bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fe/Al‐LDH Nanomedicine for Antitumor Ferroptosis‐Immunotherapy by Immunosuppression Reversal
Authors: Fang Wenming , Yu Zhiguo , Hu Ping , Shi Jianlin 
Published: May 2024

AbstractFerroptosis is recognized as a novel type of programmed cell death with efficient immunogenicity to activate T cell‐mediated adaptive immune responses. However, conventional ferroptosis‐inducers mostly show poor efficacies due to their less effectiveness in immune regulation. In addition, suppression of T cells by M2‐type macrophages within the tumor microenvironment further weaken the immunotherapeutic effect of ferroptosis. To overcome these challenges, herein, an extremely simple Fe/Al‐layered double hydroxide (Fe/Al‐LDH) nanomedicine of enhanced iron concentration is reported, which is capable of selective degradation in acidic microenvironments to induce tumor cell ferroptosis and in the meantime reversing the immunosuppressive microenvironment by utilizing tumor cell ferroptosis and macrophage M1 polarization to synergistically enhance T cell immune response. This combined strategy has achieved excellent therapeutic efficacy in an orthotopic bilateral breast cancer model, demonstrating the great application potential of Fe/Al‐layered double hydroxide nanoplatform for iron ions‐regulated cancer immunotherapy.
Iridium Cluster Anchored onto Cubic Molybdenum Carbide with Strong Electronic Interactions for Robust Hydrogen Oxidation Reaction in Alkaline Medium
Authors: Han Yuchen , Zhao Lei , Cheng Wen , Wang Mingzhe , Yang Li , Lin Yunxiang , Xu Kun 
Published: May 2024

AbstractConstructing atomic‐scale dispersed noble metal electrocatalysts holds enormous potential toward alkaline hydrogen oxidation reactions (HOR) owing to the high intrinsic activity and atom utilization. Here, this work shows that Ir clusters anchored on different types of molybdenum carbides (Ir/α‐MoC1‐x, Ir/β‐Mo2C) with tunable electronic interactions display distinct performance in alkaline HOR. Notably, the mass activity of Ir/α‐MoC1‐x with stronger electronic interaction is roughly twice that of Ir/β‐Mo2C. Moreover, the Ir/α‐MoC1‐x has reached an impressive mass‐normalized exchange current density (j0, mass) of 320 mA mg−1metal, making the HOR properties are comparable to those recently reported excellent alkaline HOR Ir‐based electrocatalysts. Both experimental and theoretical calculations have confirmed that the strong metal‐substrate interaction of Ir/α‐MoC1‐x via interfacial Ir‐Mo bonding, leading to a significantly modulated electronic structure and optimized binding energy of H* and OH*, thereby promoting the reaction kinetics of alkaline HOR. This work highlights strong metal‐support interactions can be an effective scheme for regulating the local electronic configuration and adsorption behavior of the catalyst along with an improved intrinsic catalytic activity.
Directional Formation of Reactive Oxygen Species Via a Non‐Redox Catalysis Strategy That Bypasses Electron Transfer Process
Authors: Song Junsheng , Hou Nannan , Liu Xiaocheng , Bi Guangyu , Wang Yang , Mu Yang 
Published: May 2024

AbstractA broad range of chemical transformations driven by catalytic processes necessitates the electron transfer between catalyst and substrate. The redox cycle limitation arising from the inequivalent electron donation and acceptance of the involved catalysts, however, generally leads to their deactivation, causing substantial economic losses and environmental risks. Here, a “non‐redox catalysis” strategy is provided, wherein the catalytic units are constructed by atomic Fe and B as dual active sites to create tensile force and electric field, which allows directional self‐decomposition of peroxymonosulfate (PMS) molecules through internal electron transfer to form singlet oxygen, bypassing the need of electron transfer between catalyst and PMS. The proposed catalytic approach with non‐redox cycling of catalyst contributes to excellent stability of the active centers while the generated reactive oxygen species find high efficiency in long‐term catalytic pollutant degradation and selective organic oxidation synthesis in aqueous phase. This work offers a new avenue for directional substrate conversion, which holds promise to advance the design of alternative catalytic pathways for sustainable energy conversion and valuable chemical production.
Novel A–D–A Type Naphthalenediimide Supramolecule for H2O2 Photosynthesis with Solar‐to‐Chemical Conversion 1.03%
Authors: Ji Rong , Dong Yuming , Sun Xinyu , Li Pengken , Zhang Renbao , Pan Chengsi , Zhao Hui , Zhu Yongfa 
Published: May 2024

AbstractOrganic supermolecules have shown great promise for photocatalytic hydrogen peroxide (H2O2) production. However, the limitation of intramolecular charge separation efficiency is still a crucial scientific problem. In this study, a novel acceptor–donor–acceptor (A–D–A) type naphthalenediimide supramolecule (SA‐NDI) is successfully designed for overcoming fundamental issues in organic supermolecule. Composed of one electron‐rich core (naphthalenediimide) and two electron‐poor units (aminopyridine), the supramolecule possesses strong intramolecular charge transfer ability. Meanwhile, the SA‐NDI has an obviously stronger internal electric field, which is 2.83 times higher than that of D–A type supramolecule. The A–D–A type SA‐NDI efficiently accelerates charge separation, so that the intramolecular electron quickly migrates to the acceptor for a two‐electron oxygen reduction reaction. The SA‐NDI supramolecule shows excellent H2O2 accumulation ability (13.7 mm) and stable cyclic time above 120 h. Meanwhile, the catalyst exhibits a superior solar‐to‐chemical conversion efficiency of 1.03% under simulated solar irradiation. This work provides an entirely new idea to design an organic supramolecule with an efficient intramolecular charge transfer monomer.
Forecast combination in agricultural economics: Past, present, and the future
Authors: Ramsey A. Ford , Adjemian Michael K. 
Published: May 2024

AbstractForecasts are common in agricultural settings where they are routinely used for decision‐making. The advent of the computer age has allowed for rapid generation of individual forecasts that can be updated in real time. It is well known that the selection and use of a single forecast can expose the forecaster to serious error as a result of model mis‐specification. Forecast combination avoids this problem by combining information from different forecasts. Although forecast combination can be as simple as averaging across forecasts, advances in machine learning have made it possible to combine forecasts according to more complicated weighting schemes and criteria. We provide an overview of forecast combination techniques, including those at the frontier of current practice and involving machine learning. We also provide a retrospective on the use of forecast combination in agricultural economics and prospects for the future. Several of the techniques are illustrated in an application to forecasting nationwide corn and soybean planted acreage and we demonstrate how forecast combination can improve expert USDA projections.
Comparative effects of legume‐based intercropping systems involving pigeon pea and cowpea under deep‐bed and conventional tillage systems in Malawi
Authors: Phiri Augustine , Njira Keston , Dixon Alan 
Published: May 2024

AbstractLeguminous‐based intercropping, combined with conservation agriculture, is a promising approach to improve soil fertility, crop yields, and sustainable land use for smallholder farmers in sub‐Saharan Africa, including Malawi. This study aimed to assess the effects of incorporating legume‐based intercropping systems involving pigeon pea (Cajanus cajan) and cowpea (Vigna unguiculata) into the deep bed farming (DBF) system promoted by Tiyeni in northern Malawi. The study used a split plot design with cropping systems (CS) as the main plots and tillage systems (TS) as the sub‐plots. All treatments were replicated three times. The study encompassed two cropping seasons, where CS included legume‐based treatments, sole cropped maize (Zea mays) without fertilizer (MZ) and sole cropped maize with 92 kg top dressing N fertilizer per hectare (MZ + 92), while TS included DBF and conventional tillage (CT). The study found that all plots with leguminous crops on both DBF and CT showed higher levels of ammonium (NH4+), nitrate (NO3−) and phosphorus (P) in the soil, but DBF had significantly higher levels over 2 years. Intercropping systems showed higher land productivity (land equivalent ratio > 1) than sole cropping in both years, indicating that legume‐based cropping can improve land use efficiency and yields. It can be noted from this study that intercropping systems based on cereals and legumes, implemented in DBF, has the potential to sustain agricultural intensification in sub‐Saharan African countries where access to chemical fertilizers is limited among smallholder farmers.
Chaos and mixing in NETmix
Authors: Matos Joana , Santos Ricardo J. , Dias Madalena M. , Lopes José Carlos B. 
Published: May 2024

AbstractNETmix is a network of mixing chambers interconnected by channels, in which the most efficient mixing occurs under chaotic flow regimes. Chaos is highly influenced by the topology, particularly by the ratio chamber diameter/channel width, D/d. In this work, micromixing in NETmix is characterized through Lagrangian Mixing Simulation (LMS), which enables to establish the relation between the degree of mixing and the topology, D/d. The degree of mixing is then related with the Eulerian chaoticity from hydrodynamics and spectral analysis. The best mixing is obtained at D/d = 6.65 and is associated to a thin 8 shaped strange attractor. The spectral analysis shows a principal oscillation frequency at St = 0.13. Since the quasi‐periodic regime is alternated with chaotic behavior, NETmix has an intermittent bifurcation. For the NETmix system, orderly flows in the quasi‐periodic regime have higher mixing intensity than less orderly flows in the weak or strong chaotic regimes.
Energy‐Efficient Co‐production of Benzoquinone and H2 Using Waste Phenol in a Hybrid Alkali/Acid Flow Cell
Authors: He Chengchao , Pan Duo , Chen Kai , Chen Junxiang , Zhang Qinlong , Zhang Hao , Zhang Zhifang , Wen Zhenhai 
Published: May 2024

AbstractIn both the manufacturing and chemical industries, benzoquinone is a crucial chemical product. A perfect and economical method for making benzoquinone is the electrochemical oxidation of phenol, thanks to the traditional thermal catalytic oxidation of phenol process requires high cost, serious pollution and harsh reaction conditions. Here, a unique heterostructure electrocatalyst on nickel foam (NF) consisting of nickel sulfide and nickel oxide (Ni9S8‐Ni15O16/NF) was produced, and this catalyst exhibited a low overpotential (1.35 V vs. RHE) and prominent selectivity (99 %) for electrochemical phenol oxidation reaction (EOP). Ni9S8‐Ni15O16/NF is beneficial for lowering the reaction energy barrier and boosting reactivity in the EOP process according to density functional theory (DFT) calculations. Additionally, an alkali/acid hybrid flow cell was successfully established by connecting Ni9S8‐Ni15O16/NF and commercial RuIr/Ti in series to catalyze phenol oxidation in an alkaline medium and hydrogen evolution in an acid medium, respectively. A cell voltage of only 0.60 V was applied to produce a current density of 10 mA cm−2. Meanwhile, the system continued to operate at 0.90 V for 12 days, showing remarkable long‐term stability. The unique configuration of the acid‐base hybrid flow cell electrolyzer provides valuable guidance for the efficient and environmentally friendly electrooxidation of phenol to benzoquinone.
Multiple‐State Control over Supramolecular Chirality through Dynamic Chemistry Mediated Molecular Engineering
Authors: Wang Zhuoer , Xie Xufeng , Hao Aiyou , Xing Pengyao 
Published: May 2024

AbstractDynamic chemistry utilizing both covalent and noncovalent bonds provides valid protocols in manipulating properties of self‐assemblies and functions. Here we employ dynamic chemistry to realize multiple‐route control over supramolecular chirality up to five states. N‐protected fluorinated phenylalanine in the carboxylate state self‐assembled into achiral nanoparticles ascribed to the amphiphilicity. Protonation promoted one‐dimensional growth into helices with shrunk hydrophilicity, which in the presence of disulfide pyridine undergo chirality inversion promoted by the hydrogen bonding‐directed coassembly. Further interacting with the water‐soluble reductant cleavages the disulfide bond to initiate the rearrangement of coassemblies with a chirality inversion as well. Finally, by tuning the pH environments, aromatic nucleophilic substitution reaction between reduced products and perfluorinated phenylalanine occurs, giving distinct chiral nanoarchitectures with emerged luminescence and circularly polarized luminescence. We thus realized a particular five‐state control by combining dynamic chemistry at one chiral compound, which greatly enriches the toolbox in fabricating responsive chiroptical materials.
Electrocatalytic Transfer Hydrogenation of 1‐Octene with [(tBuPCP)Ir(H)(Cl)] and Water
Authors: Mollik Patrick , Drees Markus , Frantz Alexander M. , Halter Dominik P. 
Published: May 2024

AbstractElectrocatalytic hydrogenation of 1‐octene as non‐activated model substrate with neutral water as H‐donor is reported, using [(tBuPCP)Ir(H)(Cl)] (1) as the catalyst, to form octane with high faradaic efficiency (FE) of 96 % and a kobs of 87 s−1. Cyclic voltammetry with 1 revealed that two subsequent reductions trigger the elimination of Cl− and afford the highly reactive anionic Ir(I) hydride complex [(tBuPCP)Ir(H)]− (2), a previously merely proposed intermediate for which we now report first experimental data by mass spectrometry. In absence of alkene, the stoichiometric electrolysis of 1 in THF with water selectively affords the Ir(III) dihydride complex [(tBuPCP)Ir(H)2] (3) in 88 % FE from the reaction of 2 with H2O. Complex 3 then hydrogenates the alkene in classical fashion. The presented electro‐hydrogenation works with extremely high FE, because the iridium hydrides are water stable, which prevents H2 formation. Even in strongly alkaline conditions (Bu4NOH added), the electro‐hydrogenation of 1‐octene with 1 also proceeds cleanly (89 % FE), suggesting a highly robust process that may rely on H2O activation, reminiscent to transfer hydrogenation pathways, instead of classical H+ reduction. DFT calculations confirmed oxidative addition of H2O as a key step in this context.
Bridged Pt−OH−Mn Mediator in N‐coordinated Mn Single Atoms and Pt Nanoparticles for Electrochemical Biomolecule Oxidation and Discrimination
Authors: Wei Xiaoqian , Lin Yanjuan , Wu Zhenwei , Qiu Yiwei , Tang Yinjun , Eguchi Miharu , Asahi Toru , Yamauchi Yusuke , Zhu Chengzhou 
Published: May 2024

AbstractThe rational design of efficient catalysts for uric acid (UA) electrooxidation, as well as the establishment of structure‐activity relationships, remains a critical bottleneck in the field of electrochemical sensing. To address these challenges, herein, a hybrid catalyst that integrates carbon‐supported Pt nanoparticles and nitrogen‐coordinated Mn single atoms (PtNPs/MnNC) is developed. The metal‐metal interaction during annealing affords the construction of metallic‐bonded Pt−Mn pairs between PtNPs and Mn single atoms, facilitating the electron transfer from PtNPs to the support and thereby optimizing the electronic structure of catalysts. More importantly, experiments and theoretical calculations provide visual proof for the ‘incipient hydrous oxide adatom mediator’ mechanism for UA oxidation. The Pt−Mn pairs first adsorb OH* to construct the bridged Pt−OH−Mn mediators to serve as a highly active intermediate for N−H bond dissociation and proton transfer. Benefiting from the unique electronic and geometric structure of the catalytic center and reactive intermediates, PtNPs/MnNC exhibits superior electrooxidation performance. The electrochemical sensor based on PtNPs/MnNC enables sensitive detection and discrimination of UA and dopamine in serum samples. This work offers new insights into the construction of novel electrocatalysts for sensitive sensing platforms.
A strategy for successful dual‐species protein expression of genes with non‐optimal codon usage destined for bacterial and yeast cell factories
Authors: Wäneskog Marcus , Rasmussen Trine Bertram , Jensen Emil D. 
Published: May 2024

AbstractRecombinant protein expression on an industrial scale traditionally utilizes one of two microbial workhorses: Escherichia coli or Saccharomyces cerevisiae. Additionally, random protein engineering of enzymes and proteins aimed for expression in S. cerevisiae are often mutagenized and pre‐screened in E. coli before expression in yeast. This introduces artificial bottlenecks as the bacterial expression vector needs to be substituted for a yeast expression vector via sub‐cloning, and the new library re‐evaluated before a final screening in yeast. Here, we put forward a protein expression and engineering strategy that involves the use of a dual‐host shuttle vector (pYB‐Dual) designed with both a strong inducible yeast promoter (pGAL1), and a strong inducible bacterial promoter (pT7‐RNAP), which allows for inducible protein expression in both species. Additionally, we demonstrate that by transforming the pYB‐Dual vector into the E. coli strain Rosetta 2, which has elevated levels of 7 rare tRNAs, we can achieve high‐level protein expression in both yeast and bacteria, even when using a mNeonGreen gene codon optimized for yeast. This dual expression vector is expected to remove bottlenecks during protein engineering of commercially important enzymes destined for high‐titer expression in yeast.
POST: Prototype‐oriented similarity transfer framework for cross‐domain facial expression recognition
Authors: Guo Zhe , Wei Bingxin , Cai Qinglin , Liu Jiayi , Wang Yi 
Published: May 2024

AbstractFacial expression recognition (FER) is one of the popular research topics in computer vision. Most deep learning expression recognition methods perform well on a single dataset, but may struggle in cross‐domain FER applications when applied to different datasets. FER under cross‐dataset also suffers from difficulties such as feature distribution deviation and discriminator degradation. To address these issues, we propose a prototype‐oriented similarity transfer framework (POST) for cross‐domain FER. The bidirectional cross‐attention Swin Transformer (BCS Transformer) module is designed to aggregate local facial feature similarities across different domains, enabling the extraction of relevant cross‐domain features. The dual learnable category prototypes is designed to represent potential space samples for both source and target domains, ensuring enhanced domain alignment by leveraging both cross‐domain and specific domain features. We further introduce the self‐training resampling (STR) strategy to enhance similarity transfer. The experimental results with the RAF‐DB dataset as the source domain and the CK+, FER2013, JAFFE and SFEW 2.0 datasets as the target domains, show that our approach achieves much higher performance than the state‐of‐the‐art cross‐domain FER methods.
A Highly Sensitive and Selective Fluorescent Sensor for Folic Acid Detection Based on D‐penicillamine Stabilized Ag/Cu Alloy Nanoclusters
Authors: Mei Zhang Sai , Xue Dong Jiang , Li Wu Xiao , Sen Zhao Yong , Lei Li Yan , Lin Wang Shou , Yang Yang , An Miao , Su Ming , Ya Shi Rong , Feng Gao Zhong 
Published: May 2024

AbstractIn this work, a highly sensitive and selective method for detecting folic acid (FA) was developed using D‐penicillamine (DPA) stabilized Ag/Cu alloy nanoclusters (DPA@Ag/Cu NCs). The yellow emission of DPA@Ag/Cu NCs was found to be quenched upon the addition of FA to the system. The fluorescence intensity quenching value demonstrated a linear relationship with FA concentrations ranging from 0.01 to 1200 μM, with a limit of detection (LOD) of 5.3 nM. Furthermore, the detection mechanism was investigated through various characterization analyses, including high resolution transmission electron microscopy, fluorescence spectra, ultraviolet‐visible absorption spectra, and fluorescence lifetime. The results indicated that the fluorescence quenching induced by FA was a result of electron transfer from FA to the ligands of DPA@Ag/Cu NCs. The selectivity of the FA sensor was also evaluated, showing that common amino acids and inorganic ions had minimal impact on the detection of FA. Moreover, the standard addition method was successfully applied to detect FA in human serum, chewable tablets and FA tablets with promising results. The use of DPA@Ag/Cu NCs demonstrates significant potential for detecting FA in complex biological samples.
Advances in Aluminophosphates for Catalytic Upgrading of Lignocellulose and Derived Compounds
Authors: Fang Wenting , Riisager Anders 
Published: May 2024

AbstractUtilization of lignocellulosic biomass as a renewable resource to produce liquid fuels/fuel additives and commodity chemicals offer solutions to minimize the exhaustion of nonrenewable carbon‐based fossil resources and mitigate environmental problems. Cellulose and hemicellulose derived from lignocellulose can be converted into several important platform molecules like glucose, fructose, xylose, 5‐hydroxymethylfurfural, furfural, levulinic acid, etc., which subsequently can be transformed into fuels/fuel additives and value‐added chemicals using heterogeneous catalytic processes. Aluminophosphates (AlPO‐n) are zeotype materials with tunable physicochemical properties like acidity and porosity, and this have promoted their wide use as versatile catalysts for several acid‐catalyzed reactions, including hydrolysis, dehydration, isomerization, transfer hydrogenation, reductive etherification, acetalization and aldol condensation. This review summarizes the design and synthetic advances of AlPO‐n catalysts as well as their application in the valorization of lignocellulose and derivatives to platform chemicals and fuel compounds. Perspectives for future design strategies are finally outlined.
Dynamics of electron capture in positron‐hydrogen scattering under dense semi‐classical plasmas
Authors: Das Kamalika , Das Netai , Ghoshal Arijit 
Published: May 2024

AbstractThe scattering dynamics of electron capture in ‐H(1 s) scattering under dense semi‐classical plasma (DSCP) environments has been investigated theoretically. Coupled multi‐channel two‐body Lippmann‐Schwinger equations have been solved by retaining +H(1 s) and p + Ps(1 s) channels to calculate the cross sections (CS) of the electron capture process at intermediate and high incident energies. The effective interaction of the plasma charged particles is modelled by a pseudopotential which is a function of two parameters, namely the plasma screening strength and the de Broglie wavelength. A detailed study is made to explore the changes in the CSs of the above‐mentioned process with respect to the variation in the plasma screening strength and de Broglie wavelength. Significant changes are found to take place, when the screening strength and the de Broglie wavelength are varied. Specifically, the sharp minimum in the differential CS moves toward the forward direction with increasing de Broglie wavelength at a given screening strength.