bluuebunny/crossref_metadata_2025_split huggingface dataset:
Corrugation Enabled Asymmetrically Ultrastretchable (95%) Monocrystalline Silicon Solar Cells with High Efficiency (19%)
Authors: El‐Atab Nazek , Qaiser Nadeem , Bahabry Rabab , Hussain Muhammad Mustafa 
Published: October 2019

AbstractStretchable solar cells are of growing interest due their key role in realizing many applications such as wearables and biomedical devices. Ultrastretchability, high energy‐efficiency, biocompatibility, and mechanical resilience are essential characteristics of such energy harvesting devices. Here, the development of wafer‐scale monocrystalline silicon solar cells with world‐record ultrastretchability (95%) and efficiency (19%) is demonstrated using a laser‐patterning based corrugation technique. The demonstrated approach transforms interdigitated back contacts (IBC) based rigid solar cells into mechanically reliable but ultrastretchable cells with negligible degradation in the electric performance in terms of current density, open‐circuit voltage, and fill factor. The corrugation method is based on the creation of alternating grooves resulting in silicon islands with different shapes. The stretchability is achieved by orthogonally aligning the active silicon islands to the applied tensile stress and using a biocompatible elastomer (Ecoflex) as a stretchable substrate. The resulting mechanics ensure that the brittle silicon areas do not experience significant mechanical stresses upon asymmetrical stretching. Different patterns are studied including linear, diamond, and triangular patterns, each of which results in a different stretchability and loss of active silicon area. Finally, finite element method based simulation is conducted to study the generated deformation in the different patterned solar cells.
Estimating vibrational and thermodynamic properties of adsorbates with uncertainty using data driven surrogates
Authors: Tian Huijie , Rzepa Christopher , Upadhyay Ronak , Rangarajan Srinivas 
Published: October 2019

AbstractIn this work, we propose a strategy to develop data driven local surrogate models of ab initio potential energy functions describing the interaction of adsorbates on heterogeneous catalytic materials. We show that these multivariable surrogate models, based on orthogonal polynomial expansion and trained on sampled ab‐initio energies/forces, can be used to compute harmonic vibrational frequencies and the entropy of adsorbates. Further, we show that the errors in our surrogate model can be estimated and propagated to calculate the uncertainty in the computed properties. We show proof‐of‐concept illustrations of our method to calculate the vibrational frequencies of ethene on 1D edges of molybdenum sulfide (MoS2), (b) 2D surfaces of Pt(111), and (c) 3D micropores of a HZSM‐5 zeolite; the entropy of ethane adsorbed on Pt(111); and the associated uncertainties in all the cases.
Epigenetic signatures in overgrowth syndromes: Translational opportunities
Authors: Cytrynbaum Cheryl , Choufani Sanaa , Weksberg Rosanna 
Published: October 2019

AbstractIn recent years, numerous overgrowth syndromes have been found to be caused by pathogenic DNA sequence variants in “epigenes,” genes that encode proteins that function in epigenetic regulation. Epigenetic marks, including DNA methylation (DNAm), histone modifications and chromatin conformation, have emerged as a vital genome‐wide regulatory mechanism that modulate the transcriptome temporally and spatially to drive normal developmental and cellular processes. Evidence suggests that epigenetic marks are layered and engage in crosstalk, in that disruptions of any one component of the epigenetic machinery impact the others. This interdependence of epigenetic marks underpins the recent identification of gene‐specific DNAm signatures for a variety of disorders caused by pathogenic variants in epigenes. Here, we discuss the power of DNAm signatures with respect to furthering our understanding of disease pathophysiology, enhancing the efficacy of molecular diagnostics and identifying new targets for therapeutics of overgrowth syndromes. These findings highlight the promise of the field of epigenomics to provide unprecedented insights into disease mechanisms generating a host of opportunities to advance precision medicine.
Increased risk of psoriasis in children and elderly patients with asthma: a longitudinal follow‐up study using a national sample cohort
Authors: Kim So Young , Min Chanyang , Oh Dong Jun , Choi Hyo Geun 
Published: October 2019

BackgroundSeveral previous studies reported the elevated risk of asthma in children with psoriasis. This study aimed to extend previous research regarding the risk of psoriasis in children with asthma to an entire population subdivided by age.MethodsThe 2002‐2013 Korean Health Insurance Review and Assessment Service–National Sample Cohort (HIRA‐NSC) was used. The 167,693 participants with asthma were matched with 167,693 control participants for age, sex, income, region of residence, hypertension history, diabetes history, and dyslipidemia history. In both the asthma and control groups, the occurrences of asthma were investigated. The crude and adjusted hazard ratios (HRs) and 95% confidence intervals (CIs) for psoriasis with respect to asthma status were determined using stratified Cox proportional hazards models. Subgroup analyses were conducted according to age and sex.ResultsThe prevalence of psoriasis was 0.5% (95% CI, 0.4% to 0.5%; n = 771/167,693) in the asthma group and 0.4% (95% CI, 0.3% to 0.4%; n = 589/167,693) in the control group (p < 0.001). The asthma group (adjusted HR = 1.19; 95% CI, 1.07 to 1.33; p = 0.002) demonstrated higher HRs for psoriasis than did the control group. This result was consistent in the <15 years old, ≥60 years old, and women subgroups.ConclusionAsthma was associated with the elevated risk of psoriasis. The possible risk of psoriasis needs to be considered when managing asthma patients. Future study is warranted for the risk of psoriasis according to the endotypes of asthma.
In‐Depth TEM Investigation on Structural Inhomogeneity within a Primary LixNi0.835Co0.15Al0.015O2 Particle: Origin of Capacity Decay during High‐Rate Discharge
Authors: Lee Hyesu , Jo Eunmi , Chung Kyung Yoon , Byun Dongjin , Kim Seung Min , Chang Wonyoung 
Published: October 2019

AbstractThe structural stability of cathode materials during electrochemical reactions, in particular, under high‐rate discharge, is pertinent to the design and development of new electrode materials. This study investigates the structural inhomogeneity that develops within a single LiNi0.835Co0.15Al0.015O2 (NCA83) particle during a fast discharging process under different cutoff voltages. Some of the NCA83 particles discharged from a high cutoff voltage (4.8 V) developed surface areas in which the layered structure was recovered, although the interiors retained the degraded spinel structure. These micro‐ and nano‐scale structural inversions from high cutoff voltage seem highly correlated with structural evolutions in the initial charged state, and may ultimately degrade the cycling stability. This study advances understanding of the structural inhomogeneity within primary particles during various electrochemical processes and may facilitate the development of new Ni‐rich cathode materials.
The Electron Spin as a Chiral Reagent
Authors: Metzger Tzuriel S. , Mishra Suryakant , Bloom Brian P. , Goren Naama , Neubauer Avner , Shmul Guy , Wei Jimeng , Yochelis Shira , Tassinari Francesco , Fontanesi Claudio , Waldeck David H. , Paltiel Yossi , Naaman Ron 
Published: October 2019

AbstractWe show that enantioselective reactions can be induced by the electron spin itself and that it is possible to replace a conventional enantiopure chemical reagent by spin‐polarized electrons that provide the chiral bias for enantioselective reactions. Three examples of enantioselective chemistry resulting from electron‐spin polarization are presented. One demonstrates the enantioselective association of a chiral molecule with an achiral self‐assembled monolayer film that is spin‐polarized, while the other two show that the chiral bias provided by the electron helicity can drive both reduction and oxidation in enantiospecific electrochemical reactions. In each case, the enantioselectivity does not result from enantiospecific interactions of the molecule with the ferromagnetic electrode but from the polarized spin that crosses the interface between the substrate and the molecule. Furthermore, the direction of the electron‐spin polarization defines the handedness of the enantioselectivity. This work demonstrates a new mechanism for realizing enantioselective chemistry.
Reactions of Bromine Fluoride Dioxide, BrO2F, for the Generation of the Mixed‐Valent Bromine Oxygen Cations Br3O4+ and Br3O6+
Authors: Seppelt Konrad 
Published: October 2019

AbstractA reliable synthesis of unstable and highly reactive BrO2F is reported. This compound can be converted into BrO2+SbF6−, BrO2+AsF6−, and BrO2+AsF6−⋅2 BrO2F. The latter decomposes into mixed‐valent Br3O4⋅Br2+AsF6− with five‐, three‐, one‐, and zero‐valent bromine. BrO2+ H(SO3CF3)2− is formed with HSO3CF3. Excess BrO2F yields mixed‐valent Br3O6+OSO3CF3− with five‐ and three‐valent bromine. Reactions of BrO2F and MoF5 in SO2ClF or CH2ClF result in Cl2BrO6+Mo3O3F13−. The reaction of BrO2F with (CF3CO)2O and NO2 produces O2Br‐O‐CO‐CF3 and the known NO2+Br(ONO2)2−. All of these compounds are thermodynamically unstable.
Indian Ocean humpback dolphin in the Menai Bay off the south coast of Zanzibar, East Africa is Critically Endangered
Authors: Sharpe Matt , Berggren Per 
Published: October 2019

Abstract

Cetaceans occupying coastal habitats are at high risk of impact from anthropogenic sources which can cause direct mortality or affect long‐term health. Monitoring and detecting change require long‐term studies and reliable funding, not always available especially in developing countries. Management and conservation of cetaceans must therefore use precautionary methods that allow assessment from limited data sources to identify risk of, and prevent, species extirpation or extinction.
IUCN Red List criteria for regional populations was applied to the population of Indian Ocean humpback dolphins (Sousa plumbea) resident in Menai Bay Conservation Area off the south coast of Zanzibar, East Africa which is subjected to unsustainable entanglement rates in gillnet fisheries and unregulated tourism activities. Photographic identification surveys were conducted in 2015 to generate a new abundance estimate from capture–recapture analysis. Mortality estimates were calculated using available data from 1999 to 2002 and a population viability analysis was conducted based on population, species and genus specific parameters.
The 2015 abundance estimate for humpback dolphins was 19 (95% CI 14–25) non‐calf individuals, representing a 63% reduction in abundance since 2002. The population viability analysis baseline scenario predicted chance of extinction at 0.996 (SE 0.002) with the median time to extinction at 36 years. Sensitivity analysis suggested that population recovery would only be possible with a complete prevention of bycatch mortality.
The population met the threshold for Critically Endangered for all criteria which could be directly assessed. This conservation assessment highlights the requirement for immediate management action to eliminate bycatch of humpback dolphins to prevent the local extinction of the species.
Vascular Patterns in the Heads of Dinosaurs: Evidence for Blood Vessels, Sites of Thermal Exchange, and Their Role in Physiological Thermoregulatory Strategies
Authors: Porter William Ruger , Witmer Lawrence M. 
Published: October 2019

ABSTRACTBody size has thermal repercussions that impact physiology. Large‐bodied dinosaurs potentially retained heat to the point of reaching dangerous levels, whereas small dinosaurs shed heat relatively easily. Elevated body temperatures are known to have an adverse influence on neurosensory tissues and require physiological mechanisms for selective brain and eye temperature regulation. Vascular osteological correlates in fossil dinosaur skulls from multiple clades representing different body‐size classes were identified and compared. Neurovascular canals were identified that differentiate thermoregulatory strategies involving three sites of evaporative cooling that are known in extant diapsids to function in selective brain temperature regulation. Small dinosaurs showed similarly sized canals, reflecting a plesiomorphic balanced pattern of blood supply and a distributed thermoregulatory strategy with little evidence of enhancement of any sites of thermal exchange. Large dinosaurs, however, showed a more unbalanced vascular pattern whereby certain sites of thermal exchange were emphasized for enhanced blood flow, reflecting a more focused thermal strategy. A quantitative, statistical analysis of canal cross‐sectional area was conducted to test these anatomical results, confirming that large‐bodied, and often large‐headed, species showed focused thermal strategies with enhanced collateral blood flow to certain sites of heat exchange. Large theropods showed evidence for a plesiomorphic balanced blood flow pattern, yet evidence for vascularization of the large antorbital paranasal air sinus indicates theropods may have had a fourth site of heat exchange as part of a novel focused thermoregulatory strategy. Evidence presented here for differing thermoregulatory strategies based on size and phylogeny helps refine our knowledge of dinosaur physiology. Anat Rec, 303:1075–1103, 2020. © 2019 American Association for Anatomy
Changes in emergence phenology, fatty acid composition, and xenobiotic‐metabolizing enzyme expression is associated with increased insecticide resistance in the Colorado potato beetle
Authors: Clements Justin , Olson Jake M. , Sanchez‐Sedillo Benjamin , Bradford Benjamin , Groves Russell L. 
Published: October 2019

AbstractThe Colorado potato beetle (Leptinotarsa decemlineata) is a major agricultural pest of solanaceous crops. An effective management strategy employed by agricultural producers to control this pest species is the use of systemic insecticides. Recent emphasis has been placed on the use of neonicotinoid insecticides. Despite efforts to curb resistance development through integrated pest management approaches, resistance to neonicotinoids in L. decemlineata populations continues to increase. One contributing factor may be alterations in insect fatty acids, which have multiple metabolic functions and are associated with the synthesis of xenobiotic‐metabolizing enzymes to mitigate the effects of insecticide exposure. In this study, we analyzed the fatty acid composition of L. decemlineata populations collected from an organic production field and from a commercially managed field to determine if fatty acid composition varied between the two populations. We demonstrate that a population of L. decemlineata that has a history of systemic neonicotinoid exposure (commercially managed) has a different lipid composition and differential expression of known metabolic detoxification mechanisms relative to a population that has not been exposed to neonicotinoids (organically managed). The fatty acid data indicated an upregulation of Δ6 desaturase in the commercially managed L. decemlineata population and suggest a role for eicosanoids and associated metabolic enzymes as potential modulators of insecticide resistance. We further observed a pattern of delayed emergence within the commercially managed population compared with the organically managed population. Variations in emergence timing together with specific fatty acid regulation may significantly influence the capacity of L. decemlineata to develop insecticide resistance.
Synthesis, characterization, and antimicrobial activity of some new N‐aryl‐N’‐(2‐oxoindolin‐3‐ylidene)‐benzohydrazonamides
Authors: Gomaa Mohsen A.‐M. , Hassan Doaa K. 
Published: October 2019

AbstractA green approach was developed for synthesizing a series of (isatin‐3‐ylidene)‐hydrazonamides 3a–j from the reaction between isatin, (isatin‐3‐ylidene)malononitrile, or 2‐cyano‐2‐(2‐isatin‐3‐ylidene)acetate and benzohydrazonamide in ethyl acetate solutions at ambient temperature. The structures of the new compounds were confirmed on the basis of spectral data. In this eco‐friendly medium, a variety of (isatin‐3‐ylidene)hydrazonamides were obtained free of catalyst in good to excellent yields. All the synthesized products were evaluated for their antimicrobial activity. Among the compounds tested, 3b and 3d exhibited good antibacterial activity against Staphylococcus aureus, whereas others responded moderately with reference to the standard drug ciprofloxacin.
Comparing Automatic Eye Tracking and Manual Gaze Coding Methods in Young Children with Autism Spectrum Disorder
Authors: Venker Courtney E. , Pomper Ron , Mahr Tristan , Edwards Jan , Saffran Jenny , Ellis Weismer Susan 
Published: October 2019

Eye‐gaze methods offer numerous advantages for studying cognitive processes in children with autism spectrum disorder (ASD), but data loss may threaten the validity and generalizability of results. Some eye‐gaze systems may be more vulnerable to data loss than others, but to our knowledge, this issue has not been empirically investigated. In the current study, we asked whether automatic eye‐tracking and manual gaze coding produce different rates of data loss or different results in a group of 51 toddlers with ASD. Data from both systems were gathered (from the same children) simultaneously, during the same experimental sessions. As predicted, manual gaze coding produced significantly less data loss than automatic eye tracking, as indicated by the number of usable trials and the proportion of looks to the images per trial. In addition, automatic eye‐tracking and manual gaze coding produced different patterns of results, suggesting that the eye‐gaze system used to address a particular research question could alter a study's findings and the scientific conclusions that follow. It is our hope that the information from this and future methodological studies will help researchers to select the eye‐gaze measurement system that best fits their research questions and target population, as well as help consumers of autism research to interpret the findings from studies that utilize eye‐gaze methods with children with ASD. Autism Res 2020, 13: 271‐283. © 2019 International Society for Autism Research, Wiley Periodicals, Inc.Lay SummaryThe current study found that automatic eye‐tracking and manual gaze coding produced different rates of data loss and different overall patterns of results in young children with ASD. These findings show that the choice of eye‐gaze system may impact the findings of a study—important information for both researchers and consumers of autism research.
Palladium‐Catalyzed Thio‐ and Selenocarbonylation of 2‐Iodoglycals
Authors: Darbem Mariana P. , Esteves Henrique A. , de Oliveira Isadora M. , Pimenta Daniel C. , Stefani Hélio A. 
Published: October 2019

AbstractThe carbonylative cross‐coupling reactions of 2‐iodoglycals with thiols and selenols in the presence of molybdenum hexacarbonyl as a solid source of carbon monoxide is described. This methodology permitted the synthesis of 29 C2‐glycosides bearing thioester and selenoester functionalities in moderate to excellent yields and high functional group tolerance. Moreover, this communication describes the first catalytic carbonylative coupling reaction of selenols with a carbon electrophile.
Investigating the Active Species in a [(R‐SN(H)S‐R)CrCl3] Ethene Trimerization System: Mononuclear or Dinuclear?
Authors: Venderbosch Bas , Oudsen Jean‐Pierre H. , Martin David J. , de Bruin Bas , Korstanje Ties J. , Tromp Moniek 
Published: October 2019

AbstractCr‐catalyzed ethene trimerization is an industrially important process to produce 1‐hexene. Despite its industrial relevance, the changing oxidation state and the structural rearrangements of the metal center during the catalytic cycle remain unclear. In this study, we have investigated the active species in a [(R‐SN(H)S−R)CrCl3] (R=C10H21) catalyzed ethene trimerization system using a combination of spectroscopic techniques (XAS, EPR and UV/VIS) and DFT calculations. Reaction of the octahedral CrIII complex with modified methylaluminoxane (MMAO) in absence of ethene gives rise to the formation of a square‐planar CrII complex. In the presence of ethene (1 bar), no coordination was observed, which we attribute to the endergonic nature of the coordination of the first ethene molecule. Employing an alkyne as a model for ethene coordination leads to the formation of a dinuclear cationic CrIII alkyne complex. DFT calculations show that a structurally related dinuclear cationic CrIII ethene complex could form under catalytic conditions. Comparing a mechanism proceeding via mononuclear cationic CrII/CrIV intermediates to that proceeding via dinuclear cationic CrII/CrIII intermediates demonstrates that only the mechanism involving mononuclear cationic CrII/CrIV intermediates can correctly explain the observed product selectivity.
Insight into the Nature of Active Species of Pt/Al2O3 Catalysts for low Temperature NH3 Oxidation
Authors: Svintsitskiy Dmitry A. , Kibis Lidiya S. , Stadnichenko Andrey I. , Slavinskaya Elena M. , Romanenko Anatoly V. , Fedorova Elizaveta A. , Stonkus Olga A. , Doronkin Dmitry E. , Marchuk Vasyl , Zimina Anna , Casapu Maria , Grunwaldt Jan‐Dierk , Boronin Andrei I. 
Published: October 2019

AbstractTwo series of Pt/γ‐Al2O3 catalysts for low temperature NH3 oxidation were prepared using Pt(NO3)4 and H2PtCl6 precursors. Using both precursors results in the formation of small Pt particles (d<1.5 nm), however, Cl‐containing Pt precursors give a higher fraction of highly dispersed Pt species. Such species show high stability against thermal or H2 treatment probably due to the presence of a substantial amount of chlorine on the surface. Treatment of the samples prepared from Pt(NO3)4 with H2 leads to the formation of metallic Pt nanoparticles accompanied by the improvement of catalytic activity in NH3 oxidation at T<200 °C. The main products of ammonia oxidation at temperatures below 250 °C were molecular nitrogen and nitrous oxide with the N2 selectivity reaching 80 %. Operando XANES/EXAFS revealed that even after H2 pretreatment at least 40 % of Pt surface remains in oxidized state under reaction conditions resulting in the appearance of N2O as a by‐product.
HFIP‐Promoted de Novo Synthesis of Biologically Relevant Nonnatural α‐Arylated Amino Esters and Dipeptide Mimetics
Authors: Li Zhonghua , Yu Bin 
Published: October 2019

AbstractAmino acids are fundamental building blocks, which have been extensively used in drug design and organic synthesis. However, nonnatural amino acids are relatively less studied. In this work, the authors report the first HFIP‐promoted de novo synthesis of nonnatural α‐arylated amino esters and dipeptide mimetics (27 examples, up to 99 % yield) from readily available amines, ethyl glyoxylate and electron‐rich arenes under mild conditions, in which one C−C bond, one C−N bond and one chiral center were established simultaneously. The reaction was also performed on a gram scale, giving compound 4 a in 96 % yield. In addition, this protocol was successfully applied to the late‐stage elaboration of drug molecules, such as tranylcypromine (TCP or PCPA) and troxipide. Interestingly, compound 4 h inactivated histone lysine specific demethylase 1 (LSD1) potently with an IC50 value of 0.296 μm. To the best of our knowledge, compound 4 h is the first LSD1 inhibitor derived from nonnatural α‐arylated amino esters, and therefore could be used as a hit compound for the development of new LSD1 inhibitors. The synthesized nonnatural α‐arylated amino esters and dipeptide mimetics as unique building blocks may have potential synthetic utilities.