bluuebunny/crossref_metadata_2025_split huggingface dataset:
AI‐enabled blockchain and SDN‐integrated IoT security architecture for cyber‐physical systems
Authors: Wang Sen , Zhang Jie , Zhang Tianhui 
Published: April 2023

AbstractTo address the IoT security problem, in this paper we propose and evaluate the DDoS attack mitigation method based on blockchain, and construct a DDoS abnormal information detection and sharing model. The obtained experimental results show that when the number of decision trees increases, the training time of the DDoS attack detection model based on the RF model grows with a minimum trend of 14 s. The testing time is finally maintained at 1 s, and the recognition accuracy of DDoS attacks keeps improving, ultimately reaching over 99.8%. If the amount of DDoS abnormal traffic information exceeds 100 pieces and 2000 pieces, it only takes 0.1 and 5 s to sign the DDoS abnormal traffic information using ECDSA algorithm digitally. The signature verification only takes 0.1 and 9 s, respectively. And compared to conventional network physical system IoT security architecture, a network physical system IoT security architecture that integrates AI empowerment, blockchain, and SDN integration has a higher joint defense success rate. It can be explained that this scheme will be conducive to promoting joint defense against DDoS attacks and ensuring the security of the Internet of Things.
Regulating Intramolecular Charge Transfer and Resonance Effects to Realize Ultrawide Bandgap Conjugated Polymer for High‐Performance All‐Polymer Solar Cells
Authors: Zhang Shuai , Cai Mian , Shang Chenyu , Bi Fuzhen , Feng Fan , Du Zhengkun , Sun Cheng , Li Yonghai , Bao Xichang 
Published: April 2023

AbstractAll‐polymer solar cells (APSCs) have attracted increasing attention due to the superior stability and mechanical flexibility. However, power conversion efficiencies (PCEs) of APSCs fall behind ascribed to limited efficient polymer donors (PDs). Particularly, there are rare reports of high‐performance PDs with ultrawide bandgaps, which are indispensable to maximally harvest high‐energy photons for better light utilization. Herein, the significance of intramolecular charge transfer and quinoid resonance effects in regulating bandgaps of donor‐acceptor conjugated materials is highlighted, and a novel polymer donor PBPD based on phenyl/pyridyl fused phenanthridine (PD) moiety is reported. Consequently, PBPD receives an ultrawide optical bandgap up to 2.24 eV and strong absorptivity at 487–523 nm, which exactly follows the strongest radiation of solar spectrum. The amplified light utilization of high‐energy photons endows PBPD:PY‐IT based APSCs with high power conversion efficiency of 15.29%, which ranks the best among APSCs with ultrawide bandgap PDs and challenges typical PDs with bandgaps of ≈1.80 eV. Thanks to the unique light responses and molecular orientations of PBPD, the PBPD‐contained ternary APSCs receive further optimized photon utilization and refined PCEs over 17%. This study sheds light on the design principles of ultrawide bandgap polymers and demonstrates the great promise of large bandgap PDs for efficient APSCs.
Graphene‐Enhanced Metal Transfer Printing for Strong van der Waals Contacts between 3D Metals and 2D Semiconductors
Authors: Qi Dianyu , Li Peng , Ou Haohui , Wu Di , Lian Weiguang , Wang Zhuo , Ouyang Fangping , Chai Yang , Zhang Wenjing 
Published: April 2023

Abstract2D semiconductors have shown great potentials for ultra‐short channel field‐effect transistors (FETs) in next‐generation electronics. However, because of intractable surface states and interface barriers, it is challenging to realize high‐quality contacts with low contact resistances for both p‐ and n‐ 2D FETs. Here, a graphene‐enhanced van der Waals (vdWs) integration approach is demonstrated, which is a multi‐scale (nanometer to centimeter scale) and reliable (≈100% yield) metal transfer strategy applicable to various metals and 2D semiconductors. Scanning transmission electron microscopy imaging shows that 2D/2D/3D semiconductor/graphene/metal interfaces are atomically flat, ultraclean, and defect‐free. First principles calculations indicate that the sandwiched graphene monolayer can eliminate gap states induced by 3D metals in 2D semiconductors. Through this approach, Schottky barrier‐free contacts are realized on both p‐ and n‐type 2D FETs, achieving p‐type MoTe2, p‐type black phosphorus and n‐type MoS2 FETs with on‐state current densities of 404, 1520, and 761 µA µm−1, respectively, which are among the highest values reported in literature.
Near‐Infrared‐I to III Absorption and Emission via Core Engineering of Open‐Shelled Organic Mixed‐Valence Systems
Authors: Song Qiuyan , Xu Manman , Zhang Baoli , He Mingxu , Guo Xindong , Nie Jun , Xing Yue , Liang Xiubing , Chang Yincheng 
Published: April 2023

AbstractA novel class of agents is developed based on the core engineering of open‐shelled organic mixed‐valence (MV) systems, which enable tunable absorption and emission across the near infrared (NIR)‐I to III biowindow (700–1850 nm) by adjusting the number of central nitrogen oxidation sites and the length of the conjugated bridge. Organic mixed‐valence (MV) systems are synthesized through a one‐step partial chemical oxidation of starburst oligoarylamines, with varying nitrogen oxidation sites and conjugated bridge lengths, including tris(4‐[diethylamino]phenyl)aminen+ (T4EPAn+), N,N,N',N'‐tetrakis(4‐[diisobutylamino]phenyl)‐1,4‐phenylenediaminen+ (TPDAn+), and N,N,N',N'‐tetrakis(4‐methoxyphenyl)benzidinen+ (TMPBn+). The absorption wavelength of the MV systems redshifted clearly as the number of central nitrogen oxidation sites increased or the conjugated bridge length is prolonged. T4EPAn+ with one central nitrogen oxidation site exhibits fluorescence emission in the range of 900–1400 nm, while TPDAn+ with two central nitrogen oxidation sites demonstrate strong heat generation capabilities. Additionally, the absorption peak of TMPBn+ with a biphenyl conjugated bridge reaches up to 1610 nm. Especially, these MV systems are highly stable for biological applications due to their high steric hindrance and hyperconjugation effect. These characteristics make MV systems promising candidates for constructing NIR‐I/II/III emitters and photothermal agents, representing a significant advance toward developing the next generation of NIR‐I to III agents.
Improving Electrocatalytic Nitrogen Reduction Selectivity and Yield by Suppressing Hydrogen Evolution Reaction via Electronic Metal–Support Interaction
Authors: Xie Mingsen , Dai Fangfang , Guo Huixia , Du Peiyao , Xu Xinru , Liu Jia , Zhang Zhen , Lu Xiaoquan 
Published: April 2023

AbstractThe electrochemical nitrogen reduction reaction (NRR) has the potential to replace the Haber–Bosch process for ammonia synthesis under ambient conditions. However, the selectivity and yield of the NRR are impractical, owing to the preferential binding of the electrocatalyst to H and the consequential coverage of active sites. In this study, VO2, with N2 strongly adsorbed over H atoms, is used as a support to provide a N2 source to avoid the hydrogen evolution reaction. Mo, with a high NRR activity, is introduced as the active site to promote the NRR. Meanwhile, the electronic metal–support interaction between the support and Mo creates electron‐deficient sites, which weakens H adsorption and lowers the energy barrier of the first step, protonation, thereby kinetically enhancing the NRR activity. The average NH3 yield of Mo/VO2 is 190.1 µgNH3 mgcat.−1 h−1 and the Faradaic efficiency is 32.4% at −0.5 V versus reversible hydrogen electrode, which is 10.8 and 2.8 times greater than that of VO2, respectively.
High‐rate CO2‐to‐CH4 Electrosynthesis by Undercoordinated Cu Sites in Alkaline‐Earth‐Metal Perovskites with Strong Basicity
Authors: Xu Zikai , Peng Chen , Luo Gan , Yang Songtao , Yu Pinger , Yan Shuai , Shakouri Mohsen , Wang Zhiqiang , Sham Tsun‐Kong , Zheng Gengfeng 
Published: April 2023

AbstractThe electrochemical CO2 reduction to CH4 has been extensively demonstrated, but still suffers from relatively poor activity and requires high overpotentials especially at large electrolysis rates. Perovskite oxides (AxByO) are one type of promising electrocatalyst for the CO2 reduction due to their tunable electronic structures. In this work, a Ca2CuO3 perovskite oxide catalyst is developed with alkaline‐earth A‐sites, featuring an inherently strong basic strengthand outstanding capability for CO2 adsorption, as well as the undercoordinated Cu sites generated through partial surface Ca2+ cation leaching. The Ca2CuO3 catalyst exhibitsa high partial current density of 517 ± 23 mA cm−2 for producing CH4 at a low applied potential of −0.30 V versus reversible hydrogen electrode, which further reached to a peak value of 1452 ± 156 mA cm−2. Density functional calculations show that the undercoordinated Cu sites allowed to promote the hydrogenation of *CO and subsequent *CHO intermediates, thus leading to the high CH4 activity. This work suggests an attractive design strategy for tuning the A‐sites in perovskite oxides to realize high‐rate CO2‐to‐CH4 electrosynthesis with low overpotentials.
Decade Advances of NaN3 in Three‐component Reactions
Authors: Wang Zhan‐Yong , Li Jiarong , Wang Nan , Liu Hong , Wang Kai‐Kai 
Published: April 2023

AbstractDecade advances of sodium azide (2011–2022) have been summarized via mechanisms and target products. Sodium azide is commonly used as a nucleophile (N3−) or radical source (⋅N3) in three‐component reactions. It's reactions with alkenes, alkynes, R−X (X=F, Cl, Br, I, OTs, B(OH)2, BF3K, I+ArO−Tf, N2+O−SO3‐SiO2) and other electrophiles will be discussed.
Attributions for underachievement among students experiencing disadvantage and support for public assistance to them
Authors: Lee Jung‐Sook , Lee Jihyun , Stacey Meghan 
Published: April 2023

AbstractIn this study, we investigated people's perceptions about the causes (i.e. attributions) of underachievement among students experiencing socioeconomic disadvantage and their support for public assistance to those students. Results of an online survey conducted with Australian adults (N = 1999) revealed that people preferred societal attributions to individual attributions for underachievement among those students. The respondents' attributions, particularly societal attributions, significantly predicted their support for public assistance to students and schools in need. There were statistically significant differences between people with conservative and progressive political views in their attributions and support for public assistance. However, after taking people's attributions into account, their political views add little to the prediction of their support for public assistance. These findings have implications for the promotion of equity‐oriented educational policies.
A detection model for cognitive dysfunction based on volatile organic compounds from a large Chinese community cohort
Authors: Jiao Bin , Zhang Sizhe , Bei Yuzhang , Bu Guiwen , Yuan Li , Zhu Yuan , Yang Qijie , Xu Tianyan , Zhou Lu , Liu Qianqian , Ouyang Ziyu , Yang Xuan , Feng Yong , Tang Beisha , Chen Haibin , Shen Lu 
Published: April 2023

AbstractIntroductionWe explored whether volatile organic compound (VOC) detection can serve as a screening tool to distinguish cognitive dysfunction (CD) from cognitively normal (CN) individuals.MethodsThe cognitive function of 1467 participants was assessed and their VOCs were detected. Six machine learning algorithms were conducted and the performance was determined. The plasma neurofilament light chain (NfL) was measured.ResultsDistinguished VOC patterns existed between CD and CN groups. The CD detection model showed good accuracy with an area under the receiver‐operating characteristic curve (AUC) of 0.876. In addition, we found that 10 VOC ions showed significant differences between CD and CN individuals (p < 0.05); three VOCs were significantly related to plasma NfL (p < 0.005). Moreover, a combination of VOCs with NfL showed the best discriminating power (AUC = 0.877).DiscussionDetection of VOCs from exhaled breath samples has the potential to provide a novel solution for the dilemma of CD screening.
Targeted Synthesis of a Highly Stable Aluminium Phosphonate Metal–Organic Framework Showing Reversible HCl Adsorption
Authors: Reichenau Timm M. , Steinke Felix , Wharmby Michael T. , Näther Christian , Engesser Tobias A. , Stock Norbert 
Published: April 2023

AbstractA concept for obtaining isoreticular compounds with tri‐ instead of tetravalent metal cations using highly acidic reaction conditions was developed and successfully applied in a high throughput study using N,N′‐piperazinebis(methylenephosphonic acid) (H4PMP), that resulted in the discovery of a new porous aluminium phosphonate denoted CAU‐60⋅6 HCl. The high‐throughput study was subsequently extended to other trivalent metal ions. Al‐CAU‐60⋅6 HCl demonstrates reversible desorption of HCl (18.3 wt % loading) with three distinct compositions observed with zero, four or six HCl molecules per formula unit. Structural changes were followed in detail by powder X‐ray diffraction, EDX analysis as well as IR spectroscopy. Rapid desorption of HCl in water within minutes and subsequent adsorption from the gas phase and from aqueous solution are shown. Furthermore, it is possible to adsorb HBr into the guest free Al‐CAU‐60 framework, demonstrating the high stability of this compound.
Induction of Chirality on Nanographenes
Authors: Arimura Saki , Matsumoto Ikuya , Nishitani Shohei , Sekiya Ryo , Haino Takeharu 
Published: April 2023

AbstractChirality induction is an important topic in studies of nanographenes (NGs). We report chirality enhancements of NGs through postsynthetic chemical modifications of NGs with pyrene and m‐terphenyl groups. These substituents were installed into N‐(p‐bromophenylethyl)imides on the edges of the NGs with Pd‐catalyzed cross‐coupling reactions. Circular dichroism (CD) spectra demonstrated that these bulky substituents improved the induced CD signal of the NGs compared to those previously reported and suggested that they induced the opposite chirality. Density functional theory calculations indicated possible edge structures for the NGs and indicated that π/π and CH/π interactions among the neighboring substituents influenced the orientations of the imides. These imides distorted the edges, and the distorted edges eventually generated the chiral environments of the NGs. The interactions among the substituents are, therefore, likely to allow detection of the CD signals in the visible region and induction of the opposite chirality.
Industrial Grade Resin as Reusable Catalyst for Amidoalkylation of γ‐Hydroxy Lactams
Authors: Mishra Jyotiranjan , Pratihar Sanjay , Subramanian Palani S. 
Published: April 2023

AbstractHerein, we disclose a selective, versatile, accessible, cost‐effective and highly efficient cation‐exchange industrial grade INDION 130 resin as a reusable catalyst for the synthesis of 3‐substituted isoindolinones from various γ‐hydroxy lactams and a variety of C, N, O, and S nucleophiles involving N‐acyliminium ion intermediates under mild reaction conditions. Mechanistic studies suggested the generation of a different kind of kinetically and thermodynamically controlled intermediates/eliminated products, which further converted to their corresponding products depending upon the nucleophile, reaction parameter and nitrogen substitution (benzyl vs. aryl) of the substrate (succinamidals vs. phthalimidals). The easy synthesis, efficient reactivity and selectivity, broad substrate scope with verities of C, N, O, and S nucleophiles, and efficient recycling make the catalyst and the protocol economical and sustainable.
Ultrafast Deposition of NiFe Metal‐organic Framework Catalysts Boosts BiVO4 Photoanode for Efficient Solar Water Splitting
Authors: Yuan Cang , Gao Rui‐Ting , Wang Lei 
Published: April 2023

AbstractThe severe photocorrosion of BiVO4 limits its application in solar energy conversion in the long‐term photoelectrochemical stability test. Herein, we synthesized a Fe@Ni‐MOFs/BiVO4 photoanode by a simple ultrasonic method and ultrafast deposition, which avoids the problems of damaging the surface structure of photoelectrode. The Fe@Ni‐MOFs/BiVO4 shows a photocurrent density of 4.89 mA cm−2 at 1.23 VRHE with an onset potential of 0.25 VRHE under one sun illumination. Importantly, a stability over 30 h at 0.7 VRHE can be obtained, which is so far the best stability character for MOFs‐based cocatalysts decorated on BiVO4. During operation, Fe@Ni‐MOFs transforms into a homogeneous and active hydroxide layer covering the surface, which exposes more active sites for OER reactions. This work demonstrates a simple strategy for MOFs co‐catalysts to obtain fast hole transfer capability and reduce carrier recombination, thereby improving PEC performance.
Paddle‐Wheel Dirhodium Complexes Bearing Bulky Carboxylate Ligands: Synthesis and Catalysis in Carbene Insertion Reactions
Authors: Yamashita Kotaro , Sato Kota , Tanji Yutaka , Hasegawa Jun‐ya , Fujihara Tetsuaki 
Published: April 2023

AbstractDirhodium complexes bearing bulky carboxylate ligands are synthesized and characterized. The steric bulk of carboxylate ligands could affect the reaction selectivity in Rh‐catalyzed intramolecular reactions: Rh catalysts with bulky carboxylate ligands provided five‐membered ring products preferentially via the insertion into a carbon–hydrogen bond. Meanwhile, six‐membered ring products were obtained using conventional Rh catalysts via the insertion of a carbon‐carbon double bond.
Uniform Longitudinal Zinc Growth beyond Interface Guided by Anionic Covalent Organic Framework for Dendrite‐Free Aqueous Zinc Batteries
Authors: Wang Xiaoqi , Shao Pengpeng , Bai Shengchi , Yang Rui , Jin Xu , Zhi Chunyi , Wang Bo 
Published: April 2023

AbstractAqueous zinc (Zn) batteries hold considerable promise to address safety problems that frequently occur in electric vehicle cells or energy storage applications. However, Zn metal anode suffers seriously from dendrite, corrosion, and interface water decomposition in aqueous electrolytes, especially under large areal capacity or long charging duration. This is mainly because of the uneven longitudinal Zn growth induced by the anisotropic Zn2+ diffusion, which is usually neglected in a laboratory study with low areal capacity. Herein, we report an artificial interface of the anodic covalent organic framework (COF, which can be rapidly synthesized and facilely assembled with Zn anode in a large area) to guide the uniform longitudinal Zn growth for dendrite‐free Zn batteries. In‐situ optical microscope observes that compared with the bare Zn anode, COF interface can promote the formation of the smooth and dendrite‐free surface through spatial‐triggered uniform longitudinal Zn growth. Theoretical calculation uncovers that anodic COF with a negative charge at its N sites could attract Zn2+ to achieve uniform longitudinal Zn2+ diffusion. In addition, this COF interface with superior hydrophobicity could suppress water decomposition and Zn corrosion. Consequently, the COF‐functionalized Zn anode realizes a high coulombic efficiency under severe Zn plating/stripping conditions (10 mAh cm−2), contributing to a long Zn‐I2 full battery life of over 10000 cycles. This work highlights the high‐areal‐capacity Zn anode protection in external space beyond the interface.
Statistical approach for the optimization of levulinic acid production from orange peel as agricultural waste
Authors: Jeong Gwi‐Taek 
Published: April 2023

AbstractBackgroundAcid‐catalyzed hydrothermal conversion can be considered one of the most effective methods for converting agricultural wastes into sustainable and renewable fuels and value‐added chemicals. Orange wastes are a potential renewable and sustainable resource for the synthesis of value‐added compounds because of their high organic matter content. In this study, acid‐catalyzed hydrothermal conversion of orange peel was applied to produce levulinic acid (LA) using a statistical experimental approach.ResultsThe reaction conditions for LA synthesis by sulfuric acid‐catalyzed hydrothermal conversion of orange peel was optimized at middle‐to‐high temperatures, low catalyst concentrations, and prolonged reaction times within the tested ranges. As a result, an LA yield of 17.13 wt% (biomass weight basis) or 60.77% (glucan content basis) was achieved under the condition of 185 °C, 10% biomass, 0.3 mol L−1 sulfuric acid, and 30 min. In the relationship between combined severity (CS) and LA yield, LA yield increased moderately with increasing CS value until CS 3.2, then remained stable. The highest LA yield was observed under the CS 3.7 condition.ConclusionThe findings of this study demonstrated the potential value of orange peel as a renewable agricultural waste for the manufacture of valuable chemicals and materials. © 2023 Society of Industrial Chemistry and John Wiley & Sons Ltd.
Impact of ketamine administration on chronic unpredictable stress‐induced rat model of depression during extremely low‐frequency electromagnetic field exposure: Behavioral, histological and molecular study
Authors: Salari Moein , Eftekhar‐Vaghefi Seyed Hassan , Asadi‐Shekaari Majid , Esmaeilpour Khadijeh , Solhjou Somayeh , Amiri Maryam , Ahmadi‐Zeidabadi Meysam 
Published: April 2023

AbstractObjectivesIn the study, we examined the effects of ketamine and extremely low‐frequency electromagnetic fields (ELF‐EMF) on depression‐like behavior, learning and memory, expression of GFAP, caspase‐3, p53, BDNF, and NMDA receptor in animals subjected to chronic unpredictable stress (CUS).MethodsAfter applying 21 days of chronic unpredictable stress, male rats received intraperitoneal (IP) of ketamine (5 mg/kg) and then were exposed to ELF‐EMF (10‐Hz, 10‐mT exposure conditions) for 3 days (3 h per day) and behavioral assessments were performed 24 h after the treatments. Instantly after the last behavioral test, the brain was extracted for Nissl staining, immunohistochemistry, and real‐time PCR analyses. Immunohistochemistry (IHC) was conducted to assess the effect of ketamine and ELF‐EMF on the expression of astrocyte marker (glial fibrillary acidic protein, GFAP) in the CA1 area of the hippocampus and medial prefrontal cortex (mPFC). Also, real‐time PCR analyses were used to investigate the impacts of the combination of ketamine and ELF‐EMF on the expression of caspase3, p53, BDNF, and NMDA receptors in the hippocampus in rats submitted to the CUS procedure. Results were considered statistically significant when p < .05.ResultsOur results revealed that the combination of ketamine and ELF‐EMF increased depression‐like behavior, increased degenerated neurons and decreased the number of GFAP (+) cells in the CA1 area and mPFC, incremented the expression of caspase‐3, and reduced the expression of BDNF in the hippocampus but showed no effect on the expression of p53 and NMDA‐R.ConclusionsThese results reveal that combining ketamine and ELF‐EMF has adverse effects on animals under chronic unpredictable stress (CUS).