bluuebunny/crossref_metadata_2025_split huggingface dataset:
Activation of dihydrogen by group‐14 substituted germylenes
Authors: Rahmati Somayeh , Ayoubi‐Chianeh Mojgan , Kassaee Mohamad Z. 
Published: December 2023

AbstractWe have investigated the structural and thermodynamic parameters of group‐14 substituted germylenes and their reactivity toward the H2 molecule using density functional theory (DFT). We conducted the detailed Kohn–Sham molecular orbital (KS‐MO) analysis to quantify the effective factors behind the increased reactivity of germylenes in going from C to Sn as substituents. The quantum theory of atoms in molecules (QTAIM), non‐covalent interaction (NCI), and natural bond orbital (NBO) analyses revealed the nature of bonds and interactions and demonstrated the reactivity trend of germylenes in the presence of H2. The results showed that in going from C to Sn, the reactivity increased due to an improvement in
‐donation interaction between the filled lone‐pair orbital of the germylene (LPGe) and the
*‐orbital of H2, which decreased the reaction barrier (
E‡). As the germylene substitution was varied from C to Sn, a significant reactivity was observed for the germylene toward the H2. This observation was caused by a reduction in steric repulsion between the germylene and the H2 and less activation energy due to the higher
‐donation and lower back‐donation. We have presented the reactivity of new and rationally designed germylenes toward H2 using various analyses that will serve as a guide for the activation of small molecules such as H2, which is employed in many subsequent reactions.
Recent developments in fluorine‐containing pesticides
Authors: Jeschke Peter 
Published: December 2023

AbstractTo ensure ongoing sustainability, the modern agrochemical industry is faced with enormous challenges. These arise from provision of high‐quality food to increasing water use and environmental impact as well as a growing world population. The loss of previous agrochemicals due to consumer perception, changing grower needs and ever‐changing regulatory requirements is higher than the number of active ingredients that are being introduced into the crop protection market. Therefore, the development of novel agrochemicals is essential to provide improved efficacy and environmental profiles. In this context, the introduction of fluorine atoms and fluorine‐containing motifs into a molecule is an important method to influence its physicochemical properties. These include, for example, small difluoro‐ and trifluoromethyl, or trifluoromethoxy groups at aryl or heterocyclic aryl moieties but also fragments like 2,2,2‐trifluoroethoxycarbonyl, trifluoromethylsulfonyl, trifluoroacetyl, as well as the so far unusal rest like heptafluoro‐iso‐propyl. This review gives an overview of recent developments of fluorine‐containing pesticides launched over the past 7 years and describes a selection of current fluorine‐containing development candidates. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
DFT QM/MM MD Calculations to Identify Intermolecular Interactions within the Active Sites of MraYAA Bound to Antibiotics Capuramycin, Carbacaprazamycin, and 3′‐Hydroxymureidomycin A
Authors: Astani Elahe K. , Malek Zadeh Saeid , Sardari Soroush , Khosravian Mahnaz 
Published: December 2023

AbstractThe bacterial transmembrane enzyme Phospho‐N‐acetylmuramoyl‐pentapeptide translocase from Aquifex aeolicus (MraYAA) plays an important role in the peptidoglycan biosynthesis of bacterial cell wall. The natural‐product nucleoside inhibitors such as capuramycin, carbacaprazamycin, and 3′‐hydroxymureidomycin A block the biosynthetic pathway of MraYAA by inhibiting its function. Since these MraYAA inhibitors have distinct complex chemical structures, the strengths of MraYAA‐inhibitor interactions strongly depend on the inhibitory structure. Here, the crystal structures of MraYAA‐capuramycin, MraYAA‐carbacaprazamycin, and MraYAA‐3′‐hydroxymureidomycin A were separately optimized by quantum mechanics/molecular mechanics (QM/MM) approach in conjunction with molecular dynamics (MD) simulations. Further, quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analyses at the M06‐2X/6‐31G** level were done on the active site of each optimized structure to specify the characteristics of intermolecular interactions of each cited inhibitor with the MraYAA active site residues. Our results revealed that Lys70, Thr75, Asp193, Asp196, Gly264, Asp265, and His325 play key roles in binding these inhibitors to MraYAA through hydrogen bonds of common types with strength ranging from van der Waals to covalent characters accompanying electrostatic and van der Waals interactions. MraYAA‐inhibitor interaction energies demonstrated that the MraYAA active site has the strongest intermolecular interactions with capuramycin.
Selenium‐Containing Nanocomplexes Achieve Dual Immune Checkpoint Blockade for NK Cell Reinvigoration
Authors: Xianyu Banruo , Pan Shuojiong , Gao Shiqian , Xu Huaping , Li Tianyu 
Published: December 2023

AbstractThe blockade of immune checkpoints has emerged as a promising strategy for cancer immunotherapy. However, most of the current approaches focus on T cells, leaving natural killer (NK) cell‐mediated therapeutic strategies rarely explored. Here, a selenium‐containing nanocomplex is developed that acts as a dual immune checkpoint inhibitor to reinvigorate NK cell‐based cancer immunotherapy. The Se nanocomplex can deliver and release siRNA that targets programmed death ligand‐1 (PD‐L1) in tumor cells, thereby silencing the checkpoint receptor PD‐L1. The intracellular reactive oxygen species generated by porphyrin derivatives in the nanocomplexes can oxidize the diselenide bond into seleninic acid, which blocks the expression of another checkpoint receptor, human leukocyte antigen E. The blockade of dual immune checkpoints shows synergistic effects on promoting NK cell‐mediated antitumoral activity. This study provides a new strategy to reinvigorate NK cell immunity for the development of combined cancer immunotherapy.
Overcoming Low C2+Yield in Acidic CO2Electroreduction: Modulating Local Hydrophobicity for Enhanced Performance
Authors: Yao Zhe , Lin Rui 
Published: December 2023

AbstractOperating electrochemical CO2reduction reaction (CO2RR) in acidic media has garnered considerable attention due to its sustainable electrolyte cycling and stable performance. Nevertheless, the severe parasitic hydrogen evolution reaction (HER) and decayed multi‐carbon species (C2+) yield still hampers efficient CO2RR in acid. Here, this work investigates the influence of local hydrophobicity on the acidic CO2RR. By employing direct electrodeposition, the hydrophobicity of the catalyst layer can be finely tuned over a wide range without additive. It is revealed that the hydrophobic microenvironment significantly suppressed HER, improved CO2RR performance and boosted C2+yield. A Faradaic efficiency (FE) of ≈74% for C2+is achieved in pH = 2 on electrodeposited copper with a highly hydrophobic environment. Moreover, this phenomenon can be extended to industrial application. An ≈81% total FE for the CO2RR, along with a ≈62% FE for C2+species, is achieved even with commercial copper. Remarkably, the system exhibited stable operation for a continuous period exceeding 50 h at an industrially applied current density of 300 mA cm−2. This work highlights the crucial role of interface hydrophobicity in acidic CO2RR and proposes a facile and universally applicable method for achieving efficient and stable CO2RR to high‐value products in acidic media.
Exploring CsPbX3 (X = Cl, Br, I) Perovskite Nanocrystals in Amorphous Oxide Glasses: Innovations in Fabrication and Applications
Authors: Samiei Sadaf , Soheyli Ehsan , Vighnesh Kunnathodi , Nabiyouni Gholamreza , Rogach Andrey L. 
Published: December 2023

AbstractMetal halide perovskites with excellent optical and electronic properties have become a trending material in the current research. However, their limited stability under ambient conditions degrades quality and threatens their potential commercialization as optoelectronic devices. Various approaches are adopted to improve the stability of perovskite nanocrystals (PeNC) while maintaining their advantageous optical properties, particularly strong luminescence. Among different possible improvement strategies, encapsulation of PeNCs within the amorphous glass matrices of inorganic oxides has drawn widespread attention because it ensures high resistance against chemical corrosion and high temperature, thus enhancing their chemical, thermal, and mechanical stability with improved light‐emission characteristics. In this article, two types of materials, namely all‐inorganic metal halide PeNCs and amorphous oxide glasses are briefly introduced, and then the methods are reviewed to fabricate and improve the quality of PeNC@glass composites. These methods are classified into three universal categories: compositional modification, structural modification, and dual encapsulation. In the final part of this review paper, examples of applications of PeNCs@glass composites in light‐emitting devices and displays, data storage and anti‐counterfeiting, lasing, photodetectors and X‐ray detectors, photocatalysis, optical filters, solar concentrators, and batteries are provided.
Improved Electrical Output Performance of Cellulose‐Based Triboelectric Nanogenerators Enabled by Negative Triboelectric Materials
Authors: Wang Feijie , Wang Suyang , Liu Yifan , Hou Tianmeng , Wu Zhen , Qian Jing , Zhao Zhicheng , Wang Liqiang , Jia Chao , Ma Shufeng 
Published: December 2023

AbstractCellulose‐based triboelectric nanogenerators (TENGs) have attracted widespread attention due to the low cost and environmentally friendly characteristics of cellulose. However, achieving high electrical energy output from these generators still presents significant challenges. Here, cellulose is dissolved‐regenerated to form a composite aerogel with high specific surface area, in which cellulose‐based composites with excellent negative triboelectric properties are developed by coupling the rich 3D network structure of the regenerated cellulose aerogel, modified barium titanate, and poly(vinylidene fluoride). The TENGs assembled from the composite materials exhibit an output voltage of 1040 V and a current of 1.165 mA at an external force of 8 N and a frequency of 4 Hz, outperforming all cellulose‐based negative triboelectric materials. In addition, the nanogenerators have a stable electrical energy output capacity, with no significant property degradation in 100 000 contact‐separation tests. The excellent electrical output property of the composite materials enables them to harvest energy from human movement and waterdrops, demonstrating their great application prospects in wearable devices, energy harvesting devices, self‐powered sensors, and other fields.
Mn Doping and P Vacancy Induced Fast Phase Reconstruction of FeP for Enhanced Electrocatalytic Oxygen Evolution Reaction in Alkaline Seawater
Authors: Wang Ketao , Liu Xiaobin , Yu Qingping , Wang Xuanyi , Zhu Jiawei , Li Yanyan , Chi Jingqi , Lin Haifeng , Wang Lei 
Published: December 2023

AbstractDue to the shortage of pure water resources, seawater electrolysis is a promising strategy to produce green hydrogen energy. To avoid chlorine oxidation reactions (ClOR) and the production of more corrosive hypochlorite, enhancing OER electrocatalyst activity is the key to solving the above problem. Considering that transition metal phosphides (TMPs) are promising OER eletrocatalysts for seawater splitting, a method to regulate the electronic structure of FeP by introducing Mn heteroatoms and phosphorus vacancy on it (Mn‐FePV) is developed. As an OER electrocatalyst in seawater solution, the synthesized Mn–FePV achieves extremely low overpotentials (η500 = 376, η1000 = 395 mV). In addition, the Pt/C||Mn–FePV couple only requires the voltage of 1.81 V to drive the current density of 1000 mA cm−2 for overall seawater splitting. The density functional theory (DFT) calculation shows that Mn–FePV (0.21 e−) has more charge transfer number compared with FeP (0.17 e−). In‐situ Raman analysis shows that phosphorus vacancy and Mn doping can synergistically regulate the electronic structure of FeP to induce rapid phase reconstruction, further improving the OER performance of Mn–FePV. The new phase species of FeOOH is confirmed to can enhance the adsorption kinetics of OER intermediates.
A Method Probing High‐Temperature Oxidation Behavior of Crystalline Materials
Authors: Zhang Zhengang , Wu Jisen , Zhu Quan , Ma Jianyi 
Published: December 2023

AbstractTo date, the oxidation behavior of crystal materials is not fully understood; additional research is needed to understand the oxidation of materials. Herein, density functional theory (DFT) calculations and a 3D kinetic Monte Carlo (KMC) model are used to investigate the infiltration and diffusion behaviors of oxygen atoms within the crystal. Oxygen molecules readily adsorbes on crystal surfaces of the material and rapidly dissociates, verified by both first‐principles calculations and energy‐dispersive spectrometer (EDS) results. The infiltration ability of oxygen atoms into the inner crystal layers is affected by the surrounding oxygen atom, lattice compactness, and other factors. Energy‐barrier calculations show that crystal thin/dense layers have significant effects on the crystal oxidation process, so high‐pressure technology is used to investigate this correlation experimentally. KMC calculations and thermogravimetric analyses (TGA) show the infiltration behavior of oxygen atoms in the main crystal plane (211) toward the inner layers has the highest proportion to the actual high‐temperature oxidation behavior of the title material. The results of both the KMC calculations and thermal experiments show the material peeled off upon further oxidation, which accelerates oxidation. At the same time, high‐pressure treatment increases the oxidation resistance of materials at lower temperatures (<600 °C).
Honeycomb Electron Lattice Induced Dirac Fermion with Trigonal Warping in Bilayer Electrides
Authors: Meng Weizhen , Wu Hongbo , Jiao Yalong , Ma Fengxian , Wang Shiyao , Liu Ying , Liu Guodong , Zhang Xiaoming 
Published: December 2023

AbstractEmergent fermions arising from the excess electrons of electrides provide a new perspective for exploring semimetal states with unique Fermi surface geometries. In this study, a class of unique two‐dimensional (2D) highly anisotropic Dirac fermions is designed using a sandwich structure. Based on the structural design and first‐principles calculations, 2D electride MB (M = Ca/Sr, B = Cl/Br/I) is an ideal candidate material. The excess electrons of the bilayer MB could be stably localized in the interstitial cavities, constructing a natural zigzag honeycomb electron sublattice that further forms a Dirac fermion. Compared with traditional Dirac semimetals, 2D Dirac electrides exhibited rich physical properties: i) The Fermi surface shows trigonal warping in low‐energy regions. In particular, the geometry of the Fermi surface determines the high anisotropy of the Fermi velocity. ii) A pair of Dirac fermions are protected by three‐fold rotational symmetry and exhibit strong robustness. iii) Electride MB possesses a lower work function that strongly correlates with the surface area of the emission channel. Based on these properties, an electron‐emitting device with multifunctional applications is fabricated. Therefore, this study provides an ideal platform for studying potential entanglement between structures, electrides, and topological states.
Toward effective electrocatalytic C–N coupling for the synthesis of organic nitrogenous compounds using CO2 and biomass as carbon sources
Authors: Jiang Hao , Wu Xu , Zhang Heng , Yan Qiong , Li Hui , Ma Tianyi , Yang Song 
Published: December 2023

AbstractThermochemical conversion of fossil resources into fuels, chemicals, and materials has rapidly increased atmospheric CO2 levels, hindering global efforts toward achieving carbon neutrality. With the increasing push for sustainability, utilizing electrochemical technology to transform CO2 or biomass into value‐added chemicals and to close the carbon cycle with sustainable energy sources represents a promising strategy. Expanding the scope of electrosynthesis technology is a prerequisite for the electrification of chemical manufacturing. To this end, constructing the C─N bond is considered a priority. However, a systematic review of electrocatalytic processes toward building C─N bonds using CO2 and biomass as carbon sources is not available. Accordingly, this review highlights the research progress in the electrosynthesis of organic nitrogen compounds from CO2 and biomass by C─N coupling reactions in view of catalytic materials, focusing on the enlightenment of traditional catalysis on C─N coupling and the understanding of the basis of electrochemical C─N coupling. The possibility of C─N bond in electrocatalysis is also examined from the standpoints of activation of substrates, coupling site, mechanism, and inhibition of hydrogen evolution reaction (HER). Finally, the challenges and prospects of electrocatalytic C─N coupling reactions with improved efficiency and selectivity for future development are discussed.
Generalized entropy for general subregions in quantum gravity
Authors: Jensen Kristan , Sorce Jonathan , Speranza Antony J. 
Published: December 2023

Abstract
We consider quantum algebras of observables associated with subregions in theories of Einstein gravity coupled to matter in the GN → 0 limit. When the subregion is spatially compact or encompasses an asymptotic boundary, we argue that the algebra is a type II von Neumann factor. To do so in the former case we introduce a model of an observer living in the region; in the latter, the ADM Hamiltonian effectively serves as an observer. In both cases the entropy of states on which this algebra acts is UV finite, and we find that it agrees, up to a state-independent constant, with the generalized entropy. For spatially compact regions the algebra is type II1, implying the existence of an entropy maximizing state, which realizes a version of Jacobson’s entanglement equilibrium hypothesis. The construction relies on the existence of well-motivated but conjectural states whose modular flow is geometric at an instant in time. Our results generalize the recent work of Chandrasekaran, Longo, Penington, and Witten on an algebra of operators for the static patch of de Sitter space.
Phase diagram of QCD matter with magnetic field: domain-wall Skyrmion chain in chiral soliton lattice
Authors: Eto Minoru , Nishimura Kentaro , Nitta Muneto 
Published: December 2023

Abstract
QCD matter in strong magnetic field exhibits a rich phase structure. In the presence of an external magnetic field, the chiral Lagrangian for two flavors is accompanied by the Wess-Zumino-Witten (WZW) term containing an anomalous coupling of the neutral pion π0 to the magnetic field via the chiral anomaly. Due to this term, the ground state is inhomogeneous in the form of either chiral soliton lattice (CSL), an array of solitons in the direction of magnetic field, or domain-wall Skyrmion (DWSk) phase in which Skyrmions supported by π3[SU(2)] ≃ ℤ appear inside the solitons as topological lumps supported by π2(S2) ≃ ℤ in the effective worldvolume theory of the soliton. In this paper, we determine the phase boundary between the CSL and DWSk phases beyond the single-soliton approximation, within the leading order of chiral perturbation theory. To this end, we explore a domain-wall Skyrmion chain in multiple soliton configurations. First, we construct the effective theory of the CSL by the moduli approximation, and obtain the ℂP1 model or O(3) model, gauged by a background electromagnetic gauge field, with two kinds of topological terms coming from the WZW term: one is the topological lump charge in 2+1 dimensional worldvolume and the other is a topological term counting the soliton number. Topological lumps in the 2+1 dimensional worldvolume theory are superconducting rings and their sizes are constrained by the flux quantization condition. The negative energy condition of the lumps yields the phase boundary between the CSL and DWSk phases. We find that a large region inside the CSL is occupied by the DWSk phase, and that the CSL remains metastable in the DWSk phase in the vicinity of the phase boundary.
Migration strategies of skuas in the southwest Atlantic Ocean revealed by stable isotopes
Authors: Mills William F. , Ibañez Andrés E. , Carneiro Ana P. B. , Morales Lara M. , Mariano-Jelicich Rocío , McGill Rona A. R. , Montalti Diego , Phillips Richard A. 
Published: December 2023

AbstractStable isotope ratios of carbon (δ13C) and nitrogen (δ15N) were measured in feathers to compare the non-breeding distributions and habitat use of adult brown skuas Stercorarius antarcticus lönnbergi from high-latitude colonies at Esperanza/Hope Bay (Antarctic Peninsula, 63°S) and Signy Island (South Orkneys, 60°S), with those from Bird Island (South Georgia, 54°S), which have also been tracked previously using geolocators. Breeding colony, but not sex, had a significant effect on feather δ13C and δ15N values. Feather stable isotope data from South Georgia birds mostly corresponded to oceanic, mixed subtropical–subantarctic to subantarctic waters, which agrees with the tracking data, as did a subset of the birds from the two higher latitude populations. However, other individuals displayed feather stable isotope ratios that were consistent with continental shelf or shelf-slope waters, suggesting that unlike the vast majority of brown skuas from South Georgia, many birds from higher latitude colonies spend the non-breeding season on, or near, the Patagonian Shelf. These population-level differences may have implications for exposure to anthropogenic threats or have carryover effects on subsequent breeding behaviour or performance.
Agriculture at the Phoenician site of La Fonteta (Alicante, Spain)
Authors: Pérez-Jordà Guillem , Lorrio Alberto J. , López Rosendo Ester , Torres Ortiz Mariano 
Published: December 2023

AbstractThe Phoenician settlement of La Fonteta (Alicante, Spain) was founded in the late 8th cent bc at the mouth of the Río Segura. It has provided one of the most complete archaeobotanical records of all Phoenician Mediterranean sites which points to an agricultural system based on cultivating cereals, pulses and a wide variety of fruits such as grape, fig and pomegranate. These crops then spread to the surrounding indigenous settlements. Apart from integrating new crops, these local and regional indigenous sites progressively began to take part in a Mediterranean-wide network characterised particularly by trade in agricultural produce. The agricultural system of La Fonteta was not new to the Iberian Peninsula, as there is evidence that it arrived earlier at Phoenician colonies along its Mediterranean coastline. One of the most relevant aspects of the archaeobotanical record from La Fonteta is that it represents crafts there, as a large part of the remains correspond to plants which were burnt as fuel in its numerous metal working furnaces.