Dynamic brain communication underwriting face pareidolia.

Face pareidolia is a tendency to seeing faces in nonface images that reflects high tuning to a face scheme. Yet, studies of the brain networks underwriting face pareidolia are scarce. Here, we examined the time course and dynamic topography of gamma oscillatory neuromagnetic activity while administering a task with nonface images resembling a face. Images were presented either with canonical orientation or with display inversion that heavily impedes face pareidolia. At early processing stages, the peaks in gamma activity (40 to 45 Hz) to images either triggering or not face pareidolia originate mainly from the right medioventral and lateral occipital cortices, rostral and caudal cuneus gyri, and medial superior occipital gyrus. Yet, the difference occurred at later processing stages in the high-frequency range of 80 to 85 Hz over a set of the areas constituting the social brain. The findings speak rather for a relatively late neural network playing a key role in face pareidolia. Strikingly, a cutting-edge analysis of brain connectivity unfolding over time reveals mutual feedforward and feedback intra- and interhemispheric communication not only within the social brain but also within the extended large-scale network of down- and upstream regions. In particular, the superior temporal sulcus and insula strongly engage in communication with other brain regions either as signal transmitters or recipients throughout the whole processing of face-pareidolia images.

Relationship between journal impact factor and the thoroughness and helpfulness of peer reviews.

The Journal Impact Factor is often used as a proxy measure for journal quality, but the empirical evidence is scarce. In particular, it is unclear how peer review characteristics for a journal relate to its impact factor. We analysed 10,000 peer review reports submitted to 1,644 biomedical journals with impact factors ranging from 0.21 to 74.7. Two researchers hand-coded sentences using categories of content related to the thoroughness of the review (Materials and Methods, Presentation and Reporting, Results and Discussion, Importance and Relevance) and helpfulness (Suggestion and Solution, Examples, Praise, Criticism). We fine-tuned and validated transformer machine learning language models to classify sentences. We then examined the association between the number and percentage of sentences addressing different content categories and 10 groups defined by the Journal Impact Factor. The median length of reviews increased with higher impact factor, from 185 words (group 1) to 387 words (group 10). The percentage of sentences addressing Materials and Methods was greater in the highest Journal Impact Factor journals than in the lowest Journal Impact Factor group. The results for Presentation and Reporting went in the opposite direction, with the highest Journal Impact Factor journals giving less emphasis to such content. For helpfulness, reviews for higher impact factor journals devoted relatively less attention to Suggestion and Solution than lower impact factor journals. In conclusion, peer review in journals with higher impact factors tends to be more thorough, particularly in addressing study methods while giving relatively less emphasis to presentation or suggesting solutions. Differences were modest and variability high, indicating that the Journal Impact Factor is a bad predictor of the quality of peer review of an individual manuscript.

Reading language of the eyes in female depression.

Aberrations in non-verbal social cognition have been reported to coincide with major depressive disorder. Yet little is known about the role of the eyes. To fill this gap, the present study explores whether and, if so, how reading language of the eyes is altered in depression. For this purpose, patients and person-by-person matched typically developing individuals were administered the Emotions in Masked Faces task and Reading the Mind in the Eyes Test, modified, both of which contained a comparable amount of visual information available. For achieving group homogeneity, we set a focus on females as major depressive disorder displays a gender-specific profile. The findings show that facial masks selectively affect inferring emotions: recognition of sadness and anger are more heavily compromised in major depressive disorder as compared with typically developing controls, whereas the recognition of fear, happiness, and neutral expressions remains unhindered. Disgust, the forgotten emotion of psychiatry, is the least recognizable emotion in both groups. On the Reading the Mind in the Eyes Test patients exhibit lower accuracy on positive expressions than their typically developing peers, but do not differ on negative items. In both depressive and typically developing individuals, the ability to recognize emotions behind a mask and performance on the Reading the Mind in the Eyes Test are linked to each other in processing speed, but not recognition accuracy. The outcome provides a blueprint for understanding the complexities of reading language of the eyes within and beyond the COVID-19 pandemic.

Quantitative intra- and intergeneric taxonomic relationships among Micrococcaceae strains reveal contradictions in the historical assignments of the strains and indicate the need for species reclassification.

This article reports the results of quantitative intra- and intergeneric taxonomic relationships among Micrococcaceae strains and a novel endophytic bacterium (SG) isolated from a suspension culture of Arabidopsis thaliana (L.) Heynh in our laboratory. The known strain Rothia sp. ND6WE1A was used as a reference one for SG. Whole-genome sequencing and phylogenetic analysis were based on the 16S rRNA test. Quantitative analysis for the nucleotide identity (ANI) and calculation of evolutionary distances were based on the identified amino acids (AAI) test indicating the generic assignment of the reference strain within and between the identified monophyletic groups of Micrococcaceae. The amino acid data structure of Rothia sp. ND6WE1A was compared against the UniProt database (250 million records) of close lineage of Micrococcaceae, including other Rothia spp. These data presented unique and evolutionary amino acid alignments, eventually expected in the new SG isolate as well. The metagenomic entries of the respective genome and proteome, characterized at the genus and species levels, could be considered for evolutionary taxonomic reclassification of the isolated and the reference strain (SG + Rothia sp. ND6WE1A). Therefore, our results warrant further investigations on the isolated SG strain.

Azide-based in situ preparation of fused heterocyclic imines and their multicomponent reactions.

Structurally diverse pyrroles, indoles and imidazoles bearing an N-ω-azidoalkyl moiety and an aldehyde or ketone function were prepared and successfully introduced into in situ imine generation via the intramolecular Staudinger/aza-Wittig tandem reaction. Reduction of the generated imines led to medicinally relevant nitrogen-containing fused heterocycles such as tetrahydropyrrolo[1,2-a]pyrazines and diazepines. Rare 8-membered hexahydropyrrolo[1,2-a][1,4]diazocine and 9-membered dihydro-4,8-(metheno)pyrrolo[1,2-a][1,4]diazacycloundecine were also synthesized. In addition, several one-pot transformations involving cyclic anhydrides or isocyanides (Castagnoli-Cushman, Ugi and azido-Ugi reactions) were added to the Staudinger/aza-Wittig sequence to afford novel fused polyheterocyclic delta-lactams, cyclic bisamides and tetrazoles in a multicomponent fashion. The synthesized compounds were profiled against human Trace Amine-Associated Receptor 1 (hTAAR1), and the best performing compound showed low nanomolar agonistic activity with an EC50 of 0.025 µM.

Simulating transient X-ray photoelectron spectra of Fe(CO)5 and its photodissociation products with multireference algebraic diagrammatic construction theory.

Accurate simulations of transient X-ray photoelectron spectra (XPS) provide unique opportunities to bridge the gap between theory and experiment in understanding the photoactivated dynamics in molecules and materials. However, simulating X-ray photoelectron spectra along a photochemical reaction pathway is challenging as it requires accurate description of electronic structure incorporating core-hole screening, orbital relaxation, electron correlation, and spin-orbit coupling in excited states or at nonequilibrium ground-state geometries. In this work, we employ the recently developed multireference algebraic diagrammatic construction theory (MR-ADC) to investigate the core-ionized states and X-ray photoelectron spectra of Fe(CO)5 and its photodissociation products (Fe(CO)4, Fe(CO)3) following excitation with 266 nm light. The simulated transient Fe 3p and CO 3σ XPS spectra incorporating spin-orbit coupling and high-order electron correlation effects are shown to be in a good agreement with the experimental measurements by Leitner et al. [J. Chem. Phys., 2018, 149, 044307]. Our calculations suggest that core-hole screening, spin-orbit coupling, and ligand-field splitting effects are similarly important in reproducing the experimentally observed chemical shifts in transient Fe 3p XPS spectra of iron carbonyl complexes. Our results also demonstrate that the MR-ADC methods can be very useful in interpreting the transient XPS spectra of transition metal compounds.

Efficient Spin-Adapted Implementation of Multireference Algebraic Diagrammatic Construction Theory. I. Core-Ionized States and X-ray Photoelectron Spectra.

We present an efficient implementation of multireference algebraic diagrammatic construction theory (MR-ADC) for simulating core-ionized states and X-ray photoelectron spectra (XPS). Taking advantage of spin adaptation, automatic code generation, and density fitting, our implementation can perform calculations for molecules with more than 1500 molecular orbitals, incorporating static and dynamic correlation in the ground and excited electronic states. We demonstrate the capabilities of MR-ADC methods by simulating the XPS spectra of substituted ferrocene complexes and azobenzene isomers. For the ground electronic states of these molecules, the XPS spectra computed using the extended second-order MR-ADC method (MR-ADC(2)-X) are in a very good agreement with available experimental results. We further show that MR-ADC can be used as a tool for interpreting or predicting the results of time-resolved XPS measurements by simulating the core ionization spectra of azobenzene along its photoisomerization, including the XPS signatures of excited states and the minimum energy conical intersection. This work is the first in a series of publications reporting the efficient implementations of MR-ADC methods.

Neural circuits underpinning face tuning in male depression.

Reading bodies and faces is essential for efficient social interactions, though it may be thought-provoking for individuals with depression. Yet aberrations in the face sensitivity and underwriting neural circuits are not well understood, in particular, in male depression. Here, we use cutting-edge analyses of time course and dynamic topography of gamma oscillatory neuromagnetic cortical activity during administration of a task with Arcimboldo-like images. No difference in face tuning was found between individuals with depression and their neurotypical peers. Furthermore, this behavioral outcome nicely dovetails with magnetoencephalographic data: at early processing stages, the gamma oscillatory response to images resembling a face was rather similar in patients and controls. These bursts originated primarily from the right medioventral occipital cortex and lateral occipital cortex. At later processing stages, however, its topography altered remarkably in depression with profound engagement of the frontal circuits. Yet the primary difference in depressive individuals as compared with their neurotypical peers occurred over the left middle temporal cortices, a part of the social brain, engaged in feature integration and meaning retrieval. The outcome suggests compensatory recruitment of neural resources in male depression.

Quantifying spin contamination in algebraic diagrammatic construction theory of electronic excitations.

Algebraic diagrammatic construction (ADC) is a computationally efficient approach for simulating excited electronic states, absorption spectra, and electron correlation. Due to their origin in perturbation theory, the single-reference ADC methods may be susceptible to spin contamination when applied to molecules with unpaired electrons. In this work, we develop an approach to quantify spin contamination in the ADC calculations of electronic excitations and apply it to a variety of open-shell molecules starting with either the unrestricted (UHF) or restricted open-shell (ROHF) Hartree-Fock reference wavefunctions. Our results show that the accuracy of low-order ADC approximations [ADC(2) and ADC(3)] significantly decreases when the UHF reference spin contamination exceeds 0.05 a.u. Such strongly spin-contaminated molecules exhibit severe excited-state spin symmetry breaking that contributes to decreasing the quality of computed excitation energies and oscillator strengths. In a case study of phenyl radical, we demonstrate that spin contamination can significantly affect the simulated UV/Vis spectra, altering the relative energies, intensities, and order of electronic transitions. The results presented here motivate the development of spin-adapted ADC methods for open-shell molecules.

Two-State Hydrogen Atom Transfer Reactivity of Unsymmetric [Cu2(O)(NO)]2+ Complexes.

We report the temperature-dependent spin switching of dicopper oxo nitrosyl [Cu2(O)(NO)]2+ complexes and their influence on hydrogen atom transfer (HAT) reactivity. Electron paramagnetic resonance (EPR) and Evans method analysis suggest that [Cu2(O)(NO)]2+ complexes transition from the S = 1/2 to the S = 3/2 state around ca. 202 K. At low temperatures (198 K) where S = 3/2 dominates, a strong correlation between the rate of HAT (kHAT) and the population of the S = 1/2 state was identified (R2 = 0.988), suggesting that the HAT by [Cu2(O)(NO)]2+ complexes proceeds by the S = 1/2 isomer. Installation of functional groups that introduce an unsymmetric secondary coordination environment accelerates the HAT rates through perturbation of the spin equilibria. Given the often unsymmetric coordination sphere of bimetallic active sites in natural proteins, we anticipate that similar strategies could be employed by metalloenzymes to control HAT reactions.

Simulating Spin-Orbit Coupling with Quasidegenerate N-Electron Valence Perturbation Theory.

We present the first implementation of spin-orbit coupling effects in fully internally contracted second-order quasidegenerate N-electron valence perturbation theory (SO-QDNEVPT2). The SO-QDNEVPT2 approach enables the computations of ground- and excited-state energies and oscillator strengths combining the description of static electron correlation with an efficient treatment of dynamic correlation and spin-orbit coupling. In addition to SO-QDNEVPT2 with the full description of one- and two-body spin-orbit interactions at the level of two-component Breit-Pauli Hamiltonian, our implementation also features a simplified approach that takes advantage of spin-orbit mean-field approximation (SOMF-QDNEVPT2). The accuracy of these methods is tested for the group 14 and 16 hydrides, 3d and 4d transition metal ions, and two actinide dioxides (neptunyl and plutonyl dications). The zero-field splittings of group 14 and 16 molecules computed using SO-QDNEVPT2 and SOMF-QDNEVPT2 are in good agreement with the available experimental data. For the 3d transition metal ions, the SO-QDNEVPT2 method is significantly more accurate than SOMF-QDNEVPT2, while no substantial difference in the performance of two methods is observed for the 4d ions. Finally, we demonstrate that for the actinide dioxides the results of SO-QDNEVPT2 and SOMF-QDNEVPT2 are in good agreement with the data from previous theoretical studies of these systems. Overall, our results demonstrate that SO-QDNEVPT2 and SOMF-QDNEVPT2 are promising multireference methods for treating spin-orbit coupling with a relatively low computational cost.

Extracellular vesicles in cancer nanomedicine.

To date, a lot of nanotechnological optitions are available for targeted drug delivery. Extracellular vesicles (EVs) are membrane structures that cells use for storage, transport, communication, and signaling. Recent research has focused on EVs as natural nanoparticles for drug delivery. This review sheds light on the application of EVs in cancer therapy, such as targeted chemotherapy, gene therapy, and vaccine development. Aspects of biogenesis, isolation, targeting, and loading of EVs are discussed in detail.

Electrochemical Strategy for Proton Relay Installation Enhances the Activity of a Hydrogen Evolution Electrocatalyst.

A new method to install a proton relay that enhances the reactivity near an active catalytic site for H2 production is reported, afforded by the electrochemical reduction and protonation of one of the ligands in the paddlewheel Rh2(II,II) hydrogen evolution complex, cis-[Rh2(DPhF)2(bncn)2]2+ (Rh-bncn; DPhF = N,N'-diphenylformamidinate, bncn = benzo[c]cinnoline). An electrochemical reversible prewave is observed for Rh-bncn at potentials more positive than the first bncn-centered reduction couple in the presence of strong acids, observed at -0.72 V vs Fc+/0 (Fc = ferrocene) in the cyclic voltammograms (CVs) in DMF (0.1 M TBAPF6). The origin of this prewave is shown to arise from a precatalytic transformation that originates from a concerted proton-electron transfer (CPET) event occurring at one of the bridging bncn ligands. Through electrochemical analysis, CV simulations, and electronic structure calculations, a reaction mechanism is elucidated. In this system, the electrochemically formed N-H bond on the reduced bncn ligand serves as a proton relay in the H2 formation reaction through a cooperative interligand pathway involving one of the bridging DPhF ligands after a second reduction step, accessible at approximately -1.15 V vs Fc+/0. Since calculations show that hydrogen evolution takes place at the bridging ligands and does not involve the dirhodium core, it is predicted that more abundant metal centers can be incorporated into this ligand scaffold, leading to new candidates for electrocatalytic hydrogen reduction. As such, this work delineates a new design strategy to incorporate proton relays in molecular bimetallic hydrogen evolution electrocatalysts to achieve higher efficiency.

Correction: Simulating X-ray photoelectron spectra with strong electron correlation using multireference algebraic diagrammatic construction theory.

Correction for 'Simulating X-ray photoelectron spectra with strong electron correlation using multireference algebraic diagrammatic construction theory' by Carlos E. V. de Moura and Alexander Yu. Sokolov, Phys. Chem. Chem. Phys., 2022, 24, 4769-4784, DOI: 10.1039/D1CP05476G.

Simulating X-ray photoelectron spectra with strong electron correlation using multireference algebraic diagrammatic construction theory.

We present a new theoretical approach for the simulations of X-ray photoelectron spectra of strongly correlated molecular systems that combines multireference algebraic diagrammatic construction theory (MR-ADC) [J. Chem. Phys., 2018, 149, 204113] with a core-valence separation (CVS) technique. The resulting CVS-MR-ADC approach has a low computational cost while overcoming many challenges of the conventional multireference theories associated with the calculations of excitations from inner-shell and core molecular orbitals. Our results demonstrate that the CVS-MR-ADC methods are as accurate as single-reference ADC approximations for predicting core ionization energies of weakly-correlated molecules, but are more accurate and reliable for systems with a multireference character, such as a stretched nitrogen molecule, ozone, and isomers of the benzyne diradical. We also highlight the importance of multireference effects for the description of core-hole screening that determines the relative spacing and order of peaks in the XPS spectra of strongly correlated systems.

A structured group intervention (TüTASS) with focus on self-perception and mindfulness for children with autism spectrum disorder, ASD. A pilot study.

Autism spectrum disorders (ASD) represent a set of long-lasting severe neurodevelopmental conditions and effective therapeutic interventions are needed. Recent research points to the importance of including mindfulness-based elements to improve emotion and body perception in the psychotherapy of patients with ASD. Therefore, we developed a structured group psychotherapy program The Tübinger Training for Autism Spectrum Disorders (Tübinger Training für Autismus-Spektrum-Störungen; TüTASS) which focuses on mindfulness-based training elements. This pilot study accompanying the TüTASS reports the first results on the feasibility of the program with a pre-post comparison of 25 treated children with ASD. The psychometric assessment comprised five standardized questionnaires/ scales evaluating on the basis of parents and patients self-reports the child's social responsiveness, behavior, strengths and difficulties, quality of life, and depressive symptoms before and after training completion. The results indicated that upon training completion, symptoms with respect to emotional and social problems, externalizing behavior, and attentional and schizoid-compulsive behavior substantially declined. In a questionnaire assessing feasibility and quality of the group training, patients and parents found the therapy highly beneficial, especially as to the focus on emotions and body, and strengths and failures. This training program was developed to bridge the gap of lacking mindfulness-based interventions with the aim to optimize the course of ASD, especially with respect to behavioral disturbances and social-emotional problems.

Face Tuning in Depression.

The latest COVID-19 pandemic reveals that unexpected changes elevate depression bringing people apart, but also calling for social sharing. Yet the impact of depression on social cognition and functioning is not well understood. Assessment of social cognition is crucial not only for a better understanding of major depressive disorder (MDD), but also for screening, intervention, and remediation. Here by applying a novel experimental tool, a Face-n-Food task comprising a set of images bordering on the Giuseppe Arcimboldo style, we assessed the face tuning in patients with MDD and person-by-person matched controls. The key benefit of these images is that single components do not trigger face processing. Contrary to common beliefs, the outcome indicates that individuals with depression express intact face responsiveness. Yet, while in depression face sensitivity is tied with perceptual organization, in typical development, it is knotted with social cognition capabilities. Face tuning in depression, therefore, may rely upon altered behavioral strategies and underwriting brain mechanisms. To exclude a possible camouflaging effect of female social skills, we examined gender impact. Neither in depression nor in typical individuals had females excelled in face tuning. The outcome sheds light on the origins of the face sensitivity and alterations in social functioning in depression and mental well-being at large. Aberrant social functioning in depression is likely to be the result of deeply-rooted maladaptive strategies rather than of poor sensitivity to social signals. This has implications for mental well-being under the current pandemic conditions.

Quantifying and reducing spin contamination in algebraic diagrammatic construction theory of charged excitations.

Algebraic diagrammatic construction (ADC) theory is a computationally efficient and accurate approach for simulating electronic excitations in chemical systems. However, for the simulations of excited states in molecules with unpaired electrons, the performance of ADC methods can be affected by the spin contamination in unrestricted Hartree-Fock (UHF) reference wavefunctions. In this work, we benchmark the accuracy of ADC methods for electron attachment and ionization of open-shell molecules with the UHF reference orbitals (EA/IP-ADC/UHF) and develop an approach to quantify the spin contamination in charged excited states. Following this assessment, we demonstrate that the spin contamination can be reduced by combining EA/IP-ADC with the reference orbitals from restricted open-shell Hartree-Fock (ROHF) or orbital-optimized Møller-Plesset perturbation (OMP) theories. Our numerical results demonstrate that for open-shell systems with strong spin contamination in the UHF reference, the third-order EA/IP-ADC methods with the ROHF or OMP reference orbitals are similar in accuracy to equation-of-motion coupled cluster theory with single and double excitations.

Does the right ventricle size influence the left ventricle size and function in children with Ebstein anomaly?

PURPOSE: Patients with Ebstein anomaly (EA) have a variety of clinical manifestation. The assessment of structural and geometric characteristics of the heart is important for optimal management. METHODS: We retrospectively analyzed echocardiography database from 2009 to 2020. We evaluate patients in two groups: patients with EA were in Group 1 and children without cardiovascular pathology were in Group 2. All children in both groups underwent echocardiography according to American Society of Echocardiography recommendations. The shape of the heart chambers and their function were studied in both groups. RESULTS: There were 153 in Group 1 and 2000 children without cardiovascular disease in Group 2. It was shown that in children with EA, the shape of the ventricle became less spherical, which was accompanied by a decrease in myocardial mass, and the ejection fraction was reduced 34% of patients. The functional volume (non-atrialized part) of the right ventricle in patients with EA was reduced, and its contractility was preserved in 62% of cases. Preservation of the contractile properties of the right ventricle in most cases was associated with higher systolic pressure in its cavity. CONCLUSION: TAPSE, TESV, and the velocity of the annulus fibrous ring movement according to tissue dopplerography in patients with EA do not allow us to assess the contractility of the right ventricle. The myocardial performance index (MPI) characterizes a decrease in the functional volume of the right ventricle.

Surgery for aortic recoarctation in children less than 10 years old: A single-center experience in Siberia, Russia.

BACKGROUND: Persistence or recurrence of stenosis is a complication of initial coarctation repair. This study aims to report short-term outcomes of surgical management of recurrent coarctation and initial repair analysis. METHODS: We retrospectively reviewed our experience with 51 patients undergoing recoarctation surgical repair between 2008 and 2019 using antegrade cerebral perfusion (ACP) technique. RESULTS: Surgical correction included prosthetic patch aortoplasty in 23 (45%), resection with wide end-to-end anastomosis in 15 (29%), and a tube interposition graft in 13 (25%) patients. The median age at initial correction and reintervention was 12 months and 9 years. The median interval from primary repair to reintervention was 60 months. Initial repair analysis revealed 33% of patients had initial correction in the neonatal period, 72.5% of patients were done via a left thoracotomy approach and 63% of patients had end-to-end anastomosis at initial surgery. CONCLUSION: Our study demonstrates that surgical repair of recurrent coarctation of the aorta using ACP technique can be performed safely and with excellent results.