bluuebunny/crossref_metadata_2025_split huggingface dataset:
In Situ Construction of Perovskite Pr0.5Ba0.5Mn0.8Co0.1Ru0.1O2.5+δ/CoRu Nanoparticles with Co–N–C Composite Enabling Efficient Bifunctional Electrocatalyst for Zinc‐Air Batteries
Authors: Wei Jialu , Wang Jingyu , Zhang Wei , Mao Yuezhen , Sun Chunwen 
Published: October 2024

AbstractBifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential components of rechargeable zinc‐air batteries. In this study, we synthesized a Pr0.5Ba0.5Mn0.8Co0.1Ru0.1O2.5+δ (PBMCRO) perovskite composite with in situ exsolved CoRu nanoparticles and Co–N–C, functioning as an efficient bifunctional electrocatalyst for zinc‐air batteries. The in situ exsolution of CoRu nanoparticles from the perovskite oxide was facilitated by the reducing action of 2‐methylimidazole (2‐MIM). Concurrently, Co–N–C was used to decorate PBMCRO, forming a novel bifunctional composite electrode of Co–N–C–PBMCRO. The incorporation of CoRu nanoparticles introduces a significant number of electrochemically active oxygen vacancies in the perovskite matrix, enhancing ORR and OER performance. Additionally, the Co–N–C synergistically improves electrochemical activity while preserving the structural stability of the perovskite oxide. The prepared Co–N–C–PBMCRO catalyst demonstrates significantly enhanced bifunctional performance compared to the undecorated pristine perovskite Pr0.5Ba0.5MnO3−δ (PBMO). The zinc‐air battery with Co–N–C–PBMCRO catalyst achieve a peak power density of approximately 90 mW/cm2 and exhibit remarkable cycling stability for 788 h. This study presents a novel and effective strategy to enhance the catalytic performance of perovskite‐based air electrodes for rechargeable metal‐air batteries.
Responsive Chirality: Tailoring Supramolecular Assemblies with External Stimuli as Future Platforms for Electronic/Spintronic Materials
Authors: Kataria Meenal , Seki Shu 
Published: October 2024

AbstractSupramolecular chirality is the major branch of supramolecular chemistry, which not only plays important roles in biological processes but also in synthetically designed aggregated systems. To understand the complex processing of biological systems, the only way is to design supramolecular chiral ensembles that mimic natural biomolecules such as Deoxyribonucleic acid (DNA), Ribonucleic acid (RNA), amino acids, etc. In addition, chiral systems and self‐assemblies as molecular motifs with breaking spatial inversion symmetry have been regarded as key substances in electronics and spintronics as well as in fundamental chemistry and physics. Here, in this review, our major concern is understanding modulation in spatial arrangements and packing modes under the impact of any external stimuli, which results in tailoring the handedness of resulted supramolecular chiral superstructures. We, in this review, highlighted the role of external stimuli such as solvent, chemical additives, photo exposure, etc. in altering the supramolecular chirality for their future utility as “active switches” in optoelectronic and spintronic devices and applications.
Luminescent Radical Polymers
Authors: Zhang Ziteng , Zhang Jianyu , Zhi Sun Jing , Zhang Haoke , Zhang Xinghong , Zhong Tang Ben 
Published: October 2024

AbstractOrganic radicals are gaining significant interest in luminescent materials due to their unique properties, which present unprecedented opportunities for innovation across various fields, from display technology to biomedical applications. However, addressing challenges related to stability and low fluorescence efficiency is crucial to unlocking their full potential for practical applications. Polymerization has emerged as an effective strategy to enhance intra‐ and interchain through‐space interactions, enabling the creation of stable luminescent radicals with excellent processing and multifunctional properties. This concept emphasizes the strategic use of polymerization in designing and synthesizing stable main‐chain and side‐chain radical polymers. This approach not only broadens the scope of stable radicals but also improves their luminescence properties as photofunctional materials.
In Situ Self‐Assembly of Antibody‐Rhamnose Complex as a Pre‐Targeting Strategy for Enhanced Cancer Immunotherapy
Authors: Hong Haofei , Zhou Kun , Lin Han , Li Yanchun , Wu Zhimeng 
Published: October 2024

AbstractEnhancing the Fc effector functions of monoclonal antibodies (mAbs) is a proven strategy for improving cancer immunotherapy. In this study, we present a novel pre‐targeting approach that integrates host‐guest chemistry with an antibody‐recruiting concept to create mAbs with superior effector functions. Using rituximab (RTX), a clinically approved anti‐CD20 mAb, as our model, we modified RTX by conjugating it with adamantane (Ada) derivatives and various polyethylene glycol (PEG) linkers to produce RTX‐Ada conjugates. These conjugates effectively formed RTX‐rhamnose (Rha) complexes in situ through self‐assembly, driven by host‐guest interactions with Rha‐modified β‐cyclodextrin. This mechanism successfully redirected endogenous anti‐Rha antibodies to target cells, enhancing the availability of Fc domains for improved effector functions, including complement‐dependent cytotoxicity (CDC). A structure‐activity relationship study indicated that the potency of these in situ complexes was significantly influenced by the length of the PEG linker used; shorter PEG linkers correlated with higher CDC activity. Given the variability in endogenous antibody levels among individuals, this strategy presents a flexible and promising platform for enhancing the efficacy of mAb‐based cancer immunotherapy.
Late‐Stage Functionalization Using a Popular Titrating Agent: Aryl‐Chlorides and ‐Fluorides Activation by the Diphenylacetic Acid Dianion
Authors: Cerveri Alessandro , Russo Giulia , Sparascio Sara , Merli Daniele , Maggi Raimondo , Della Ca' Nicola , Lanzi Matteo , Maestri Giovanni 
Published: October 2024

AbstractAryl‐chlorides and ‐fluorides are common building blocks, but their use in synthesis is limited by the high stability of their Ar−X bonds. The generation of aryl radicals via activation of strong Ar−X bonds is possible through the irradiation of tailor‐made organic anions, which become reductants stronger than lithium metal. We report that the combination of visible light with the cheap diphenylacetic acid dianion is an even better tool, showing excellent activity across a variety of complex substrates and providing opportunities for late‐stage drug modification. Ar−X bonds are chemoselectively activated in the presence of more easily reducible functions, such as Alk‐Cl ones and carbonyl groups. These results pave the way to original synthetic strategies that would be otherwise considered impossible.
Investigation of Muscarinic Acetylcholine Receptor M3 Activation in Atomistic Detail: A Chemist's Viewpoint
Authors: Drabek Matthäus , Emmerich Rolf , Djulic Nuri , Bünemann Moritz , Schlitzer Martin , Kolb Peter 
Published: October 2024

AbstractWe analyzed the precise ligand:receptor interactions required for activation of the muscarinic acetylcholine receptor M3, a prototypical G protein‐coupled receptor and potential diabetes target. Starting from literature‐known compounds and docking solutions, ligands were tailored for the modulation of this receptor's activation. Several aspects of the structure‐activity relationship of agonists were investigated in atomistic detail, in order to delineate how the receptor can be activated via the orthosteric site. Such exquisitely precise knowledge is instrumental for designing potent and effiacious ligands. We put this strategy into practice and acquired or synthesized and measured a diverse set of 55 ligands ranging from small fragment‐like amines coordinating D3.32 to bigger molecules extending towards helices 5 and 6 with diphenyl moieties. In the course of these investigations, we showed that the polarizability of the amine nitrogen and the rigidity and size of the moieties in the space delimited by helices 5 and 6 are the two key elements distinguishing potent and efficacious ligands from those that are not. The resulting data set will be highly useful in drug design and molecular machine learning alike.
Facile Fabrication of LaFeO3 Supported Pd Nanoparticles as Highly Effective Heterogeneous Catalyst for Suzuki–Miyaura Coupling Reaction
Authors: Sun Ying , Yin Juanjuan , Wang Ying , Zhang Ping , Ma Lingjuan , Li Jisen 
Published: October 2024

AbstractSupported Pd catalysts have been widely studied due to their enormous potential as candidates for heterogeneous Suzuki–Miyaura coupling reactions. However, the sintering and low activity of active sites still remain challenges. A vesicle‐shaped LaFeO3‐supported Pd catalyst (I−Pd/LaFeO3) was successfully fabricated using the impregnation method and tested for the Suzuki–Miyaura coupling reaction. Compared to P−Pd/LaFeO3 prepared with photo‐deposition and Pd/Al2O3 prepared with impregnation, the I−Pd/LaFeO3 catalyst exhibits significantly higher catalytic activity, stability, and reusability. The chemical composition and electron states of different Pd‐based catalysts were well studied based on various characterizations and the results indicated that the excellent performance of I−Pd/LaFeO3 can be attributed to its unique nanostructure and the strong interactions between LaFeO3 and palladium nanoparticles. The impregnation method and the choice of the LaFeO3 support show a great influence on the electronic properties of Pd species, their reducibility, and, consequently, their reaction behavior. This unique LaFeO3 supported Pd catalyst provided an environmentally friendly heterogeneous method for the Suzuki–Miyaura coupling reaction.
Improving QoS in cloud resources scheduling using dynamic clustering algorithm and SM‐CDC scheduling model
Authors: Varmeziar Tayebeh , Shiri Mohamad Ebrahim , Rahmani Parisa 
Published: October 2024

SummaryQuality of Service (QoS) regulates and controls network resources by setting priorities for specific data types. Many clustering algorithms are used to cluster cloud workloads, most of which are static. However, the lack of dynamic algorithms is seen in the face of huge databases that are real‐time and according to the existing clustering conditions. Additionally, fair allocation of tasks on servers and efficient resource utilization pose challenges. In this research, two solutions are proposed to improve the quality of service: the first solution uses the chameleon dynamic algorithm, a method to improve service quality. The chameleon algorithm has been able to show significant performance due to its high accuracy in detecting the smallest distance between clusters. This dynamic algorithm outperforms static algorithms with classification accuracy and response speed, which are the most important parameters of service quality. The second part of the proposed solution is to use the Scheduling Model using Cloud Data Centers (SM‐CDC) system to select the best service provider based on the clustering done in the previous step. A SM‐CDC technique is developed to handle cloud storage center tasks that are stored in electronic devices. According to the comparison with existing scheduling policies, SM‐CDC offered 36% decrease on response time, 50% reduction on cost of resources, and 40% improvement on QoS Satisfaction.
A Review on Network Covert Channel Construction and Attack Detection
Authors: Khadse Mrinal Ashish , Dakhane Dhananjay Manohar 
Published: October 2024

ABSTRACTA covert network channel is a communication channel in which the message is secretly transmitted to the recipient. Sometimes, covert network channels are vulnerable to multiple attacks. Therefore, the message must be properly secure. In most cases, the covert channel is used to ensure data protection and allow users to freely access the Internet. In this paper, several recent studies are reviewed on covert network channels and examine the existing works from 2015 to 2024. This review article also discusses the undetectability and reliability of different types of covert network channels. Furthermore, a detailed description of the covert network channel's ability to hide in containers is provided. Existing research on covert network channels explains a few techniques for detecting attacks in secret data communication. However, several machine learning and deep learning techniques have been discussed in this article. Additionally, this article describes the accuracy of detection through an overview of current technologies. In addition, various countermeasures to prevent attacks in covert channels are also discussed in detail. However, in this case, the bandwidth limitations, data set limitations, and covert channel capacity are clearly defined, which will help future researchers build covert network channels and detect attacks. Finally, this work considers the challenges faced by covert network channels and the future scope of application.
High‐Performance Organic Field‐Effect Transistors and Inverters with Good Flexibility and Low Operating Voltage
Authors: Yang Fukang , Liu Shining , Li Congling , Lv Aifeng 
Published: October 2024

AbstractOrganic field‐effect transistors (OFETs) with good flexibility and low operating voltage, are of great meaning for the low power stretchable and wearable electronic devices. The operating voltage and flexibility are easily affected by the dielectric layers in the OFETs. Bilayer dielectrics comprising both high‐ and low‐permittivity (k) insulating polymers, have been reported. The flexible bilayer dielectrics can combine the advantages of both insulating polymers, which are high charge carriers from low‐k polymers and low operating voltage from high‐k polymers. However, the effect of film thicknesses in the bilayer dielectrics on the OFET performance is seldom investigated. Here, bilayer dielectrics comprising high‐k polyvinyl alcohol (PVA) and low‐k polymethylmethacrylate (PMMA) were fabricated. And PVA/PMMA bilayers with three different PVA film thicknesses are carefully investigated. The 300 nm PVA/100 nm PMMA bilayer dielectric makes the pentacene OFETs show the highest hole mobility of 1.24 cm2 V−1s−1 and the corresponding inverters give a high voltage gain of 40 and a noise margin of 2.3 V (77 % of 1/2 VDD) at low operating voltage of 6 V. Both the pentacene transistors and the inverters still work properly under bending radium of 5.85 mm, proving the good prospects of the PVA/PMMA bilayer dielectric in practical applications.
Graphene Oxide and its Composites: Advanced Membranes for Selective Water Permeation
Authors: Lee Byeongho , Kim Choonsoo 
Published: October 2024

AbstractGraphene oxide (GO) membranes have gained significant attention as a promising material for separation by selective permeation processes due to their advantageous structural and chemical properties, including high water permeability, chemical resistance, and mechanical strength. In this study, we explore the potential applications of GO membranes in pervaporation to separate liquid mixtures. The layered structure and hydrophilic nature of GO membrane facilitate rapid and selective water transport through angstrom‐scale interlayer spacings, resulting in superior performance over conventional polymeric and inorganic membranes. The unique mass transport mechanisms – slip flow and molecular alignment – enable GO membranes to selectively permeate water over organic solvents. For chemical dehydration, GO membranes are the most potential candidates. Furthermore, advancements in composite GO membranes and cross‐linking techniques that improve their stability and separation performance are discussed. This study highlights the advantages of GO membranes and their potential to replace or complement existing technologies, by emphasizing their role in advancing membrane‐based separation and promoting environmental sustainability. Future research is expected to optimize the fabrication techniques for GO membranes and expand their application scope.
Post‐CCSD(T) Thermochemistry of Chlorine Fluorides as a Challenging Test Case for Evaluating Density Functional Theory and Composite Ab Initio Methods
Authors: Karton Amir , Haasler Matthias , Kaupp Martin 
Published: October 2024

AbstractQuantum chemistry plays a key role in exploring the chemical properties of highly reactive chlorine polyfluoride compounds (ClFn). Here, we investigate the thermochemical properties of ClFn species (n=2–6) by means of high‐level thermochemical procedures approximating the CCSDT(Q) and CCSDTQ5 energies at the complete basis set limit. We consider total atomization energies (TAEs), Cl−F bond dissociation energies (BDEs), F2 elimination energies (F2 elim.), ionization potentials (IPs), and electron affinities (EAs). The TAEs have significant contributions from post‐CCSD(T) correlation effects. The higher‐order triple excitations, CCSDT−CCSD(T), are negative and amount to −0.338 (ClF2), −0.727 (ClF3), −0.903 (ClF4), −1.335 (ClF5), and −1.946 (ClF6) kcal/mol. However, the contributions from quadruple (and, where available, also quintuple) excitations are much larger and positive and amount to +1.335 (ClF2), +1.387 (ClF3), +2.367 (ClF4), +2.399 (ClF5), and +3.432 (ClF6) kcal/mol. Thus, the contributions from post‐CCSD(T) excitations exceed the threshold of chemical accuracy in nearly all cases. Due to their increasing hyper‐valency and multireference character, the ClFn series provides an interesting and challenging test case for both density functional theory and low‐level composite ab initio procedures. Here, we highlight the limitations in achieving overall chemical accuracy across all DFT and most composite ab initio procedures.
Triel Bonds with Methyl Groups as Electron Donors. A Pentacoordinate Carbon Atom
Authors: Wang Xin , Cheng Yuwei , Li Qingzhong , Scheiner Steve 
Published: October 2024

AbstractThe triel bond (TrB) formed between Be(CH3)2/Mg(CH3)2 and TrX3 (Tr=B, Al, and Ga; X=H, F, Cl, Br, and I) is investigated via the MP2/aug‐cc‐pVTZ(PP) quantum chemical protocol. The C atoms of the methyl groups in M(CH3)2 are characterized by a negative electrostatic potential and act as an electron donor in a triel bond with the π‐hole above the Tr atom of planar TrX3. The interaction energy spans a wide range between −2 and −69 kcal/mol. Mg(CH3)2 forms a stronger TrB than does Be(CH3)2, which comports with the more negative electrostatic potential on its methyl groups. Some of the complexes involving Mg display a high degree of transfer of the methyl group from Mg to Tr, which is accompanied by an inversion of the bridging methyl and a sizable pyramidalization of the TrX3 unit. The geometries of these complexes have the properties of the long sought pentacoordinate C which has eluded identification and characterization in the past.
Lattice Strain Regulated by Hetero/Homo Atom Interface Merging on NiMo Nanocluster for High‐Performance Hydrogen Production
Authors: Xie Yulu , Liu Baiqiang , Mo Feifan , Qin Xiaochen , Shu Hang , Deng Renchao , Ye Tingfang , Meng Meng , Li Puhai , Hu Yu‐wen , Li Yuquan , Liu Wei , Yang Hao 
Published: October 2024

AbstractLattice strain engineering represents a cutting‐edge approach capable of delivering enhanced performance across various applications. The lattice strain can affect the performance of electrochemical catalysts by changing the binding energy between the surface‐active sites and intermediates. In this work, lattice strain is regulated through a homo/heterogeneous atomic interface merging. The strong lattice strain and electronic interactions between Ni and Mo facilitated the reaction kinetic of HER. The prepared NiMo@SSM exhibits excellent HER catalytic performance with 70 mV overpotential at the current density of 10 mA cm−2 and long‐term stability. The method of controlling lattice strain through hetero/homo atom interface merging provides a new strategy for designing high‐performance alkaline HER electrocatalysts.
Microwave‐Assisted Conversion of 5‐Hydroxymethylfurfural into 2,5‐Furandicarboxylic Acid over CuCo Oxide
Authors: Prasad Shivshankar , Kumar Ajay , Dutta Suman , Ahmad Ejaz 
Published: October 2024

AbstractA series of CuCo bimetallic catalysts were prepared via the co‐precipitation method for the catalytic transformation of biomass‐derived 5‐hydroxymethylfurfural (HMF) into 2,5‐furandicarboxylic acid (FDCA). FDCA acts as a precursor for biodegradable biopolymer polyethylene furanoate production, thereby achieving a carbon‐neutral approach. Out of all the synthesized catalysts, CuCo(1 : 1) showed remarkable catalytic activity and yielded 70.67 % FDCA while achieving 100 % HMF conversion in 5 minutes at 50 °C temperature in the presence of tert‐butyl hydroperoxide as an oxidant. Synergistic effects of the catalyst, such as adsorbed oxygen, relative oxygen vacancy, lesser pore size, and pore volume, were key factors attributed to the catalyst's excellent activity. The synthesized catalyst showed good recyclability with a minimal decrease in FDCA yield up to 5 cycles. Pre and post‐characterization of catalysts such as BET, TEM, FE‐SEM, XRD, H2‐TPR, CO2 TPD, ICP‐OES, and XPS were done to correlate the catalyst's properties with its activity. In addition, the effect of reaction parameters such as stirring speed, temperature reaction time, catalyst weight, base, and oxidant were studied to achieve optimum reaction conditions. The reaction products were analyzed quantitatively and qualitatively using HPLC and HR‐MS.
Aromatic Ring‐Fused Amidine Based Allosteric Receptors Activated by Guest‐Induced π‐Conjugation Switching
Authors: Kataoka Takayuki , Matsumura Kotaro , Ono Kosuke , Tsuchido Yoshitaka , Kawai Hidetoshi 
Published: October 2024

AbstractAmidine‐substituted allosteric receptors 2 a and 2 b for benzenediols were synthesized. Receptor 2 a with five‐membered amidines exhibited greater allostericity than the amide‐substituted receptor 1, while 2 b with six‐membered amidines exhibited less allostericity. NMR titration experiments revealed that a significant enthalpic factor was involved in the allostericity of these receptors. X‐ray and DFT optimized structures of 2 a and 2 b revealed that 2 a adopted a coplanar conformation with π‐conjugation between the amidines and the phenylene ring of the hydrindacene framework, resulting in high allostericity due to inactivation of the initial binding.