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The soil mantle of the tropical karstic landscapes of Southern Mexico was shaped by specific processes of pedogenesis and long-term human impacts of ancient Maya agriculture. To understand the interaction between natural and human-induced soilforming processes in the calcareous mountains of Chiapas state, we studied soil toposequences around the Classic Maya site of Budsilhá and related them to the archaeological evidence of settlement and land-use distribution. Soil chemical analysis, micromorphological observations, and clay mineral identification were carried out in key soil profiles at the main geoforms. Limestone hills are occupied by shallow Rendolls which are usually perceived as incipient soils. However, high content of silicate clay composed of kaolinite and vermiculite and ferruginous clayey soil material observed at macro- and microscale backed the hypothesis that these soils were formed from the residues of thick Terra Rossa after their erosion. Swampy lowlands are occupied by thick clayey gleyic soils with clay mineral assemblages similar to those in the upland Rendolls. We suppose that the mineral matrix of the lowland soils is largely derived from the pedosediments of eroded upland Terra Rossa, which lost original ferruginous pigmentation and aggregation due to redoximorphic processes. Some wetland soils contain neoformed gypsum that is atypical for humid tropics; sulfidesulfate transformation under fluctuating redox conditions could promote gypsum synthesis. Ancient Maya land use was closely related to soil-geomorphic conditions: settlements with homegardens occupied calcareous hills, whereas the primary agricultural domain was developed on lowland soils after their drainage by artificial canals. [ABSTRACT FROM AUTHOR]

Conceptual density functional theory (CDFT) and the quantum reactivity descriptors stemming from it have proven to be valuable tools for understanding the chemical behavior of molecules. This article is presented as being intrinsically of dual character. In a first part, it briefly reviews, in a deliberately didactical way, the main ensembles in CDFT, while the second half presents two additional ensembles, where the chemical hardness acts as a natural variable, and their respective reactivity descriptors. The evaluation of these reactivity descriptors on common organic chemical reagents are presented and discussed. [ABSTRACT FROM AUTHOR]

Background: Classical pulmonary thromboembolism (TE) and local pulmonary thrombosis (PT) have been suggested as mechanisms of thrombosis in COVID‐19. However, robust evidence is still lacking because this was mainly based on retrospective studies, in which patients were included when TE was suspected. Methods: All patients with COVID‐19 pneumonia underwent computed tomography and pulmonary angiography in a prospective study. The main objective was to determine the number and percentage of thrombi surrounded by lung opacification (TSO) in each patient, as well as their relationship with percentage of lung involvement (TLI), to distinguish classical TE (with a random location of thrombi that should correspond to a percentage of TSO equivalent to the TLI) from PT. We determined TLI by artificial intelligence. Analyses at patient level (TLI and percentage of TSO) and at thrombi level (TLI and TSO) were performed. Results: We diagnosed TE in 70 out of 184 patients. Three (2–8) thrombi/patient were detected. The percentage of TSO was 100% (75–100) per patient, and TLI was 19.9% (4.6–35.2). Sixty‐five patients (92.9%) were above the random scenario with higher percentage of TSO than TLI. Most thrombi were TSO (n = 299, 75.1%). When evaluating by TLI (<10%, 10%–20%, 20%–30% and >30%), percentage of TSO was higher in most groups. Thrombi were mainly in subsegmental/segmental arteries, and percentage of TSO was higher in all locations. Conclusions: Thrombi in COVID‐19 were found within lung opacities in a higher percentage than lung involvement, regardless of TLI and clot location, supporting the hypothesis of local PT rather than "classic TE". [ABSTRACT FROM AUTHOR]

Through their talk, actions and interactions, children actively shape and develop notions of gender and sexuality. This research delves into the realm of children's agency to explore the ways children act and react to instances of sexism and LGBTI+ phobia. Within the context of a Gender Equity Education Program in a Chilean primary school, this study employs participatory‐action research, integrating participatory methods and participant observation, acknowledging the significance of children's agencies in knowledge construction. Analytically, a feminist post‐structuralist lens is applied to examine children's experiences, unveiling distinct categories of agencies, namely ‘reproducers’ and ‘challengers’ of the dominant discourse. [ABSTRACT FROM AUTHOR]

Disentangling nucleation and growth in materials that crystallize on the nanosecond time scale is experimentally quite challenging since the relevant processes also take place on very small, i.e., sub‐micrometer length scales. Phase change materials are bad glass formers, which often crystallize rapidly. Here systematic changes in crystallization kinetics are shown in pseudo‐binary compounds of GeTe and Sb2Te3 and related solids subjected to short laser pulses. Upon systematic changes in stoichiometry, the speed of crystallization changes by three orders of magnitude concomitantly with pronounced changes in stochasticity. Resolving individual grains with electron backscatter diffraction (EBSD) permits to disentangle of the process of nucleation and growth. From these experiments, supported by multiphysics simulations of crystallization, it can be concluded that high crystallization speeds with small stochasticity characterize phase change materials with fast nucleation, while compounds that nucleate slowly crystallize much more stochastically. [ABSTRACT FROM AUTHOR]

The various mechanisms of primary antioxidant action of a series of 2‐Methoxyphenols are investigated in the present work. The electronic properties have just been studied in a joint article, so that we focus here on Hydrogen Atom Transfer (HAT), Single Electron Transfer–Proton Transfer (SET–PT) and Sequential Proton‐Loss Electron‐Transfer (SPLET) mechanisms. The two computational approaches used in the previous study of the structure and reactivity of these compounds [Computational and Theoretical Chemistry 1229 (2023) 114287] provide identical mechanisms trends in gas phase. In gas media, hydrogen atom transfer (HAT) is more favored. On the contrary, the solvent polarity has a significant effect on the mechanism of the antioxidant activity, since the polarity of the solvent increases the contribution of the SPLET mechanism. [ABSTRACT FROM AUTHOR]

Multi‐principal element alloys (MPEAs) are gaining interest in corrosion and electrocatalysis research due to their electrochemical stability across a broad pH range and the design flexibility they offer. Using the equimolar CrCoNi alloy, we observe significant metal dissolution in a corrosive electrolyte (0.1 M NaCl, pH 2) concurrently with the oxygen evolution reaction (OER) in the transpassive region, despite the absence of hysteresis in polarization curves or other obvious corrosion indicators. We present a characterization scheme to delineate the contribution of OER and alloy dissolution, using scanning electrochemical microscopy (SECM) for OER‐onset detection, and quantitative chemical analysis with inductively coupled‐mass spectrometry (ICP‐MS) and ultraviolet visible light (UV/Vis) spectrometry to elucidate metal dissolution processes. In situ electrochemical atomic force microscopy (EC‐AFM) revealed that the transpassive metal dissolution on CrCoNi is dominated by intergranular corrosion. These results have significant implications for the stability of MPEAs in corrosion systems, emphasizing the necessity of analytically determining metal ions released from MPEA electrodes into the electrolyte when evaluating Faradaic efficiencies of OER catalysts. The release of transition metal ions not only reduces the Faradaic efficiency of electrolyzers but may also cause poisoning and degradation of membranes in electrochemical reactors. [ABSTRACT FROM AUTHOR]

Multi‐Hauptelement‐Legierungen (MPEAs) gewinnen in der Korrosions‐ und Elektrokatalyseforschung aufgrund ihrer elektrochemischen Stabilität über einen breiten pH‐Bereich und der Vielfalt der möglichen chemischen Zusammensetzungen zunehmend an Interesse. In unseren Untersuchungen mit der äquimolaren CrCoNi‐Legierung in einem sauren Elektrolyten (0.1 M NaCl, pH 2) beobachteten wir eine signifikante Metallauflösung, die mit der Sauerstoffentwicklungsreaktion (OER) im transpassiven Bereich einhergeht, obwohl in zyklischen Polarisationskurven keine Hysterese auftrat oder andere offensichtliche Korrosionsindikatoren vorlagen. In diesem Artikel wird ein Charakterisierungskonzept eingeführt, dass die Beiträge der OER und der Legierungsauflösung differenziert. Hierfür kommt die elektrochemische Rastermikroskopie (SECM) zum Nachweis des Beginns der OER und die quantitative chemische Analyse mit induktiv gekoppelter Massenspektrometrie (ICP‐MS) und UV/Vis‐Spektrometrie zur Aufklärung der Metallauflösungsprozesse zum Einsatz. Die elektrochemische In situ‐Atomkraftmikroskopie (EC‐AFM) zeigte, dass die intergranulare Korrosion der dominierende Mechanismus der transpassive Metallauflösung von CrCoNi ist. Diese Ergebnisse besitzen erhebliche Auswirkungen für die Beurteilung der Stabilität von MPEAs in Korrosionssystemen und der Stromausbeute von OER‐Katalysatoren auf der Basis von MPEAs. Die Daten unterstreichen die Notwendigkeit der analytischen Bestimmung von Metallionen, die von MPEA‐Elektroden freigesetzt werden. Die Freisetzung von Übergangsmetallionen verringert nicht nur die Stromausbeute von Elektrolyseuren, sondern kann zu einer Schädigung von Membranen in elektrochemischen Reaktoren führen. [ABSTRACT FROM AUTHOR]

Malignant peripheral nerve sheath tumors (MPNSTs) are aggressive soft‐tissue sarcomas with a poor survival rate, presenting either sporadically or in the context of neurofibromatosis type 1 (NF1). The histological diagnosis of MPNSTs can be challenging, with different tumors exhibiting great histological and marker expression overlap. This heterogeneity could be partly responsible for the observed disparity in treatment response due to the inherent diversity of the preclinical models used. For several years, our group has been generating a large patient‐derived orthotopic xenograft (PDOX) MPNST platform for identifying new precision medicine treatments. Herein, we describe the expansion of this platform using six primary tumors clinically diagnosed as MPNSTs, from which we obtained six additional PDOX mouse models and three cell lines, thus generating three pairs of in vitro–in vivo models. We extensively characterized these tumors and derived preclinical models, including genomic, epigenomic, and histological analyses. Tumors were reclassified after these analyses: three remained as MPNSTs (two being classic MPNSTs), one was a melanoma, another was a neurotrophic tyrosine receptor kinase (NTRK)‐rearranged spindle cell neoplasm, and, finally, the last was an unclassifiable tumor bearing neurofibromin‐2 (NF2) inactivation, a neuroblastoma RAS viral oncogene homolog (NRAS) oncogenic mutation, and a SWI/SNF‐related matrix‐associated actin‐dependent regulator of chromatin (SMARCA4) heterozygous truncated variant. New cell lines and PDOXs faithfully recapitulated histology, marker expression, and genomic characteristics of the primary tumors. The diversity in tumor identity and their specific associated genomic alterations impacted treatment responses obtained when we used the new cell lines for testing compounds against known altered pathways in MPNSTs. In summary, we present here an extension of our MPNST precision medicine platform, with new PDOXs and cell lines, including tumor entities confounded as MPNSTs in a real clinical scenario. This platform may constitute a useful tool for obtaining correct preclinical information to guide MPNST clinical trials. [ABSTRACT FROM AUTHOR]

Cardiac catheterization remains the gold standard for the diagnosis and management of pediatric pulmonary hypertension (PH). There is lack of consensus regarding optimal anesthetic and airway regimen. This retrospective study describes the anesthetic/airway experience of our single center cohort of pediatric PH patients undergoing catheterization, in which obtaining hemodynamic data during spontaneous breathing is preferential. A total of 448 catheterizations were performed in 232 patients. Of the 379 cases that began with a natural airway, 274 (72%) completed the procedure without an invasive airway, 90 (24%) received a planned invasive airway, and 15 (4%) required an unplanned invasive airway. Median age was 3.4 years (interquartile range [IQR] 0.7–9.7); the majority were either Nice Classification Group 1 (48%) or Group 3 (42%). Vasoactive medications and cardiopulmonary resuscitation were required in 14 (3.7%) and eight (2.1%) cases, respectively; there was one death. Characteristics associated with use of an invasive airway included age <1 year, Group 3, congenital heart disease, trisomy 21, prematurity, bronchopulmonary dysplasia, WHO functional class III/IV, no PH therapy at time of case, preoperative respiratory support, and having had an intervention (p < 0.05). A composite predictor of age <1 year, Group 3, prematurity, and any preoperative respiratory support was significantly associated with unplanned airway escalation (26.7% vs. 6.9%, odds ratio: 4.9, confidence interval: 1.4–17.0). This approach appears safe, with serious adverse event rates similar to previous reports despite the predominant use of natural airways. However, research is needed to further investigate the optimal anesthetic regimen and respiratory support for pediatric PH patients undergoing cardiac catheterization. [ABSTRACT FROM AUTHOR]

Aim: Febrile urinary tract infection is a common bacterial infection in childhood. The kidney damage after acute pyelonephritis (APN) could be related to the stimulation of the proinflammatory response. We aimed to investigate the role of inflammatory cytokines and the effect of dexamethasone after a first episode of APN. Methods: Subanalysis of the DEXCAR RCT in which children with confirmed APN (1 month–14 years) were randomly assigned to receive a 3 days course of either intravenous dexamethasone or placebo. Urinary cytokine levels at diagnosis and after 72 h of treatment were measured. Results: Ninety‐two patients were recruited. Younger patients, males and those with abnormalities in the ultrasound study or vesicoureteral reflux showed higher values of urinary cytokines. Patients with severe APN had higher Tumour Necrosis Factor (TNF)α levels (81.0 ± 75.8 vs. 33.6 ± 48.5 pg/mg creatinine, p = 0.015). Both intervention groups showed similar basal clinical characteristics, including urinary cytokine levels. Treatment reduced urinary cytokine levels irrespective of dexamethasone administration. Neither the intervention group nor the urinary cytokine levels modulated the development of kidney scars. Conclusion: Basal urinary cytokines were associated with age, abnormal ultrasound and vesicoureteral reflux. Patients with severe APN had higher TNFa urinary levels. Administration of dexamethasone in children with APN does not improve the control of the proinflammatory cytokine cascade. [ABSTRACT FROM AUTHOR]

Large area single and bilayer graphene are grown on Pt/Ti/SiO2 substrates by hot filament chemical vapor deposition (HFCVD) with and without the assistance of Cu foil. The quality and number of graphene layers deposited on the substrate are assessed by Raman Spectroscopy. Atomic Force Microscopy (AFM) is used for assessing the surface topography of the graphene films grown on the Pt/Ti/SiO2 substrates. The microstructure and elemental analyses are performed by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). The results show that bilayer graphene growth is facilitated by a copper foil placed nearby Pt/Ti/SiO2 substrate and by a high filament temperature in the HFCVD reactor. Monolayer graphene grows only when no copper foil is placed near the Pt/Ti/SiO2 substrate at a low filament temperature. The approach paves a novel pathway towards the layer‐controlled growth of graphene on Pt/Ti/SiO2 substrates by HFCVD for frontier applications. [ABSTRACT FROM AUTHOR]

Few studies have constrained the magnitudes and timescales associated with large‐scale drainage captures (areas >103 km2), even though these constraints are crucial to reconstruct sediment budgets, assess the potential for drainage reorganization to be preserved in the rock record, and determine the extent to which environmental signals (i.e., structures, composition and fossil assemblages within sedimentary rocks that are influenced by sediment supply and transport) are representative of conditions during deposition. In this work, we characterize the Pleistocene capture of the Zhada Basin, an ~23 000 km2 extensional basin in southern Tibet, by the Sutlej River, a prominent tributary to the Indus River. We quantify the magnitudes and timescales of capture‐driven erosion using knickpoint celerity modelling, paleotopographic reconstructions, 10Be‐derived denudation rates, and topographic analyses of drainage divides. We find that capture has removed 2010 ± 400 km3 of sediment from the Zhada Basin, increasing sediment supply to the Sutlej network by 17%–29% since 735 ± 269 ka. This work represents a crucial step towards reconstructing the Pleistocene sediment budget of the Indus sedimentary system and identifying potential impacts from sediment redistribution. We also identify several plausible tectonic or autogenic mechanisms that may have facilitated capture of the Zhada Basin, including: (1) preferential erosion of weak lithologies along active faults, (2) headward erosion in response to prior capture of the Spiti River and (3) headward erosion generated by breaching of a structural culmination downstream (the Kullu‐Rampur Window). This provides a framework to assess the mechanistic links between arc‐parallel extension, large‐scale drainage capture, landscape evolution and orogenic wedge deformation. [ABSTRACT FROM AUTHOR]

This article discusses a case study of a female patient and her affected niece who have a homozygous frameshift variant of the CLPP gene, which is associated with severe Perrault syndrome. The proband has symptoms including hearing loss, primary ovarian insufficiency, abnormal brain white matter, and developmental delay. The study describes the genetic variant and its predicted effects, as well as the clinical features of the patients. The authors suggest that severe Perrault syndrome may result from biallelic null-alleles of CLPP, while hypomorphic variants may be associated with milder symptoms. The research was supported by various funding sources and the authors declare no conflicts of interest. [Extracted from the article]

Subduction forearcs are subject to seismic hazard from upper plate faults that are often invisible to instrumental monitoring networks. Identifying active faults in forearcs therefore requires integration of geomorphic, geologic, and paleoseismic data. We demonstrate the utility of a combined approach in a densely populated region of Vancouver Island, Canada, by combining remote sensing, historical imagery, field investigations, and shallow geophysical surveys to identify a previously unrecognized active fault, the XEOLXELEK‐Elk Lake fault, in the northern Cascadia forearc, ∼10 km north of the city of Victoria. Lidar‐derived digital terrain models and historical air photos show a ∼2.5‐m‐high scarp along the surface of a Quaternary drumlinoid ridge. Paleoseismic trenching and electrical resistivity tomography surveys across the scarp reveal a single reverse‐slip earthquake produced a fault‐propagation fold above a blind southwest‐dipping fault. Five geologically plausible chronological models of radiocarbon dated charcoal constrain the likely earthquake age to between 4.7 and 2.3 ka. Fault‐propagation fold modeling indicates ∼3.2 m of reverse slip on a blind, 50° southwest‐dipping fault can reproduce the observed deformation. Fault scaling relations suggest a M 6.1–7.6 earthquake with a 13 to 73‐km‐long surface rupture and 2.3–3.2 m of dip slip may be responsible for the deformation observed in the paleoseismic trench. An earthquake near this magnitude in Greater Victoria could result in major damage, and our results highlight the importance of augmenting instrumental monitoring networks with remote sensing and field studies to identify and characterize active faults in similarily challenging environments. Plain Language Summary: Faults occurring in the upper plate above a subduction zone are often located near densely populated coastal areas, but their hazard is often underappreciated due to their low deformation rates. In the northern Cascadia forearc on the west coast of North America, high‐resolution topography and geologic mapping show a ∼2.3‐m‐high scarp across a ∼14,000 year‐old land surface 10 km north of downtown Victoria, British Columbia, Canada. This newly identified fault, the XEOLXELEK‐Elk Lake fault (XELF), crosses Saanich Peninsula within Greater Victoria and poses a hazard to the region's ∼400,000 inhabitants. Therefore, determining whether it produced recent large earthquakes is important for updating regional earthquake hazard models and increasing earthquake preparedness. To study the earthquake history of the fault, we used shallow geophysical techniques and excavated a trench across the scarp to examine the sedimentary record of deformation. These combined methodologies determined a single large earthquake, of magnitude 6.1–7.6, likely occurred on the XELF between ∼4,700 and 2,300 years ago. A similar future earthquake on the XELF Lake fault could cause major damage to the Greater Victoria area. Thus, our results can improve future earthquake hazard assessments. Key Points: We document a single Holocene earthquake on a previously unidentified fault in the northern Cascadia forearc near Victoria, CanadaTrenching, shallow geophysics, and fault‐fold modeling show 2.3–3.2 m of dip slip during an M 6.1–7.6 earthquake between 4.7 and 2.3 kaA combination of methodologies can enhance the study of active faults in forearcs, urbanized areas, and previously glaciated terrain [ABSTRACT FROM AUTHOR]

Background: A positive conception of sexuality among people with intellectual disabilities is crucial and relies on several social and interpersonal contexts. The goal of this study is to analyse the interaction and impact of three different contextual groups: individuals with intellectual disabilities, their parents, and professionals working with them. Methods: Survey data were collected from 330 people with intellectual disabilities attending occupational centres in eastern Spain, 330 parents, and 100 professionals. Results: Correlation and variance analyses of dyad‐level data show significant differences among the three groups in all variables. Professionals perceived people with intellectual disabilities to have higher knowledge of socio‐sexual norms than people with intellectual disabilities actually appear to be, but they are also more concerned about aspects related to this area of people with intellectual disabilities. Compared to people with intellectual disabilities and professionals, parents perceived people with intellectual disabilities to have lower sexual knowledge. Conclusions: Our study demonstrates inconsistent perceived knowledge of people with intellectual disabilities' socio‐sexual norms and sexual knowledge among the three groups, leading to disparate levels of concern regarding people with intellectual disabilities sexuality. Thus, the need to collect information from different perspectives for more accurate reporting and the critical need for sex education programs that involve the target population, but also parents and professionals who frequently interact with people with intellectual disabilities are highlighted. [ABSTRACT FROM AUTHOR]

Gadolinium (Gd) and Nickel (Ni) doped bismuth ferrite (BiFeO3) nanoparticles Bi0.925Gd.075Fe0.95Ni0.05O3 (BGFNO) with spontaneous polarization (2.5 μC/cm2) were mechano‐chemically synthesized and used to achieve high capacity retention in lithium sulfur (Li−S) batteries. The BGFNO particles were coupled with single walled carbon nanotubes (SWCNT)/sulfur (S) composite cathodes as well as coated on separator. The X‐ray diffraction of BGFNO@S/SWCNT cathodes show an orthorhombic structure with particle size distribution of 20–26 nm, while Raman spectra substantiate efficient coupling of BGFNO with S/SWCNT cathodes, in agreement with SEM images, showing the interconnected network of composites. The specific discharge capacity of S60BGFNO30SWCNT10 composite cathode @ 200 mA/g together with BGFNO coated separator gains maximum capacity up to 1611 mAh/g and retains up to 1294 mAh/g after 50th cycle with improved capacity retention of 80 % showing suppression of polysulfides formation. The coated separator controls transport of carrier ions and side reactions, however modified cathodes with BGFNO particles acts as trapping center for polysulfides to enhance the electrochemical performance of the cells. The Coulombic efficiency(CE) for BGFNO/S/SWCNT composites @ 100 mA/g attained >98 % and CE @ 200 mA/g it is attained > 80 to 90 % compared to S/SWCNT composites in terms of improved cycle stability and reaction kinetics. [ABSTRACT FROM AUTHOR]

Consider an M‐th order linear differential operator, M≥2$M\ge 2$,L(M)=∑k=0Mρk(z)dkdzk,$$\begin{equation*} \mathcal {L}^{(M)}=\sum _{k=0}^{M}\rho _{k}(z)\frac{d^k}{dz^k}, \end{equation*}$$where ρM$\rho _M$ is a monic complex polynomial such that deg[ρM]=M$\mbox{{ \textrm {deg}}}[\rho _M ]=M$ and (ρk)k=0M−1$(\rho _k)_{k=0}^{M-1}$ are complex polynomials such that deg[ρk]≤k,0≤k≤M−1$\mbox{{ \textrm {deg}}}[\rho _k ]\le k, 0\le k \le M-1$. It is known that the zero counting measure of its eigenpolynomials converges in the weak star sense to a measure μ. We obtain an asymptotic expansion of the eigenpolynomials of L(M)$\mathcal {L}^{(M)}$ in compact subsets out of the support of μ. In particular, we solve a conjecture posed in Masson and Shapiro [On polynomial eigenfunctions of a hypergeometric type operator. Exper Math. 2001;10:609‐618]. [ABSTRACT FROM AUTHOR]

We have carried a structural study across Kodiak accretionary complex in Alaska, USA, in order to describe its thermal structure and decipher the processes of exhumation. The accretionary complex consists of a stack of tectonic mélanges and coherent units. Mélanges are characterized by simple shear deformation with a pervasive network of top‐to‐the‐trench shear zones, whereas coherent units are affected principally by horizontal shortening, except for spatially limited outcrops in Kodiak Central Belt. Peak temperatures estimated using Raman spectroscopy of carbonaceous material range from 220 to 400°C through most of the complex. These temperatures coincide with estimates from metamorphic parageneses and are interpreted as temperatures of deformation achieved under a high gradient due to contemporaneous ridge subduction. The highest temperatures are recorded in the central part of the complex, pointing to a dome‐like structure. Lower temperatures (∼120°C) are recorded along the southeastern border of the complex, in slope sediments unconformably overlying accreted units. Based on the combination of structural and thermal data, we conclude that the rocks constituting the Kodiak complex experienced at least two stages of burial and then exhumation, with vertical motions reaching up to ∼13 km from the Paleocene to the present. Given the pervasive horizontal shortening within the wedge, exhumation resulted from prism thickening contemporaneous with surficial erosion. Recorded subsidence episodes may be local phenomena associated with thrusting or large‐scale processes associated with basal erosion. The rates of vertical motion range from 0.2 to 1.3 mm/yr, comparable with estimates in modern margins. Plain Language Summary: In this study, we examined several units from the Kodiak accretionary complex, an archetypal example of the accretionary wedge in southern Alaska, to improve our understanding of the processes that influence convergent margins. These units were subducted to significant depths, but the mechanisms responsible for their exhumation back to the surface remain unclear. Estimated peak‐burial temperatures in basally accreted units across the complex are in the range 220–400°C, with a temperature gap between basally accreted units and slope sediments (100–140°C). Temperatures and pressures suggest a burial down to depths of ∼7–13 km. Based on deformation kinematics and temperature estimates in basally accreted units and slope sediments, we propose that the exhumation periods result from basal accretion, horizontal shortening, and surficial erosion. In contrast, subsidence most likely resulted from thrusting in the upper plate or basal erosion. Key Points: A maximum temperature of the order of 300–400°C is observed in the central part of the complex, decreasing to ∼220–300°C landward and seawardThe accretionary complex experienced two sequences of rock burial and then exhumation since the PaleoceneExhumation at rates of ∼0.2–1.3 mm/yr resulted from uplift associated with surficial erosion [ABSTRACT FROM AUTHOR]

This article explores the sustainability of the resettlement of unaccompanied refugee children from their perspective. Against the backdrop of a critical assessment of the multilevel governance of resettlement, it compares two rural municipalities. Unaccompanied refugee children in the municipality with a disempowering local governance model were hindered to engage with civil society, while in the municipality with an enabling model, their integration was enhanced. Achieving safety by legal residency does not by itself resolve the liminalities of belonging to unaccompanied refugee children. Beyond positive engagement by professionals, supporting encounters with civil society were found to enhance integration and belonging, while the lack of these strengthened marginalities. Unaccompanied refugee children resettlement is largely influenced by the benevolence of local actors when the state vacates its responsibility to co‐ordinate efforts. While civil society has an important role to play, a helping civil society cannot be assumed. Tensions rose also due to the collision between institutional styles. The marketisation of refugee reception at the national level led to loss of ability to plan schooling in rural municipalities, reinforcing practices of physical and symbolic segregation of children in the refugee context education. These accounts shed also light on the resilience of unaccompanied refugee children encountering local resettlement efforts emerging in the context of increasingly securitised asylum policies. [ABSTRACT FROM AUTHOR]

That question is of interest to EU policymakers who have sought to align agricultural policy with the objectives of wider sustainability policies (also apparent in Ferrari et al., McCarthy et al.). Keywords: in transition and across scales; justice; politics of knowledge production; power and identity; sustainability; wellbeing EN in transition and across scales justice politics of knowledge production power and identity sustainability wellbeing 379 389 11 07/31/23 20230701 NES 230701 INTRODUCTION The term "sustainability" has exploded in academic writing in recent years and rural studies is no exception. We highlight the complexity of sustainability to help our understanding of the concept and identify the implications for the future of rural areas in Europe. Both Asztalos Morell and Florin show how different scales of governments, sometimes across countries, as well as a range of stakeholders beyond government are needed for sustainable lives. [Extracted from the article]

Hereditary deafness and retinal dystrophy are each genetically heterogenous and clinically variable. Three small unrelated families segregating the combination of deafness and retinal dystrophy were studied by exome sequencing (ES). The proband of Family 1 was found to be compound heterozygous for NM_004525.3: LRP2: c.5005A > G, p.(Asn1669Asp) and c.149C > G, p.(Thr50Ser). In Family 2, two sisters were found to be compound heterozygous for LRP2 variants, p.(Tyr3933Cys) and an experimentally confirmed c.7715 + 3A > T consensus splice‐altering variant. In Family 3, the proband is compound heterozygous for a consensus donor splice site variant LRP2: c.8452_8452 + 1del and p.(Cys3150Tyr). In mouse cochlea, Lrp2 is expressed abundantly in the stria vascularis marginal cells demonstrated by smFISH, single‐cell and single‐nucleus RNAseq, suggesting that a deficiency of LRP2 may compromise the endocochlear potential, which is required for hearing. LRP2 variants have been associated with Donnai–Barrow syndrome and other multisystem pleiotropic phenotypes different from the phenotypes of the four cases reported herein. Our data expand the phenotypic spectrum associated with pathogenic variants in LRP2 warranting their consideration in individuals with a combination of hereditary hearing loss and retinal dystrophy. [ABSTRACT FROM AUTHOR]

The selectivity and the nature of the molecular mechanism of the [3 + 2] cycloaddition (32CA) reaction between 2‐(dimethylamino)‐1H‐indene‐1,3(2H)‐dione (AY11) and trans(E)‐3,3,3‐trifluoro‐1‐nitroprop‐1‐ene(FNP10) has been studied, in which the molecular electron density theory using density functional theory methods at the MPWB1K/6‐31G(d) computational level was used. Analysis of the global reactivity indices permits us to characterize FNP10 as a strong electrophile and AY11 as a strong nucleophile. Four reactive pathways associated with the ortho/meta regioselective channels and endo/exo stereoselective approaches modes have been explored and characterized in the gas phase and in the benzene solvent. The analysis of the relative energies associated with the different reaction pathways indicates that the 32CA reactions of the azomethine ylide (AY) with the nitroalkene (FNP) is meta regioselective with high endo stereoselectivity. This result is in good agreement with the experimental observations. electron localization function topological analysis of the most favored reactive pathways allows for characterizing the mechanism of this 32CA reactions as a non‐concerted two‐stage one‐step mechanism. Finally, non‐covalent interactions and quantum theory of atoms in molecule analyses at the meta/endo transition state structure indicate that the presence of different several weak interactions, namely, CF and NH contributed in favoring the formation of a meta‐endo cycloadduct. [ABSTRACT FROM AUTHOR]

The incidence and prevalence of age‐related neurodegenerative dementias have been increasing. There is no curative therapy and conventional drug treatment can cause problems for patients. Medicinal plants traditionally used for problems associated with ageing are emerging as a therapeutic resource. The main aim is to give a proposal for use and future research based on scientific knowledge and tradition. A literature search was conducted in several searchable databases. The keywords used were related to neurodegenerative dementias, ageing and medicinal plants. Boolean operators and filters were used to focus the search. As a result, there is current clinical and preclinical scientific information on 49 species used in traditional medicine for ageing‐related problems, including neurodegenerative dementias. There are preclinical and clinical scientific evidences on their properties against protein aggregates in the central nervous system and their effects on neuroinflammation, apoptosis dysregulation, mitochondrial dysfunction, gabaergic, glutamatergic and dopaminergic systems alterations, monoamine oxidase alterations, serotonin depletion and oestrogenic protection. In conclusion, the potential therapeutic effect of the different medicinal plants depends on the type of neurodegenerative dementia and its stage of development, but more clinical and preclinical research is needed to find better, safer and more effective treatments. [ABSTRACT FROM AUTHOR]

Intracranial myxoid mesenchymal tumor, FET::CREB fusion positive is a rare, recently described central nervous system neoplasm. It is characterized by EWSR1::CREB family transcription factor fusion, typically arises in children and adolescents, and is locally aggressive even after gross total resection. Currently, there are little data available to guide management and gauge long‐term prognosis. Furthermore, there have been no reports of these lesions occurring simultaneously with other intracranial neoplasms or in patients with a history of malignancy. Here we describe the first case of a very unusual patient with intracranial myxoid mesenchymal tumor of the right lateral ventricle with a concurrent fourth ventricular ependymoma who had a remote history of Ewing sarcoma of the right fibula. [ABSTRACT FROM AUTHOR]

Purpose: To evaluate the diagnostic performance of lung ultrasound (LUS) in screening for SARS‐CoV‐2 infection in patients requiring surgery. Methods: Patients underwent a LUS protocol that included a scoring system for screening COVID‐19 pneumonia as well as RT‐PCR test for SARS‐CoV‐2. The receiver operator characteristic (ROC) curve was determined for the relationship between LUS score and PCR test results for COVID‐19. The optimal threshold for the best discrimination between non‐COVID‐19 patients and COVID‐19 patients was calculated. Results: Among 203 patients enrolled (mean age 48 years; 82 males), 8.3% were COVID‐19‐positive; 4.9% were diagnosed via the initial RT‐PCR test. Of the patients diagnosed with SARS‐CoV‐2, 64.7% required in‐hospital management and 17.6% died. The most common ultrasound findings were B lines (19.7%) and a thickened pleura (19.2%). The AUC of the ROC curve of the relationship of LUS score with a cutoff value >8 versus RT‐PCR test for the assessment of SARS‐CoV‐2 pneumonia was 0.75 (95% CI 0.61–0.89; sensitivity 52.9%; specificity 91%; LR (+) 6.15, LR (−) 0.51). Conclusion: The LUS score in surgical patients is not a useful tool for screening patients with potential COVID‐19 infection. LUS score shows a high specificity with a cut‐off value of 8. [ABSTRACT FROM AUTHOR]

Background: The cultural and social norms in India stipulate that family and preferably children of the older person, provide the support and care that is needed. In recent years, we have witnessed an overall upsurge in interest in informal care from all countries in the developed world considering their ageing populations. The older people living alone group is, especially interesting in this matter, since it seems to deviate from the expectations of extended family living. Objective: The aim was to describe older persons' experiences of informal care when living alone in India. Methods: The study has a hermeneutic design, analysing interviews of older persons living alone in India. Results: Findings revealed informal care as the thematic patterns: Informal care as a fundamental human responsibility, an obligation and thereby a way to act in 'common sense'. It was a way of 'paying‐back' care that they had received from others in their life history, motivated by governmental care was not presented as an option. Informal care also created safety by the provision of alert and actionable care by loved ones, including spatial safety. Most of the informants experienced themselves as informal caregivers assisting others in need even if they themselves were old and fragile. Providing self care was also seen as a part of informal care conducted by capable and worthy persons. They also pointed out their own obligation to seek informal care and even to listen to the suggestions of younger generations regarding the type and scope of care. Conclusions/Implications for practice: Informal care in India is not only dependent on having children who ensure that you receive the care you need. Extended family, neighbours and friends feel a basic human obligation to care for the older people in their environment. This responsibility is deeply rooted even within the older people who become fragile in old age. [ABSTRACT FROM AUTHOR]

The San Juan fault (SJF), on southern Vancouver Island, Canada, juxtaposes the oceanic Wrangellia and Pacific Rim terranes in the northern Cascadia forearc, and has been suggested to play a role in multiple Mesozoic‐Cenozoic terrane accretion events. However, direct observations of the SJF's kinematics have not been documented and its exact role in accommodating strain arising from terrane accretion is unknown. To test if, how, and when the SJF accommodated accretion‐related strain, we use geologic mapping, kinematic inversion of fault‐plane slickenlines, and dating of marine sediments to constrain the timing and direction of brittle slip of the SJF. P‐ and T‐axes from kinematic inversions indicate predominantly left‐lateral slip. Left‐lateral brittle faulting cross‐cuts ∼51 Ma magmatic intrusions and foliation, providing a maximum age of brittle deformation. The fault zone is non‐conformably overlain by a >300 m‐thick sequence of clastic marine shelf and slope sediments that are not left‐laterally offset. A strontium isotope age of foraminifers helps constrain the depositional age of the sediments to late Eocene–early Oligocene, bracketing left‐lateral slip to the Eocene. Eocene left‐lateral slip is temporally and kinematically consistent with regional southwest‐northeast compression during accretion of the Siletzia ocean island plateau, suggesting brittle slip on the SJF accommodated strain resulting from the accretion of this terrane. This result does not support hypotheses that brittle slip along the SJF directly accommodated earlier accretion of the Pacific Rim terrane to Wrangellia, instead it offsets the older accretionary boundary between these two terranes. Key Points: The San Juan fault is a high‐angle fault that accommodated brittle left‐lateral slipCross‐cutting relations between the fault, metamorphic foliation, and overlying sediments, constrain left lateral slip to the EoceneEocene left‐lateral slip is consistent with strain induced by the accretion of the Siletzia terrane [ABSTRACT FROM AUTHOR]

Background: This paper presents psychometric properties of an instrument for the Assessment of Sexual Behaviour and Knowledge of people with Intellectual Disability (ASBKID), other‐reported by professionals who are in daily contact with them. Methods and procedures: Assessments of 236 individuals with intellectual disability were obtained from 100 professionals. Results: Confirmatory factor analysis revealed a four‐factor structure: concern about the user's inappropriate or uninhibited sexual behaviour; perception of the user's knowledge about privacy and social norms; perception of the user's knowledge about sexuality; and concerns about the user's sexuality. A multi‐group CFA was also conducted in men and women, confirming the adequacy of this four‐factor structure by gender. The reliability of the factors ranged from 0.74 to 0.92. Conclusions: The psychometric results obtained support the use of the ASBKID as a valid and reliable measure for the assessment of sexual behaviour and knowledge in both men and women with intellectual disability. [ABSTRACT FROM AUTHOR]

Background: COVID‐19 disease progression is characterized by hyperinflammation and risk stratification may aid in early aggressive treatment and advanced planning. The aim of this study was to assess whether suPAR and other markers measured at hospital admission can predict the severity of COVID‐19. Methods: The primary outcome measure in this international, multi‐centre, prospective, observational study with adult patients hospitalized primarily for COVID‐19 was the association of WHO Clinical Progression Scale (WHO‐CPS) with suPAR, ferritin, CRP, albumin, LDH, eGFR, age, procalcitonin, and interleukin‐6. Admission plasma suPAR levels were determined using the suPARnostic® ELISA and suPARnostic® Turbilatex assays. Results: Seven hundred and sixty‐seven patients, 440 (57.4%) males and 327 (42.6%) females, were included with a median age of 64 years. Log‐suPAR levels significantly correlated with WHO‐CPS score, with each doubling of suPAR increasing the score by one point (p <.001). All the other markers were also correlated with WHO‐CPS score. Admission suPAR levels were significantly lower in survivors (7.10 vs. 9.63, 95% CI 1.47–3.59, p <.001). A linear model (SALGA) including suPAR, serum albumin, serum lactate dehydrogenase, eGFR, and age can best estimate the WHO‐CPS score and survival. Combining all five parameters in the SALGA model can improve the accuracy of discrimination with an AUC of 0.80 (95% CI: 0.759–0.836). Conclusions: suPAR levels significantly correlated with WHO‐CPS score, with each doubling of suPAR increasing the score by one point. The SALGA model may serve as a quick tool for predicting disease severity and survival at admission. [ABSTRACT FROM AUTHOR]

Aim: The present study aimed to measure the prevalence and severity of food insecurity in people with a severe mental illness, defined as schizophrenia and related psychoses, and bipolar disorder; and explore relationships between food insecurity status, and sociodemographic and clinical characteristics. Methods: This cross‐sectional study recruited community‐dwelling people with severe mental illness receiving clozapine and/or a long‐acting injectable antipsychotic medication within three mental health services in Sydney, Australia. Participants completed the 18‐item Household Food Insecurity Access Scale. Sociodemographic and medical information was obtained from participants' medical records. Independent samples t‐test and chi‐square analyses were used to test for between group differences based on food insecurity status. Binary logistic regression analyses adjusting for age and gender were used to determine the odds ratio. Results: One‐hundred and eighty‐eight people completed the assessment: 63% were male, mean age was 49.2 ± 12.4 years, and the majority (85%) had a diagnosis of schizophrenia. Food insecurity was detected in 31% of participants. Of those who were food insecure, 12% were classified as severe, 13% as moderate and 7% as mild. Tobacco smoking was higher in food insecure people compared to food secure people (odds ratio = 3.1, 95% CI 1.3 to 7.1, p = 0.01). Food insecurity status was not associated with demographic, diagnostic or other clinical data. Conclusions: Food insecurity is highly prevalent among community‐dwelling people with severe mental illness receiving clozapine and/or long‐acting injectable antipsychotic medication. Food security screening should be considered as routine care for this population group. [ABSTRACT FROM AUTHOR]

Background: The combination of pathogen reduction technologies (PRTs) and cryopreservation can contribute to building a safe and durable platelet (PLT) inventory. Information about cryopreserved riboflavin and UV light-treated PLTs is scarce.Study Design and Methods: Twenty-four buffy coat (BC) PLT concentrates were grouped into 12 type-matched pairs, pooled, and divided into 12 non-PRT-treated control units and 12 riboflavin and UV light PRT-treated test units. Both were cryopreserved with 5% DMSO and stored at -80°C for 1 year. The cryopreservation method used was designed to avoid the formation of aggregates. PLT variables (PLT recovery, swirling, pH, MPV, and LDH) and hemostatic function measured by thromboelastography (TEG) were analyzed before cryopreservation (day 1) and post-cryopreservation at day 14 and months 3, 6, and 12 of storage at -80°C. The analyses were carried out within 1-h post-thaw.Results: No aggregates were found in either PLT group at any time. Swirling was observed in both groups. MPV increased and mean pH values decreased over time (p < .001), but the mean pH value was never below 6.4 in either group after 12 months of storage at -80°C. PLT recovery was good and clotting time became significantly shorter over the storage period in both groups (p < .001).Conclusion: Our cryopreservation and thawing method prevented aggregate formation in cryopreserved riboflavin-UV-light-treated PLTs, which exhibited good recovery, swirling, pH > 6.4, and procoagulant potential, as evidenced by a reduced clotting time after 12 months of storage at -80°C. The clinical relevance of these findings should be further investigated in clinical trials. [ABSTRACT FROM AUTHOR]

Underlying the idea of the middle classes there is a contradictory positionality, the relations of which ultimately enhance capital accumulation. By opening Marxist critique to Weberian approaches to class, we explain how the self‐ascription of short‐term rental (STR) suppliers to the middle‐class idea boosts exploitation and accumulation. Housing income, and recently that originating in STRs, has been used to maintain the symbolic and material status of the so‐called middle classes in Spain, and specifically in Palma. Based on statistical data analysis and interviews with STR suppliers, managers and workers, we analyse the contradictory class positionality of STR suppliers in Palma (Majorca, Spain). First, we argue, that STR suppliers are part of the middle classes since they bear attributes of rent, labour and also capital, as they employ workers to produce a tourism commodity. Second, we contend that STR overnight stays should not only be considered as land rent payments, but also as the sale of a tourism commodity. Third, we claim that the contradictory positionality of the middle classes fuels self‐exploitation, for STR suppliers misalign their interests with those of capital. [ABSTRACT FROM AUTHOR]

Ocean acidification is changing surface water chemistry, but natural variability due to nearshore processes can mask its effects on ecosystem responses. We present an approach of quantitatively resolving net ecosystem metabolism from an array of long‐term time series stations, offering perhaps the longest record of such processes over a reef to date. We used 8 and 6 yr of in situ, high‐quality frequency observations to characterize the changes in dissolved inorganic carbon and oxygen in La Parguera, Puerto Rico and Cheeca Rocks, Florida, respectively. Net respiration and net dissolution are the dominant metabolic processes at both systems, with a narrow window of ~ 4 months under net calcification. The annual mean net ecosystem calcification (NEC) rates for La Parguera (−0.68 ± 0.91 kg CaCO3 m−2 yr−1) and Cheeca Rocks (−0.48 ± 0.89 kg CaCO3 m−2 yr−1) were on the lower end of typical NEC ranges determined for other reef areas using chemistry‐ and census‐based approaches. At Cheeca Rocks, 53% of the variance in NEC can be explained by net ecosystem production (NEP) and 30% by aragonite saturation state (Ωarag). At La Parguera, NEC is primarily driven by changes in NEP. The linear relationship between NEC and NEP showed a significant slope (± standard error) of 1.00 ± 0.005 and 0.88 ± 0.04 for La Parguera and Cheeca Rocks, respectively. These results suggest that NEP appears to play a prominent role on NEC, and Ωarag probably is not the most informative measure to monitor when attempting to resolve the long‐term impacts of ocean acidification. [ABSTRACT FROM AUTHOR]

We used lidar differencing and field observations to map volumes, and interpret the origins of, sediment mobilized from mountain canyons by large post‐wildfire debris flows near Montecito, CA, USA in 2018. The debris flows progressively entrained and partially redeposited 550,000 m3 of previously stored channel sediments throughout the canyon networks. The observations that scour depths and volumes were highest where the largest volumes of bouldery colluvium and debris‐flow deposits had accumulated, and that scour persisted beyond the mountain front, indicates that debris‐flow volumes in this extreme event were ultimately controlled by the coarse sediment reservoir available for scour. Because the volumes of available stored sediment result from the stochastic interaction of colluvial mass wasting, the magnitude and frequency of previous debris flows, and the accommodation space provided by valley morphology, the study reinforces the importance of estimating stored sediment volumes when developing debris‐flow hazard assessments. Plain Language Summary: We measured the volumes, and identified the origins of, sediment evacuated from a mountain range by large debris flows near Montecito, CA, USA in 2018. We measured sediment volumes by subtracting the ground surface topography of creek bottoms estimated using lidar scanning equipment before and after the events. We conducted field campaigns to investigate the type of sediment removed during the debris flows. The flows evacuated and partially redeposited a total of 550,000 m3 of material, with the greatest removal occurring in large canyons where previous boulder‐rich debris‐flow deposits had accumulated. Our results indicate that estimates of stored sediment are necessary when assessing debris‐flow hazard in similar high‐value environments. Key Points: Lidar differencing reveals range‐wide volumes of scour and re‐deposition by post‐wildfire debris flows within Santa Ynez Range canyonsScoured coarse‐grained sediment, emplaced by prior colluvial and debris‐flow processes, constituted ∼70% of the entire debris‐flow volumesVolumes of sediment available for debris‐flow scour depend on the stochastic interaction of accumulation processes and large scouring events [ABSTRACT FROM AUTHOR]

Landscapes after wildfire commonly experience accelerated hillslope erosion, which often contributes to the mobilization and volume of debris flows. However, quantitative studies of the erosion and its relationship to rainfall, runoff, and landscape characteristics have been limited to a narrow range of physiographic conditions. We estimated the volume and delivery rate of slurry (a water-sediment mixture) supplied to stream channels during a post-wildfire rainstorm that generated large debris flows in six catchments above Montecito, CA, in 2018. We mapped the distribution of rills and measured their cross-sectional geometries to quantify the influences of runoff, lithology, and hillslope characteristics on the sediment volumes released by rill erosion, and we scaled the results up to the 19.5 km2 of burned hillslopes in the source catchments. We computed the likely rate of surface runoff during the rainstorm and developed an empirical model for the evolution of a representative hillslope-spanning rill to illustrate the magnitude and speed of the erosion process. Rilling was the dominant form of erosion across the hillslopes of the source catchments, and the rapid evacuation and mixing of water and sediment during rill formation supplied a slurry with high solids concentrations to stream channels. Colluvium on shale formations was more continuous, finer-grained, and probably less permeable than colluvium on sandstones, and these differences affected the extent and dimensions of rills. As a result, shale hillslopes were the dominant source of slurry to the debris flows and supplied over twice as much slurry per unit burn area as sandstones. [ABSTRACT FROM AUTHOR]

Background & Aims: Little is known about cholestasis, including its most severe variant secondary sclerosing cholangitis (SSC), in critically ill patients with coronavirus disease 19 (COVID‐19). In this study, we analysed the occurrence of cholestatic liver injury and SSC, including clinical, serological, radiological and histopathological findings. Methods: We conducted a retrospective single‐centre analysis of all consecutive patients admitted to the intensive care unit (ICU) as a result of severe COVID‐19 at the University Hospital Zurich to describe cholestatic injury in these patients. The findings were compared to a retrospective cohort of patients with severe influenza A. Results: A total of 34 patients with severe COVID‐19 admitted to the ICU were included. Of these, 14 patients (41%) had no cholestasis (group 0), 11 patients (32%, group 1) developed mild and 9 patients (27%, group 2) severe cholestasis. Patients in group 2 had a more complicated disease course indicated by significantly longer ICU stay (median 51 days, IQR 25‐86.5) than the other groups (group 0: median 9.5 days, IQR 3.8‐18.3, P =.001; and group 1: median 16 days, IQR 8‐30, P <.05 respectively). Four patients in group 2 developed SSC compared to none in the influenza A cohort. The available histopathological findings suggest an ischaemic damage to the perihilar bile ducts. Conclusions: The development of SSC represents an important complication of critically ill COVID‐19 patients and needs to be considered in the diagnostic work up in prolonged cholestasis. The occurrence of SSC is of interest in the ongoing pandemic since it is associated with considerable morbidity and mortality. [ABSTRACT FROM AUTHOR]

Objectives/Hypothesis: To identify the incidence and nature of positive findings on imaging studies ordered for evaluation of unilateral vocal fold paralysis (UVFP) of unknown etiology, to analyze these findings based on laterality, and to examine the use of the expanded‐field computed tomography (CT) neck protocol in this evaluation. Study Design: Retrospective review. Methods: A total of 145 patients from 2000 to 2018 with UVFP of unknown etiology were studied. Data on imaging studies ordered, laterality of paralysis, and significant positive results were studied. An expanded‐field CT neck protocol that included the entire course of the vagus and recurrent laryngeal nerves was instituted during the study period. Results: A total of 20.7% of patients had an etiology for paralysis identified on imaging. Malignancies comprised the majority of findings overall (19/30), whether in the chest (12/18) or the neck (7/12). Etiology was more often found in the chest for left‐sided paralysis (15/21) and in the neck for right‐sided paralysis (6/9). In 26 patients who underwent both expanded‐field CT neck and CT chest, no findings related to the UVFP were seen on CT chest that were not captured by expanded‐field CT neck. Conclusions: This is one of the largest retrospective studies examining the incidence of positive findings on imaging studies for evaluation of UVFP of unknown etiology. Imaging in one of five patients with UVFP of unknown etiology will reveal a causative lesion, most often malignant. Left‐sided paralysis tends to localize to the chest, and right‐sided paralysis to the neck. Expanded‐field CT neck may allow practitioners to forego dedicated CT chest in evaluation of UVFP. Level of Evidence: 4 Laryngoscope, 131:1840–1844, 2021 [ABSTRACT FROM AUTHOR]

The present work reports the computational study of the major Diels–Alder reaction between 2‐bromocycloalkenone and a variety of mono‐ and di‐substituted dienes. Through density functional theory (DFT) calculations and subsequent activation strain model/energy decomposition analysis/conceptual DFT (C‐DFT) analyses, the key factors governing the activation barriers heights, and thus reactivity, are characterized. In contrast with a previous study, steric effects do not appear to control reactivity. Conversely, in all presented cases, a subtle interplay between deformation and interaction energies is evidenced at transition states. In the end, neither term alone is enough to explain or predict reactivity. Yet a simple C‐DFT descriptor allows to predict with a reasonable efficiency the activation barriers: the excitation energy needed to observe a charge transfer from the diene to the dienophile. Theoretical elements are provided to support the use of this descriptor. [ABSTRACT FROM AUTHOR]

The selectivity and the mechanism of the uncatalyzed and AlCl3 catalyzed hetero‐Diels–Alder reaction (HDR) between ([E]‐4‐methylpenta‐2,4‐dienyloxy)(tert‐butyl)dimethylsilane 1 and benzaldehyde 2 have been studied using density functional theory at the MPWB1K/6‐31G(d) level of theory. The uncatalyzed HDR between diene 1 and alkene 2 is characterized by a polar character and proceeds via an asynchronous one‐step mechanism for the meta paths and synchronous for the ortho ones. In the presence of AlCl3 catalyst, the mechanism changes to be stepwise, while the first step is the rate‐determining step. The activation energies widely decrease, and the polar character increases dramatically. A large analysis of the mechanism is performed using the activation strain model/energy decomposition analysis (ASM/EDA) model, the natural bond orbital (NBO) and state specific dual descriptors (SSDDs). The obtained results indicate that the combined interaction energy associated with the distortion of the reactants in these HDR are at the origin of the observed kinetics. NBO analyses were applied to estimate the Lewis‐acid catalyst donor‐acceptor interaction with the molecular system. The SSDD analysis shed light into the orientation effects on the reaction kinetics by providing important information about charge transfer interactions during the chemical reaction. It indicates that the more favorable HDR pathway have the lowest excitation energies, facilitating the interaction between diene 1 and benzaldehyde 2 moieties. Non‐covalent interaction (NCI) and QTAIM analyses of the meta‐endo structure indicate that the presence of several weak NCIs formed at this approach is at the origin of the meta‐endo selectivity. [ABSTRACT FROM AUTHOR]

Some Mo‐oxo complexes bearing pyridine rings have the capability for dihydrogen production from water. However, energy barrier and overall energy vary depending on the effect exerted by several substituent groups located at different positions around one or more pyridine rings which are ligands of these compounds. Based on the Karunadasa and coworkers investigation where the para‐position was experimentally tested in compounds derivatised from the 2,6‐bis[1,1‐bis(2‐pyridil)ethyl]‐pyridine oxo‐molybdenum complex synthesized (Karunadasa et al., Nature, 2010, 464, 1329), we tested the combined effect of electron‐withdrawing and electron‐donating groups simulated as perturbations represented by point‐charges. Then, we used the density polarization concept, δρ(r), a local reactivity descriptor corresponding to the partially integrated linear response function, χ(r, r′) (a non‐local reactivity descriptor), which is able to reveal different displacements of π‐electrons on molecular structures. We perturbed the para‐positions in the pentadentate ligand 2,6‐bis[1,1‐bis(2‐pyridil)ethyl]‐pyridine in the Mo‐based complex by means of point‐charges. They were located in three different configurations of the organic ligand (trans, geminal, and cis) which could help to explain energy barriers and overall energy of reactions catalyzed by this type of Mo‐complexes. Our results indicate that the trans configuration of point‐charges induces the most amount of fraction of electron shifted on the complex. A Mo‐based complex bearing the same trans configuration for electron‐withdrawing and electron‐donating substituent groups (cyano and amino, respectively), leads to a kinetically more favorable H2 release than the cis or geminal configuration of the substituent groups aforementioned. [ABSTRACT FROM AUTHOR]