bluuebunny/crossref_metadata_2025_split huggingface dataset:
High‐Entropy Ag−Ru‐Based Electrocatalysts with Dual‐Active‐Center for Highly Stable Ultra‐Low‐Temperature Zinc‐Air Batteries
Authors: Qiu Ziming , Guo Xiaotian , Cao Shuai , Du Meng , Wang Qinchao , Pi Yecan , Pang Huan 
Published: October 2024

AbstractThe development of advanced bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is significant for rechargeable zinc‐air batteries (ZABs). Herein, a unique dual active center alloying strategy is proposed to achieve the efficient bifunctional oxygen catalysis, and the high entropy effect is further exploited to modulate the structure and performance of the catalysts. The MOF‐assisted pyrolysis‐replacement‐alloying method was employed to construct the CoCuFeAgRu high‐entropy alloy (HEA), which are uniformly anchored in porous nitrogen‐doped carbon nanosheets. Notably, the obtained HEA catalyst exhibits excellent catalytic performance for both ORR and OER, and a peak power density of 136. 53 mW cm−2 and an energy density of 987.9 mAh gZn−1, surpassing the most of the previously reported bifunctional oxygen electrocatalysts. Moreover, the assembled flexible rechargeable ZAB enables excellent performance even at the ultralow temperature of −40 °C, with an energy density of 601.6 mAh gZn−1 and remarkable cycling stability up to 1,650 hours. Combined experimental and theoretical calculation results reveal that the excellent bifunctional catalytic activity of the HEA catalyst originated from the synergistic effect of the Ag and Ru dual active centers, and the optimization of the electronic structure by alloying effect.
Luminescence Modulation in Boron‐Cluster‐Based Luminogens via Boron Isotope Effects
Authors: Ma Wenli , Zhang Jianyu , Zong Jibo , Ren Hongyuan , Tu Deshuang , Xu Qinfeng , Zhong Tang Ben , Yan Hong 
Published: October 2024

AbstractRecent advances in luminescent materials highlight the significant impact of hydrogen isotope effects on improving optoelectronic properties. However, the research on the influence of the boron isotope effects on photophysical properties remains underdeveloped. This study focused on exploring the boron isotope effects in boron‐cluster‐based luminogens. In doing so, we designed and synthesized carborane‐based luminogens containing 98 % 10B and 95 % 11B, respectively, and observed distinct photophysical behaviors. Compared to the 10B‐enriched luminogens, the 11B‐enriched counterparts can significantly enhance luminescence efficiency, prolong emission lifetime, and reduce full‐width at half‐maximum. Additionally, increased thermal stability, redshifted B−H vibrations, and a fourfold enhanced electrochemiluminescence intensity have also been observed. On the other hand, the biological assessments of a 10B‐enriched luminogen reveals low cytotoxicity, high boron uptake, and excellent fluorescence imaging capability, indicating the potential application in boron neutron capture therapy (BNCT). This work presents the first comprehensive exploration on the boron isotope effects in boron clusters, and provides valuable insights into the rational design of organic luminogens for advanced optoelectronic and biomedical applications.
In situ Monitoring of Photocatalysis on Polymeric Carbon Nitride Thin Films
Authors: Dauth Bastian , Giusto Paolo , König Burkhard , Gschwind Ruth M. 
Published: October 2024

AbstractPolymeric carbon nitride has attracted significant interest in heterogeneous photocatalysis due to its activity under visible‐light irradiation. Herein, we report on using carbon nitride‐coated NMR tubes for in situ studies of photocatalytic reaction mechanisms. In a first step, we exploited carbon nitride‐coated crimp vials as batch photoreactors for visible photocatalytic fluorinations of unactivated C(sp3)−H bonds, with moderate to excellent yields and reusability over multiple cycles. Eventually, carbon nitride‐coated NMR tubes were used as a photoreactor by coupling them with optical fiber irradiation directly inside the spectrometer. This enabled us to follow the reaction with in situ NMR spectroscopy identifying reactive intermediates otherwise elusive in conventional analyses. The method provides advantages for the study of photocatalytic mechanisms of complex reactions and substantially reduces the need of comparative tests for depicting reaction intermediates and conversion pathways.
Tandem Methanolysis and Catalytic Transfer Hydrogenolysis of Polyethylene Terephthalate to p‐Xylene Over Cu/ZnZrOx Catalysts
Authors: Helmer Ryan , Borkar Siddhesh S. , Li Aojie , Mahnaz Fatima , Vito Jenna , Bishop Michelle , Iftakher Ashfaq , Hasan M. M. Faruque , Rangarajan Srinivas , Shetty Manish 
Published: October 2024

AbstractWe demonstrate a novel approach of utilizing methanol (CH3OH) in a dual role for (1) the methanolysis of polyethylene terephthalate (PET) to form dimethyl terephthalate (DMT) at near‐quantitative yields (~97 %) and (2) serving as an in situ H2 source for the catalytic transfer hydrogenolysis (CTH) of DMT to p‐xylene (PX, ~63 % at 240 °C and 16 h) on a reducible ZnZrOx supported Cu catalyst (i.e., Cu/ZnZrOx). Pre‐ and post‐reaction surface and bulk characterization, along with density functional theory (DFT) computations, explicate the dual role of the metal‐support interface of Cu/ZnZrOx in activating both CH3OH and DMT and facilitating a lower free‐energy pathway for both CH3OH dehydrogenation and DMT hydrogenolysis, compared to Cu supported on a redox‐neutral SiO2 support. Loading studies and thermodynamic calculations showed that, under reaction conditions, CH3OH in the gas phase, rather than in the liquid phase, is critical for CTH of DMT. Interestingly, the Cu/ZnZrOx catalyst was also effective for the methanolysis and hydrogenolysis of C−C bonds (compared to C−O bonds for PET) of waste polycarbonate (PC), largely forming xylenol (~38 %) and methyl isopropyl anisole (~42 %) demonstrating the versatility of this approach toward valorizing a wide range of condensation polymers.
CdWO4 Sub‐1 nm Nanowires for Visible‐Light CO2 Photoreduction
Authors: Liu Yan‐Chun , Zhu Chang‐Yan , Zhao Xia , Tan Hua‐Qiao , Cheng Si‐Hang , Yang Dan , Wang Xun , Li Yang‐Guang 
Published: October 2024

AbstractQuantum size effect usually causes energy level splitting and band broadening as material size decreases. However, this may change again by the surface adsorbents, doping and defects, which rarely attracts much attention. Herein, CdWO4 sub‐1 nm nanowires (SNWs) with oleylamine adsorption, PO43−‐doping and oxygen defects are synthesized by combining Cd(CH3COO)2, H3PW12O40 (PW12) and oleylamine (abbreviated as PO43−‐CdWO4‐X SNWs). Compared with bulk CdWO4, they exhibit unexpected absorption spectra (extended from 292 nm to 453 nm) and band gap (reduced from 4.25 eV to 2.74 eV), thus bringing remarkable visible‐light CO2 photoreduction activity. Under 410 nm LED light irradiation, PO43−‐CdWO4‐40 SNWs exhibit the highest photocatalytic performance with a CO2‐to‐CO generation rate of 1685 μmol g−1 h−1. Density functional theory (DFT) calculations demonstrate the adsorbed oleylamine raises the valence band and enhances the adsorption of reaction substrate and intermediates, thus decreasing their reduction energy barriers. Furthermore, PO43−‐doping and oxygen defects will generate defect energy band below the conduction band of PO43−‐CdWO4‐40 SNWs, resulting in remarkable visible light absorption and superior photocatalytic CO2 reduction performance. This work highlights the significant impacts of surface adsorbents, doping and defects on the physicochemical and catalytic properties of sub‐nano materials.
Facial fire with use of high‐flow nasal oxygen during laser surgery
Authors: Shankla S. , De Zoysa N. , Bird J. , Girgis M. 
Published: October 2024

SummaryUse of high‐flow nasal oxygen to enable apnoeic oxygenation during tubeless airway surgery is well‐established. The use of an ignition source in this oxygen‐rich environment increases the risk of surgical fire. We present a case of facial fire secondary to the use of carbon dioxide laser and high‐flow nasal oxygen during a surgical procedure for subglottic stenosis. The incident occurred when the laser was being tested near the patient, resulting in superficial burns to the patient's face and neck. The airway was unaffected and the burns were managed conservatively. This case highlights important safety consideration for the use of an ignition source in the presence of high‐flow nasal oxygen and the role of human factors and in‐built risk mitigation features.
Innovative Nanoarchitectures: CuO:Er2O3 Synergy for Enhanced Performance in Energy Storage and Generation Applications
Authors: Azhar Sundus , Ahmad Khuram Shahzad , Abrahams Isaac , Ingsel Tenzin , Gupta Ram K. , Al‐Ammar Essam A. , Ashraf Ghulam Abbas , Gul Mahwash Mahar 
Published: October 2024

ABSTRACTIn this study, we have synthesized facile Cu‐based CuO:Er2O3 nanoelectrode material for energy storage and generation. CuO:Er2O3 nanomaterial was synthesized employing phyto‐extract of Amaranthus viridis L. (AVL) as stabilizing and reducing agents. Spherical‐shaped CuO:Er2O3 nanomaterial was initially employed to study supercapacitor behavior. The specific capacitance of 82.25 F/g was found at 0.5 A/g by galvanostatic charge–discharge, whereas the value of 319 F/g was achieved at 2 mV/s by cyclic voltammetry (CV) measurements. Furthermore, CuO:Er2O3 electrode was investigated for water splitting energy generation potential and revealed an overpotential value of 323 mV at 10 mA/cm2 for hydrogen evolution reaction (HER). However, for the oxygen evolution reaction (OER), an overpotential value of 370 mV was found. The electrochemical impedance analysis revealed the faster flow of electrons and ions, suggesting great conductivity and lower resistance of the fabricated electrode. Thus, current electrochemical results are proposing CuO:Er2O3 as an competent electrode for overall energy‐generating as well as storage applications.
Dicarbatriphyrin(2.1.1) and its Carbacalix[1]Phyrin Analogue: Structure‐Property Relationships and Application as a Fe(III) Chemosensor
Authors: Kayal Adrija , Ranjan Pradhan Sourav , Kumar Prasad Chetan , Das Mainak , Srinivasan A. 
Published: October 2024

AbstractThe investigation of unsaturated or π‐conjugated hydrocarbons, particularly within the macrocyclic framework, has garnered significant interest due to their fundamental properties and practical applications. This research focuses on the synthesis and characterization of a novel stable dicarbatriphyrin(2.1.1) which was constructed by amending the [14]triphyrin(2.1.1) framework by, replacing two pyrrole rings with meta‐connected phenyl rings and introducing an o‐benzene bridge at the C2 position. The structural modification resulted in a saddle‐shaped macrocyclic core with negative Gaussian curvature, as confirmed by crystal structure analysis. This unique molecular topology offers acumens into the structure‐property relationships in the curved locally π‐conjugated contracted porphyrinoids. The macrocycle exhibits fluorescent emission in solution, which is selectively quenched by Fe(III) ions, highlighting its potential as a chemosensor for Fe(III) cations. Additionally, the formation of carbacalix[1]phyrin(2.1.1), a phlorin analogue of dicarbatriphyrin(2.1.1), which exhibits a chair conformation in contrast to the saddle‐shaped structure of its oxidized counterpart. Remarkably, the emergence of a mono‐pyrrolic calixbenziphyrin marks an unprecedented advancement in the field of calixphyrin chemistry. Moreover, theoretical studies provide strong support for the experimental findings, reinforcing the conclusions drawn from the structural and functional analyses.
Organic All‐Solid‐State Lithium Metal Battery Using Polymer/Covalent Organic Framework Electrolyte
Authors: Canals Jef , Irié‐Bi Boris , Dolhem Franck , Becuwe Matthieu , Gautron Eric , Seznec Vincent , Dedryvère Rémi 
Published: October 2024

AbstractIn this work, we have designed an all‐organic and all‐solid‐state lithium metal battery based on 7,7,8,8‐tetracyano‐p‐quinodimethane (TCNQ) as the organic electroactive material and a COF (Covalent Organic Framework)/PEO (PolyEthylene Oxide) composite as solid electrolyte. The use of a solid electrolyte allows fixing the solubility problem of organic electroactive materials in classical liquid electrolytes. This is the first time an all‐solid‐state organic battery based on TCNQ versus lithium metal is reported, since no liquid additive was included in the formulation of the electrolyte. We obtained a reversible capacity of 88 mAh g−1 at the second discharge, and still 58 mAh g−1 at the tenth discharge. The redox processes were investigated by X‐ray Photoelectron Spectroscopy (XPS). We could evidence the involvement of the two lithiation steps of TCNQ (LiTCNQ and Li2TCNQ) in the reversible capacity. Optimization of the electrode manufacturing and formulation, and replacing the salt (LiI) by alternative ones opens the door to future improvements in the electrochemical performances. This study demonstrates the interest of COF‐type organic structures in the formulation of organic solid electrolytes.
Chemical Variability of the Leaf Essential Oil of Two Subspecies of Juniperus oxycedrus L. From Northwestern Algeria
Authors: Malti Charaf Eddine Watheq , Bekhechi Chahrazed , Salhi Khadidja , Babali Brahim , Casanova Joseph , Paoli Mathieu , Tomi Félix 
Published: October 2024

AbstractThirty‐seven essential oil samples have been isolated from leaves of individual plants of Juniperus oxycedrus (subspecies oxycedrus and macrocarpa) growing wild in Tlemcen and Aïn Témouchent provinces (Northwestern Algeria). Analysis of eight selected oil samples by GC(RI), GC/MS and 13C NMR, allowed the identification of 88 components that accounted for 84.4–99.5 % of the whole compositions. The 37 compositions were subjected to statistical analysis which suggested the existence of groups and sub‐groups I, IIA and IIB. Group I, the most important group with 24 oil samples out of 37, differed from sub‐groups IIA and IIB, essentially by the high content of α‐pinene (mean value, 69.2 %; SD 6.24). Sub‐groups IIA and IIB were differentiated by their content of α‐pinene (Mean values, 49.7 % and 27.3 %, respectively) as well as δ‐3‐carene (10.3 %, sub‐group IIA), sabinene and (Z)‐6‐pentadecen‐2‐one (8.7 % and 4.9 %, respectively, sub‐group IIB).
GC‐MS Profiling, Pharmacological Predictions, Molecular Docking, and ADME Studies of Different Parts of Thymus Linearis against Multiple Target Proteins in Wound Healing
Authors: Saleem Sumaira , Mushtaq Aamir , Muhammad Gulzar , Wajid Muhammad , Siddique Farhan , Alshabrmi Fahad M. , Aba Alkhayl Faris F. , Alatawi Eid A. 
Published: October 2024

AbstractThymus linearis from the Himalayan woodlands of Gilgit Baltistan, Pakistan, is a phytomedicine that has not been well‐studied. Traditionally, it is recognized for its potential in treating conditions such as dermatitis, psoriasis, weight loss, and discomfort. The study investigates the wound‐healing properties of methanolic extracts from the plant's stems, leaves, and roots. GC‐MS disclosed cadaverine, dihydroxy‐3,3‐dimethyl‐3‐hydroxy‐N‐isopropylbutyramide, phthalic acid‐di(2‐propylpentyl)ester, and benzo[h]quinolone‐2,4‐dimethyl in stem along with betamethasone valerate, 17‐pentatriacontene, 1,1‐cyclobutanedicarboxmide, heptadecane‐9‐hexyl, cyclohexanol‐2‐methylene‐3(1‐methylethenyl) and pentacyclo[12.3.0.0(1,13).0(2,10).0(5,9)]hepatodecane‐6‐ol‐15‐one in leaf extracts and 2‐myristynonyl pantetheine, 7,8‐epoxylanostan‐11‐ol‐3‐acetoxy, heneicosane (1‐(1‐ethyl propyl)), 2‐piperidinone‐N‐[4‐bromobutyl] and 1‐monolinoleoylglycerol trimethyl silyl ether in the root extract. The antioxidant activity was assessed using several assays including DPPH, bound iron %, ABTS, total flavonoid content, and total phenolic content. The methanolic stem extract (MSE) showed the highest antioxidant capacity compared to the leaf and root extracts. The stem extract demonstrated the highest wound‐healing potential, followed by leaves and roots in albino mice. The findings were supported by computational analysis, which revealed that the binding interactions of phytochemicals from stem have more affinity than leaf and root with specific receptor sites. The in‐silico analysis ascertains that dihydroxy‐3,3‐dimethyl‐3‐hydroxy‐N‐isopropylbutyramide from MSE is the most effective wound‐healing agent. Moreover, ADME predictions demonstrated the drug‐like properties of the hit compounds.
Porous and B‐site Substituted Y2[Mn0.2Ru0.8]2O7 Pyrochlore for Boosting Acidic Water Oxidation Activity and Stability
Authors: Tian Zhan , Yang Xin , Jia Hongrui , Liu Huan , Li Guoqiang 
Published: October 2024

AbstractBoosting the reaction stability without sacrificing the activity and cost is extremely important but full of challenges for the RuO2‐based oxygen evolution catalysts. Herein, porous and B‐site substituted Y2[Mn0.2Ru0.8]2O7 (p‐Y2[Mn0.2Ru0.8]2O7) pyrochlore toward oxygen evolution reaction is innovatively synthesized. The formed meso‐/macroporous structure can increase the specific surface area and corresponding active sites, meanwhile, Mn‐substitution can modulate the electronic structure, stabilize the morphology, and reduce the dosage of Ru species. Interestingly, the p‐Y2[Mn0.2Ru0.8]2O7 performs 50 h stable operation, significantly outperforming the commercial RuO2(CM) counterpart with less than 2 h life. Furthermore, the required overpotential to achieve 10 mA cm−2 is only 266 mV, accompanied with favorable reaction kinetics and catalyst utilization.
Next‐Gen Crop Monitoring: MTEG‐RTU Algorithm and UAV Synergy for Precise Disease Diagnosis
Authors: S Hemalatha , Jayachandran Jai Jaganath Babu 
Published: October 2024

ABSTRACTThe rapidly changing climatic scenarios are highly favorable for the rising diseases that lead to increasing threats to food production and supply. Various scholars and scientists make long steps to hasten the process of making innovations in farming for managing these issues. In this context, UAV is applied for the purpose of managing and monitoring plant health. The abiotic stresses available in plant diagnosis through traditional strategies are highly labor‐intensive and unfit for large‐scale deployment. Conversely, UAVs designed with mobile sensors, multispectral, radar, and so on make them flexible, affordable, and more effective. Thus, this study proposes a novel meta ensemble transfer extreme gradient‐based random tactical unit (MTEG‐RTU) algorithm for diagnosing crop illnesses precisely. The proposed MTEG‐RTU methodology entails three methods such as transfer learning, adaptive boost, and meta‐ensemble, and the hyper parameters are tuned using random tactical unit algorithm. Healthier and disordered crop images gained from the crop disease dataset comprise 8000 images and are preprocessed. The more optimal features from the preprocessed images are learned through the ResNet method, and these features enter into the classification phase. Random tactical unit algorithm enhanced the performance by optimizing the hyperparameters of MTEG classifier. The experimental results conducted based on the various assessment components and validation dataset indicate that the developed method outperformed the other chosen models, achieving precision, recall, and accuracy of 98.5%, 97.9%, and 98.6%, respectively. The other achievements made by the model are offering technical guidance for conducting the precise diagnosis and treatment of plant pathologies with less time of 9 s.
Biocompatible Flash Chemiluminescent Assay Enabled by Sterically Hindered Spiro‐Strained‐Oxetanyl‐1,2‐Dioxetane
Authors: Shelef Omri , Krinsky Anne , Jospe‐Kaufman Moriah , Babjaková Zuzana , Fridman Micha , Satchi‐Fainaro Ronit , Spitz Urs , Shabat Doron 
Published: October 2024

AbstractChemiluminescence is the emission of light that occurs as a result of a chemical reaction. Depending on the rate of chemiexcitation, light emission can occur as a long‐lasting, low‐intensity, glow‐type reaction or a rapid, highly intense flash‐type reaction. Assays using a flash‐type mode of action provide enhanced detection sensitivity compared to those using a glow‐type mode. Recently, our group discovered that applying spiro‐strain to 1,2‐dioxetanes significantly increases their chemiexcitation rate, thereby transforming glow‐type chemiluminescence into flash‐type chemiluminescence. However, further examination of the structure‐activity relationships revealed that the spiro‐strain severely compromises the chemical stability of the 1,2‐dioxetanes. We hypothesized that a combination of spiro‐strain, steric hindrance, and an electron‐withdrawing effect, will result in a chemically stable spiro‐strained dioxetane with an accelerated chemiexcitation rate. Indeed, spiro‐fused tetramethyl‐oxetanyl exhibited a 128‐fold faster chemiexcitation rate compared to adamantyl while maintaining similar chemical stability, with a half‐life of over 400 hours in PBS 7.4 buffer at room temperature. Turn‐on probes composed of tetramethyl‐oxetanyl spiro‐dioxetane exhibited significantly improved chemical stability in bacterial and mammalian cell media compared to previously developed dioxetane probes fused to a cyclobutyl unit. The superior chemical stability enables a tetramethyl‐oxetanyl dioxetane probe to detect β‐Galactosidase (β‐gal) activity with enhanced sensitivity in Escherichia coli (E. coli) bacterial assays and leucine aminopeptidase activity in tumoral cell lines. Overall, the development of the tetramethyl‐oxetanyl dioxetane luminophore enables us to enhance the detection sensitivity of chemiluminescent probes while maintaining high chemical stability. The results obtained in this study should assist in designing improved chemiluminescent probes and underscore the significance of strain‐release techniques in enhancing the detection sensitivity of chemiluminescence assays.
Electronic Structure Modulating of W18O49 Nanospheres by Niobium Doping for Efficient Hydrogen Evolution Reaction
Authors: Guo Hui , Pan Lu , Gao Mengyou , Kong Linghui , Zhang Jingpeng , Khan Aslam , Siddiqui Nasir A. , Lin Jianjian 
Published: October 2024

AbstractHydrogen, known for its high energy density and environmental benefits, serves as a prime substitute for fossil fuels. Nonetheless, the hydrogen evolution reaction (HER), essential in electrolysis, encounters challenges with slow kinetics and significant overpotential, which elevate costs and reduce efficiency. Thus, developing efficient electrocatalysts to reduce HER overpotential is vital to enhance hydrogen production efficiency and minimize energy consumption. Adjusting the electronic structure of transition metal oxides via elemental doping is a potent strategy to improve the effectiveness of electrocatalysts for hydrogen evolution. In this work, we synthesized a set of niobium‐doped tungsten oxides (Nbx‐W18O49) under anoxic conditions using a straightforward “one‐pot” solvothermal approach. After doping Nb, the oxygen vacancy content inside W18O49 was increased, which induced a synergistic effect with the active sites of tungsten. In acidic environments, the hydrogen evolution activity of the Nb0.6‐W18O49 electrocatalyst is second only by 20 wt % Pt/C. It attains a current density of −10 mA cm−2 at an overpotential of 102 mV. By comparison with W18O49, Nb0.4‐W18O49 and Nb0.5‐W18O49, Nb0.6‐W18O49 demonstrates a reduced charge transfer resistance, which significantly enhances its conductivity and the speed of electron movement across interfaces. Coupled with this feature are notably faster HER kinetics. Additionally, it exhibits excellent stability, meaning it maintains its performance and structural integrity over prolonged periods and under various operational conditions. This article provides a new perspective for discovering inexpensive and efficient hydrogen evolution electrocatalyst materials.