Chemical and Redox Noninnocence of Pentane-2,4-dione Bis(S-methylisothiosemicarbazone) in Cobalt Complexes and Their Application in Wacker-Type Oxidation.

Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical and redox noninnocence of pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series of cobalt complexes has been studied by a range of methods, including spectroscopy [UV-vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption spectroscopy (XAS)], cyclic voltammetry, X-ray diffraction, and density functional theory (DFT) calculations. Two complexes [CoIII(H2LSMe)I]I and [CoIII(LSMe)I2] were found to act as precatalysts in a Wacker-type oxidation of olefins using phenylsilane, the role of which was elucidated through isotopic labeling. Insights into the mechanism of the catalytic transformation as well as the substrate scope of this selective reaction are described, and the essential role of phenylsilane and the noninnocence of PBIT are disclosed. Among the several relevant species characterized was an unprecedented Co(III) complex with a dianionic diradical PBIT ligand ([CoIII(LSMe••)I]).

Impact of Vaccination Status on Outcome of Patients With COVID-19 and Acute Ischemic Stroke Undergoing Mechanical Thrombectomy.

BACKGROUND: Data on impact of COVID-19 vaccination and outcomes of patients with COVID-19 and acute ischemic stroke undergoing mechanical thrombectomy are scarce. Addressing this subject, we report our multicenter experience. METHODS AND RESULTS: This was a retrospective analysis of patients with COVID-19 and known vaccination status treated with mechanical thrombectomy for acute ischemic stroke at 20 tertiary care centers between January 2020 and January 2023. Baseline demographics, angiographic outcome, and clinical outcome evaluated by the modified Rankin Scale score at discharge were noted. A multivariate analysis was conducted to test whether these variables were associated with an unfavorable outcome, defined as modified Rankin Scale score >3. A total of 137 patients with acute ischemic stroke (48 vaccinated and 89 unvaccinated) with acute or subsided COVID-19 infection who underwent mechanical thrombectomy attributable to vessel occlusion were included in the study. Angiographic outcomes between vaccinated and unvaccinated patients were similar (modified Thrombolysis in Cerebral Infarction ≥2b: 85.4% in vaccinated patients versus 86.5% in unvaccinated patients; P=0.859). The rate of functional independence (modified Rankin Scale score, ≤2) was 23.3% in the vaccinated group and 20.9% in the unvaccinated group (P=0.763). The mortality rate was 30% in both groups. In the multivariable analysis, vaccination status was not a significant predictor for an unfavorable outcome (P=0.957). However, acute COVID-19 infection remained significant (odds ratio, 1.197 [95% CI, 1.007-1.417]; P=0.041). CONCLUSIONS: Our study demonstrated no impact of COVID-19 vaccination on angiographic or clinical outcome of COVID-19-positive patients with acute ischemic stroke undergoing mechanical thrombectomy, whereas worsening attributable to COVID-19 was confirmed.

Reconstruction of multiplex networks via graph embeddings.

Multiplex networks are collections of networks with identical nodes but distinct layers of edges. They are genuine representations of a large variety of real systems whose elements interact in multiple fashions or flavors. However, multiplex networks are not always simple to observe in the real world; often, only partial information on the layer structure of the networks is available, whereas the remaining information is in the form of aggregated, single-layer networks. Recent works have proposed solutions to the problem of reconstructing the hidden multiplexity of single-layer networks using tools proper for network science. Here, we develop a machine-learning framework that takes advantage of graph embeddings, i.e., representations of networks in geometric space. We validate the framework in systematic experiments aimed at the reconstruction of synthetic and real-world multiplex networks, providing evidence that our proposed framework not only accomplishes its intended task, but often outperforms existing reconstruction techniques.

Intravenous Thrombolysis Before Thrombectomy Improves Functional Outcome After Stroke Independent of Reperfusion Grade.

BACKGROUND: We studied the association of bridging intravenous thrombolysis (IVT) before thrombectomy for anterior circulation large-vessel occlusion and functional outcome and scrutinized its dependence on grade of reperfusion and distal thrombus migration. METHODS AND RESULTS: We included consecutive patients with anterior circulation large-vessel occlusion from our prospective registry of thrombectomy-eligible patients treated from January 1, 2017 to January 1, 2023 at a tertiary stroke center in Germany in this retrospective cohort study. To evaluate the association of bridging IVT and functional outcome quantified via modified Rankin Scale score at 90 days we used multivariable logistic and lasso regression including interaction terms with grade of reperfusion quantified via modified Thrombolysis in Cerebral Infarction (mTICI) scale and distal thrombus migration adjusted for demographic and cardiovascular risk profiles, clinical and imaging stroke characteristics, onset-to-recanalization time and distal thrombus migration. We performed sensitivity analysis using propensity score matching. In our study population of 1000 thrombectomy-eligible patients (513 women; median age, 77 years [interquartile range, 67-84]), IVT emerged as a predictor of favorable functional outcome (modified Rankin Scale score, 0-2) independent of modified mTICI score (adjusted odds ratio, 0.49 [95% CI, 0.32-0.75]; P=0.001). In those who underwent thrombectomy (n=812), the association of IVT and favorable functional outcome was reproduced (adjusted odds ratio, 0.49 [95% CI, 0.31-0.74]; P=0.001) and was further confirmed on propensity score analysis, where IVT led to a 0.35-point decrease in 90-day modified Rankin Scale score (ß=-0.35 [95 CI%, -0.68 to 0.01]; P=0.04). The additive benefit of IVT remained independent of modified mTICI score (ß=-1.79 [95% CI, -3.43 to -0.15]; P=0.03) and distal thrombus migration (ß=-0.41 [95% CI, -0.69 to -0.13]; P=0.004) on interaction analysis. Consequently, IVT showed an additive association with functional outcome in the subpopulation of patients undergoing thrombectomy who achieved successful reperfusion (mTICI ≥2b; ß=-0.46 [95% CI, -0.74 to -0.17]; P=0.002) and remained beneficial in those with unsuccessful reperfusion (mTICI ≤2a; ß=-0.47 [95% CI, -0.96 to 0.01]; P=0.05). CONCLUSIONS: In thrombectomy-eligible patients with anterior circulation large-vessel occlusion, IVT improves functional outcome independent of grade of reperfusion and distal thrombus migration.

Moving and Static Faces, Bodies, Objects, and Scenes Are Differentially Represented across the Three Visual Pathways.

Models of human cortex propose the existence of neuroanatomical pathways specialized for different behavioral functions. These pathways include a ventral pathway for object recognition, a dorsal pathway for performing visually guided physical actions, and a recently proposed third pathway for social perception. In the current study, we tested the hypothesis that different categories of moving stimuli are differentially processed across the dorsal and third pathways according to their behavioral implications. Human participants (n = 30) were scanned with fMRI while viewing moving and static stimuli from four categories (faces, bodies, scenes, and objects). A whole-brain group analysis showed that moving bodies and moving objects increased neural responses in the bilateral posterior parietal cortex, parts of the dorsal pathway. By contrast, moving faces and moving bodies increased neural responses, the superior temporal sulcus, part of the third pathway. This pattern of results was also supported by a separate ROI analysis showing that moving stimuli produced more robust neural responses for all visual object categories, particularly in lateral and dorsal brain areas. Our results suggest that dynamic naturalistic stimuli from different categories are routed in specific visual pathways that process dissociable behavioral functions.

Community detection in hypergraphs via mutual information maximization.

The hypergraph community detection problem seeks to identify groups of related vertices in hypergraph data. We propose an information-theoretic hypergraph community detection algorithm which compresses the observed data in terms of community labels and community-edge intersections. This algorithm can also be viewed as maximum-likelihood inference in a degree-corrected microcanonical stochastic blockmodel. We perform the compression/inference step via simulated annealing. Unlike several recent algorithms based on canonical models, our microcanonical algorithm does not require inference of statistical parameters such as vertex degrees or pairwise group connection rates. Through synthetic experiments, we find that our algorithm succeeds down to recently-conjectured thresholds for sparse random hypergraphs. We also find competitive performance in cluster recovery tasks on several hypergraph data sets.

Integrative processing in artificial and biological vision predicts the perceived beauty of natural images.

Previous research shows that the beauty of natural images is already determined during perceptual analysis. However, it is unclear which perceptual computations give rise to the perception of beauty. Here, we tested whether perceived beauty is predicted by spatial integration across an image, a perceptual computation that reduces processing demands by aggregating image parts into more efficient representations of the whole. We quantified integrative processing in an artificial deep neural network model, where the degree of integration was determined by the amount of deviation between activations for the whole image and its constituent parts. This quantification of integration predicted beauty ratings for natural images across four studies with different stimuli and designs. In a complementary functional magnetic resonance imaging study, we show that integrative processing in human visual cortex similarly predicts perceived beauty. Together, our results establish integration as a computational principle that facilitates perceptual analysis and thereby mediates the perception of beauty.

Cost-Effectiveness of Late Endovascular Thrombectomy vs. Best Medical Management in a Clinical Trial Setting and Real-World Setting.

BACKGROUND AND PURPOSE: To assess cost-effectiveness of late time-window endovascular treatment (EVT) in a clinical trial setting and a "real-world" setting. METHODS: Data are from the randomized ESCAPE trial and a prospective cohort study (ESCAPE-LATE). Anterior circulation large vessel occlusion patients presenting > 6 hours from last-known-well were included, whereby collateral status was an inclusion criterion for ESCAPE but not ESCAPE-LATE. A Markov state transition model was built to estimate lifetime costs and quality-adjusted life-years (QALYs) for EVT in addition to best medical care vs. best medical care only in a clinical trial setting (comparing ESCAPE-EVT to ESCAPE control arm patients) and a "real-world" setting (comparing ESCAPE-LATE to ESCAPE control arm patients). We performed an unadjusted analysis, using 90-day modified Rankin Scale(mRS) scores as model input and analysis adjusted for baseline factors. Acceptability of EVT was calculated using upper/lower willingness-to-pay thresholds of 100,000 USD/50,000 USD/QALY. RESULTS: Two-hundred and forty-nine patients were included (ESCAPE-LATE:n = 200, ESCAPE EVT-arm:n = 29, ESCAPE control-arm:n = 20). Late EVT in addition to best medical care was cost effective in the unadjusted analysis both in the clinical trial and real-world setting, with acceptability 96.6%-99.0%. After adjusting for differences in baseline variables between the groups, late EVT was marginally cost effective in the clinical trial setting (acceptability:49.9%-61.6%), but not the "real-world" setting (acceptability:32.9%-42.6%). CONCLUSION: EVT for LVO-patients presenting beyond 6 hours was cost effective in the clinical trial setting and "real-world" setting, although this was largely related to baseline patient differences favoring the "real-world" EVT group. After adjusting for these, EVT benefit was reduced in the trial setting, and absent in the real-world setting.

Coherent categorical information triggers integration-related alpha dynamics.

To create coherent visual experiences, the brain spatially integrates the complex and dynamic information it receives from the environment. We previously demonstrated that feedback-related alpha activity carries stimulus-specific information when two spatially and temporally coherent naturalistic inputs can be integrated into a unified percept. In this study, we sought to determine whether such integration-related alpha dynamics are triggered by categorical coherence in visual inputs. In an EEG experiment, we manipulated the degree of coherence by presenting pairs of videos from the same or different categories through two apertures in the left and right visual hemifields. Critically, video pairs could be video-level coherent (i.e., stem from the same video), coherent in their basic-level category, coherent in their superordinate category, or incoherent (i.e., stem from videos from two entirely different categories). We conducted multivariate classification analyses on rhythmic EEG responses to decode between the video stimuli in each condition. As the key result, we significantly decoded the video-level coherent and basic-level coherent stimuli, but not the superordinate coherent and incoherent stimuli, from cortical alpha rhythms. This suggests that alpha dynamics play a critical role in integrating information across space, and that cortical integration processes are flexible enough to accommodate information from different exemplars of the same basic-level category.NEW & NOTEWORTHY Our brain integrates dynamic inputs across the visual field to create coherent visual experiences. Such integration processes have previously been linked to cortical alpha dynamics. In this study, the integration-related alpha activity was observed not only when snippets from the same video were presented, but also when different video snippets from the same basic-level category were presented, highlighting the flexibility of neural integration processes.

Sulfonium Rearrangements Enable the Direct Preparation of Sulfenyl Imidinium Salts.

Sulfenyl imidinium salts are a virtually unexplored class of intermediates in organic chemistry. Herein, we demonstrate how sulfonium rearrangements can be deployed to access these versatile synthetic intermediates, bearing three contiguous (and congested) stereogenic centers, with high levels of selectivity. The synthetic value of the scaffold was unraveled by selective transformations into a range of building blocks, including 1,4-dicarbonyl derivatives and sulfonolactones.

Stereodivergent 1,3-difunctionalization of alkenes by charge relocation.

Alkenes are indispensable feedstocks in chemistry. Functionalization at both carbons of the alkene-1,2-difunctionalization-is part of chemistry curricula worldwide1. Although difunctionalization at distal positions has been reported2-4, it typically relies on designer substrates featuring directing groups and/or stabilizing features, all of which determine the ultimate site of bond formation5-7. Here we introduce a method for the direct 1,3-difunctionalization of alkenes, based on a concept termed 'charge relocation', which enables stereodivergent access to 1,3-difunctionalized products of either syn- or anti-configuration from unactivated alkenes, without the need for directing groups or stabilizing features. The usefulness of the approach is demonstrated in the synthesis of the pulmonary toxin 4-ipomeanol and its derivatives.

Individual differences in internal models explain idiosyncrasies in scene perception.

According to predictive processing theories, vision is facilitated by predictions derived from our internal models of what the world should look like. However, the contents of these models and how they vary across people remains unclear. Here, we use drawing as a behavioral readout of the contents of the internal models in individual participants. Participants were first asked to draw typical versions of scene categories, as descriptors of their internal models. These drawings were converted into standardized 3d renders, which we used as stimuli in subsequent scene categorization experiments. Across two experiments, participants' scene categorization was more accurate for renders tailored to their own drawings compared to renders based on others' drawings or copies of scene photographs, suggesting that scene perception is determined by a match with idiosyncratic internal models. Using a deep neural network to computationally evaluate similarities between scene renders, we further demonstrate that graded similarity to the render based on participants' own typical drawings (and thus to their internal model) predicts categorization performance across a range of candidate scenes. Together, our results showcase the potential of a new method for understanding individual differences - starting from participants' personal expectations about the structure of real-world scenes.

Non-ischemic cerebral enhancing (NICE) lesions after flow diversion for intracranial aneurysms: a multicenter study.

BACKGROUND: Non-ischemic cerebral enhancing (NICE) lesions have been reported as a rare complication of various neuroendovascular procedures, but information on their incidence after flow diversion is scant. It is unclear if specific devices or novel coating technologies may impact their occurrence. METHODS: We conducted a multicenter study on the incidence of NICE lesions after flow diverter (FD) implantation for cerebral aneurysm treatment. RESULTS: Eight centers identified 15 patients and provided detailed data. The clinical presentation ranged from asymptomatic to hemiplegia and cognitive impairment. The mean time to diagnosis after treatment was 65.1±101.5 days. Five centers disclosed information on all of their 1201 FD procedures during the inclusion period (2015-2022), during which 12 patients were diagnosed with NICE lesions in these institutions-that is, an incidence of 1%. FD coatings did not increase the incidence (6/591 patients (1%) treated with surface-modified FD vs 6/610 patients (1%) treated with bare FD; P=1.00). Significantly increased rates of 3.7% (6 cases in 161 procedures; P<0.01) and 3.3% (5 cases in 153 procedures; P<0.01) were found with stents of two specific product lines. The use of one product line was associated with a significantly lower incidence (0 cases in 499 procedures (0%); P<0.01). CONCLUSIONS: Novel stent coatings are not associated with an increased incidence of NICE lesions. The incidence rate of 1% suggests that these lesions may occur more often after flow diversion than after other endovascular treatments. We found a concerning accumulation of NICE lesion cases when FDs from two product families were used.

Endovascular Treatment for Acute Isolated Internal Carotid Artery Occlusion : A Propensity Score Matched Multicenter Study.

PURPOSE: The benefit of endovascular treatment (EVT) in patients with acute symptomatic isolated occlusion of the internal carotid artery (ICA) without involvement of the middle and anterior cerebral arteries is unclear. We aimed to compare clinical and safety outcomes of best medical treatment (BMT) versus EVT + BMT in patients with stroke due to isolated ICA occlusion. METHODS: We conducted a retrospective multicenter study involving patients with isolated ICA occlusion between January 2016 and December 2020. We stratified patients by BMT versus EVT and matched the groups using propensity score matching (PSM). We assessed the effect of treatment strategy on favorable outcome (modified Rankin scale ≤ 2) 90 days after treatment and compared reduction in NIHSS score at discharge, rates of symptomatic intracranial hemorrhage (sICH) and 3­month mortality. RESULTS: In total, we included 149 patients with isolated ICA occlusion. To address imbalances, we matched 45 patients from each group using PSM. The rate of favorable outcomes at 90 days was 56% for EVT and 38% for BMT (odds ratio, OR 1.89, 95% confidence interval, CI 0.84-4.24; p = 0.12). Patients treated with EVT showed a median reduction in NIHSS score at discharge of 6 points compared to 1 point for BMT patients (p = 0.02). Rates of symptomatic intracranial hemorrhage (7% vs. 4%; p = 0.66) and 3­month mortality (11% vs. 13%; p = 0.74) did not differ between treatment groups. Periprocedural complications of EVT with early neurological deterioration occurred in 7% of cases. CONCLUSION: Although the benefit on functional outcome did not reach statistical significance, the results for NIHSS score improvement, and safety support the use of EVT in patients with stroke due to isolated ICA occlusion.

TMS disruption of the lateral prefrontal cortex increases neural activity in the default mode network when naming facial expressions.

Recognizing facial expressions is dependent on multiple brain networks specialized for different cognitive functions. In the current study, participants (N = 20) were scanned using functional magnetic resonance imaging (fMRI), while they performed a covert facial expression naming task. Immediately prior to scanning thetaburst transcranial magnetic stimulation (TMS) was delivered over the right lateral prefrontal cortex (PFC), or the vertex control site. A group whole-brain analysis revealed that TMS induced opposite effects in the neural responses across different brain networks. Stimulation of the right PFC (compared to stimulation of the vertex) decreased neural activity in the left lateral PFC but increased neural activity in three nodes of the default mode network (DMN): the right superior frontal gyrus, right angular gyrus and the bilateral middle cingulate gyrus. A region of interest analysis showed that TMS delivered over the right PFC reduced neural activity across all functionally localised face areas (including in the PFC) compared to TMS delivered over the vertex. These results suggest that visually recognizing facial expressions is dependent on the dynamic interaction of the face-processing network and the DMN. Our study also demonstrates the utility of combined TMS/fMRI studies for revealing the dynamic interactions between different functional brain networks.

Alpha-frequency feedback to early visual cortex orchestrates coherent naturalistic vision.

During naturalistic vision, the brain generates coherent percepts by integrating sensory inputs scattered across the visual field. Here, we asked whether this integration process is mediated by rhythmic cortical feedback. In electroencephalography (EEG) and functional magnetic resonance imaging (fMRI) experiments, we experimentally manipulated integrative processing by changing the spatiotemporal coherence of naturalistic videos presented across visual hemifields. Our EEG data revealed that information about incoherent videos is coded in feedforward-related gamma activity while information about coherent videos is coded in feedback-related alpha activity, indicating that integration is indeed mediated by rhythmic activity. Our fMRI data identified scene-selective cortex and human middle temporal complex (hMT) as likely sources of this feedback. Analytically combining our EEG and fMRI data further revealed that feedback-related representations in the alpha band shape the earliest stages of visual processing in cortex. Together, our findings indicate that the construction of coherent visual experiences relies on cortical feedback rhythms that fully traverse the visual hierarchy.

Improved Visualization and Quantification of Net Water Uptake in Recent Small Subcortical Infarcts in the Thalamus Using Computed Tomography.

Diagnosing recent small subcortical infarcts (RSSIs) via early computed tomography (CT) remains challenging. This study aimed to assess CT attenuation values (Hounsfield Units (HU)) and net water uptake (NWU) in RSSI and explore a postprocessing algorithm's potential to enhance thalamic RSSI detection. We examined non-contrast CT (NCCT) data from patients with confirmed thalamic RSSI on diffusion-weighted magnetic resonance imaging (DW-MRI) between January 2010 and October 2017. Co-registered DW-MRI and NCCT images enabled HU and NWU quantification in the infarct area compared to unaffected contralateral tissue. Results were categorized based on symptom onset to NCCT timing. Postprocessing using window optimization and frequency-selective non-linear blending (FSNLB) was applied, with interpretations by three blinded Neuroradiologists. The study included 34 patients (median age 70 years [IQR 63-76], 14 women). RSSI exhibited significantly reduced mean CT attenuation compared to unaffected thalamus (29.6 HU (±3.1) vs. 33.3 HU (±2.6); p < 0.01). Mean NWU in the infarct area increased from 6.4% (±7.2) at 0-6 h to 16.6% (±8.7) at 24-36 h post-symptom onset. Postprocessed NCCT using these HU values improved sensitivity for RSSI detection from 32% in unprocessed CT to 41% in FSNLB-optimized CT, with specificities ranging from 86% to 95%. In conclusion, CT attenuation values and NWU are discernible in thalamic RSSI up to 36 h post-symptom onset. Postprocessing techniques, particularly window optimization and FSNLB, moderately enhance RSSI detection.