bluuebunny/crossref_metadata_2025_split huggingface dataset:
Construction of Dihydropyrano[2,3‐c]pyrazolone via Photo‐induced Wolff Rearrangement/Chiral Isothiourea Catalyzed [4+2] Cyclization Reaction
Authors: Zhang Zhou , Shi Siyu , Guo Hai , Shen Zhiqiang , Liu Xia , Huang Jinqi , Yan Wenjin 
Published: August 2024

AbstractA photoinduced Wolff rearrangement/chiral isothiourea catalyzed [4+2] cycloaddition reaction of pyrazolone derivatives and α‐diazoketones was developed, affording the corresponding dihydropyrano[2,3‐c]pyrazolone derivatives in moderate to good yields (50–94 %) with satisfactory to excellent diastereoselectivities (>20 : 1 dr, in almost all cases) and enantioselectivities of 31–99 %. This protocol features readily available substrates, mild reaction conditions, and effective construction of vicinal tertiary and quaternary carbon stereocenters.
Singing in the rain! Climate constraints on the occurrence of indri's song
Authors: Ferrario Valeria , Raimondi Teresa , De Gregorio Chiara , Carugati Filippo , Cristiano Walter , Torti Valeria , Lewis Rebecca N. , Valente Daria , Williams Leah J. , Raisin Claire , Gamba Marco , Von Hardenberg Achaz , Giacoma Cristina 
Published: August 2024

AbstractThe study of how animals adapt their behaviors depending on weather variables has gained particular significance in the context of climate change. This exploration offers insights into endangered species' potential threats and provides information on the direction to take in conservation activities. In this context, noninvasive, cost‐effective, and potentially long‐term monitoring systems, such as Passive Acoustic Monitoring (PAM), become particularly appropriate. Our study investigates the relationship between weather variables and the vocal behavior of Indri indri, the sole singing lemur species, within Madagascar's Maromizaha New Protected Area. Using PAM, we explore the factors shaping the vocalization patterns of this primate species in response to some environmental factors in their natural habitat. Analysis of an extensive audio data set collected across different years revealed the differential influence of temperature and precipitation on Indri indri vocal activity. We found that rainfall negatively influenced the emission of the vocalizations while warmer temperatures correlated with a greater emission of songs. The various environmental factors we considered also affected the timing of vocal emissions, showing the same pattern. Furthermore, our study confirms, once again, the strength of PAM as a valuable tool for studying vocal animal communication quickly, giving us information about long‐term behavioral patterns that would be difficult to get in other ways. This research gives us further valuable information about how indris use vocalizations in their environment and how they adjust to environmental changes.
Educational disparities in brain health and dementia across Latin America and the United States
Authors: Gonzalez‐Gomez Raul , Legaz Agustina , Moguilner Sebastián , Cruzat Josephine , Hernández Hernán , Baez Sandra , Cocchi Rafael , Coronel‐Olivero Carlos , Medel Vicente , Tagliazuchi Enzo , Migeot Joaquín , Ochoa‐Rosales Carolina , Maito Marcelo Adrián , Reyes Pablo , Santamaria Garcia Hernando , Godoy Maria E. , Javandel Shireen , García Adolfo M. , Matallana Diana L. , Avila‐Funes José Alberto , Slachevsky Andrea , Behrens María I. , Custodio Nilton , Cardona Juan F. , Brusco Ignacio L. , Bruno Martín A. , Sosa Ortiz Ana L. , Pina‐Escudero Stefanie D. , Takada Leonel T. , Resende Elisa de Paula França , Valcour Victor , Possin Katherine L. , Okada de Oliveira Maira , Lopera Francisco , Lawlor Brian , Hu Kun , Miller Bruce , Yokoyama Jennifer S. , Gonzalez Campo Cecilia , Ibañez Agustin 
Published: August 2024

AbstractBACKGROUNDEducation influences brain health and dementia. However, its impact across regions, specifically Latin America (LA) and the United States (US), is unknown.METHODSA total of 1412 participants comprising controls, patients with Alzheimer's disease (AD), and frontotemporal lobar degeneration (FTLD) from LA and the US were included. We studied the association of education with brain volume and functional connectivity while controlling for imaging quality and variability, age, sex, total intracranial volume (TIV), and recording type.RESULTSEducation influenced brain measures, explaining 24%–98% of the geographical differences. The educational disparities between LA and the US were associated with gray matter volume and connectivity variations, especially in LA and AD patients. Education emerged as a critical factor in classifying aging and dementia across regions.DISCUSSIONThe results underscore the impact of education on brain structure and function in LA, highlighting the importance of incorporating educational factors into diagnosing, care, and prevention, and emphasizing the need for global diversity in research.Highlights
Lower education was linked to reduced brain volume and connectivity in healthy controls (HCs), Alzheimer's disease (AD), and frontotemporal lobar degeneration (FTLD).
Latin American cohorts have lower educational levels compared to the those in the United States.
Educational disparities majorly drive brain health differences between regions.
Educational differences were significant in both conditions, but more in AD than FTLD.
Education stands as a critical factor in classifying aging and dementia across regions.
Facet‐Dependent Diversity of Pt−O Coordination for Pt1/CeO2 Catalysts Achieved by Oriented Atomic Deposition
Authors: Yan Han , Lei Haofan , Qin Xuetao , Liu Jin‐Cheng , Cai Lihua , Hu Sunpei , Xiao Zizhen , Peng Fenglin , Wang Wei‐Wei , Jin Zhao , Yi Xianfeng , Zheng Anmin , Ma Chao , Jia Chun‐Jiang , Zeng Jie 
Published: August 2024

AbstractThe surface chemistry of CeO2 is dictated by the well‐defined facets, which exert great influence on the supported metal species and the catalytic performance. Here we report Pt1/CeO2 catalysts exhibiting specific structures of Pt−O coordination on different facets by using adequate preparation methods. The simple impregnation method results in Pt−O3 coordination on the predominantly exposed {111} facets, while the photo‐deposition method achieves oriented atomic deposition for Pt−O4 coordination into the “nano‐pocket” structure of {100} facets at the top. Compared to the impregnated Pt1/CeO2 catalyst showing normal redox properties and low‐temperature activity for CO oxidation, the photo‐deposited Pt1/CeO2 exhibits uncustomary strong metal‐support interaction and extraordinary high‐temperature stability. The preparation methods dictate the facet‐dependent diversity of Pt−O coordination, resulting in the further activity‐selectivity trade‐off. By applying specific preparation routes, our work provides an example of disentangling the effects of support facets and coordination environments for nano‐catalysts.
Copper Atom Pairs Stabilize *OCCO Dipole Toward Highly Selective CO2 Electroreduction to C2H4
Authors: Chen Shenghua , Zheng Xiaobo , Zhu Peng , Li Yapeng , Zhuang Zechao , Wu Hangjuan , Zhu Jiexin , Xiao Chunhui , Chen Mingzhao , Wang Pingshan , Wang Dingsheng , He Ya‐Ling 
Published: August 2024

AbstractDeeply electrolytic reduction of carbon dioxide (CO2) to high‐value ethylene (C2H4) is very attractive. However, the sluggish kinetics of C−C coupling seriously results in the low selectivity of CO2 electroreduction to C2H4. Herein, we report a copper‐based polyhedron (Cu2) that features uniformly distributed and atomically precise bi‐Cu units, which can stabilize *OCCO dipole to facilitate the C−C coupling for high selective C2H4 production. The C2H4 faradaic efficiency (FE) reaches 51 % with a current density of 469.4 mA cm−2, much superior to the Cu single site catalyst (Cu SAC) (~0 %). Moreover, the Cu2 catalyst has a higher turnover frequency (TOF, ~520 h−1) compared to Cu nanoparticles (~9.42 h−1) and Cu SAC (~0.87 h−1). In situ characterizations and theoretical calculations revealed that the unique Cu2 structural configuration could optimize the dipole moments and stabilize the *OCCO adsorbate to promote the generation of C2H4.
Vacancy Effect on the Luminescent and Water Responsive Properties of Vacancy‐Ordered Double Perovskite Derivatives
Authors: Wang Zeping , Huang Dandan , Liu Yi , Lin Haowei , Zhang Zhizhuan , Ablez Abdusalam , Zhuang Tinghui , Du Kezhao , Li Jing , Huang Xiaoying 
Published: August 2024

AbstractVacancy‐ordered perovskites and derivatives represent an important subclass of hybrid metal halides with promise in applications including light emitting devices and photovoltaics. Understanding the vacancy‐property relationship is crucial for designing related task‐specific materials, yet research in this field remains sporadic. For the first time, we use the Connolly surface to quantitatively calculate the volume of vacancy (V□, □=vacancy) in vacancy‐ordered double perovskite derivatives (VDPDs). A relationship between void fraction and the structure, photoluminescent properties and humidity stability was established based on zero‐dimensional (0‐D) [N(alkyl)4]2Sb□Cl5□′‐type VDPDs. Compared with the more commonly studied A2M(IV)X6□‐type double perovskite (A=cation, M=metal ion, X=halide), [N(alkyl)4]2Sb□Cl5□′ features double vacancy sites. Our results demonstrate an inverse relationship between the photoluminescent quantum yield and V□ in 0‐D VDPDs. Additionally, structural transformation from A2SbCl5 to A3Sb2Cl9 was first reported, during which the novel ‘gate‐opening’ gas adsorption phenomenon was observed in VDPDs for the first time, as evidenced by ‘S’‐shaped sorption isotherms for water vapor, indicating a cation‐controlled water‐vapor response behavior. A mixed‐cation strategy was developed to modulate the humidity stability of VDPDs. Characterized by controllable water‐responsive behavior and unique ‘on‐off‐on’ luminescent switching, A2M(III)□X5□′‐type materials show great promise for multi‐level information anti‐counterfeiting applications.
Main‐Group Metal‐Nonmetal Dynamic Proton Bridges Enhance Ammonia Electrosynthesis
Authors: Sun Yuntong , Dai Liming , Dong Kai , Sui Nicole L. D. , Li Yinghao , Sun Jingwen , Zeng Jianrong , Fan Wenjun , Tian Meng , Zhu Junwu , Lee Jong‐Min 
Published: August 2024

AbstractThe electrochemical nitrogen reduction reaction (eNRR) is a crucial process for the sustainable production of ammonia (NH3) for energy and agriculture applications. However, the reaction's efficiency is highly dependent on the activation of the inert N≡N bond, which is hindered by the electron back‐donation to the π* orbitals of the N≡N bond, resulting in low eNRR capacity. Herein, we report a main‐group metal‐nonmetal (O−In−S) eNRR catalyst featuring a dynamic proton bridge, with In−S serving as the polarization pair and O functioning as the dynamic electron pool. In situ spectroscopic analysis and theoretical calculations reveal that the In−S polarization pair acts as asymmetric dual‐sites, polarizing the N≡N bond by concurrently back‐donating electrons to both the πx* and πy* orbitals of N2, thereby overcoming the significant band gap limitations, while inhibiting the competitive hydrogen evolution reaction. Meanwhile, the O dynamic electron pool acts as a “repository” for electron storage and donation to the In−S polarization pair. As a result, the O−In−S dynamic proton bridge exhibits exceptional NH3 yield rates and Faradaic efficiencies (FEs) across a wide potential window of 0.3 V, with an optimal NH3 yield rate of 80.07±4.25 μg h−1 mg−1 and an FE of 38.01±2.02 %, outperforming most previously reported catalysts.
Peptide Degrader‐Based Targeting of METTL3/14 Improves Immunotherapy Response in Cutaneous Melanoma
Authors: Han Hong , Li Zenghui , Feng Yuqing , Song He , Fang Zhixiong , Zhang Dingxiao , Yuan Dan , Shi Junfeng 
Published: August 2024

AbstractMETTL3 has emerged as a promising therapeutic target in cancer treatment, although its oncogenic functions in melanoma development and potential for therapeutic targeting drug have not been fully explored. In this study, we define the oncogenic role of METTL3 in melanoma development and progression. Building on this insight, we examine our recently designed peptide inhibitor RM3, which targets the binding interface of METTL3/14 complex for disruption and subsequent ubiquitin‐mediated proteasomal degradation via the E3 ligase STUB1. RM3 treatment reduces proliferation, migration, and invasion, and induces apoptosis in melanoma cells in vitro and in vivo. Subsequent transcriptomic analysis identified changes in immuno‐related genes following RM3‐mediated suppression of METTL3/14 N6‐methyladenosine (m6A) methyltransferase activity, suggesting a potential for interaction with immunotherapy. A combination treatment of RM3 with anti‐PD‐1 antibody results in significantly higher beneficial tumor response in vivo, with a good safety profile. Collectively, these findings not only delineate the oncogenic role of METTL3 in melanoma but also showcase RM3, acting as a peptide degrader, as a novel and promising strategy for melanoma treatment.
Quantifying the Hydration‐Dependent Dynamics of Cu Migration and Activity in Zeolite Omega for the Partial Oxidation of Methane
Authors: Wieser Johannes , Wardecki Dariusz , Fischer Jörg W. A. , Newton Mark A. , Dejoie Catherine , Knorpp Amy J. , Hansen Thomas C. , Jeschke Gunnar , Rzepka Przemyslaw , van Bokhoven Jeroen A. 
Published: August 2024

AbstractCopper‐exchanged zeolite omega (Cu‐omega) is a potent material for the selective conversion of methane‐to‐methanol (MtM) via the oxygen looping approach. However, its performance exhibits substantial variation depending on the operational conditions. Under an isothermal temperature regime, Cu‐omega demonstrates subdued activity below 230 °C, but experiences a remarkable increase in activity at 290 °C. Applying a high‐temperature activation protocol at 450 °C causes a rapid deactivation of the material. This behavioral divergence is investigated by combining reactivity studies, neutron diffraction and in situ high‐resolution anomalous X‐ray powder diffraction (HR‐AXRPD), as well as electron paramagnetic resonance spectroscopy, to reveal that the migration of Cu throughout the framework is the primary cause of these behaviors, which in turn is predominantly governed by the degree of hydration of the system. This work suggests that control over the Cu migration throughout the zeolite framework may be harnessed to significantly increase the activity of Cu‐omega by generating more active sites for the MtM conversion. These results underscore the power of in situ HR‐AXRPD for unraveling the behavior of materials under reaction conditions and suggest that a re‐evaluation of Cu‐zeolites priorly deemed inactive for the MtM conversion across a broader range of conditions and looping protocols may be warranted.
High‐Energy Aqueous S‐MnO2 Batteries with Redox Charge Carriers
Authors: Yang Jinzhang , Bi Songshan , Wang Huimin , Zhang Yanyu , Yan Haoxuan , Niu Zhiqiang 
Published: August 2024

AbstractThe energy densities of conventional aqueous batteries are often unsatisfactory due to the limited capacities of electrode materials. Therefore, the design of creative aqueous batteries has to be considered. Herein, aqueous S‐MnO2 batteries are constructed by matching S/Cu2S redox couples and MnO2 deposition/dissolution. In such batteries, S/Cu2S redox couples undergo the solid‐solid conversion reaction with four‐electron transfer, ensuring a high specific capacity of 2220 mAh g−1 in S anodes. Furthermore, the conversion reaction of S/Cu2S redox couples can take place stably in acidic electrolyte that is essential for the MnO2 deposition/dissolution. As a result, the S/Cu2S redox couples can match MnO2 deposition/dissolution well, which endow the batteries with a membrane‐free configuration. As a proof of concept, Ah‐level prismatic and single‐flow batteries were assembled and could operate stably for over 1000 h, demonstrating their great potential for large‐scale energy storage. This work broadens the horizons of aqueous batteries beyond metal‐manganese chemistry.
Improved Nitrate‐to‐Ammonia Electrocatalysis through Hydrogen Poisoning Effects
Authors: Li Yuefei , Tan Yuan , Zhang Mingkai , Hu Jun , Chen Zhong , Su Laisuo , Li Jiayuan 
Published: August 2024

AbstractElectrochemical conversion from nitrate to ammonia is a key step in sustainable ammonia production. However, it suffers from low productive efficiency or high energy consumption due to a lack of desired electrocatalysts. Here we report nickel cobalt phosphide (NiCoP) catalysts for nitrate‐to‐ammonia electrocatalysis that display a record‐high catalytic current density of −702±7 mA cm−2, ammonia production rate of 5415±26 mmol gcat−1 h−1 and Faraday efficiency of 99.7±0.2 % at −0.3 V vs. RHE, affording the estimated energy consumption as low as 22.7 kWh kgammonia−1. Theoretical and experimental results reveal that these catalysts benefit from hydrogen poisoning effects, which leave behind catalytically inert adsorbed hydrogen species (HI*) at Co‐hollow sites and thereupon enable ideally reactive HII* at secondary Co−P sites. The dimerization between HI* and HII* for H2 evolution is blocked due to the catalytic inertia of HI* thereby the HII* drives nitrate hydrogenation timely. With these catalysts, the continuous ammonia production is further shown in an electrolyser with a real energy consumption of 18.9 kWh kgammonia−1.
Multiple Structural and Phase Transformations of MOF and Selective Hydrocarbon Gas Separation in its Amorphous, Glass Phase States
Authors: Li Jian , Wu Jia‐Xin , Liu Tao , Yang Jian , Wei Mei‐Ling , Yang Chuang , Dong Qiubing , Yin Zheng , Kurmoo Mohamedally , Zeng Ming‐Hua 
Published: August 2024

AbstractThe first wide‐view image of multiple structural and phase transformations for MOFs, ranging from crystal state transformations to the extreme limit approaching liquid/glass phase, was presented. The process involves i) an initial crystalline transformation from square‐layer framework [Co2(pybz)2(CH3COO)2] ⋅ DMF (Co2) to a 3‐fold interpenetrated and ordered vacancies contained framework [Co(pybz)2(CH3OH)2] ⋅ 2CH3OH (CoM) due to in situ disassemble‐reassemble, ii) thermal induced departure of a pair of cis‐form coordinated methanol in CoM leads to amorphous framework a‐dCoM, iii) glass transition to super‐cooled liquid scl‐dCoM, iv) obtaining MOF glass g‐dCoM upon quenching the super‐cooled liquid, and v) re‐crystallization of super‐cooled liquid generates 6‐fold interpenetrated dia‐net framework [Co(pybz)2]6n (rec‐dCoM) under further heating. The access to glass from CoM, provides a new self‐perturbation strategy to create MOF glasses without melting. The wider pore size distribution in amorphous/glassy MOFs than crystalline precursor achieved the first time selective hydrocarbon gas separation by breakthrough experiments, which bring efficient separation of 1 : 99 C2H2/C2H4 by either a‐dCoM or g‐dCoM and produce polymer grade C2H4 with purity≥99.5 % after a single adsorption process. Furthermore, the mixture of 50 : 50 C3H6/C3H8 can be separated by a‐dCoM.
Photo‐BQCA: Positive Allosteric Modulators Enabling Optical Control of the M1 Receptor
Authors: Gerwe Hubert , Schaller Eva , Sortino Rosalba , Opar Ekin , Martínez‐Tambella Joaquín , Bermudez Marcel , Lane J. Robert , Gorostiza Pau , Decker Michael 
Published: August 2024

AbstractThe field of G protein‐coupled receptor (GPCR) research has greatly benefited from the spatiotemporal resolution provided by light controllable, i.e., photoswitchable ligands. Most of the developed tools have targeted the Rhodopsin‐like family (Class A), the largest family of GPCRs. However, to date, all such Class A photoswitchable ligands were designed to act at the orthosteric binding site of these receptors. Herein, we report the development of the first photoswitchable allosteric modulators of Class A GPCRs, designed to target the M1 muscarinic acetylcholine receptor. The presented benzyl quinolone carboxylic acid (BQCA) derivatives, Photo‐BQCisA and Photo‐BQCtrAns, exhibit complementary photopharmacological behavior and allow reversible control of the receptor using light as an external stimulus. This makes them valuable tools to further investigate M1 receptor signaling and a proof of concept for photoswitchable allosteric modulators at Class A receptors.
Enhancing d/p‐2π* Orbitals Hybridization via Strain Engineering for Efficient CO2 Photoreduction
Authors: Zhou Guosheng , Liu Xinlin , Xu Yangrui , Feng Sheng , Lu Ziyang , Liu Zhao‐Qing 
Published: August 2024

AbstractThe photoconversion of CO2 into valuable chemical products using solar energy is a promising strategy to address both energy and environmental challenges. However, the strongly adsorbed CO2 frequently impedes the seamless advancement of the subsequent reaction by significantly increasing the reaction activation energy. Here, we present a BiFeO3 material with lattice strain that collaboratively regulates the d/p‐2π* orbitals hybridization between metal sites and *CO2 as well as *COOH intermediates to achieve rapid conversion of solidly adsorbed CO2 to critical *COOH intermediates, accelerating the overall CO2 reduction kinetics. Quasi in situ X‐ray photoelectron spectroscopy and in situ Fourier Transform infrared spectroscopy combined with theoretical calculation reveals that the optimized Fe sites enhance the adsorption and activation effect of CO2, and continuous internal electrons are rapidly transferred to the reaction sites and injected into the surface *CO2 and *COOH under the condition of illumination, which promotes the rapid formation and stability of *COOH. Certainly, the performance of CO2 photoreduction to CO is improved by 12.81‐fold compared with the base material. This work offers a new perspective for the rapid photoreduction process of strongly adsorbed CO2.
Unconventional Luminescence Polymer with Color‐Tunability based on Solvent‐Induced Electrostatic Potential Distribution of Fluorophore
Authors: He Yanyun , Qiao Yujie , Li Zheng , Feng Weixu , Zhao Yan , Tian Wei , Zhong Tang Ben , Yan Hongxia 
Published: August 2024

AbstractTuning full‐color emission of polymers holds significant promise. However, preparing unconventional luminescence polymers with color‐tunability in dilute solution and understanding the relationship between non‐covalent interactions and luminescent behavior remains a great challenge. We report two emitters (P1 and P2) incorporating tetracoordinate boron. The P1 with non‐conjugated D‐π‐A structure, exhibited red delayed fluorescence at 645 nm with quantum yield of 9.15 % in aggregates. Notably, the emission wavelength of P1 can be tuned from 418 to 588 nm at different solvent. Similarly, the emission wavelength of P2 can also be adjusted by manipulating the interactions between the solvent and fluorophore. Experimental characterization and theoretical calculations indicate that the B←N bond and electronic interactions between solvent and fluorophore significantly regulate the equilibrium the electrostatic potential (ESP) and the intramolecular O⋅⋅⋅O interactions of P1, thereby modulating its emission wavelength. Additionally, these polymers showed excellent potential in fluoride ions detection. This work provides new insights into the complex effects of intermolecular interactions on luminescent properties.