Redox‐active hybrid polyoxometalate‐stabilised gold nanoparticles

We report the design and preparation of multifunctional hybrid nanomaterials through the stabilization of gold nanoparticles with thiol‐functionalised hybrid organic–inorganic polyoxometalates (POMs). The covalent attachment of the hybrid POM forms new nanocomposites that are stable at temperatures and pH values which destroy analogous electrostatically functionalised nanocomposites. Photoelectrochemical analysis revealed the unique photochemical and redox properties of these systems

Older adults’ coping strategies during the COVID-19 pandemic – a longitudinal mixed-methods study

IntroductionOlder age is a main risk factor for severe COVID-19. In 2020, a broad political debate was initiated as to what extent older adults need special protection and isolation to minimize their risk for SARS-CoV-2 infection. However, isolation might also have indirect negative psychological (e.g., loneliness, stress, fear, anxiety, depression) or physical (e.g., lack of exercise, missing medical visits) consequences depending on individual strategies and personality traits to cope longitudinally with this crisis.MethodsTo examine the impact of individuals’ coping with the pandemic on mental health, a large sample of 880 older adults of the prospective longitudinal cohort TREND study were surveyed six times about their individual coping strategies in the COVID-19 pandemic between May 2020 (05/2020: Mage = 72.1, SDage = 6.4, Range: 58–91 years) and November 2022 in an open response format. The relevant survey question was: “What was helpful for you to get through the last months despite the COVID-19 pandemic? E.g., phone calls, going for a walk, or others.”Results and DiscussionIn total, we obtained 4,561 records containing 20,578 text passages that were coded and assigned to 427 distinct categories on seven levels based on qualitative content analysis using MAXQDA. The results allow new insights into the impact of personal prerequisites (e.g., value beliefs, living conditions), the general evaluation of the pandemic (e.g., positive, irrelevant, stressful) as well as the applied coping strategies (e.g., cognitive, emotional- or problem-focused) to deal with the COVID-19 pandemic by using an adapted Lazarus stress model. Throughout the pandemic emotional-focused as well as problem-focused strategies were the main coping strategies, whereas general beliefs, general living conditions and the evaluation were mentioned less frequently

Attention Reshapes Center-Surround Receptive Field Structure in Macaque Cortical Area MT

Directing spatial attention to a location inside the classical receptive field (cRF) of a neuron in macaque medial temporal area (MT) shifts the center of the cRF toward the attended location. Here we investigate the influence of spatial attention on the profile of the inhibitory surround present in many MT neurons. Two monkeys attended to the fixation point or to 1 of 2 random dot patterns (RDPs) placed inside or next to the cRF, whereas a third RDP (the probe) was briefly presented in quick succession across the cRF and surround. The probe presentation responses were used to compute a map of the excitatory receptive field and its inhibitory surround. Attention systematically reshapes the receptive field profile, independently shifting both center and surround toward the attended location. Furthermore, cRF size is changed as a function of relative distance to the attentional focus: attention inside the cRF shrinks it, whereas directing attention next to the cRF expands it. In addition, we find systematic changes in surround inhibition and cRF amplitude. This nonmultiplicative push–pull modulation of the receptive field's center-surround structure optimizes processing at and near the attentional focus to strengthen the representation of the attended stimulus while reducing influences from distractors

Aufmerksamkeitsmechanismen bei kontextueller Angst und reizspezifischer Furcht und deren Einfluss auf die Verarbeitung von sozialen Reizen

Anxiety is an affective state characterized by a sustained, long-lasting defensive response, induced by unpredictable, diffuse threat. In comparison, fear is a phasic response to predictable threat. Fear can be experimentally modeled with the help of cue conditioning. Context conditioning, in which the context serves as the best predictor of a threat due to the absence of any conditioned cues, is seen as an operationalization of sustained anxiety. This thesis used a differential context conditioning paradigm to examine sustained attention processes in a threat context compared to a safety context for the first time. In three studies, the attention mechanisms during the processing of contextual anxiety were examined by measuring heart rate responses and steady-state-visually evoked potentials (ssVEPs). An additional focus was set on the processing of social cues (i.e. faces) and the influence of contextual information on these cues. In a last step, the correlates of sustained anxiety were compared to evoked responses by phasic fear, which was realized in a previously established paradigm combining predictable and unpredictable threat. In the first study, a contextual stimulus was associated with an aversive loud noise, while a second context remained unpaired. This conditioning paradigm created an anxiety context (CTX+) and a safety context (CTX-). After acquisition, a social agent vs. an object was presented as a distractor in both contexts. Heart rate and cortical responses, with ssVEPs by using frequency tagging, to the contexts and the distractors were assessed. Results revealed enhanced ssVEP amplitudes for the CTX+ compared to the CTX− during acquisition and during presentation of distractor stimuli. Additionally, the heart rate was accelerated in the acquisition phase, followed by a heart rate deceleration as a psychophysiological marker of contextual anxiety. Study 2 used the same context conditioning paradigm as Study 1. In contrast to the first study, persons with different emotional facial expressions were presented in the anxiety and safety contexts in order to compare the differential processing of these cues within periods of threat and safety. A similar anxiety response was found in the second study, although only participants who Abstract VIII were aware of the contingency between contexts and aversive event showed a sensory amplification of the threat context, indicated by heart rate response and ssVEP activation. All faces irrespective of their emotional expression received increased attentional resources when presented within the anxiety context, which suggests a general hypervigilance in anxiety contexts. In the third study, the differentiation of predictable and unpredictable threat as an operationalization of fear and anxiety was examined on a cortical and physiological level. In the predictable condition, a social cue was paired with an aversive event, while in the unpredictable condition the aversive event remained unpaired with the respective cue. A fear response to the predictable cue was found, indicated by increased oscillatory response and accelerated heart rate. Both predictable and unpredictable threat yielded increased ssVEP amplitudes evoked by the context stimuli, while the response in the unpredictable context showed longer-lasting ssVEP activation to the threat context. To sum up, all three studies endorsed anxiety as a long-lasting defensive response. Due to the unpredictability of the aversive events, the individuals reacted with hypervigilance in the anxiety context, reflected in a facilitated processing of sensory information and an orienting response. This hypervigilance had an impact on the processing of novel cues, which appeared in the anxiety context. Considering the compared stimuli categories, the stimuli perceived in a state of anxiety received increased attentional resources, irrespective of the emotional arousal conveyed by the facial expression. Both predictable and unpredictable threat elicited sensory amplification of the contexts, while the response in the unpredictable context showed longer-lasting sensory facilitation of the threat context.Angst wird als ein langanhaltender Zustand, induziert durch eine unvorhersehbare, diffuse Bedro-hung, gesehen. Furcht hingegen wird als eine kürzere Reaktion auf einen spezifischen Bedrohungsreiz definiert. Diese phasische Reaktion kann durch Furchtkonditionierung induziert werden. Bei der Kontextkonditionierung hingegen wird durch die Abwesenheit vorhersagender Hinweisreize der Kontext zum besten Prädiktor für den aversiven Reiz und induziert dadurch eine chronische Erwartung der Bedrohung und einen langanhaltenden Angstzustand. Diese Promotionsarbeit präsentiert ein neu angepasstes differentielles Kontextkonditionierungspara-digma, welches implementiert wurde, um ein kontinuierliches Maß langanhaltender Angst im Be-drohungskontext zu erhalten. In drei Studien wurden Aufmerksamkeitsmechanismen mittels Erhebung von Herzrate und steady-state visuell evozierte Potentiale (ssVEPs) untersucht. Ein zusätzlicher Fokus lag in der Verarbeitung von sozialen Reizen (d.h. Gesichtern) und dem Einfluss von kontextuellen Informationen. Zusätzlich wurden mittels eines bereits etablierten Paradigma, welches die Vorhersagbarkeit von Bedrohungsreizen moduliert, die elektrokortikalen und physiologischen Korrelate von Angst mit Furchtreaktionen verglichen. In der ersten Studie wurde ein Kontextstimulus mit einem aversiven lauten unvorhersagbaren Geräusch assoziiert, während ein zweiter Kontextstimulus ungepaart blieb. In diesem differenti-ellen Paradigma entstanden so ein Angstkontext (CTX+) und ein Sicherheitskontext (CTX-). Nach der Akquisition wurden ein sozialer Agent und ein Objekt als Distraktoren in beiden Kontexten präsentiert. Die Herzrate und die kortikale Aktvierung mittels ssVEPs in Reaktion auf beide Kontexte und beide Distraktoren wurden gemessen. Die Ergebnisse zeigten erhöhte ssVEP-Amplituden in Reaktion auf den CTX+ im Vergleich zum CTX- während der Akquisitionsphase und der simultanen Präsentation der Distraktoren. Diese langanhaltende Angstreaktion wurde unterstützt durch Befunde von einer Akzeleration der Herzrate während der Konditionierungsphase und einer darauffolgenden Dezeleration im Angstkontext. Studie 2 verwendete dasselbe Kontextkonditionierungsparadigma wie die erste Studie, allerdings wurden hier Personen mit unterschiedlichen emotionalen Gesichtsausdrücken als Distraktoren Zusammenfassung X im Angst- und Sicherheitskontext präsentiert, um die differentielle Verarbeitung von emotionalen Reizen innerhalb von Phasen der Angst und Sicherheit zu untersuchen. Es konnte eine ähnliche Angstreaktion wie in der ersten Studie nachgewiesen werden, allerdings zeigte sich diese nur bei den kontingenzbewussten Probanden, die den Zusammenhang zwischen den aversiven Konse-quenzen und den beiden Kontexten richtig wiedergeben konnten. Sie zeigte sich in einer sensorischen Verstärkung des CTX+, abgeleitet durch Herzrate und ssVEP-Aktivierung. Alle Gesichter, unabhängig ihres emotionalen Gehalts, evozierten verstärkte Aufmerksamkeitsres-sourcen im CTX+, was auf eine generelle Hypervigilanz in Angstkontexten hindeutet. In der dritten Studie wurde die Differenzierung von vorhersagbarer und unvorhersagbarer Be-drohung, als Operationalisierung von Furcht und Angst, auf kortikaler und physiologischer Ebene untersucht. In der vorhersagbaren Bedingung wurde ein sozialer Reiz mit einem aversiven Ereignis gepaart; in der unvorhersagbaren Bedingung wurde dieses aversive Ereignis zufällig prä-sentiert. Eine Furchtreaktion auf den vorhersagbaren Reiz konnte mit erhöhten ssVEP-Amplituden sowie einer erhöhten Herzrate gezeigt werden. Sowohl die vorhersagbare als auch die unvorhersagbare Bedrohung lösten eine sensorische Verstärkung der Kontexte gegenüber der Sicherheitsbedingung aus, wobei die Reaktion auf den unvorhersagbaren Kontext eine länger an-dauernde ssVEP-Aktivierung beinhaltete. Die Ergebnisse von den drei Studien konnten Angst als eine langanhaltende defensive Reaktion bestätigen. Aufgrund der Unvorhersagbarkeit der aversiven Ereignisse reagieren Individuen mit einer erhöhten Wachsamkeit im Angstkontext, gezeigt in einer erleichterten Verarbeitung von sensorischer Information und einer Orientierungsreaktion. Diese erhöhte Wachsamkeit hatte auch einen Einfluss auf die Verarbeitung von neuen Reizen, welche im Angstkontext erschienen. Abhängig von den Vergleichsstimuli, erhielten Stimuli die im Angstkontext wahrgenommen wurden, erhöhte Aufmerksamkeitsressourcen, unabhängig vom emotionalen Gehalt der Gesichter. Sowohl vorhersagbare als auch unvorhersagbare Bedrohungen förderten eine ver-stärkte sensorische Verarbeitung der Kontexte, während diese im Angst- im Gegensatz zum Furchtkontext länger andauerte

Neural Evidence for Distracter Suppression during Visual Search in Real-World Scenes

Selecting visual information from cluttered real-world scenes involves the matching of visual input to the observer’s attentional set -- an internal representation of objects that are relevant for current behavioral goals. When goals change, a new attentional set needs to be instantiated, requiring the suppression of the previous set to prevent distraction by objects that are no longer relevant. In the present fMRI study, we investigated how such suppression is implemented at the neural level. We measured human brain activity in response to natural scene photographs that could contain objects from (i) a currently relevant (target) category, and/or (ii) a previously but not presently relevant (distracter) category, and/or (iii) a never relevant (neutral) category. Across conditions, multi-voxel response patterns in object-selective cortex (OSC) carried information about objects present in the scenes. However, this information strongly depended on the task relevance of the objects. As expected, information about the target category was significantly increased relative to the neutral category, indicating top-down enhancement of task-relevant information. Importantly, information about the distracter category was significantly reduced relative to the neutral category, indicating that the processing of previously relevant objects was suppressed. Such active suppression at the level of high-order visual cortex may serve to prevent the erroneous selection of, or interference from, objects that are no longer relevant to ongoing behavior. We conclude that the enhancement of relevant information and the suppression of distracting information both contribute to the efficient selection of visual information from cluttered real-world scenes

Neural Evidence for Distracter Suppression during Visual Search in Real-World Scenes

Selecting visual information from cluttered real-world scenes involves the matching of visual input to the observer’s attentional set -- an internal representation of objects that are relevant for current behavioral goals. When goals change, a new attentional set needs to be instantiated, requiring the suppression of the previous set to prevent distraction by objects that are no longer relevant. In the present fMRI study, we investigated how such suppression is implemented at the neural level. We measured human brain activity in response to natural scene photographs that could contain objects from (i) a currently relevant (target) category, and/or (ii) a previously but not presently relevant (distracter) category, and/or (iii) a never relevant (neutral) category. Across conditions, multi-voxel response patterns in object-selective cortex (OSC) carried information about objects present in the scenes. However, this information strongly depended on the task relevance of the objects. As expected, information about the target category was significantly increased relative to the neutral category, indicating top-down enhancement of task-relevant information. Importantly, information about the distracter category was significantly reduced relative to the neutral category, indicating that the processing of previously relevant objects was suppressed. Such active suppression at the level of high-order visual cortex may serve to prevent the erroneous selection of, or interference from, objects that are no longer relevant to ongoing behavior. We conclude that the enhancement of relevant information and the suppression of distracting information both contribute to the efficient selection of visual information from cluttered real-world scenes

Functions of the human frontoparietal attention network: Evidence from neuroimaging

Human frontoparietal cortex has long been implicated as a source of attentional control. However, the mechanistic underpinnings of these control functions have remained elusive due to limitations of neuroimaging techniques that rely on anatomical landmarks to localize patterns of activation. The recent advent of topographic mapping via functional magnetic resonance imaging (fMRI) has allowed the reliable parcellation of the network into 18 independent subregions in individual subjects, thereby offering unprecedented opportunities to address a wide range of empirical questions as to how mechanisms of control operate. Here, we review the human neuroimaging literature that has begun to explore space-based, feature-based, object-based and category-based attentional control within the context of topographically defined frontoparietal cortex

Automatic guidance of attention during real-world visual search

Looking for objects in cluttered natural environments is a frequent task in everyday life. This process can be difficult, as the features, locations, and times of appearance of relevant objects are often not known in advance. A mechanism by which attention is automatically biased toward information that is potentially relevant may thus be helpful. Here we tested for such a mechanism across five experiments by engaging participants in real-world visual search and then assessing attentional capture for information that was related to the search set but was otherwise irrelevant. Isolated objects captured attention while preparing to search for objects from the same category embedded in a scene, as revealed by lower detection performance (Experiment 1A). This capture effect was driven by a central processing bottleneck rather than the withdrawal of spatial attention (Experiment 1B), occurred automatically even in a secondary task (Experiment 2A), and reflected enhancement of matching information rather than suppression of non-matching information (Experiment 2B). Finally, attentional capture extended to objects that were semantically associated with the target category (Experiment 3). We conclude that attention is efficiently drawn towards a wide range of information that may be relevant for an upcoming real-world visual search. This mechanism may be adaptive, allowing us to find information useful for our behavioral goals in the face of uncertainty

Controlled reactivity tuning of metal-functionalized vanadium oxide clusters

Controlling the assembly and functionalization of molecular metal oxides [MxOy]n− (M=Mo, W, V) allows the targeted design of functional molecular materials. While general methods exist that enable the predetermined functionalization of tungstates and molybdates, no such routes are available for molecular vanadium oxides. Controlled design of polyoxovanadates, however, would provide highly active materials for energy conversion, (photo‐) catalysis, molecular magnetism, and materials science. To this end, a new approach has been developed that allows the reactivity tuning of vanadium oxide clusters by selective metal functionalization. Organic, hydrogen‐bonding cations, for example, dimethylammonium are used as molecular placeholders to block metal binding sites within vanadate cluster shells. Stepwise replacement of the placeholder cations with reactive metal cations gives mono‐ and difunctionalized clusters. Initial reactivity studies illustrate the tunability of the magnetic, redox, and catalytic activity