bluuebunny/crossref_metadata_2025_split huggingface dataset:
Addressing a potential weakness in indices of predation, herbivory, and parasitism
Authors: Adams Jean V. 
Published: January 2023

AbstractQuantification of predation, herbivory, and parasitism is critical to understanding the dynamics and trophic interactions of populations in an ecosystem. Such quantification can be challenging if the availability or consumption of the taxa are difficult to assess. Sometimes the consumption of a single prey, forage, or host is used as an overall index of the predation, herbivory, or parasitism for a population of interest. Occasionally, human‐manipulated baits are used to derive similar indices. However, all such indices are susceptible to influence by variation in the abundance of the preferred taxon relative to other taxa as the result of preference switching. In this article, I describe a test for preference switching (and an adjustment, if detected) that does not require availability and consumption of the prey (forage, or host) to be measured on the same scale. The ability to detect and adjust for preference switching in such situations may advance the understanding of biological preference in taxa not previously studied in this respect.
Dosimetric accuracy of the Convolution algorithm for Leksell Gamma Plan radiosurgery treatment planning: Evaluation in the presence of clinically relevant inhomogeneities
Authors: Pantelis Evaggelos , Logothetis Andreas , Zoros Emmanouil , Pappas Eleftherios P. , Papagiannis Panagiotis , Paddick Ian , Nordström Håkan , Kollias George , Karaiskos Pantelis 
Published: January 2023

AbstractPurposeThe Leksell Gamma Plan Convolution algorithm (LGP‐Convolution) has not been widely adopted. This mainly stems from the higher calculated beam‐on times relative to the standard ray tracing‐based LGP‐TMR10 dose calculation algorithm. This study aims to evaluate the accuracy of the LGP‐Convolution in scenarios where the treated lesions are in the vicinity of or encompassed by bone and/or air inhomogeneities.MethodsThe solid water dosimetry phantom provided by the vendor was modified to include bone and air inhomogeneities. Two treatment planning scenarios were investigated involving a single shot and multiple shots, respectively. Treatment planning and dose prescription were performed using the LGP‐Convolution algorithm. Triple channel film dosimetry was performed using GafChromic EBT3 films calibrated in terms of absorbed dose to water in a 60Co beam. Monte Carlo (MC) simulation dosimetry was also performed in the inhomogeneous experimental geometry using the EGSnrc MC platform and a previously validated sector‐based phase‐space source model. MC simulations were also employed to determine correction factors required for converting EBT3 measurements at points within the bone and air inhomogeneities from dose‐to‐water values to the corresponding dose to medium values.Results and ConclusionsEBT3 dose to medium correction factors ranged with field size (4, 8, or 16 mm) within 0.941–0.946 for bone and 0.745–0.749 for air inhomogeneities. An excellent agreement was found between the LGP‐Convolution calculations with corresponding EBT3 and MC dose to medium results at all measurement points, except those located inside the air inhomogeneity. The latter is of no clinical importance and excluding them yielded gamma index passing rates of nearly 100% for 3% local dose difference and 1 mm distance‐to‐agreement criteria. The excellent agreement observed between LGP‐Convolution calculations and film as well as MC results of dose to medium indicates that the latter is the quantity reported by the LGP‐Convolution.
Ligand Coupling and Decoupling Modulates Stem Cell Fate
Authors: Thangam Ramar , Kim Seong Yeol , Kang Nayeon , Hong Hyunsik , Lee Hyun‐Jeong , Lee Sungkyu , Jeong Daun , Tag Kyong‐Ryol , Kim Kanghyeon , Zhu Yangzhi , Sun Wujin , Kim Han‐Jun , Cho Seung‐Woo , Ahn Jae‐Pyoung , Jang Woo Young , Kim Jong Seung , Paulmurugan Ramasamy , Khademhosseini Ali , Kim Hong‐Kyu , Kang Heemin 
Published: January 2023

AbstractIn natural microenvironment, various proteins containing adhesive ligands in fibrous and non‐fibrous structures dynamically couple and decouple to regulate stem cell fate. Herein, materials presenting movably couplable ligands are developed by grafting liganded gold nanoparticles (AuNPs) to a substrate followed by flexibly grafting liganded movable linear nanomaterials (MLNs) to the substrate via a long bendable linker, thereby creating a space between the MLNs and the AuNPs in the decoupled state. Magnetic control of the MLNs decreases this space via the bending of the linker to couple the MLNs to the AuNPs. Remote control of ligand coupling stimulates integrin recruitment to the coupled ligands, thereby non‐toxically facilitating the focal adhesion, mechanosensing, and potential differentiation of stem cells, which is suppressed by ligand decoupling. Versatile tuning of size, aspect ratio, distributions, and ligands of the MLNs can help to decipher dynamic ligand‐coupling‐dependent stem cell fate to advance regenerative therapies.
A General Route for Encapsulating Monodispersed Transition Metal Phosphides into Carbon Multi‐Chambers toward High‐Efficient Lithium‐Ion Storage with Underlying Mechanism Exploration
Authors: Cui Xiang , Chen Jiaxin , Sun Zhefei , Wang Lei , Peng Qianqian , Xiao Bensheng , Zhao Ligong , Zheng He , Wang Yong , Wang Jianbo , Chen Xianfei , Zhang Qiaobao , Chen Shuangqiang 
Published: January 2023

AbstractTransition metal phosphides (MPx) with high theoretical capacities and low cost are regarded as the most promising anodes for lithium‐ion batteries (LIBs), but the large volume variations and sluggish kinetics largely restrict their development. To solve the above challenges, herein a generic but effective method is proposed to encapsulate various monodispersed MPx into flexible carbon multi‐chambers (MPx@NC, MNi, Fe, Co, and Cu, etc.) with pre‐reserved voids, working as anodes for LIBs and markedly boosting the Li+ storage performance. Ni2P@NC, one representative example of MPx@NC anode, shows high reversible capacity (613 mAh g−1, 200 cycles at 0.2 A g−1), and superior cycle stability (475 mAh g−1, 800 cycles at 2 A g−1). Full cell coupled with LiFePO4 displays a high reversible capacity (150.1 mAh g−1 at 0.1 A g−1) with stable cycling performance. In situ X‐ray diffraction and transmission electron microscope techniques confirm the reversible conversion reaction mechanism and robust structural integrity, accounting for enhanced rate and cycling performance. Theoretical calculations reveal the synergistic effect between MPx and carbon shells, which can significantly promote electron transfer and reduce diffusion energy barriers, paving ways to design high‐energy‐density materials for energy storage systems.
New‐Generation Anion‐Pillared Metal–Organic Frameworks with Customized Cages for Highly Efficient CO2 Capture
Authors: Hu Yongqi , Jiang Yunjia , Li Jiahao , Wang Lingyao , Steiner Mathias , Neumann Rodrigo F. , Luan Binquan , Zhang Yuanbin 
Published: January 2023

AbstractThe rational design of porous materials for CO2 capture under realistic process conditions is highly desirable. However, trade‐offs exist among a nanopore's capacity, selectivity, adsorption heat, and stability. In this study, a new generation of anion‐pillared metal‐organic frameworks (MOFs) are reported with customizable cages for benchmark CO2 capture from flue gas. The optimally designed TIFSIX‐Cu‐TPA exhibits a high CO2 capacity, excellent CO2/N2 selectivity, high thermal stability, and chemical stability in acid solution and acidic atmosphere, as well as modest adsorption heat for facile regeneration. Additionally, the practical separation performance of the synthesized MOFs is demonstrated by breakthrough experiments under various process conditions. A highly selective separation is achieved at 298–348 K with the impressive CO2 capacity of 2.1–1.4 mmol g−1. Importantly, the outstanding performance is sustained under high humidity and over ten repeat process cycles. The molecular mechanism of MOF's CO2 adsorption is further investigated in situ by CO2 dosed single crystal structure and theoretical calculations, highlighting two separate binding sites for CO2 in small and large cages featured with high CO2 selectivity and loading, respectively. The simultaneous adsorption of CO2 inside these two types of interconnected cages accounts for the high performance of these newly designed anionic pillar‐caged MOFs.
Ferroptosis: The Entanglement between Traditional Drugs and Nanodrugs in Tumor Therapy
Authors: Liu Kexuan , Huang Lei , Qi Shuangyan , Liu Shuchen , Xie Wangni , Du Liuyi , Cui Jing , Zhang Xu , Zhang Boya , Liu Lijun , Li Daowei , Sun Hongchen 
Published: January 2023

AbstractFerroptosis is a non‐apoptotic programmed cell death caused by the accumulation of lipid peroxide. System Xc‐/glutathione peroxidase 4 (GPX4) axis and iron axis are two main pathways regulating ferroptosis. Simultaneously, multiple pathways are also involved in the ferroptosis regulation. Ferroptosis is an intense area of the current study. With the improvement of the regulatory mechanisms that underlie ferroptosis, a variety of drugs associated with ferroptosis have been discovered and developed for cancer therapy. Among them, traditional drugs were developed initially. Small molecule compounds that regulate ferroptosis signaling pathway and iron complexes that promote the Fenton reaction have become important drugs for inducing ferroptosis. In recent years, the emerging development of nanotechnology has promoted the research of ferroptosis nanodrugs. Iron‐based nanomaterials are extensively tested as ferroptosis‐inducing agents. Furthermore, nanoscale drug delivery systems offer a suitable scaffold for traditional drug therapies. Traditional drugs and nanodrugs are complementary, each with their own strengths and limitations. This review describes the latest studies on the regulation of ferroptosis in tumor cells and focuses on the entanglement between traditional drugs and nanodrugs. To conclude, the challenges and perspectives in this field are put forward.
Moisture‐Enabled Electricity from Hygroscopic Materials: A New Type of Clean Energy
Authors: Xu Tong , Ding Xiaoteng , Cheng Huhu , Han Gaoyi , Qu Liangti 
Published: January 2023

AbstractWater utilization is accompanied with the development of human beings, whereas gaseous moisture is usually regarded as an underexploited resource. The advances of highly efficient hygroscopic materials endow atmospheric water harvesting as an intriguing solution to convert moisture into clean water. The discovery of hygroelectricity, which refers to the charge buildup at a material surface dependent on humidity, and the following moisture‐enabled electric generation (MEG) realizes energy conversion and directly outputs electricity. Much progress has been made since then to optimize MEG performance, pushing forward the applications of MEG into a practical level. Herein, the evolvement and development of MEG are systematically summarized in a chronological order. The optimization strategies of MEG are discussed and comprehensively evaluated. Then, the latest applications of MEG are presented, including high‐performance powering units and self‐powered devices. In the end, a perspective on the future development of MEG is given for inspiring more researchers into this promising area.
Copper‐Catalyzed Olefination of 4‐CF3‐Substituted Cyclohexadienones Using Sulfonylmethyl Isocyanides: An Electrostatic Repulsion‐Controlled Regioselectivity Switch Strategy
Authors: Lee Seungwon , Ahmed Abozeid Mohamed , Young Kim Hun , Oh Kyungsoo 
Published: January 2023

AbstractA Cu(OTf)2‐catalyzed olefination of cyclohexadienones was developed using sulfonylmethyl isocyanides. A CF3 moiety at the 4‐position of cyclohexadienones was shown to exert a pronounced electrostatic repulsion effect to give the olefination products via a preferential [3+2] cycloaddition with the ketone moiety followed by a facile fragmentation of transient oxazoline intermediates. The current Cu(II)‐catalyzed olefination of 4‐CF3‐substituted cyclohexadienones demonstrates the reaction dichotomy involving a CF3‐controlled 1,2‐addition over a Van Leusen 1,4‐addition pathway through the electrostatic repulsion effect.magnified image
Synthesis of o‐Bis(3‐indolyl)arenes under Brønsted Acid Catalysis: Carbonyl Compounds as Sources of Aryl Groups
Authors: Tokunaga Rei , Okusa Takumi , Tsuchimoto Teruhisa 
Published: January 2023

AbstractA method of synthesizing o‐bis(3‐indolyl)arenes was developed by reacting indoles with 7‐oxabicyclo[2.2.1]hept‐5‐en‐2‐one and derivatives thereof having no aromatic ring. All 23 unknown o‐bis(3‐indolyl)arenes could be obtained using this method. Palladium catalysis is useful for enlarging the π‐conjugated area of o‐bis(3‐indolyl)arenes, delivering aryl‐, alkynyl‐, and alkenyl‐unit‐installed o‐bis(3‐indolyl)arenes, and benzo[c]indolo[2,3‐a]carbazoles, the derivatization to which is effective for raising fluorescence quantum yield. A possible reaction mechanism is proposed based on several mechanistic studies.magnified image
Electrochemical Deoxygenative Hydrogenation and Deuteration of Aldehydes/Ketones by Protic Acids in Water
Authors: Sun Zhihui , Ji Ruixue , Wu Jintao , Zhao Jianyou , Fang Fang , Wang Fan , Jiang Chao , Liu Zhong‐Quan 
Published: January 2023

AbstractWe report herein a modified Clemmensen reduction. When reacted with aqueous H(D)Cl in an undivided cell, aliphatic and aromatic aldehydes and ketones undergo deoxygenative hydrogenation and deuterization to give hydrocarbons and deuterocarbons. The general features of this transformation are: 1) H+/D+ as the sources of H/D; 2) mild reaction conditions (room temperature, open flask, CH3CN and water as cosolvent); 3) easily scaled‐up to 100 grams. A series of D‐labeled drugs were synthesized by this method.magnified image
Exploring the effects of weaning age on adult infectious disease mortality among 18th–19th century Italians
Authors: Smith April K. , Reitsema Laurie J. , Fornaciari Antonio , Sineo Luca 
Published: January 2023

AbstractObjectivesThe developmental origins of health and disease (DOHaD) hypothesis describes how early childhood stress affects morbidity and mortality later in life. The role of early childhood stress in mortality from infectious disease is understudied. Stressors in early childhood that weaken the immune system may result in increased susceptibility to infectious disease in adulthood. Weaning is one of the earliest potential periods of significant stress in early childhood. This research investigates the effect of weaning after ~6 months of age on cholera mortality among 18th–19th‐century Italian populations by determining if earlier breastfeeding cessation is associated with earlier mortality, analyzing childhood dietary variation and physiological stress markers, and determining if age‐at‐weaning completion differs between catastrophic and attritional populations.MethodsSerial dentin stable carbon and nitrogen isotope analyses from canines are compared between catastrophic (n = 45) and attritional groups (n = 23). Canines are sectioned serially from crown to apex, and the increment's δ15N and δ13C are used to estimate age‐at‐weaning completion.ResultsCatastrophic and attritional groups exhibit similar age‐at‐weaning completion (~2.8 years). Seventy‐four percent of individuals lack elevated δ15N values in dentin that formed during infancy.ConclusionsAge‐at‐weaning completion was not a predisposing factor in cholera mortality in adulthood in this sample. Age‐at‐weaning completion may not be significantly associated with infectious disease mortality because weaning completion likely occurred after infants had adapted to consuming contaminated weanling foods. Individuals without detectable weaning curves may represent infants who received supplementary foods since birth or were weaned before the age of 6–9 months.
The relationship between objective physical activity and change in cognitive function
Authors: Sewell Kelsey R. , Rainey‐Smith Stephanie R. , Peiffer Jeremiah , Sohrabi Hamid R. , Taddei Kevin , Ames David , Maruff Paul , Masters Colin L. , Rowe Christopher C. , Martins Ralph N. , Erickson Kirk I. , Brown Belinda M. 
Published: January 2023

AbstractIntroductionThe current study investigated the association between objectively measured physical activity and cognition in older adults over approximately 8 years.MethodsWe utilized data from 199 cognitively unimpaired individuals from the Australian Imaging, Biomarkers and Lifestyle (AIBL) study, aged ≥60. Actigraphy was used to measure physical activity (intensity, total activity, and energy expenditure) at baseline. Cognition was assessed using a comprehensive cognitive battery every 18‐months.ResultsHigher baseline energy expenditure predicted better episodic recall memory and global cognition over the follow‐up period (p = 0.031; p = 0.047, respectively). Those with higher physical activity intensity and greater total activity also had better global cognition over time (both p = 0.005). Finally, higher total physical activity predicted improved episodic recall memory over time (p = 0.022).DiscussionThese results suggest that physical activity can preserve cognition and that activity intensity may play an important role in this association.Highlights
Greater total physical activity predicts preserved episodic memory and global cognition.
Moderate intensity physical activity (>3.7 metabolic equivalents of task [MET]) predicts preserved global cognition.
Expending > 373 kilocalories per day may benefit episodic memory and global cognition.
Metal‐Mediated Oligomerization Reactions of the Cyaphide Anion
Authors: Yang Eric S. , Wilson Daniel W. N. , Goicoechea Jose M. 
Published: January 2023

AbstractThe cyaphide anion, CP−, is shown to undergo three distinct oligomerization reactions in the coordination sphere of metals. Reductive coupling of Au(IDipp)(CP) (IDipp=1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene) by Sm(Cp*)2(OEt2) (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl), was found to afford a tetra‐metallic complex containing a 2,3‐diphosphabutadiene‐1,1,4,4‐tetraide fragment. By contrast, non‐reductive dimerization of Ni(SIDipp)(Cp)(CP) (SIDipp=1,3‐bis(2,6‐diisopropylphenyl)‐imidazolidin‐2‐ylidene; Cp=cyclopentadienyl), gives rise to an asymmetric bimetallic complex containing a 1,3‐diphosphacyclobutadiene‐2,4‐diide moiety. Spontaneous trimerization of Sc(Cp*)2(CP) results in the formation of a trimetallic complex containing a 1,3,5‐triphosphabenzene‐2,4,6‐triide fragment. These transformations show that while cyaphido transition metal complexes can be readily accessed using metathesis reactions, many such species are unstable to further oligomerization processes.
Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2O Vapor Sorption
Authors: Azmy Ali , Li Shunran , Angeli Giasemi K. , Welton Claire , Raval Parth , Li Min , Zibouche Nourdine , Wojtas Lukasz , Reddy G. N. Manjunatha , Guo Peijun , Trikalitis Pantelis N. , Spanopoulos Ioannis 
Published: January 2023

AbstractIn this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure‐directing agents and counter‐cations. Reaction of the [2.2.2] cryptand (DHS) linker with PbII in acidic media gave rise to the first porous and water‐stable 2D metal halide semiconductor (DHS)2Pb5Br14. The corresponding material is stable in water for a year, while gas and vapor‐sorption studies revealed that it can selectively and reversibly adsorb H2O and D2O at room temperature (RT). Solid‐state NMR measurements and DFT calculations verified the incorporation of H2O and D2O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half‐maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid‐state batteries) for this class of hybrid semiconductors.
Glycinimin – Das schwer fassbare α‐Iminosäure‐Intermediat bei der Reduktiven Aminierung der Glyoxylsäure
Authors: Paczelt Viktor , Wende Raffael C. , Schreiner Peter R. , Eckhardt André K. 
Published: January 2023

AbstractEinfache ungehinderte Aldimine neigen dazu, zu hydrolysieren oder zu oligomerisieren und sind daher spektroskopisch nicht gut charakterisiert. Wir berichten hier über die Bildung und spektroskopische Charakterisierung der einfachsten Iminosäure, nämlich Glycinimin, mittels kryogener Matrixisolation, IR‐ und UV/Vis‐Spektroskopie. Glycinimin bildet sich nach UV‐Bestrahlung von 2‐Azidoessigsäure durch N2‐Freisetzung in anti‐(E,E)‐ und anti‐(Z,Z)‐Konformationen, die photochemisch ineinander umgewandelt werden können. In Pyrolyseversuchen gekoppelt mit Matrixisolation von 2‐Azidoessigsäure kann Glycinimin nicht isoliert werden, da es weiter zu Aminomethylen decarboxyliert. In wässriger Lösung wird Glycinimin zu Hydroxyglycin und hydratisierter Glyoxylsäure hydrolysiert. Bei höheren Konzentrationen oder in Gegenwart von FeIISO4 als Reduktionsmittel reduziert sich Glycinimin durch oxidative Decarboxylierung selbst. Glycinimin kann als ein Schlüsselintermediat zwischen präbiotischer Aminosäure‐ und Zuckerbildung angesehen werden.
Pressure‐Tuned Multicolor Emission of 2D Lead Halide Perovskites with Ultrahigh Color Purity
Authors: Gao Fei‐Fei , Song Haipeng , Li Zhi‐Gang , Qin Yan , Li Xiang , Yao Zhao‐Quan , Fan Jia‐Hui , Wu Xiang , Li Wei , Bu Xian‐He 
Published: January 2023

AbstractThe chemical diversity and structural flexibility of lead halide perovskites (LHPs) offer tremendous opportunities to tune their optical properties through internal molecular engineering and external stimuli. Herein, we report the wide‐range and ultrapure photoluminescence emissions in a family of homologous 2D LHPs, [MeOPEA]2PbBr4−4xI4x (MeOPEA=4‐methoxyphenethylammonium; x=0, 0.2, 0.425, 0.575, 1) enabled through internal chemical pressure and external hydrostatic pressure. The chemical pressure, induced by the C−H⋅⋅⋅π interactions and halogen doping/substitution strengthens the structural rigidity to give sustained narrow emissions, and regulates the emission energy, respectively. Further manipulation of physical pressure leads to wide‐range emission tuning from 412 to 647 nm in a continuous and reversible manner. This work could open up new pathways for developing 2D LHP emitters with ultra‐wide color gamut and high color purity which are highly useful for pressure sensing.
Concerted and Selective Electrooxidation of Polyethylene‐Terephthalate‐Derived Alcohol to Glycolic Acid at an Industry‐Level Current Density over a Pd−Ni(OH)2 Catalyst
Authors: Liu Fulai , Gao Xutao , Shi Rui , Guo Zhengxiao , Tse Edmund C. M. , Chen Yong 
Published: January 2023

AbstractElectro‐reforming of Polyethylene‐terephthalate‐derived (PET‐derived) ethylene glycol (EG) into fine chemicals and H2 is an ideal solution to address severe plastic pollution. Here, we report the electrooxidation of EG to glycolic acid (GA) with a high Faraday efficiency and selectivity (>85 %) even at an industry‐level current density (600 mA cm−2 at 1.15 V vs. RHE) over a Pd−Ni(OH)2 catalyst. Notably, stable electrolysis over 200 h can be achieved, outperforming all available Pd‐based catalysts. Combined experimental and theoretical results reveal that 1) the OH* generation promoted by Ni(OH)2 plays a critical role in facilitating EG‐to‐GA oxidation and removing poisonous carbonyl species, thereby achieving high activity and stability; 2) Pd with a downshifted d‐band center and the oxophilic Ni can synergistically facilitate the rapid desorption and transfer of GA from the active Pd sites to the inactive Ni sites, avoiding over‐oxidation and thus achieving high selectivity.