bluuebunny/crossref_metadata_2025_split huggingface dataset:
p‐Orbital Ferromagnetism Arising from Unconventional O− Ionic State in a New Semiconductor Sr2AlO4 with Insufficiently Bonded Oxygen
Authors: Zheng Xu‐Guang , Xu Chao‐Nan , Uchiyama Tomoki , Yamauchi Ichihiro , Galica Tomasz , Nishibori Eiji , Chen Ying 
Published: November 2024

AbstractOxygen in solids usually exists in an O2− ionic state. As a result, it loses its magnetic nature of a single atom, wherein two unpaired electrons exist in its outer 2p orbitals. Here, it is shown that an unconventional stable ionic state of O− is realized in a new semiconductor material Sr2AlO4, leading to an intrinsic p‐orbital ferromagnetism stable until ≈900 K. Experimental and theoretical investigations have clarified that one‐fourth of the oxygen atoms in Sr2AlO4 are insufficiently bonded in the crystal structure, resulting in a unique O−‐state and p‐orbital ferromagnetism. To date, the O− state is reported to exist only in non‐equilibrium conditions, and p‐orbital magnetism is only suggested in impurity bands with small ferromagnetic moments. The present work provides a new route for creating ferromagnetism in semiconductors and exploring new p‐orbital physics and chemistry. In addition, the material shows elastic‐mechanoluminescence that may enable unprecedented mechano‐photonic‐spintronics.
Detecting the presence of different Retzius periodicities at the population level from repetitive linear enamel hypoplasia among Lufengpithecus lufengensis and Pongo pygmaeus
Authors: Skinner Mark Fretson , Ji Xueping 
Published: November 2024

AbstractObjectivesReconstruction of life histories for fossil and living primates draws on rate of enamel layering, termed Retzius periodicity (RP in days) expressed as surface perikymata, during dental crown formation. Disclosure of RP through thin sectioning is destructive; consequently, sample sizes are inadequate to detect the range of RPs present in discrete taxa. We propose an additional method to detect RPs at the population level based on twice‐yearly average recurrence of linear enamel hypoplasia (rLEH) in apes shown by prior studies.Materials and MethodsCasts of teeth from orangutans (Pongo pygmaeus) (n = 40) and Lufengpithecus lufengensis (n = 57) from Late Miocene Shihuiba, China, (133 and 138 LEH, respectively) were recorded with scanning electron microscope (SEM) and confocal microscopy to yield perikymata counts between episodes of LEH. Frequency distributions of aggregated perikymata counts between LEH were compared to frequency distribution of tooth‐specific ratios of perikymata counts between successive LEH (this latter step removes effects of RP differences within a sample).ResultsDrawing on prior research, two successive intervals between LEH span 1 year on average. Ratios of successive to previous intervals between LEH show that orangutans and Lufengpithecus exhibit two asymmetric intervals centered on 5.3 and 6.7 months, likely reflecting the effect of axial tilt insolation on phenology. Estimated RPs are not unimodal but show a range from 7 to 12 in Lufenpithecus and 8 to 11 in Pongo, comparable to published values.DiscussionRepetitive LEH is sufficiently regular to detect additional RPs which, in the case of Lufengpithecus, have yet to be demonstrated histologically.
Nickel‐Catalyzed Atroposelective Carbo‐Carboxylation of Alkynes with CO2: En Route to Axially Chiral Carboxylic Acids
Authors: Li Chao , Chen Xiao‐Wang , Liao Li‐Li , Gui Yong‐Yuan , Yang Jing‐Wei , Zhang Shuo , Yue Jun‐Ping , Zhou Xiangge , Ye Jian‐Heng , Lan Yu , Yu Da‐Gang 
Published: November 2024

AbstractPrecise synthesis of carboxylic acids via catalytic carboxylation with CO2 is highly appealing. Although considerable advancements have been achieved in difunctionalizing carboxylation of unsaturated hydrocarbons, the asymmetric variants are conspicuously underdeveloped, particularly in addressing axially chiral alkenes. Herein, we report the first catalytic atroposelective carboxylation of alkynes with CO2. A variety of valuable axially chiral carboxylic acids are obtained with good yields and high chemo‐, regio‐, Z/E and enantio‐selectivities. Notably, an unexpected anti‐selective carbo‐carboxylation is observed in the sp2‐hybrid carbo‐electrophile‐initiated reductive carboxylation of alkynes. Mechanistic studies including DFT calculation elucidate the origin of chiral induction and anti‐selectivity in vinyl‐carboxylation of alkynes.
Enhanced Coplanarity and Giant Birefringence in Hydroxypyridinium Nitrate via Hydrogen Bonding between Planar Donors and Planar Acceptors
Authors: Yin Jian‐Ping , Guo Jingyu , Huo Hao , Liu Xin , Cheng Xue‐Jie , Lin Zheshuai , Wu Li‐Ming , Chen Ling 
Published: November 2024

AbstractBirefringent crystals, which possess optical anisotropy, are important optical components. However, designing and synthesizing birefringent crystals faces the challenge of achieving anisotropic structures, especially coplanar geometries. Herein, we achieve a significant birefringence in an ionic compound (C5H6ON)+(NO3)−, (4‐hydroxypyridinium nitrate, 4HPN) by hydrogen bonding between planar donors and planar acceptors. We demonstrate that the interactions between the planar hydrogen bond donor ((C5H6ON)+) and planar hydrogen bond acceptor ((NO3)−) ensure the coplanarity during the crystal packing, generating the desired giant optical anisotropy. On two manually cut crystal chips, we observe a
=0.494 (
=0.593), which is the largest among nitrates, or hydroxypyridinium derivatives. This
value already surpasses those of the benchmark crystals, e.g., YVO4 and CaCO3, commonly used in the UV to visible and near IR spectral range. 4HPN also exhibits a strong second harmonic generation response (9.55×KDP). This strategy offers a promising avenue for the design and development of birefringent crystals with potential applications in optical communication, sensing and signal processing devices.
The Perils of Molecular Interpretations from Vibrational Spectra of Complex Samples
Authors: Eissa Tarek , Voronina Liudmila , Huber Marinus , Fleischmann Frank , Žigman Mihaela 
Published: November 2024

AbstractVibrational spectroscopy is a widely used technique for chemical characterizations across various analytical sciences. Its applications are increasingly extending to the analysis of complex samples such as biofluids, providing high‐throughput molecular profiling. While powerful, the technique suffers from an inherent limitation: The overlap of absorption information across different spectral domains hinders the capacity to identify individual molecular substances contributing to measured signals. Despite the awareness of this challenge, the difficulty of analyzing multi‐molecular spectra is often underestimated, leading to unsubstantiated molecular interpretations. Here, we examine the prevalent overreliance on spectral band assignment and illuminate the pitfalls of correlating spectral signals to discrete molecular entities or physiological states without rigorous validation. Focusing on blood‐based infrared spectroscopy, we provide examples illustrating how peak overlap among different substances, relative substance concentrations, and preprocessing steps can lead to erroneous interpretations. We advocate for a viewpoint shift towards a more careful understanding of complex spectra, which shall lead to either accepting their fingerprinting nature and leveraging machine learning analysis – or involving additional measurement modalities for robust molecular interpretations. Aiming to help translate and improve analytical practices within the field, we highlight the limitations of molecular interpretations and feature their viable applications.
Location‐Specific Microenvironment Modulation Around Single‐Atom Metal Sites in Metal–Organic Frameworks for Boosting Catalysis
Authors: Hu Shuaishuai , Huang Jiajia , Gao Ming‐Liang , Lin Zhongyuan , Qian Yunyang , Yang Weijie , Jiao Long , Jiang Hai‐Long 
Published: November 2024

AbstractDespite coordination environment of catalytic metal sites has been recognized to be of great importance in single‐atom catalysts (SACs), a significant challenge remains in the understanding how the location‐specific microenvironment in the higher coordination sphere influences their catalysis. Herein, a series of Cu‐based SACs, namely Cu1/UiO‐66‐X (X=‐NO2, ‐H, and ‐NH2), are successfully constructed by anchoring single Cu atoms onto the Zr‐oxo clusters of metal–organic frameworks (MOFs), i.e., UiO‐66‐X. The ‐X functional groups dangling on the MOF linkers could be regarded as location‐specific remote microenvironment to regulate electronic properties of the single Cu atoms. Remarkably, they exhibit significant differences in the catalysis toward the hydroboration of alkynes. The activity follows the order of Cu1/UiO‐66‐NO2 > Cu1/UiO‐66 > Cu1/UiO‐66‐NH2 under identical reaction conditions, where Cu1/UiO‐66‐NO2 showcases the phenylacetylene conversion of 92 %, ~3.5 times higher efficiency than that of Cu1/UiO‐66‐NH2. Experimental and calculation results jointly support that the Cu electronic structure is modulated by the location‐specific microenvironment, thereby regulating the product desorption and promoting the catalysis.
Confinement Effects and Manipulation Strategies of Nanocomposite Membranes towards Molecular Separation
Authors: Chen Guining , Zhu Haipeng , Liu Guozhen , Liu Gongping , Jin Wanqin 
Published: November 2024

AbstractMaterials featuring well‐defined nanoscale channels offer inherent advantages in the selective transport of gases, liquids, and ions, making them pivotal in applications such as molecular separation, catalysis and energy storage. A crucial challenge lies in assembling ordered nanochannel structures and translating these microscopic architectures into macroscopic regular distributions to enhance performance. Nanocomposites provide a promising solution by incorporating nanoscale material (e.g., filler) that significantly enhances macroscale properties of matrix (e.g., polymer). In this review, we spotlight nanocomposite membranes nanocomposite membranes that utilize confinement effects between filler and matrix to precisely control nanochannel apertures, surface properties, and channel distribution for efficient separation of target systems. We discussed the underlying design principles, channel architectures, and strategies for optimizing polymer‐filler interfaces and nanochannel manipulation within functional membranes. Emphasis is placed on the fundamental mechanisms of mass transport, and the structure‐property‐performance relationships within the nanocomposite membranes towards molecular separation. This work aims to provide a comprehensive understanding of how these nanocomposite membranes can be further developed to meet the demands of industrial and environmental applications.
An active ester‐cured resveratrol‐based epoxy film with excellent thermal and dielectric performances for high‐frequency applications
Authors: Wang Xiang , Zhao Zhixi , Tian Jizhen , Zou Huawei , Liu Pengbo 
Published: November 2024

AbstractIn the field of electronic packaging, epoxy resins with good thermal and dielectric performances have attracted extensive attention. In this work, a novel epoxy resin was synthesized from resveratrol, and its structure was characterized by NMR and FTIR. The resveratrol‐based epoxy resin was cured with an active ester, and the properties of the cured system were further studied. The results showed that the resveratrol‐based epoxy cured with active ester had excellent comprehensive properties, its dielectric constant (Dk) was 2.63, dissipation factor (Df) was 4.91‰ at high frequency of 10 GHz; moreover, its glass transition temperature (Tg) was 188°C, coefficient of thermal expansion (CTE) was 70.7 ppm/°C, 5% mass loss temperature (Td5%) was 390°C. These results suggested that a biomass epoxy resin with excellent thermal and dielectric performances had been successfully synthesized, which had potential application in the field of high‐frequency communication.
High Vulnerability of Rhodolith Bed Frameworks and Underlying Sediment to Ongoing Ocean Climate Change
Authors: Hicks Aidan , Millar Kyle R. , Gagnon Patrick 
Published: November 2024

ABSTRACTRhodoliths are non‐geniculate, free‐living coralline red algae that can accumulate on the seafloor and form structurally complex habitats supporting highly biodiverse communities termed rhodolith beds. Limited understanding of key rhodolith kinetical attributes and how they scale with environmental variability limits ability to predict changes in rhodolith bed distribution and abundance in a globally changing ocean climate. We carried out two experiments in an oscillatory wave tank to test the effects of (1) rhodolith (Boreolithothamnion glaciale) density and wave velocity on rhodolith displacement and abrasion over a hard substratum and (2) rhodolith density on rhodolith displacement and the stability of underlying sediment. We established that on a hard substratum, (1) a threshold wave velocity of ~0.3 m s−1 is required to induce noticeable displacement in average‐sized rhodoliths and (2) rhodolith abrasion increases (quasi‐linearly) with wave velocity up to this threshold. We also showed that (3) for a same rhodolith density, rhodolith displacement is at least two times smaller on a sedimentary than hard substratum and (4) the loss of sediment underneath rhodoliths decreases (quasi‐linearly) with an increase in rhodolith density. Rates documented and strong scaling with changes in water motion and rhodolith density indicate that relatively small changes in the density of rhodoliths or hydrodynamic forces can quickly destabilize rhodolith bed frameworks and underlying sediment. These rates can be used to develop predictive models of change in rhodolith bed distribution and abundance that can in turn inform development of more accurate, science‐based rhodolith bed conservation strategies.
Solvent Dictated Organic Transformations
Authors: Khandelia Tamanna , Panigrahi Pritishree , Ghosh Subhendu , Mandal Raju , Doley Barlina , Patel Bhisma K. 
Published: November 2024

AbstractSolvent plays an important role in many chemical reactions. The C−H activation has been one of the most powerful tools in organic synthesis. These reactions are often assisted by solvents which not only provide a medium for the chemical reactions but also facilitate reaching to the product stage. The solvent helps the reaction profile both chemically and energetically to reach the targeted product. Organic transformations via C−H activation from the solvent assistance perspective has been discussed in this review. Various solvents such as tetrahydrofuran (THF), MeCN, dichloromethane (DCM), dimethoxyethane (DME), 1,2‐dichloroethane (1,2‐DCE), dimethylformamide (DMF), dimethylsulfoxide (DMSO), isopropyl nitrile (iPrCN), 1,4‐dioxane, AcOH, trifluoroacetic acid (TFA), Ac2O, PhCF3, chloroform (CHCl3), H2O, N‐methylpyrrolidone (NMP), acetone, methyl tert‐butyl ether (MTBE), toluene, p‐xylene, alcohols, MeOH, 1,1,1‐trifluoroethanol (TFE), 1,1,1,3,3,3‐hexafluoroisopropanol (HFIP), tert‐amyl alcohol and their roles are discussed. The exclusive role of the solvent in various transformations has been deliberated by highlighting the substrate scope, along with the proposed mechanisms. For easy classification, the review has been divided into three parts: (i) solvent‐switched divergent C−H activation; (ii) C−H bond activation with solvent as the coupling reagent, and (iii) C−H activation with solvent caging and solvent‐assisted electron donor acceptor (EDA) complex formation and autocatalysis.
Evolution of Ultrathin CoFe‐Nanomesh for Oxygen Evolution Reaction: From Slit Pores to Ink‐Bottle Pores
Authors: Sharma Shashank , Paul Amit 
Published: November 2024

AbstractThe time‐dependent mechanism underlying the formation of Co0.8Fe0.2(OH)x‐t nanomesh (nanomesh having 80 % Co and 20 % Fe, “t” represents materials synthesis time) has been identified towards the development of a highly effective catalyst for the oxygen evolution reaction (OER). Utilizing 2‐ethyl imidazole (2‐HEIM) as an etching reagent and the Ostwald ripening process enabled the evolution of nanomesh formation with a precise pore size of ink‐bottle shape. Characterization techniques, including N2‐adsorption/desorption, and transmission electron microscopy (TEM) analyses, confirmed the evolution of pore structure from layered double hydroxide‐like structure to hierarchical slit‐pores to uniform ink‐bottle pores after 24 h of synthesis with limited pore shrinkage attributable to iron redeposition at the pore entrances. Atomic force microscopy (AFM) showed a gradual reduction in nanomesh thickness with an increase in synthesis time up to 24 h, indicative of successful exfoliation. The best catalyst (Co0.8Fe0.2(OH)x‐24 h) was developed after 24 h of synthesis, having 3.8 nm ink‐bottle‐shaped pores on the basal plane of nanosheets with only 3–4 layers. Co0.8Fe0.2(OH)x‐24 h nanomesh exhibited the best catalytic performance, characterized by a 330 mV overpotential, a mass activity of 309.1 A/g, and a turnover frequency of 2.28 s−1. Furthermore, electrochemical impedance spectroscopy indicated a low charge transfer resistance (5.9 Ω) and pseudoresistance (35.3 Ω), highlighting efficient electron transfer at the electrode/electrolyte interface and enhanced oxygen evolution reaction kinetics, respectively. An increased electrochemical surface area (70.74 cm2) and a high roughness factor of approximately 1010 underlined the importance of narrow mesopores in facilitating catalyst‐electrolyte interactions and improving mass transport. The best material demonstrated remarkable stability during 25 h of electrolysis with a high average current density of 14.5 mA/cm2. Hence, this research underscores the critical role of pore morphology in nanomeshes for optimizing catalytic performance and providing stability under vigorous gas evolution due to catalysis.
Simulation von Betonstrukturen mit mineralisch gebundener Carbonfaserbewehrung
Authors: Zernsdorf Kai , Mechtcherine Viktor , Curbach Manfred , Bösche Thomas 
Published: November 2024

AbstractDas Verbundverhalten zwischen Bewehrung und Beton sowie die Betonschädigung sind entscheidend für die Gebrauchstauglichkeit von Bauteilen. Die Prognose von Verformungen, Rissabständen und ‐öffnungen in Strukturen unter Zug‐ und Biegebeanspruchung stellt aufgrund des Schädigungsverhaltens des Betons sowie seines nichtlinearen Verbundverhaltens eine Herausforderung dar. Die Studie ist auf die experimentelle und numerische Untersuchung von Betonstrukturen ausgerichtet, die mit mineralisch gebundenen Carbonfasern (MCF) bewehrt sind. Ziel der Arbeit ist es, numerische Struktur‐ und Materialmodelle zu definieren und zu validieren, die eine präzise Vorhersage des Trag‐, Verformungs‐ und Rissbildungsverhaltens MCF‐bewehrter Bauteile ermöglichen. Im Folgenden werden die eigens durchgeführten experimentellen Dehnkörperversuche sowie der 4‐Punkt‐Biegezugversuch dargelegt. Der Beschreibung der experimentellen Untersuchungen folgen die Definition und die Erläuterung der numerischen Modelle, die in dieser Studie zugrunde gelegt werden. Abschließend werden die Modelle danach bewertet, wie gut sie die experimentellen Versuche wiedergegeben. Durch Definition und Validierung numerischer Struktur‐ und Materialmodelle für MCF‐bewehrte Betonstrukturen sollen die Berechnung und die Bemessung ermöglicht werden, um die Anwendung des innovativen Bewehrungsmaterials in weiteren Bauteilen zu fördern.
Macronutrient interactions and models of obesity: Insights from nutritional geometry
Authors: Wali Jibran A. , Ni Duan , Raubenheimer David , Simpson Stephen J. 
Published: November 2024

AbstractThe global obesity epidemic results from a complex interplay of genetic and environmental factors, with diet being a prominent modifiable element driving weight gain and adiposity. Although excess intake of energetic macronutrients is implicated in causing obesity, ongoing debate centers on whether sugar or fat or both are driving the rising obesity rates. This has led to competing models of obesity such as the “Carbohydrate Insulin Model”, the “Energy Balance Model”, and the “Fructose Survival Hypothesis”. Conflicting evidence from studies designed to focus on individual energetic macronutrients or energy rather than macronutrient mixtures underlies this disagreement. Recent research in humans and animals employing the nutritional geometry framework (NGF) emphasizes the importance of considering interactions among dietary components. Protein interacts with carbohydrates, fats, and dietary energy density to influence both calorie intake (“protein leverage”) and, directly and indirectly, metabolic physiology and adiposity. Consideration of these interactions can help to reconcile different models of obesity, and potentially cast new light on obesity interventions.
Cr3+‐Activated Deep Trap Electron‐Trapping Biphasic Mixture of Zn (Al,Ga)2O4 and Zn2GeO4 for Multilevel Information Storage by Trap Multiplexing and Wavelength Multiplexing
Authors: Wang Zhigang , Wang Jiayu , Gao Dangli , Xu Wenqian , Gao Wenna , Zhang Xiangyu , Yun Sining , Wang Xiaojun 
Published: November 2024

ABSTRACTDouble wavelength emitting phosphors with hypersensitive thermal response are important for optical/thermal sensors and multiplexing optical data storage technology. However, it is a daunting challenge to develop multicolor electron‐trapping materials with superheat sensitivity and anomalous quenching luminescence characteristics for information storage. Here, based on the selection of host lattice and the control of doping ion types, we have designed Mn2+‐ and/or Cr3+‐activated persistent materials with excellent fluorescence properties. Among these phosphors, Mn,Cr co‐activated biphasic mixture exhibits not only sensitive anomalous thermosensitive fluorescence properties but also multicolor and multimode fluorescence emission characteristics derived from Mn and Cr simultaneously. The corresponding multimode fluorescence mechanism is proposed based on afterglow energy transfer and deepening trap effect. Especially, based on the excellent fluorescence performances, these phosphors as information storage medium demonstrate multilevel information storage by a combination of the trap multiplexing and wavelength multiplexing technologies. The study here provides not only the ideas for designing and synthesizing new electronic materials but also a material foundation for the fourth generation of optical information storage and encryption.
Lysosome‐Targeted Bifunctional Fluorescent Probe and Type I/II Photosensitizer for Viscosity Imaging and Cancer Photodynamic Therapy
Authors: Liu Du , An Hongyan , Li Xianglong , Wang Benhua , Zhao Shaojing , Lan Minhuan , Yang Zhanhong , Song Xiangzhi 
Published: November 2024

ABSTRACTAbnormal lysosomal viscosity is closely associated with cancer progression, underscoring the need for bifunctional fluorescent probes and photosensitizers (PSs) that can both monitor viscosity and facilitate imaging‐guided therapy for simultaneous cancer diagnosis and treatment. Despite advances in lysosome‐targeted PSs development, few have demonstrated the ability to generate both Type I and Type II reactive oxygen species (ROS). In this study, we present BTTPA, a lysosome‐targeted fluorescent probe and photosensitizer, designed to integrate cancer diagnosis via viscosity imaging and cancer treatment through photodynamic therapy (PDT). Our findings reveal that BTTPA selectively targets lysosomes, enabling dynamic monitoring of cellular viscosity and distinguishing cancer cells from normal cells. Upon light activation, BTTPA efficiently generates both Type I and Type II ROS. Apoptosis assays further confirm BTTPA's effectiveness in inducing cancer cell apoptosis, highlighting its potential as a powerful tool for cancer diagnosis and therapy.