bluuebunny/crossref_metadata_2025_split huggingface dataset:
Delocalizing Excitation for Highly‐Active Organic Photovoltaic Catalysts
Authors: Zhang Zhenzhen , Xu Chaoying , Sun Qianlu , Zhu Yufan , Yan Wenlong , Cai Guilong , Li Yawen , Si Wenqin , Lu Xinhui , Xu Weigao , Yang Ye , Lin Yuze 
Published: April 2024

AbstractLocalized excitation in traditional organic photocatalysts typically prevents the generation and extraction of photo‐induced free charge carriers, limiting their activity enhancement under illumination. Here, we enhance delocalized photoexcitation of small molecular photovoltaic catalysts by weakening their electron‐phonon coupling via rational fluoro‐substitution. The optimized 2FBP‐4F catalyst we develop here exhibits a minimized Huang–Rhys factor of 0.35 in solution, high dielectric constant and strong crystallization in the solid state. As a result, the energy barrier for exciton dissociation is decreased, and more importantly, polarons are unusually observed in 2FBP‐4F nanoparticles (NPs). With the increased hole transfer efficiency and prolonged charge carrier lifetime highly related to enhanced exciton delocalization, the PM6 : 2FBP‐4F heterojunction NPs at varied concentration exhibit much higher optimized photocatalytic activity (207.6–561.8 mmol h−1 g−1) for hydrogen evolution than the control PM6 : BP‐4F and PM6 : 2FBP‐6F NPs, as well as other reported photocatalysts under simulated solar light (AM 1.5G, 100 mW cm−2).
The 18F‐Difluoromethyl Group: Challenges, Impact and Outlook
Authors: Ford Joseph , Ortalli Sebastiano , Gouverneur Véronique 
Published: April 2024

AbstractThe difluoromethyl functionality has proven useful in drug discovery, as it can modulate the properties of bioactive molecules. For PET imaging, this structural motif has been largely underexploited in (pre)clinical radiotracers due to a lack of user‐friendly radiosynthetic routes. This Minireview provides an overview of the challenges facing radiochemists and summarises the efforts made to date to access 18F‐difluoromethyl‐containing radiotracers. Two distinct approaches have prevailed, the first of which relies on 18F‐fluorination. A second approach consists of a 18F‐difluoromethylation process, which uses 18F‐labelled reagents capable of releasing key reactive intermediates such as the [18F]CF2H radical or [18F]difluorocarbene. Finally, we provide an outlook for future directions in the radiosynthesis of [18F]CF2H compounds and their application in tracer radiosynthesis.
A MOF@Metal Oxide Heterostructure Induced by Post‐Synthetic Gamma‐Ray Irradiation for Catalytic Reduction
Authors: Zhang Mingxing , Chen Junchang , Zhao Xiaofang , Mao Xuanzhi , Li Chunyang , Diwu Juan , Wu Guozhong , Chai Zhifang , Wang Shuao 
Published: April 2024

AbstractMetal‐organic framework (MOF) based heterostructures, which exhibit enhanced or unexpected functionality and properties due to synergistic effects, are typically synthesized using post‐synthetic strategies. However, several reported post‐synthetic strategies remain unsatisfactory, considering issues such as damage to the crystallinity of MOFs, presence of impure phases, and high time and energy consumption. In this work, we demonstrate for the first time a novel route for constructing MOF based heterostructures using radiation‐induced post‐synthesis, highlighting the merits of convenience, ambient conditions, large‐scale production, and notable time and energy saving. Specifically, a new HKUST‐1@Cu2O heterostructure was successfully synthesized by simply irradiating a methanol solution dispersed of HKUST‐1 with gamma ray under ambient conditions. The copper source of Cu2O was directly derived from in situ radiation etching and reduction of the parent HKUST‐1, without the use of any additional copper reagents. Significantly, the resulting HKUST‐1@Cu2O heterostructure exhibits remarkable catalytic performance, with a catalytic rate constant nearly two orders of magnitude higher than that of the parent HKUST‐1.
Cyclodextrin ‘Chaperones’ Enable Quasi‐Ideal Supramolecular Network Formation and Enhanced Photodimerization of Hydrophobic, Red‐shifted Photoswitches in Water
Authors: Hoenders Daniel , Ludwanowski Simon , Barner‐Kowollik Christopher , Walther Andreas 
Published: April 2024

AbstractPrecision‐engineered light‐triggered hydrogels are important for a diversity of applications. However, fields such as biomaterials require wavelength outside the harsh UV regime to prevent photodamage, typically requiring chromophores with extended π‐conjugation that suffer from poor water solubility. Herein, we demonstrate how cyclodextrins can be used as auxiliary agents to not only solubilize such chromophores, but even to preorganize them in a 2 : 2 host‐guest inclusion complex to facilitate photodimerization. We apply our concept to styrylpyrene‐end‐functionalized star‐shaped polyethylene glycols (sPEGs). We initially unravel details of the host‐guest inclusion complex using spectroscopy and mass spectrometry to give clear evidence of a 2 : 2 complex formation. Subsequently, we show that the resultant supramolecularly linked hydrogels conform to theories of supramolecular quasi‐ideal model networks, and derive details on their association dynamics using in‐depth rheological measurements and kinetic models. By comparing sPEGs of different arm length, we further elucidate the model network topology and the accessible mechanical property space. The photo‐mediated dimerization proceeds smoothly, allowing to transform the supramolecular model networks into covalent ones. We submit that our strategy opens avenues for executing hydrophobic photochemistry in aqueous environments with enhanced control over reactivity, hydrogel topology or programmable mechanical properties.
Cyclometallated Imides as Templates for the H‐Bond Directed Iridium‐Catalyzed Asymmetric Hydrogenation of N‐Methyl, N‐Alkyl and N‐Aryl Imines
Authors: Wen Yisong , Fernández‐Sabaté Marc , Lledós Agustí , Sciortino Giuseppe , Eills James , Marco‐Rius Irene , Riera Antoni , Verdaguer Xavier 
Published: April 2024

AbstractA combined computational and experimental approach allowed us to develop overall the most selective catalyst for the direct hydrogenation of N‐methyl, N‐alkyl and N‐aryl imines described to date. Iridium catalysts with a cyclometallated cyclic imide group provide selectivity of up to 99 % enantiomeric excess. Computational studies show that the selectivity results from the combined effect of H‐bonding of the imide C=O with the substrate iminium ion and a stabilizing π–π interaction with the cyclometallated ligand. The cyclometallated ligand thus exhibits a unique mode of action, serving as a template for the H‐bond directed approach of the substrate which results in enhanced selectivity. The catalyst (2) has been synthesized and isolated as a crystalline air‐stable solid. X‐ray analysis of 2 confirmed the structure of the catalyst and the correct position of the imide C=O groups to engage in an H‐bond with the substrate. 19F NMR real‐time monitoring showed the hydrogenation of N‐methyl imines catalyzed by 2 is very fast, with a TOF of approx. 3500 h−1.
Machine Learning Molecular Dynamics Shows Anomalous Entropic Effect on Catalysis through Surface Pre‐melting of Nanoclusters
Authors: Gong Fu‐Qiang , Liu Yun‐Pei , Wang Ye , E Weinan , Tian Zhong‐Qun , Cheng Jun 
Published: April 2024

AbstractDue to the superior catalytic activity and efficient utilization of noble metals, nanocatalysts are extensively used in the modern industrial production of chemicals. The surface structures of these materials are significantly influenced by reactive adsorbates, leading to dynamic behavior under experimental conditions. The dynamic nature poses significant challenges in studying the structure–activity relations of catalysts. Herein, we unveil an anomalous entropic effect on catalysis via surface pre‐melting of nanoclusters through machine learning accelerated molecular dynamics and free energy calculation. We find that due to the pre‐melting of shell atoms, there exists a non‐linear variation in the catalytic activity of the nanoclusters with temperature. Consequently, two notable changes in catalyst activity occur at the respective temperatures of melting for the shell and core atoms. We further study the nanoclusters with surface point defects, i.e. vacancy and ad‐atom, and observe significant decrease in the surface melting temperatures of the nanoclusters, enabling the reaction to take place under more favorable and milder conditions. These findings not only provide novel insights into dynamic catalysis of nanoclusters but also offer new understanding of the role of point defects in catalytic processes.
The application of three‐dimensional printing in the management of a difficult airway due to Treacher Collins syndrome
Authors: Trincado Cobos M. , Tapia Salinas B. , Gutiérrez Venturini A. , Aragón Niño I. , Del Castillo Pardo de Vera J. L. , Cebrián Carretero J. L. , Uña Orejón R. 
Published: April 2024

SummaryWe describe the use of three‐dimensional printing to create precise airway models for a patient with Treacher Collins syndrome who presented for bimaxillary temporomandibular joint prostheses, and for whom airway management was predicted to be difficult. The model was based on pre‐operative cone beam computed tomography images and printed in the 3D Lab of Hospital Universitario La Paz. Transparent models allowed clear visualisation for simulation and iterative refinement of airway management techniques and aided in risk assessment and instrument sizing. This case report emphasises the utility of this approach in complex airway scenarios.
Variable breeding success and its implication in the conservation of endangered yellow‐eyed penguin (Megadyptes antipodes) at the New Zealand subantarctic Auckland Islands
Authors: Muller C. G. , Chilvers B. L. , French R. K. , Battley P. F. 
Published: April 2024

Abstract
Knowledge of breeding success is essential for conservation, as it is required for monitoring populations and survival trends. Seabird reproductive success can be negatively affected by prey availability, marine‐based stochasticity, extreme weather events, individual breeders' performance and direct threats such as disease, predation and fisheries interactions.
The endangered yellow‐eyed penguin (Megadyptes antipodes) is declining in mainland New Zealand, however, little is known about its breeding success in the subantarctic where the majority of the species breeds.
Yellow‐eyed penguin breeding success data were collected from a total of 167 nests on subantarctic Enderby Island, Auckland Islands, New Zealand, from the 2015 to 2017 breeding seasons. This included egg and chick mortality and fledging rates, plus a wider sample of the fledgling condition of 276 chicks.
Fledging success was higher than in mainland New Zealand in some years, although chicks were smaller and lighter on average, highlighting the need for more information on juvenile survival probabilities in the subantarctic.
Breeding success measures were similar in 2015 and 2016, but a large egg mortality in 2017 caused a significant reduction in breeding success that year. Such variability requires more investigation into the correlates of breeding success, including possible stressors such as foraging success, adverse weather and environmental effects, and pathogens.
These results demonstrate the need for ongoing monitoring of yellow‐eyed penguin breeding success across the subantarctic in order to establish baselines for normal variation and to determine whether anthropogenic (manageable) factors may be contributing to low productivity.
This research highlights an important consideration for endangered species conservation; that breeding success may not be consistent over time, or across a species' entire range. Additional monitoring of all breeding populations should be carried out to ensure up‐to‐date information is available to inform conservation management decisions for the species.
Selective Hydrogenation of Diethyl Malonate to 1,3‐Propanediol Over Ga‐Promoted Cu/SiO2 Catalysts With Enhanced Activity and Stability
Authors: Zhang Jia , Shi Hongxuan , Yang Jian , Yao Xiaolan , Liu Hailong , Li Xuemei , Gao Guang , Li Fuwei , Huang Zhiwei 
Published: April 2024

AbstractCu catalysts with different compositions and different Cu and promoter contents were prepared by precipitation‐gel method and studied for the selective hydrogenation of syngas or biomass‐based diethyl malonate (DEM) to valuable 1,3‐propanediol (1,3‐PDO). The Ga‐promoted 70Cu6Ga/SiO2 catalyst was found to exhibit the highest catalytic performance, achieving 100 % DEM conversion and 76.6 % 1,3‐PDO selectivity under reaction conditions of 160 °C and 8 MPa H2. The 70Cu6Ga/SiO2 bimetallic catalyst also presented obviously better stability than that of the monometallic 70Cu/SiO2 catalyst in a continuous flow reactor over 180 h time‐on stream. Characterization results showed that the incorporation of Ga increased the interaction between Cu and Ga species, hindered the full reduction of Cu2+ species, and thus increased the proportion of Cu+ and the number of Lewis acidic sites on the catalyst surface. The synergistic effect between Cu0 and Cu+ enhanced the adsorption and activation of ester carbonyl groups and their subsequent hydrogenation, eventually contributed to the outstanding performances of the CuGa/SiO2 bimetallic catalysts.
The Categorization of Continuous Attributes
Authors: Wang Yusu 
Published: April 2024

ABSTRACTA continuous attribute (e.g., calorie count) can be classified into separate categories (e.g., high vs. low), and a similar attribute value can fall into different categories depending on where the category boundaries are drawn. This research explores the effect of categorization on judgments of options (e.g., products and incentive‐compatible games) with continuous attributes. I predict and find a systematic preference shift between two options that were presented with different categorization criteria: When two options involve a tradeoff between two continuous attributes, people tend to prefer the option with both attributes classified into the favorable categories given the categorization criteria. I further show that this effect is driven by larger perceived differences between attribute values across category boundaries and is moderated by people's tendency to rely on category information. Overall, this effect holds even when people are highly familiar with the attributes and feel confident to make similarity evaluations, when people are cued that the categories provide little informational value, and when people are incentivized to make deliberate decisions. The findings in this research carry both theoretical and practical implications.
A novel nonparametric time‐dependent precision–recall curve estimator for right‐censored survival data
Authors: Beyene Kassu Mehari , Chen Ding‐Geng , Kifle Yehenew Getachew 
Published: April 2024

AbstractIn order to assess prognostic risk for individuals in precision health research, risk prediction models are increasingly used, in which statistical models are used to estimate the risk of future outcomes based on clinical and nonclinical characteristics. The predictive accuracy of a risk score must be assessed before it can be used in routine clinical decision making, where the receiver operator characteristic curves, precision–recall curves, and their corresponding area under the curves are commonly used metrics to evaluate the discriminatory ability of a continuous risk score. Among these the precision–recall curves have been shown to be more informative when dealing with unbalanced biomarker distribution between classes, which is common in rare event, even though except one, all existing methods are proposed for classic uncensored data. This paper is therefore to propose a novel nonparametric estimation approach for the time‐dependent precision–recall curve and its associated area under the curve for right‐censored data. A simulation is conducted to show the better finite sample property of the proposed estimator over the existing method and a real‐world data from primary biliary cirrhosis trial is used to demonstrate the practical applicability of the proposed estimator.
Sample size planning for rank‐based multiple contrast tests
Authors: Pöhlmann Anna , Brunner Edgar , Konietschke Frank 
Published: April 2024

AbstractRank methods are well‐established tools for comparing two or multiple (independent) groups. Statistical planning methods for the computing the required sample size(s) to detect a specific alternative with predefined power are lacking. In the present paper, we develop numerical algorithms for sample size planning of pseudo‐rank‐based multiple contrast tests. We discuss the treatment effects and different ways to approximate variance parameters within the estimation scheme. We further compare pairwise with global rank methods in detail. Extensive simulation studies show that the sample size estimators are accurate. A real data example illustrates the application of the methods.
Influence of performance measures and sample characteristics on the relationship between corporate environmental management and firm performance: A meta‐analytic review
Authors: Kaur Charanjeet , Dharni Khushdeep 
Published: April 2024

AbstractEnvironmental and climate concerns have made corporate environmental management a raging topic for discussion among academicians and industrialists. The current study explores the association between corporate environmental management and firm performance; and examines the influence of different performance measurement methods and sample characteristics on this association. The meta‐analysis, homogeneity test, and publication bias test have been performed on 318 effect sizes from 117 studies. The results indicate a significant positive association between the overall corporate environmental management and firm performance association. The findings suggest a significant influence of the nature of the data, corporate environmental management measures, corporate performance measures, region, economic development, time phase, nature of data, and period of study in the given context. The findings will help managers to better understand and choose the appropriate corporate environmental management measures to attain internal and external efficiencies.
Furfural Hydrogenation Over Reduced Pure (LaBO3) and Substituted (LaB0.5B'0.5O3) (B, B': Fe, Co, Ni) Perovskites
Authors: Lara Katherine , Arias Dana , Sepulveda Catherine , Buljan Antonio , Lizana Ignacio , Delgado Eduardo J. , Pecchi Gina , Herrera Carla 
Published: April 2024

AbstractA series of pure and 50 % substituted Fe‐containing (LaFeO3, LaFe0.5Ni0.5O3 and LaFe0.5Co0.5O3) and Co/Ni‐containing (LaCoO3, LaNiO3, and LaCo0.5Ni0.5O3) perovskites were used as precursors to synthesize metallic reduced catalysts to be tested for the liquid hydrogenation of furfural. The catalytic reaction was carried out in a batch reactor at 200 °C and 3.0 MPa of H2 pressure. The calcined perovskites and reduced catalysts were characterized by X‐ray diffraction (XRD), N2 physisorption at 77 K, temperature programmed reduction (H2‐TPR), temperature programmed CO2 and NH3 desorption (CO2‐TPD and NH3‐TPD), Atomic Absorption Spectroscopy (AAS) and X‐ray photoelectron spectroscopy (XPS) techniques. The LaCo0.5Ni0.5O3 reduced catalyst display the highest activity in furfural conversion, which was attributed to a cooperative effect between highly dispersed nickel and cobalt metal nanoparticles after reduction process. The effect of the nature of B‐cation have a high impact on the products selectivity in the hydrogenation of furfural, suggesting that enriched‐Ni metal surface was selectivity to tetrahydrofurfuryl alcohol, meanwhile enriched‐Co metal surface was selective to furfuryl alcohol formation, which was also supported with adsorption mode of furfural over the active sites obtained by quantum calculation.
Innovations in Photocatalytic and Photoelectrocatalytic Water Splitting: Pathways to Efficiently Convert Biomass into Renewable Energy and Chemicals
Authors: Liu Yiming , Zhang Wanggang , Wang Yue , Tian Rufeng , Wang Jian 
Published: April 2024

AbstractThis review comprehensively explores the integration of photocatalytic (PC) and photoelectrocatalytic (PEC) technologies for hydrogen production via water splitting, in synergy with the efficient conversion of biomass resources. This synergistic strategy significantly boosts hydrogen production rates in both PC and PEC systems and enhances solar energy conversion efficiency. Furthermore, it enables selective conversion of cost‐effective biomass via precise modulation of catalyst structures, paving a novel pathway for green hydrogen generation and synthesis of high‐value chemicals. Specifically, the manuscript highlights recent progress in the oxidation and coupling reactions of biomass derivatives, such as methanol, ethanol, glycerol, and 5‐hydroxymethylfurfural, in PC/PEC systems. It reveals their potential to enhance hydrogen production efficiency and the synthesis of high‐value organic compounds. Future research should focus on employing in‐situ characterization techniques and theoretical simulations to deeply understand reaction mechanisms, thus advancing the field of biomass conversion through photocatalytic/photoelectrocatalytic methods.
A Magnesium Binding Site And The Anomeric Effect Regulate The Abiotic Redox Chemistry Of Nicotinamide Nucleotides
Authors: Sebastianelli Lorenzo , Kaur Harpreet , Chen Ziniu , Krishnamurthy Ramanarayanan , Mansy Sheref S. 
Published: April 2024

AbstractNicotinamide adenine dinucleotide (NAD+) is a redox active molecule that is universally found in biology. Despite the importance and simplicity of this molecule, few reports exist that investigate which molecular features are important for the activity of this ribodinucleotide. By exploiting the nonenzymatic reduction and oxidation of NAD+ by pyruvate and methylene blue, respectively, we were able to identify key molecular features necessary for the intrinsic activity of NAD+ through kinetic analysis. Such features may explain how NAD+ could have been selected early during the emergence of life. Simpler molecules, such as nicotinamide, that lack an anomeric carbon are incapable of accepting electrons from pyruvate. The phosphate moiety inhibits activity in the absence of metal ions but facilitates activity at physiological pH and model prebiotic conditions by recruiting catalytic Mg2+. Reduction proceeds through consecutive single electron transfer events. Of the derivatives tested, including nicotinamide mononucleotide, nicotinamide riboside, 3‐(aminocarbonyl)‐1‐(2,3‐dihydroxypropyl)pyridinium, 1‐methylnicotinamide, and nicotinamide, only NAD+ and nicotinamide mononucleotide would be capable of efficiently accepting and donating electrons within a nonenzymatic electron transport chain. The data are consistent with early metabolic chemistry exploiting NAD+ or nicotinamide mononucleotide and not simpler molecules.
HFIP‐Mediated Desulfinative Friedel–Crafts Cyclobutenylation Reaction
Authors: Yanai Hikaru , Kurogi Shota , Hoshikawa Shoki , Matsumoto Takashi 
Published: April 2024

AbstractIn 1,1,1,3,3,3‐hexafluoroisopropyl alcohol (HFIP), gem‐bis(triflyl)cyclobutenes, which can be prepared by the (2+2) cycloaddition reaction of Tf2C=CH2 with alkynes, underwent desulfination to generate the corresponding cyclobutenyl cation. This unique reactivity was successfully applied to the Friedel–Crafts type cyclobutenylation reaction of several (hetero)aromatic compounds.