bluuebunny/crossref_metadata_2025_split huggingface dataset:
Spectroscopic and Crystallographic Characterization of the R3N+−C−H⋅⋅⋅X Interaction
Authors: Capilato Joseph N. , Harry Stefan A. , Siegler Maxime A. , Lectka Thomas 
Published: January 2022

AbstractAs appreciation for nonclassical hydrogen bonds has progressively increased, so have efforts to characterize these interesting interactions. Whereas several kinds of C−H hydrogen bonds have been well‐studied, much less is known about the R3N+−C−H⋅⋅⋅X variety. Herein, we present crystallographic and spectroscopic evidence for the existence of these interactions, with special relevance to Selectfluor chemistry. Of particular note is the propensity for Lewis bases to engage in nonclassical hydrogen bonding over halogen bonding with the electrophilic F atom of Selectfluor. Further, the first examples of 1H NMR experiments detailing R3N+−C−H⋅⋅⋅X (X=O, N) hydrogen bonds are described.
Early and late recurrent cardiovascular events among high‐risk patients with an acute coronary syndrome: Meta‐analysis of phase III studies and implications on trial design
Authors: Chi Gerald , Lee Jane J. , Kazmi Syed H. A. , Fitzgerald Clara , Memar Montazerin Sahar , Kalayci Arzu , Korjian Serge , Heise Mark , Deckelbaum Lawrence I. , Libby Peter , Bhatt Deepak L. , Gibson C. Michael 
Published: January 2022

AbstractBackgroundDespite low‐density lipoprotein cholesterol‐lowering therapies and other standard‐of‐care therapy, there remains a substantial residual atherosclerotic risk among patients with an acute coronary syndrome (ACS). This study aims to estimate the risk of early and late recurrent major adverse cardiovascular events (MACE) and address its implications on trial design.MethodsA literature search was performed to collect phase III interventional trials on high‐risk ACS patients. Pooled event rates at 90 and 360 days were estimated by fitting random‐effects models using the DerSimonian–Laird method. Under the assumption of a total sample size of 10,000 and 1:1 allocation at a one‐sided alpha of 0.025 using the log‐rank test, the relationship between power and relative risk reduction (RRR) or absolute risk reduction (ARR) was explored for early versus late MACE endpoint.ResultsSeven trials representing 82,727 recent ACS patients were analyzed. The pooled rates of recurrent MACE were 4.1% and 8.3% at 90 and 360 days. Approximately 49% of events occurred within the first 90 days. Based on the estimated risks at 90 and 360 days, to attain 90% statistical power, a lower magnitude of RRR is required for late MACE than early MACE (22% vs. 30%), whereas a lower magnitude of ARR is required for early MACE than late MACE (1.2% vs. 1.8%).ConclusionThe initial 90‐day window after ACS represents a vulnerable period for recurrent events. From a trial design perspective, determining a clinically important benefit by RRR versus ARR may influence the decision between early and late MACE as the study endpoint.
Validation of the International Adjustment Disorder Questionnaire in Israel and Switzerland
Authors: Levin Yafit , Bachem Rahel , Hyland Philip , Karatzias Thanos , Shevlin Mark , Ben‐Ezra Menachem , Maercker Andreas 
Published: January 2022

AbstractThe ICD‐11 has introduced a new conceptualization of adjustment disorder (AjD) as a stress response syndrome with core symptoms of preoccupations and failure to adapt to the stressor. The current study aimed to assess the reliability and validity of the International Adjustment Disorder Questionnaire (IADQ) in two culturally distinct samples from Israel and Switzerland. Two samples were recruited in Israel (N = 1142) and Switzerland (N = 699) during the initial stages of the COVID‐19 pandemic. Confirmatory factor analysis indicated that a correlated two‐factor model provided an excellent fit to the Israeli and Swiss sample data. The IADQ scores correlated strongly with another measure of AjD symptoms and with symptoms of depression, anxiety, acute stress and negative emotions, whereas correlations with posttraumatic stress disorder, complex posttraumatic stress disorder and positive emotions were weaker. In the Swiss sample, 18.8% met diagnostic criteria for probable AjD and 10.2% in the Israeli sample. The current study provides the first evidence of the validity of the German and Hebrew versions of the IADQ and can be used for the screening of this debilitating condition.
Time‐Resolved X‐Ray Spectroscopy to Study Luminophores with Relevance for OLEDs
Authors: Vogt Matthias , Smolentsev Grigory 
Published: January 2022

AbstractOrganic light‐emitting diodes (OLEDs) are employed in innovative display technologies and have the potential to be used widely in large area lighting. Luminophores containing 4d or 5d metals are efficient in electro‐luminescent devices due to their phosphorescent properties but are scarce and expensive. Alternatives take advantage of temperature‐activated delayed fluorescence (TADF), e. g. in Cu(I) complexes. We show modern X‐ray spectroscopy methods exemplified on Ru, Ir and Cu‐based luminophores offering insight into the capabilities of such techniques to researchers from various fields. Knowledge of structural rearrangements in the excited state is crucial to understand non‐radiative energy losses and to develop efficient luminophores. Pump‐probe X‐ray absorption spectroscopy (XAS) gives information about the molecular structure in the excited state and the electronic structure. We show how this information can be complemented with X‐ray emission spectroscopy at X‐ray free‐electron lasers (XFEL) and discuss the potential of time‐resolved X‐ray excited optical luminescence (TR‐XEOL) to provide additional selectivity of XAS to luminescent sites.
Efficient Photocatalytic H2 Evolution by Hexaniobate Nanosheets Grafted with Copper Nanoclusters
Authors: Nascimento Nunes Barbara , Bahnemann Detlef W. , Otavio T. Patrocinio Antonio 
Published: January 2022

AbstractHexaniobate nanosheets (K4−xHxNb6O17) were combined with Cu2+ ions by grafting, a green one‐step methodology. The resulted nanocomposite exhibits high surface area with most of the Cu2+ ions strongly connected to the hexaniobate layers as amorphous nanoclusters. Photocatalytic experiments evidence that the Cu‐grafted hexaniobate can act as an efficient photocatalyst for H2 evolution. The best performance for the Cu‐grafted hexaniobate was reached when the Cu concentration was 0.5 wt% (1.62±0.10 mmo g−1 h−1), whereas hexaniobate layers with 0.5 wt % photodeposited Pt exhibited a hydrogen evolution rate of 0.95±0.04 mmol h−1 g−1 under the same experimental conditions. Grafting leads to covalently bounded Cu species onto the hexaniobate surface, ensuring a strong electronic interaction. Detailed XPS and EPR studies evidence that the initial Cu2+ species are promptly reduced to Cu1+/Cu0 under illumination. The prominent performance of Cu‐grafted samples was related to the improved charge‐separation efficiency as shown by ns‐transient spectroscopy. Therefore, the present methodology offers a green option to produce efficient Earth‐abundant‐based photocatalysts for H2 evolution.
A novel asymmetrically clipped optical orthogonal frequency division multiplexing system based on lifting wavelet transform for visible light communications
Authors: Avcı Büşra , Aykırı Gazihan , Savaşcıhabeş Asuman , Özen Ali 
Published: January 2022

SummaryIn multicarrier visible light communication (VLC) systems, orthogonal frequency division multiplexing (OFDM) has attracted a lot of attention due to its high data rate, simple equalization, and resistance to intersymbol interference (ISI). However, high peak‐to‐average‐power ratio (PAPR) and Light Emitting Diodes (LED) nonlinearity have important effects on the performance of indoor VLC‐OFDM systems. Asymmetrically clipped optical (ACO)‐OFDM is a technique that waste spectral efficiency to transmit a single pole frequency division multiplexed signal over a single pole channel. In this study, a new ACO‐OFDM method based on lifting wavelet transform (LWT)‐ACO‐OFDM is proposed to restore this spectral efficiency and increase the performance of the ACO‐OFDM system. The performance of the proposed method is verified by computer simulation studies over additive white Gaussian noise (AWGN) channel and multipath optical channel for analytical and simulated bit error rate (BER) performance criterion. From the obtained simulation results, it is seen that the proposed method provides approximately 16‐dB SNR gain against the classic VLC‐OFDM, roughly 12‐dB Signal to Noise Ratio (SNR) improvement versus the Direct Current (DC)‐biased optical (DCO)‐OFDM, and nearly 6‐dB SNR enhancement against ACO‐OFDM on the additive white Gaussian noise channel. It is observed from computer simulation results that similar SNR gains are obtained in multipath optical channels.
Should we hail the Red King? Evolutionary consequences of a mutualistic lifestyle in genomes of lichenized ascomycetes
Authors: Ametrano Claudio G. , Lumbsch H. Thorsten , Di Stefano Isabel , Sangvichien Ek , Muggia Lucia , Grewe Felix 
Published: January 2022

AbstractThe Red Queen dynamic is often brought into play for antagonistic relationships. However, the coevolutionary effects of mutualistic interactions, which predict slower evolution for interacting organisms (Red King), have been investigated to a lesser extent. Lichens are a stable, mutualistic relationship of fungi and cyanobacteria and/or algae, which originated several times independently during the evolution of fungi. Therefore, they represent a suitable system to investigate the coevolutionary effect of mutualism on the fungal genome. We measured substitution rates and selective pressure of about 2000 protein‐coding genes (plus the rDNA region) in two different classes of Ascomycota, each consisting of closely related lineages of lichenized and non‐lichenized fungi. Our results show that independent lichenized clades are characterized by significantly slower rates for both synonymous and non‐synonymous substitutions. We hypothesize that this evolutionary pattern is connected to the lichen life cycle (longer generation time of lichenized fungi) rather than a result of different selection strengths, which is described as the main driver for the Red Kind dynamic. This first empirical evidence of slower evolution in lichens provides an important insight on how biotic cooperative interactions are able to shape the evolution of symbiotic organisms.
Dinitrogen Binding Relevant to FeMoco of Nitrogenase: Clear Visualization of σ‐Donation and π‐Backdonation from Deformation Electron Densities around Carbon/Silicon‐Iron Site
Authors: Devi Kavita , Gorantla Sai Manoj N. V. T. , Mondal Kartik Chandra 
Published: January 2022

AbstractDinitrogen (N2) binding and electron transfer reduction of N2 to ammonia (NH3) by the FeMoco cofactor of the nitrogenase enzyme are captivating. They are a part of the textbook for general chemistry. The nature of N2 bonding by reduced FeMoco is speculated based on the experimental evidence. The inorganic core MoFe7S9C1− possesses a Fe6(μ6‐C4−) unit. The mode of N2‐binding at one of the Fe‐centers of the elusive Fe6(μ6‐C4−) unit and the role of light element C4− is intriguing. In the past, the mode of N2‐binding and the kinetics of N2 reduction have been studied by spectroscopic and other tools. Herein, we report on the energy decomposition analysis coupled with natural orbital for chemical valence (EDA‐NOCV) calculations/analyses to shed light on the deeper insight of the N2 binding and especially on the influence of the C‐atom of previously reported Fe‐complexes with an EP3 donor set (E=C, Si). The role of the C‐atom in the iron‐carbon site has been studied by elaboration with deformation electron densities. The intrinsic interaction energy of the bond between Fe and N2 and pairwise orbital interactions between them have been quantitatively estimated. The influence of σ‐donation of three phosphine ligands and their effects on the Fe−N2 bond have been thoroughly studied.
Predicting ion concentration polarization and analyte stacking/focusing at nanofluidic interfaces
Authors: Flores‐Galicia Fatima , Eden Alexander , Pallandre Antoine , Pennathur Sumita , Haghiri‐Gosnet Anne‐Marie 
Published: January 2022

AbstractWe report on the investigation of electropreconcentration phenomena in micro‐/nanofluidic devices integrating 100 μm long nanochannels using 2D COMSOL simulations based on the coupled Poisson–Nernst–Planck and Navier–Stokes system of equations. Our numerical model is used to demonstrate the influence of key governing parameters such as electrolyte concentration, surface charge density, and applied axial electric field on ion concentration polarization (ICP) dynamics in our system. Under sufficiently extreme surface‐charge‐governed transport conditions, ICP propagation is shown to enable various transient and stationary stacking and counter‐flow gradient focusing mechanisms of anionic analytes. We resolve these spatiotemporal dynamics of analytes and electrolyte ICP over disparate time and length scales, and confirm previous findings that the greatest enhancement is observed when a system is tuned for analyte focusing at the charge, excluding microchannel, nanochannel electrical double layer (EDL) interface. Moreover, we demonstrate that such tuning can readily be achieved by including additional nanochannels oriented parallel to the electric field between two microchannels, effectively increasing the overall perm‐selectivity and leading to enhanced focusing at the EDL interfaces. This approach shows promise in providing added control over the extent of ICP in electrokinetic systems, particularly under circumstances in which relatively weak ICP effects are observed using only a single channel.
Investigating protein translocation in the presence of an electrolyte concentration gradient across a solid‐state nanopore
Authors: Saharia Jugal , Bandara Y. M. Nuwan D. Y. , Kim Min Jun 
Published: January 2022

AbstractElectrolyte chemistry plays an important role in the transport properties of analytes through nanopores. Here, we report the translocation properties of the protein human serum transferrin (hSTf) in asymmetric LiCl salt concentrations with either positive (Ctrans/Ccis < 1) or negative chemical gradients (Ctrans/Ccis > 1). The cis side concentration was fixed at 4 M for positive chemical gradients and at 0.5 M LiCl for negative chemical gradients, while the trans side concentration varied between 0.5 to 4 M which resulted in six different configurations, respectively, for both positive and negative gradient types. For positive chemical gradient conditions, translocations were observed in all six configurations for at least one voltage polarity whereas with negative gradient conditions, dead concentrations where no events at either polarity were observed. The flux of Li+ and Cl− ions and their resultant cation or anion enrichment zones, as well as the interplay of electrophoretic and electroosmotic transport directions, would determine whether hSTf can traverse across the pore.
A multicell structural battery composite laminate
Authors: Xu Johanna , Geng Zeyang , Johansen Marcus , Carlstedt David , Duan Shanghong , Thiringer Torbjörn , Liu Fang , Asp Leif E. 
Published: January 2022

AbstractMultifunctional materials facilitate lightweight and slender structural solutions for numerous applications. In transportation, construction materials that can act as a battery, and store electrical energy, will contribute to realization of highly energy efficient vehicles and aircraft. Herein, a multicell structural battery composite laminate, with three state‐of‐the‐art structural battery composite cells connected in series is demonstrated. The experimental results show that the capacity of the structural battery composite cells is only moderately affected by tensile loading up to 0.36% strain. The multicell structural battery laminate is made embedding the three connected structural battery composite cells between carbon fiber/glass fiber composite face sheets. Electrochemical performance of the multicell structural battery is demonstrated experimentally. High charge transfer resistance for the pack as well as the individual cells is reported. Mechanical performance of the structural battery laminate is estimated by classical laminate theory. Computed engineering in‐plane moduli for the multicell structural battery laminate are on par with conventional glass fiber composite multiaxial laminates.image
Risk-Based Prioritization of Organic Chemicals and Locations of Ecological Concern in Sediment From Great Lakes Tributaries
Authors: Baldwin Austin K. , Corsi Steven R. , Stefaniak Owen M. , Loken Luke C. , Villeneuve Daniel L. , Ankley Gerald T. , Blackwell Brett R. , Lenaker Peter L. , Nott Michelle A. , Mills Marc A. 
Published: January 2022

Abstract
With improved analytical techniques, environmental monitoring studies are increasingly able to report the occurrence of tens or hundreds of chemicals per site, making it difficult to identify the most relevant chemicals from a biological standpoint. For the present study, organic chemical occurrence was examined, individually and as mixtures, in the context of potential biological effects. Sediment was collected at 71 Great Lakes (USA/Canada) tributary sites and analyzed for 87 chemicals. Multiple risk-based lines of evidence were used to prioritize chemicals and locations, including comparing sediment concentrations and estimated porewater concentrations with established whole-organism benchmarks (i.e., sediment and water quality criteria and screening values) and with high-throughput toxicity screening data from the US Environmental Protection Agency's ToxCast database, estimating additive effects of chemical mixtures on common ToxCast endpoints, and estimating toxic equivalencies for mixtures of alkylphenols and polycyclic aromatic hydrocarbons (PAHs). This multiple-lines-of-evidence approach enabled the screening of more chemicals, mitigated the uncertainties of individual approaches, and strengthened common conclusions. Collectively, at least one benchmark/screening value was exceeded for 54 of the 87 chemicals, with exceedances observed at all 71 of the monitoring sites. Chemicals with the greatest potential for biological effects, both individually and as mixture components, were bisphenol A, 4-nonylphenol, indole, carbazole, and several PAHs. Potential adverse outcomes based on ToxCast gene targets and putative adverse outcome pathways relevant to individual chemicals and chemical mixtures included tumors, skewed sex ratios, reproductive dysfunction, hepatic steatosis, and early mortality, among others. The results provide a screening-level prioritization of chemicals with the greatest potential for adverse biological effects and an indication of sites where they are most likely to occur. Environ Toxicol Chem 2022;41:1016–1041. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.
Abstract
Relative priority for bioeffects due to organic chemical exposure in sediment from Great Lakes tributaries.
Low Formaldehyde Binders for Mineral Wool Insulation: A Review
Authors: Bennett Thomas M. , Allan John F. , Garden Jennifer A. , Shaver Michael P. 
Published: January 2022

AbstractInsulating materials are ubiquitous in a built environment and play a critical role in reducing the energy consumed to maintain habitable indoor environments. Mineral wool insulation (MWI) products, including glass, stone, and slag variants, are the most widely used class of insulating materials in Europe and account for more than 50% of the total market by volume. MWI typically consists of two key components: a mesh of inorganic fibers that are several micrometers in diameter, and an organic thermosetting adhesive commonly referred to as the “binder.” Traditional phenol‐formaldehyde‐urea (PFU) binders used in the manufacture of MWI are increasingly being scrutinized for the formaldehyde released during their manufacture and service lifetime. The recent classification of formaldehyde as a carcinogen by various safety organizations has accelerated a paradigm shift within the industry toward alternative binder technologies that minimize or indeed eliminate formaldehyde emissions. This review examines more recent strategies for achieving low‐ or zero‐added formaldehyde binders for MWI, with a particular focus on the patent literature. The chemistry underpinning traditional PFU binders is presented and compared to new strategies involving scavenging molecules that decrease formaldehyde emissions, as well as zero‐added formaldehyde binder technologies such as polyester, Maillard, and epoxide thermosets.
Invasive hemodynamics are equivocal for functional outcomes after MitraClip
Authors: Power Juliette E. , Reiff Chris , Tsangaris Adamantios , Hall Alexandra , Raveendran Ganesh , Yannopoulos Demetris , Gurevich Sergey 
Published: January 2022

AbstractObjectivesTo evaluate invasive hemodynamics in assessing MC therapy success as well as evaluate its effectiveness as a predictor of functional outcomes.BackgroundMitral regurgitation grade is a poor predictor of functional outcomes after a MitraClip. There is a paucity of data on invasive hemodynamics as a predictor of outcomes.MethodsSixty‐nine patients underwent MC between 2015 and 2018 at the University of Minnesota Medical Center and were retrospectively analyzed. Invasive hemodynamics were performed before and after device deployment with transesophageal echocardiographic guidance. Statistical analysis was performed using STATA version 16. Student's t test was used for continuous variables and Pearson's chi‐squared test for categorical variables. Mann‐Whitney test was performed for continuous variables where data were not normally distributed. Logistic and linear regression were used to investigate relationships between variables and outcomes.ResultsA total of 69 patients were included in the study. The mean age was 83 (75‐87) years and 38 (55%) were male. Eighty‐one percentage had >/= NYHA III symptoms. Eighty‐seven percentage had severe MR. Pulmonary capillary wedge pressure was 20 (15‐24). Overall, there was significant improvement in left atrial pressure including mean left atrial pressure index, MR, and NYHA class after MC (<.001). There was no significant association between invasive hemodynamics (including left atrial mean pressure index or its reduction rate) and functional outcomes (p = NS). MR grade was also not predictive of functional outcomes.ConclusionLeft atrial pressure may not be a significant predictor of functional outcomes, and, in isolation, may not be an improvement over MR grade.