1-xLnxO2-x/2 (Ln = Pr, Tb, particle size < 10 nm) was prepared mechanochemically from CeCl3 and Na2CO3 followed by short calcination. Lanthanide metals could be incorporated into the CeO2 host without solubility limit, as shown for Tb. The distribution of the Ln3+ defect sites in the CeO2 host structure was analyzed by electron spin resonance spectroscopy. Ce3+ and superoxide O2- species are present at surface sites. Their formation is promoted by increasing dopant concentration. Ce1-xLnxO2-x/2 was prepared in copious amounts by ball-milling. This energy-saving and residue-free method can be upscaled to industrial scale. The surface defect chemistry of Ce1-xLnxO2-x/2 was unravelled by vibrational spectroscopy. It is associated with the mechanochemical preparation and leads to enhanced catalytic activity. Although Ce0.9Pr0.1O1.95 had a lower BET surface area than pure CeO2, its catalytic activity, calibrated by oxidative bromination of phenol red, was much higher because the ζ-potential increased from 15 mV (for CeO2) to 30 mV (for Ce0.9Pr0.1O1.95). This facilitates adsorption of Br- in aqueous conditions and explains the high catalytic activity of the Ln-substituted CeO2. Ce1-xLnxO2-x/2 is an effective and "green" nanoparticle haloperoxidase mimic for antifouling applications, as no chemicals other than the ubiquitous Br- and H2O2 (generated in daylight) are required, and only natural metabolites are released into the environment.

Digitalisation of the Brief Visuospatial Memory Test-Revised and Evaluation with a Machine Learning Algorithm.

The disease multiple sclerosis (MS) is characterized by various neurological symptoms. This paper deals with a novel tool to assess cognitive dysfunction. The Brief Visuospatial Memory Test-Revised (BVMT-R) is a recognized method to measure optical recognition deficits and their progression. Typically, the test is carried out on paper. We present a way to make this process more efficient, without losing quality by having the patients using a tablet App and having the drawings rated with the use of a machine learning (ML) algorithm. A dataset of 1'525 drawings were digitalized and then randomly split in a training dataset and in a test dataset. In addition to the training dataset the already trained drawings from a preliminary paper were added to the training dataset. The ratings done by two neuropsychologists matched for 81% of the test dataset. The ratings done automatically with the ML algorithm matched 72% with the ones of the first neuropsychologist and 79% of the ones of the second neuropsychologist. For a semi-automated rating we defined a threshold value for the reliability of the rating of 78.8%, under which the drawing is routed for manual rating. With this threshold value the ML algorithm matched 80.3% and 86.6% of the ratings of the first and second neuropsychologists. The neuropsychologists have in that case to manually check 17.4% of the drawings. With our results is it possible to execute the BVMT-R Test in a digital way. We found out, that our ML algorithms have with the semi-automated method the similar matching as the two professional raters.

Automated Rating of Multiple Sclerosis Test Results Using a Convolutional Neural Network.

This work concerns methods for automated rating of the progression of Multiple Sclerosis (MS). Often, MS patients develop cognitive deficits. The Brief Visuospatial Memory Test-Revised (BVMT-R) is a recognized method to measure optical recognition deficits and their progression. Typically, the test is carried out on paper using geometric figures which the patient should recognize and trace. The results are rated manually by a physician. The goal of this work was to digitize the BVMT-R and to support the interpretation of the test results using a machine learning (ML) algorithm. A convolutional neural network (CNN) was used to rate the drawings of a patient. As a result, the correct point value of the BVMT-R could be determined with an accuracy between 57% and 76% based on a training set of 624 patient drawings obtained from 135 patients. These drawings had been previously physician rated to serve as a gold standard. In our experiment, we obtained reasonable accuracy above 80% when more than 40 drawings were available, but our training sample was too small for more detailed analysis. Conclusion: At the currently achieved classification accuracy, results analysis will remain a physician task, potentially supported with ML based preclassification, but there is hope that ML accuracy can be further improved to enable automated follow-ups.

The effect of element spacing on hemispheric asymmetries for global/local processing.

In several studies with hierarchical stimuli it has been shown that the left and the right hemispheres are specialized for the processing of local and global information, respectively. However, although corresponding visual-field (VF) effects regularly show up for incongruent stimuli, they are often absent for congruent ones. In this study, it was investigated whether the spacing between the elements of the stimuli has any effect on this phenomenon. Therefore, in Experiment 1, stimuli with narrowly spaced elements were applied. As a result, VF-effects occurred independently of the congruency condition. For comparison, stimuli with wider element spacing were used in Experiment 2. Under these conditions, VF-effects occurred again, as expected, only for incongruent stimuli. These results show that element spacing can have an effect on VF-effects. The results are interpreted in the sense that narrowly spaced elements are perceived as texture, which always leads to an elaborate mental representation of the stimulus that differs between the hemispheres.

Functional hemispheric differences for the categorization of global and local information in naturalistic stimuli.

Up to now functional hemispheric asymmetries for global/local processing have mainly been investigated with hierarchical letters as stimuli. In the present study, three experiments were conducted to examine whether corresponding visual-field (VF) effects can also be obtained with more naturalistic stimuli. To this end, images of animals with a pattern placed on their body were displayed as stimuli. The task for the global level and for the local level was to categorize the animals and the patterns, respectively. As a result, VF-effects were also found for these stimuli and tasks. It is concluded that the hemispheric differences observed for hierarchical letters also hold for naturalistic stimuli.

The direction of hemispheric asymmetries for object categorization at different levels of abstraction depends on the task.

In this study hemispheric asymmetries for categorizing objects at the basic versus subordinate level of abstraction were investigated. As predictions derived from different theoretical approaches are contradictory and experimental evidence is inconclusive in this regard, we conducted two categorization experiments, where we contrasted two experimental paradigms. In the first experiment, subjects had to verify whether a word and a laterally presented picture matched or not. In the second experiment, subjects had to identify laterally presented pictures of animals either at the basic or subordinate level by pressing a corresponding response key. Whereas the first experiment revealed an advantage of the left hemisphere (LH) for categorizing objects at the basic level and of the right hemisphere (RH) for categorizing at the subordinate level, just the opposite brain asymmetry was found in the second experiment. As the stimuli were identical in both experiments, hemispheric asymmetries seem to be strongly task dependent.

Hemispheric differences for global/local processing in divided attention tasks: further evidence for the integration theory.

Functional hemispheric asymmetries with respect to global/local processing have been observed more reliably in divided-attention than in selective-attention tasks. This difference has been accounted for by assuming that the hemispheres operate differently in the two tasks. In our study, the alternative hypothesis was tested that the interference between the global and local levels is increased under divided attention, and that this makes it necessary to base response selection on a more elaborated mental stimulus representation in which the levels and their content are integrated. Because the hemispheres systematically differ in this integration process, the increased interference between the levels explains why the corresponding asymmetries occur more reliably under divided attention. Two experiments supporting this hypothesis are reported, one with a divided and one with a selective attention task.