bluuebunny/crossref_metadata_2025 huggingface dataset:
Inducing Polar Phase in Poly(Vinylidene Fluoride) with a Molecular Ferroelectric Copper(II) Complex for Piezoelectric Energy Harvesting
Authors: Haldar Rajashi , Sarkar Utsa , Kumar Ajay , Mandal Dipankar , Shanmugam Maheswaran
Published: June 2024

Piezoelectric nanogenerators (PENGs), the current pathway to sustainable energy harvesting, are mostly comprised of bulk oxide ceramics which are toxic, rigid, and costly to synthesize. A suitable alternative to them is flexible polar polymers like polyvinylidene fluoride (PVDF), but stabilizing its polar phase is also a daunting task. all these aforementioned issues by employing a biocompatible have been solved, above‐room‐temperature (Tc > 390 K) ferroelectric discrete molecular complex [Cu(L‐His)(bpy)]ClO4.1.5H2O (Cu‐FE) which is not only suitable for piezoelectric energy harvesting due to its large values of piezoelectric co‐efficient (d33 = 17 pm V−1) but also is capable of imparting polar β‐phase in PVDF via hydrogen bonding interactions under mild condition (60 °C). Among the PENG devices prepared with the composite films of PVDF and various weight % (w/V) compositions of Cu‐FE, the highest output voltage of 8 V (peak to peak) has been obtained, a power density of 4 µW cm−2, and an output current of 3 µA from the 1 wt.% composite film. The fabricated PENG device also exhibits swift capacitor charging in 40 s, and acts as an excellent pressure sensor, with exceptional sensitivity to low pressures (7 kPa), giving an output of 0.4 V.
Topological Spin Textures: Basic Physics and Devices
Authors: Zhou Yuqing , Li Shuang , Liang Xue , Zhou Yan
Published: June 2024

In the face of escalating modern data storage demands and the constraints of Moore's Law, exploring spintronic solutions, particularly the devices based on magnetic skyrmions, has emerged as a promising frontier in scientific research. Since the first experimental observation of skyrmions, topological spin textures have been extensively studied for their great potential as efficient information carriers in spintronic devices. However, significant challenges have emerged alongside this progress. This review aims to synthesize recent advances in skyrmion research while addressing the major issues encountered in the field. Additionally, current research on promising topological spin structures in addition to skyrmions is summarized. Beyond 2D structures, exploration also extends to 1D magnetic solitons and 3D spin textures. In addition, a diverse array of emerging magnetic materials is introduced, including antiferromagnets and 2D van der Waals magnets, broadening the scope of potential materials hosting topological spin textures. Through a systematic examination of magnetic principles, topological categorization, and the dynamics of spin textures, a comprehensive overview of experimental and theoretical advances in the research of topological magnetism is provided. Finally, both conventional and unconventional applications are summarized based on spin textures proposed thus far. This review provides an outlook on future development in applied spintronics.
Large‐Scale Synthesis of High‐Loading Single Metallic Atom Catalysts by a Metal Coordination Route
Authors: Duan Youyu , Wang Yang , Zhang Weixuan , Ban Chaogang , Feng Yajie , Tao Xiaoping , Li Ang , Wang Kaiwen , Zhang Xu , Han Xiaodong , Fan Wenjun , Zhang Bin , Zou Hanjun , Gan Liyong , Han Guang , Zhou Xiaoyuan
Published: June 2024

Single atom catalyst (SAC) is one of the most efficient and versatile catalysts with well‐defined active sites. However, its facile and large‐scale preparation, the prerequisite of industrial applications, has been very challenging. This dilemma originates from the Gibbs–Thomson effect, which renders it rather difficult to achieve high single atom loading (< 3 mol%). Further, most synthesizing procedures are quite complex, resulting in significant mass loss and thus low yields. Herein, a novel metal coordination route is developed to address these issues simultaneously, which is realized owing to the rapid complexation between ligands (e.g., biuret) and metal ions in aqueous solutions and subsequent in situ polymerization of the formed complexes to yield SACs. The whole preparation process involves only one heating step operated in air without any special protecting atmospheres, showing general applicability for diverse transition metals. Take Cu SAC for an example, a record yield of up to 3.565 kg in one pot and an ultrahigh metal loading 16.03 mol% on carbon nitride (Cu/CN) are approached. The as‐prepared SACs are demonstrated to possess high activity, outstanding selectivity, and robust cyclicity for CO2 photoreduction to HCOOH. This research explores a robust route toward cost‐effective, massive production of SACs for potential industrial applications.
Ultrafast Interfacial Self‐Assembly toward Bioderived Polyester COF Membranes with Microstructure Optimization
Authors: Du Jingcheng , Yao Ayan , Sun Qian , Liu Linghao , Song Ziye , He Wen , Wang Chengming , Dou Pengjia , Guan Jian , Liu Jiangtao
Published: June 2024

The precise manipulation of the microstructure (pore size, free volume distribution, and connectivity of the free‐volume elements), thickness, and mechanical characteristics of membranes holds paramount significance in facilitating the effective utilization of self‐standing membranes. In this contribution, the synthesis of two innovative ester‐linked covalent–organic framework (COF) membranes is first reported, which are generated through the selection of plant‐derived ellagic acid and quercetin phenolic monomers in conjunction with terephthaloyl chloride as a building block. The optimization of the microstructure of these two COF membranes is systematically achieved through the application of three different interfacial electric field systems: electric neutrality, positive electricity, and negative electricity. It is observed that the positively charged system facilitates a record increase in the rate of membrane formation, resulting in a denser membrane with a uniform pore size and enhanced flexibility. In addition, a correlation is identified wherein an increase in the alkyl chain length of the surfactants leads to a more uniform pore size and a decrease in the molecular weight cutoff of the COF membrane. The resulting COF membrane exhibits an unprecedented combination of high water permeance, superior sieving capability, robust mechanical strength, chemical robustness for promising membrane‐based separation science and technology.
Statistical and Correlative Characterization of Individual Nanoparticle in Gap Plasmon Resonator Sensors
Authors: Poungsripong Peeranuch , Kannampalli Vyshnav , Santinacci Lionel , Grosso David , Chatain Dominique , Duché David , Margeat Olivier , Sciacca Beniamino
Published: June 2024

Plasmonic nanocavities are receving increased attention from the nanophotonics, nanoelectronics, and quantum optics community due to their ability to confine light in extremely small volumes. Coupling colloidal plasmonic nanocrystals to metal films is an inexpensive approach to fabricate virtually unlimited individual resonators that can be tuned by adjusting nanoparticle size, gap thickness, and refractive index. The focus is on silver nanocubes separated from a gold mirror by thin amorphous dielectric layers (Al2O3, TiO2). The optical response is measured and correlative electron microscopy is performed on a large number (>800) of individual resonators to unveil the statistical distribution of gap plasmon modes and assess systematically their sensitivity. A sensitivity as large as 8 nm/nm to nanocube size variation, 50 nm/nm to Al2O3 thickness variation, and 130 nm/RIU for index change of the spacer layer is found. With the help of numerical simulations, this approach enables to infer a quantitative statistical distribution of molecular coatings present on the nanocubes surface, such as polyvinylpyrrolidone, which can affect the performance of nanoelectronic devices and assess the strategy to remove it. Finally, polarization‐resolved measurements enable to unveil a birefringent behavior when nanocubes are supported on annealed TiO2 layers (2–4 nm).
Exploring Microwave Reconfigurable Intelligent Surface for Wireless VOC Detection: A Comparative Study of Porous and Solid PDMS Interfaces
Authors: Mirzaei Hamed , Niksan Omid , Arjmand Mohammad , Zarifi Mohammad H.
Published: June 2024

Microwave gas monitoring with a low‐profile design and enhanced selectivity remains a persistent challenge. This study introduces an innovative approach employing a real‐time wireless reconfigurable intelligent surface (RIS) for comparative investigation of the interaction of two distinct polydimethylsiloxane (PDMS) interfaces, i.e., solid and porous, with acetone gas molecules. The developed PDMS‐coated microwave RIS detects varying concentrations of acetone vapor by wirelessly monitoring variations in the resonant characteristics of the resonating RIS beneath the sensitive interface. This PDMS‐coated microwave RIS is validated through exposure to incremental (15–75) parts per thousand (ppt) acetone concentrations and demonstrated a sensitivity of ≈4.4 MHz/ppt and ≈4.3 MHz/ppt of acetone for solid and porous PDMS, respectively. Integrating PDMS and microwave‐based RIS systems provides a sensitive tool for tracking the interaction of acetone gas and PDMS and demonstrates this system's capability for sensitive gas detection. This study introduces a unique development in the wireless detection of VOCs and presents a compact and passive approach with enhanced sensitivity, making it suitable for monitoring the interaction of polymers and hazardous VOCs. This technology is particularly suited for use in challenging and hard‐to‐reach environments.
Enzalutamide Sensitizes Castration‐Resistant Prostate Cancer to Copper‐Mediated Cell Death
Authors: Gao Xiang , Zhao Haolin , Liu Jiao , Wang Min , Dai Zhihong , Hao Wenjun , Wang Yanlong , Wang Xiang , Zhang Min , Liu Pixu , Cheng Hailing , Liu Zhiyu
Published: June 2024

Despite the initial efficacy of enzalutamide in castration‐resistant prostate cancer (CRPC), inevitable resistance remains a significant challenge. Here, the synergistic induction of copper‐dependent cell death (cuproptosis) in CRPC cells is reported by enzalutamide and copper ionophores (elesclomol/disulfiram). Mechanistically, enzalutamide treatment increases mitochondrial dependence in CRPC cells, rendering them susceptible to cuproptosis, as evidenced by specific reversal with the copper chelator tetrathiomolybdate. This susceptibility is characterized by hallmarks of cuproptosis, including lipoylated protein aggregation and iron‐sulfur cluster protein instability. Interestingly, the mitochondrial matrix reductase, FDX1, specifically correlates with elesclomol sensitivity, suggesting a potential mechanistic divergence between the two copper ionophores. Notably, this synergistic effect extends beyond in vitro models, demonstrating efficacy in 22Rv1 xenografts, mouse Pten p53 knockout organoids. Importantly, enzalutamide significantly enhances copper ionophore‐mediated cytotoxicity in enzalutamide‐resistant cells. Collectively, these findings indicate that enzalutamide and copper ionophores synergistically induce cuproptosis, offering a promising therapeutic avenue for CRPC, potentially including enzalutamide‐resistant cases.
First Principles Study of Aluminum Doped Polycrystalline Silicon as a Potential Anode Candidate in Li‐ion Batteries
Authors: Bhimineni Sree Harsha , Ko Shu‐Ting , Cornwell Casey , Xia Yantao , Tolbert Sarah H. , Luo Jian , Sautet Philippe
Published: June 2024

Addressing sustainable energy storage remains crucial for transitioning to renewable sources. While Li‐ion batteries have made significant contributions, enhancing their capacity through alternative materials remains a key challenge. Micro‐sized silicon is a promising anode material due to its tenfold higher theoretical capacity compared to conventional graphite. However, its substantial volumetric expansion during cycling impedes practical application due to mechanical failure and rapid capacity fading. A novel approach is proposed to mitigate this issue by incorporating trace amounts of aluminum into the micro‐sized silicon electrode using ball milling. Density functional theory (DFT) is employed to establish a theoretical framework elucidating how grain boundary sliding, a key mechanism involved in preventing mechanical failure is facilitated by the presence of trace aluminum at grain boundaries. This, in turn, reduces stress accumulation within the material, reducing the likelihood of failure. To validate the theoretical predictions, capacity retention experiments are conducted on undoped and Al‐doped micro‐sized silicon samples. The results demonstrate significantly reduced capacity fading in the doped sample, corroborating the theoretical framework and showcasing the potential of aluminum doping for improved Li‐ion battery performance.
Highly Reversible and Stable Sulfur‐Containing Cathodes for Magnesium Batteries with Two‐Plateau Redox Reactions Enabled by Kinetically Favored Mg─S Decomposition
Authors: Xu Hao , Xie Tian , Li Yue , Sun Fengzhan , Zhang Chao , Li Zhao , Yao Yingying , Li Yinghui , Zhan Yang , Zou Xinshu , Shi Chenyang , Wu Zhao , Laine Richard , Zou Jianxin
Published: June 2024

Rechargeable magnesium sulfur batteries (MSBs) face issues like polysulfide shuttling, sluggish redox kinetics, and high cost, leading to dissatisfied practical demonstrations. Herein, simple battery configurations utilizing 100% sulfur are proposed on nine collectors and a low‐cost phenolate‐based magnesium complex (PMC) electrolyte to address these problems. Comprehensive studies indicate that the Cu collector is the most conducive to improving battery performance, not only facilitating the generation of magnesium sulfides during discharging but also effectively dissociating Mg─S bonds during charging. Moreover, Cu surfaces can effectively adsorb magnesium polysulfides (MgSx) and induce an insulator‐to‐metal transition of MgS, leading to a more effective suppression of the shuttle effect and the transfer of electrons. MXene interlayers are further introduced between electrodes to inhibit MgSx shuttling and enhance the interfacial electronic conductivity, as reflected by the reinforced high discharge voltage plateau at ≈1.7 V and stable long discharge voltage plateau at ≈1.2 V. The assembled MSBs exhibit the highest reported capacity of 1260 mAh g−1S and an energy density of 1230 Wh kg−1S with a cycle life of over 1000 cycles. This research contributes to the fundamental understanding of rechargeable MSBs and marks a significant advancement in optimizing cell designs for better performance.
Pyridazine‐Promoted Construction of Vinylene‐Linked Covalent Organic Frameworks with Exceptional Capability of Stepwise Water Harvesting
Authors: Mou Kaiwen , Meng Fancheng , Zhang Zixing , Li Xiaomeng , Li Mengqi , Jiao Yang , Wang Zhiheng , Bai Xue , Zhang Fan
Published: June 2024

In this study, we successfully developed two novel vinylene‐linked covalent organic frameworks (COFs) using 2‐connected 3,6‐dimethylpyridazine through Knoevenagel condensation. These COFs featured finely tailored micro‐/nano‐scale pore sizes, high surface areas and stable non‐polar vinylene linkages. Finely resolved powder X‐ray diffraction patterns demonstrated highly crystalline structures with a hexagonal lattice in the AA layer stacking. The resulting one‐dimensional channels possess strong hydrogen‐bond accepting sites arising from the decorated cis‐azo/azine units with two pairs of fully exposed lone pair electrons, endowing the as‐prepared COFs with exceptional water absorption properties. The g‐DZPH‐COF exhibited successive steep water uptake steps starting from low relative pressures (P/PSTA=0.1), with the remarkable water uptake capacity of 0.26 g/g at P/PSTA=0.2 (25 °C), which is the optimal value recorded among the reported COFs. Dynamic vapour sorption measurements revealed the fast kinetics of these COFs, even in the cluster formation process. Water uptake and release cycling tests demonstrated their outstanding hydrolytic stability, durability, and adsorption–desorption retention ability.
Bimetallic Single Atom/Nanoparticle Ensemble for Efficient Photochemical Cascade Synthesis of Ethylene from Methane
Authors: Wang Yin‐Feng , Qi Ming‐Yu , Conte Marco , Tang Zi‐Rong , Xu Yi‐Jun
Published: June 2024

Light‐driven photoredox catalysis presents a promising approach for the activation and conversion of methane (CH4) into high value‐added chemicals under ambient conditions. However, the high C−H bond dissociation energy of CH4 and the absence of well‐defined C−H activation sites on catalysts significantly limit the highly efficient conversion of CH4 toward multicarbon (C2+) hydrocarbons, particularly ethylene (C2H4). Herein, we demonstrate a bimetallic design of Ag nanoparticles (NPs) and Pd single atoms (SAs) on ZnO for the cascade conversion of CH4 into C2H4 with the highest production rate compared with previous works. Mechanistic studies reveal that the synergistic effect of Ag NPs and Pd SAs, upon effecting key bond‐breaking and ‐forming events, lowers the overall energy barrier of the activation process of both CH4 and the resulting C2H6, constituting a truly synergistic catalytic system to facilitate the C2H4 generation. This work offers a novel perspective on the advancement of photocatalytic directional CH4 conversion toward high value‐added C2+ hydrocarbons through the subtle design of bimetallic cascade catalyst strategy.
Nano silica grafted on modified polyacrylonitrile fiber improves the interfacial strength of fiber‐reinforced concrete
Authors: Wei Fayun , Xu Xiao , Wang Hailou , Yu Bin , Zhang Guangyu , Zhang Wei
Published: June 2024

Cement is known to be brittle and usually reinforced with fibers. However, there is a lack of effective chemical bonding between organic fibers and inorganic cement, resulting in a weaker interfacial bonding strength. In this paper, amino hyperbranched polymer (HBP) was used to modify the surface of polyacrylonitrile (PAN) fibers, and then silica nanoparticles (SiO2 NPs) were grafted on the surface of modified PAN fibers to realize the inorganic treatment of organic fibers. The modified PAN fibers applied to cement concrete can significantly enhance the interfacial strength between the fibers and cement. The morphology and chemical composition of the modified PAN fibers were characterized by scanning electron microscope, atomic force microscope, electron energy dispersive spectroscopy, and Fourier transform infrared spectroscopy, and the influence of grafting conditions on grafting effect was analyzed. The results show that SiO2 NPs were evenly distributed on the surface of PAN fiber. When SiO2 NPs concentration was 4%, grafting temperature was 50°C, and grafting time was 4 h, the grafting degree of SiO2 NPs grafted PAN fiber can reach to 1.4%. After coating with SiO2 NPs, the pullout bonding strength of the PAN fiber was increased from 5.5 to 6.5 cN.
Utility of green chemistry for feasible spectrofluorometric determination of trifluridine via metal complexation: Application to dosage forms
Authors: Salem Hesham , Emad Nadeen , Fares Joy , Ahmed Habeba , Kamal Habiba , Zein Dina
Published: June 2024

The goal of the current research was to establish a quick and practical fluorometric technique for trifluridine analysis. The approach relied on the drug's complex formation with the zinc ion to produce a high‐fluorescence product. The fluorescence was further enhanced by adding sodium dodecyl sulfate, and it was observed at 450 nm following excitation at 400 nm. With a determination coefficient of 0.9994, the association between emission intensity and trifluridine concentration was linear between 1 and 125 ng mL−1. The quantitation limit was 0.987 ng mL−1 while 0.333 ng mL−1 was the detection limit. The buffer type, pH and concentration, type of surfactant and concentration, and finally the diluting solvent were among the reaction conditions that were closely examined. With great precision and reliability, the drug in question was quantified using this method in dosage formulations. The proposed method's level of greenness was assessed using two methodologies: the analytical greenness metric (AGREE) and the Green Analytical Procedure Index (GAPI).
Superficial retrocalcaneal bursae and nerves: From anatomy to ultrasound‐guided procedures
Authors: Ricci Vincenzo , Chang Ke‐Vin , Naňka Ondřej , Özçakar Levent
Published: June 2024

The pertinent literature widely describes ultrasound‐guided procedures targeting the retrocalcaneal bursa and the tendon tissue to manage insertional Achilles tendinopathy. Synovial bursae and cutaneous nerves of the superficial retrocalcaneal pad are often overlooked pain generators and are poorly considered by clinicians and surgeons. A layer‐by‐layer dissection of the superficial soft tissues in the retrocalcaneal region of two fresh frozen cadavers was matched with historical anatomical tables of the textbook Traite d'Anatomie Topographique Avec Applications Médico‐Chirurgicales (1909 by Testut and Jacob). An accurate and detailed description of the superficial retrocalcaneal pad with its synovial bursae and cutaneous nerves was provided. Cadaveric dissections confirmed the compartmentalized architecture of the superficial retrocalcaneal fat pad and its histological continuum with the superficial lamina of the crural fascia. Superficial synovial tissue islands have been demonstrated on the posterior aspect of the Achilles tendon in one cadaver and on the posterolateral surface of the tendon in the other one. Digitalization of the original anatomical tables of the textbook Traite d'Anatomie Topographique Avec Applications Médico‐Chirurgicales (1909 by Testut and Jacob) showed five potential locations of the superficial calcaneal bursa and a superficial retrocalcaneal nerve plexus within the Achilles tendon‐fat pad interface. In clinical practice, in addition to the previously described interventions regarding the retrocalcaneal bursa and the tendon tissue, ultrasound‐guided procedures targeting the synovial and neural tissues of the superficial retrocalcaneal pad should be considered to optimize the management of insertional Achilles tendinopathy.
Food and housing insecurity among community college student‐veterans
Authors: Soria Krista M. , Smith Amish B.
Published: June 2024

In this manuscript, the authors examined the rates of food and housing insecurity experienced by student‐veterans enrolled at community colleges in fall 2020. The results of a multi‐institutional survey of student‐veterans at 113 community colleges suggested that 37.6% of community college student‐veterans experienced food insecurity and 52.5% of community college student‐veterans experienced housing insecurity. Additionally, 17.8% of community college student‐veterans experienced homelessness in the past year. The results also suggest that community college student‐veterans who experienced food and housing insecurity had lower grade point averages, higher rates of clinically significant generalized anxiety disorder, and higher rates of clinically significant major depressive disorder. Examples of strategies to support community college student‐veterans experiencing food and housing insecurity are included.
Enhancing Suppression of Chain Transfer via Installing Bulky N‐ortho‐Aryl Substituents into α‐Diimine Nickel System
Authors: Ma Zhanshan , Nie Nan , Pang Wenmin , Chen Ao , Peng Dan
Published: June 2024

Recently, the important role of sterically bulky aromatic substituents at the axial position of the metal center for synthesizing high‐performance catalysts were recognized. In this study, a series of α‐diimine nickel complexes with bulky N‐ortho‐aryl substituents were designed and synthesized. The as‐synthesized nickel complexes showed high activities (up to 2.3×107 g ⋅ mol−1 ⋅ h−1) and superior thermostability, giving access to moderately branched polyethylenes (35–86/1000 C) with high molecular weights (up to 197.5×104 g ⋅ mol−1). The polyethylene materials generated by these nickel complexes at 80 °C exhibited outstanding tensile mechanical. In addition, these nickel complexes could also catalyze the copolymerization of ethylene and polar monomer with modest activity (such as undecenoic acid, 10‐undecen‐1‐ol and 6‐chlorohex‐1‐ene), yielding functionalized polyolefin with adjustable molecular weights (6.8–222.9×104 g ⋅ mol−1) and incorporation ratios (0.2–4.3 mol %).
Old Yellow Enzymes as Oxime Reductases: New Variants by Substrate‐Based Enzyme Engineering
Authors: Polidori Nakia , Breukelaar Willem B. , Stelzer Svila , Reiter Tamara , Glueck Silvia M. , Kroutil Wolfgang , Gruber Karl
Published: June 2024

The reduction of oximes was recently identified as a promiscuous activity of Old Yellow Enzymes (OYEs). This reaction involves a two‐step reduction of α‐oxime‐ß‐ketoesters to the corresponding amines, which spontaneously dimerise to yield pyrazine derivatives. This biotransformation is currently limited to substrates with small substituents like methyl/ethyl on the keto moiety. We used a structure‐based approach to engineer 12‐oxophytodienoate reductase 3 (OPR3) from Solanum lycopersicum as a prototypical OYE to accept oximes with bulkier substituents. To this end, three single and two double variants were prepared and tested on six oxime substrates. The engineered variants indeed showed activity on some of the bulkier substrates, which had not been converted at all by the wild‐type enzyme, including the diester compound diethyl‐2‐(hydroximino) malonate. While we were unable to identify variants capable of converting substrates with branched and aromatic substituents, the results demonstrate the validity of our engineering approach, suggesting potential pathways for expanding the substrate scope of OYEs.
Multisite Amino‐Allylidene Ligands from Thermal CO Elimination in Diiron Complexes and Catalytic Activity in Hydroboration Reactions
Authors: Zappelli Chiara , Taglieri Francesco , Schoch Silvia , Bresciani Giulio , Funaioli Tiziana , Marchetti Fabio , Zacchini Stefano , Di Giuseppe Andrea , Crucianelli Marcello
Published: June 2024

The new diiron(I) complexes [Fe2Cp2(μ‐CO){μ‐k3C,kN‐C(R1)C(R2)C(CN)NMe(R)}], 3 a–o (R=alkyl or 4‐C6H4OMe; R1=alkyl, aryl, ferrocenyl (Fc), thiophenyl, CO2Me or SiMe3; R2=H, Me or CO2Me) were synthesized in moderate to high yields from the thermal decarbonylation of the bis‐carbonyl precursors 2 a–o, and were structurally characterized by IR and NMR spectroscopy, and single crystal X‐ray diffraction in four cases. Electrochemical behavior of one complex was also investigated. Complexes 3 a–o comprise a highly functionalized, multisite amino‐(cyano)allylidene ligand, including metal coordination of a tertiary amine group. Selected complexes displayed negligible to moderate catalytic activity in CO2/propylene oxide coupling, working under ambient conditions. Additionally, they were investigated as catalysts for the conversion of benzaldehyde to the corresponding borate ester 6 a, using pinacolborane (HBpin) as the borylating agent. Most complexes achieved good conversions at room temperature with 1 % catalyst loading, and data highlight the significant influence of the multisite ligand substituents on the catalytic performance. Notably, complex 3 m (featuring R=4‐methoxyphenyl, R1=Fc, R2=H) displayed the highest activity and effectively catalyzed the hydroboration of various aldehydes and ketones. A plausible mechanistic cycle involves metal coordination of the carbonyl substrate, its activation being possibly facilitated by intramolecular interactions.
Multiscale structural NaTi2(PO4)3 anode for sodium‐ion batteries with long cycle, high areal capacity, and wide operation temperature
Authors: Xu Guobao , Yang Liyue , Yan Zhihao , Huang Zhikai , Li Xue , Guo Gencai , Tian Ye , Yang Liwen , Huang Jianyu , Liang Yaru , Chou Shulei
Published: June 2024

Though plenty of research has been conducted to improve the low intrinsic electronic conductivity of NASICON‐structured NaTi2(PO4)3 (NTP), realizing sodium‐ion batteries with high areal/volumetric capacity still remains a formidable challenge. Herein, a multiscale design from anode material to electrode structure is proposed to obtain a gadolinium‐ion‐doped and carbon‐coated NTP composite electrode (NTP‐Gd‐C), in which gadolinium ion doping, oxygen vacancy, optimized structure, N‐doped carbon coating, and bridging on the three‐dimensional network are simultaneously achieved. In the whole electrode, the excellent hierarchical electronic/ionic conductivity and structural stability are simultaneously improved via the synergistic optimization of NTP‐Gd‐C. As a result, excellent electrochemical performances of NTP‐Gd‐C electrode with a high areal/volumetric capacity of 1.0 mAh cm−2/142.8 mAh cm−3, high rate capability (58.3 mAh g−1 at 200 C), long cycle life (ultralow capacity fading of 0.004% per cycle under 10,000 cycles), and wide‐temperature electrochemical performances (97.0 mAh g−1 at 2 C under −20°C) are achieved. Moreover, the NTP‐Gd‐C//Na3V2(PO4)3/C full cell also delivers an excellent rate capacity of 42.0 mAh g−1 at 200 C and long‐term high‐capacity retention of 66.2% after 4000 cycles at 20 C.
Designing a heavy metal electrochemical sensor for Pb detection in water—A generalized approach for electrochemical sensing using low‐cost materials
Authors: Rajesh Singuru , Kumawat Adhidesh S.
Published: June 2024

This work attempts to design an elemental method for detecting heavy metals in water. The presence of heavy metals in water is a critical issue that needs a check at every level of water consumption. To facilitate the checking, a simple method needs to be identified and developed. Electrochemical sensing is essentially a surface phenomenon and requires a higher surface area for greater accuracy and reliability. We have attempted to use a readily available Cu wire for detecting Pb to 50 μM concentration with 90% reliability. It is important to note that the sensing electrode (Cu wire) utilized for this work has been employed in a facile manner that enhances the ease of use for heavy metal electrochemical sensor. Moreover, post‐usage, the replacement of sensor material for subsequent usage is easy. The low cost and simplicity of the method make it ideal for resource‐constrained environments and portability, resulting in increasing the accessibility of water quality monitoring. The study examines the reliability of a low‐cost electrode for Pb concentration detection in water samples to the concentration of 50 μM using a simple low‐cost electrochemical sensor arrangement.
A Comprehensive Computational Study on the Thermodynamics and Kinetics of Tetrahydrobiopterin Regeneration Process
Authors: Samanta Suvadip , Mondal Padmabati
Published: June 2024

One of the most crucial enzymatic cofactors in the human body is tetrahydrobiopterin, which is acquired through biological synthesis and self‐regeneration. During this regenerative process, it undergoes oxidation, deprotonation, further oxidation, and subsequent deprotonation, resulting in the formation of quinonoid‐dihydrobiopterin, which then undergoes tautomerization to yield dihydrobiopterin. This study presents the thermodynamic and kinetic properties associated with each stage of the regeneration process using theoretical calculations. The redox potentials for oxidation steps and the pKa values for deprotonation steps are determined employing the Born‐Haber cycle and the direct change of free energy in implicit solvent models. The redox metabolites are characterized and confirmed from their calculated absorption spectra using the time‐dependent density functional theory method. For the tautomerization steps, an IRC calculation is executed, and rate constants are computed using Eyring's Transition State Theory (TST). The tunnelling probability of the H atom during the tautomerization process is incorporated using Wigner's tunnelling correction in the calculation of the rate constant. Notably, we identify the N3 atom as the most probable deprotonation site for H3B+ and predict its geometry based on our calculations. Furthermore, we elucidate the spectral properties of intermediates involved in the regeneration process, highlighting key electronic transitions responsible for their excitations. Our results indicate that each step of tautomerization occurs along vibrational bending modes. We have observed that these tautomerization processes have high activation energies by optimising transition states. Additionally, considering tunnelling correction can significantly affect the reaction rates associated with these processes. These results provide a comprehensive understanding of the thermodynamics and kinetics of the regeneration process of tetrahydrobiopterin, which will help in the modulation of its biological activity.
Decoupling analysis for different exciting modes in MIMO DRA using absorbing surface walls
Authors: Yadav Abhay Krishna , Verma Sudhanshu , Sigroha Deepak , Das Gourab , Sharma Deepak Kumar , Sharma Anand
Published: June 2024

In this paper, a decoupling mechanism is discussed for different mode excitations in the cylindrical dielectric resonator antenna (cDRA) by utilizing absorbing surface wall. In the cDRA, the fundamental radiating mode is HE11δ. Another higher order mode for radiation purpose in cDRA is HE12δ. Both HE11δ and HE12δ create broadside radiation. To analyze multiple‐input multiple‐output (MIMO) performance, two different dual‐port DRAs are proposed. Each antenna structure consists of two DRA with dual similar ports supporting the same mode. Therefore, two different antenna structures are proposed for two different modes. For each antenna, two 2 × 3 absorber array walls are designed, and they are placed in between the DRA to reduce the mutual coupling. When the absorber array walls are placed in between the antenna elements, they blocked the free‐space electromagnetic (EM) field interaction in between the DRA. Due to the reduction of free‐space radiation interaction, the mutual coupling between the ports is improved tremendously. For both HE11δ and HE12δ modes, the mutual coupling is reduced by more than 10 dB. To analyze efficacy of the proposed method, the antenna structure featuring the HE11δ mode is fabricated and experimentally tested.
Detection of circulating tumor cells in blood using two‐step random forest
Authors: Wei Hua , Natori Takahiro , Tanaka Tomohiro , Aoki Shin , Kuriyama Sho , Yamada Takeshi , Aikawa Naoyuki
Published: June 2024

Cancer has been the leading cause of death among Japanese since 1981, and many people die from it every year worldwide. While various measures have been taken to reduce the mortality rate of cancer, circulating tumor cells (CTCs) in the blood have been attracting attention in recent years. In the past, CTCs were detected by visual inspection by a physician or by an expensive machine, but these methods required much effort by the physician and required only EpCAM‐expressing cells to be detected. In addition, detection by image processing has been used, but it has the problem that the area of interest is only a part of the area and there are many false positives. In this paper, we propose a two‐step classification method that focuses on the shape and surface of cells. In the proposed method, multiple shape and surface features are obtained for four types of cells in blood images: Clusters, CTCs, Normal Cells, and Vertical Cells. Based on the features, cells are classified using a two‐step Random Forest and their accuracy is evaluated. Furthermore, the effectiveness of the proposed method is demonstrated by comparing it with conventional methods.
Sc(OTf)3‐Catalyzed Synthesis of 3‐Substituted Lawsones through a Buchner‐Curtius‐Schlotterbeck Reaction
Authors: Gogula Sailam Sri , Prasanna Dasari Vijaya , Sridhar B. , Lincoln Ch. Abraham , Reddy P. Muralidhar , Reddy B. V. Subba
Published: June 2024

An efficient strategy has been developed for the synthesis of 3‐substituted lawsones using a catalytic amount of Sc(OTf)3 in toluene at −78 °C through a Buchner‐Curtius‐Schlotterbeck reaction. It is a versatile method to produce a large number of 3‐aryl, 3‐styryl, 3‐alkyl, and 3‐heteroaryl substituted lawsones under mild conditions. This is a first report on the synthesis of 3‐substituted lawsones in high yields with in short reaction times.
An optimal attention PLSTM‐based classification model to enhance the performance of IoMT attack detection in healthcare application
Authors: Dhanushkodi Kavitha , Shunmugiah Jeyalakshmi , Velladurai Santhana Marichamy , Rajendran Saranya
Published: June 2024

The Internet of Medical Things (IoMT) has revolutionized the healthcare industry by allowing remote monitoring of patients suffering from chronic diseases. However, security concerns arise due to the potential life‐threatening damage that can be caused by attacks on IoMT devices. To enhance the security of IoMT devices, researchers propose the use of novel artificial intelligence‐based intrusion detection techniques. This article presents a hybrid alex net model and an orthogonal opposition‐based learning Yin‐Yang‐pair optimization (OOYO) optimized attention‐based Peephole long short term memory (PLSTM) model to distinguish between malicious and normal network traffic in the IoMT environment. To improve the scalability of the model in handling the random and dynamic behavior of malicious attacks, the hyper parameters of the PLSTM framework are optimized using the OOYO algorithm. The proposed model is evaluated on different IoT benchmark datasets such as N‐BaIoT and IoT healthcare security. Experimental results demonstrate that the proposed model provides a classification accuracy of 99% and 98% on the healthcare security and N‐BaIoT datasets, respectively. Moreover, the proposed model exhibits high generalization ability for multi‐class classifications and is effective in reducing the false discovery rate. Overall, the proposed model achieves high accuracy, scalability, and generalization ability in identifying malicious traffic, which can help improve the security solution of IoMT devices.
A general pressure equation based method for incompressible two‐phase flows
Authors: Bodhanwalla Hormuzd , Raghunathan Dheeraj , Sudhakar Y.
Published: June 2024

We present a fully‐explicit, iteration‐free, weakly‐compressible method to simulate immiscible incompressible two‐phase flows. To update pressure, we circumvent the computationally expensive Poisson equation and use the general pressure equation which is solved explicitly. In addition, a less diffusive algebraic volume‐of‐fluid approach is used as the interface capturing technique and in order to facilitate improved parallel computing scalability, the technique is discretised temporally using the operator‐split methodology. Our method is fully‐explicit and stable with simple local spatial discretization, and hence, it is easy to implement. Several two‐ and three‐dimensional canonical two‐phase flows are simulated. The qualitative and quantitative results prove that our method is capable of accurately handling problems involving a range of density and viscosity ratios and surface tension effects.
Physiological and biochemical characteristics of milk thistle (Silybum marianum (L.) Gaertn) as affected by some plant growth regulators
Authors: Fanai Sahar , Bakhshi Davood , Abbaszadeh Bohloul
Published: June 2024

Milk thistle (Silybum marianum (L.) Gaertn) is a globally and widely used medicinal plant that contains silymarin. This plant has antioxidant, antimicrobial, anticancer, hepatoprotective, cardiovascular‐protective, and neuroprotective effects. Plant quality, yield, and phytochemicals, especially silymarin content, change under various conditions like drought stress. Therefore, this research studied plant growth regulators (PGRs) like salicylic acid, spermidine, and brassinosteroid to increase plant tolerance to drought stress. Experimental treatments include different levels of irrigation (25%, 50%, 75%, and 90% field capacity), and foliar spraying including salicylic acid (75 and 150 mg/L), spermine (70 and 140 mg/L), and brassinosteroid (1 and 1.2 μM), separately, and water as a control and a secondary factor. The results revealed that the highest amount of leaf phenolic compounds was observed in the highest drought stress level (25%) and 75 mg/L salicylic acid application. Furthermore, brassinosteroid at different concentrations and salicylic acid (75 mg/L) increased leaf flavonoid content compared to other treatments. In 50% field capacity, foliar application of salicylic acid (150 mg/L) significantly increased seed yield by approximately 75% compared to control under the same stress level. Brassinosteroid application (1 μM) under 75% field capacity significantly increased the seed's taxifolin amount by 159%. Additionally, salicylic acid noticeably increased the silychristin concentration. The concentration of silydianin in the seed has also been increased under drought stress and foliar spraying with PGRs. Compared to the control, using spermidine below 75% field capacity caused an increase in its concentrations by over seven times. The highest silybin A amount was obtained in 50% field capacity and foliar150 mg/L salicylic acid. Taxifolin, silychristin, silydianin, silybinin B, iso‐silybinin A, and iso‐silybinin B compounds were identified in the seed extract. Generally, foliar spraying using plant growth regulators increased the number of silymarin compounds under drought stress conditions and field cultivation conditions.
Revitalizing traditional Turkish tort cheese into spreadable form: Enhancing bioactive and sensory attributes with utilization of carob molasses pulp that is a food waste
Authors: Özbek Çağla , Özdemir Yüksel
Published: June 2024

Tort cheese is a traditional cheese that is a gastronomically valuable product, especially in the Mediterranean Region of Turkey, obtained by prolonged boiling of whey, which is one of the most important dairy byproducts. Due to the difficulty of production and its short shelf life, this cheese, which is produced in limited quantities and has low nutritional value, is among the forgotten products. In this study, a spreadable new cheese formulation was developed to increase the edibility and nutritional value of traditional Tort cheese. In this context, pulp (carob molasses pulp (CMP)) from carob molasses production was added to the cheese in different proportions (5%, 10%, and 15%), and some physicochemical, textural, and sensory properties of the cheeses were examined. As a result of the research, it was determined that the addition of CMP caused a decrease in the pH, fat, and protein content of the cheeses, while significantly increasing the dry matter, acidity, ash, carbohydrate, antioxidant activity, and total phenolic content. With CMP addition, the hardness and water‐holding capacity of the cheeses increased, while spreadability, adhesiveness, and syneresis decreased. As the concentration of CMP increased, the L* and b* values decreased, while the a* value increased. In terms of sensory properties, the least preferred sample was the control, while the sample with 5% CMP addition, which is the most spreadable cheese, was the most preferred. As a result, a new product with lower fat content that was more durable and stable, rich in bioactive properties, and with improved sensory attributes was developed.
Pre‐diagnostic plasma inflammatory proteins and risk of hepatocellular carcinoma in three population‐based cohort studies from the United States and the United Kingdom
Authors: Zhao Longgang , Zhang Xinyuan , Birmann Brenda M. , Danford Christopher J. , Lai Michelle , Simon Tracey G. , Chan Andrew T. , Giovannucci Edward L. , Ngo Long , Libermann Towia A. , Zhang Xuehong
Published: June 2024

Previous studies suggest a role for inflammation in hepatocarcinogenesis. However, no study has comprehensively evaluated associations between circulating inflammatory proteins and risk of hepatocellular carcinoma (HCC) among the general population. We conducted a nested case–control study in the Nurses' Health Study (NHS) and the Health Professionals Follow‐up Study (HPFS) with 56 pairs of incident HCC cases and controls. External validation was performed in the UK Biobank (34 HCC cases and 48,471 non‐HCC controls). Inflammatory protein levels were measured in pre‐diagnostic plasma using the Olink® Inflammation Panel. We used conditional logistic regression to calculate multivariable odds ratios (ORs) with 95% confidence intervals (CIs) for associations between a 1‐standard deviation (SD) increase in biomarker levels and HCC risk, considering a statistically significant threshold of false discovery rate (FDR)‐adjusted p < .05. In the NHS/HPFS, among 70 analyzed proteins with call rates >80%, 15 proteins had significant associations with HCC risk (pFDR < .05). Two proteins (stem cell factor, OR per SD = 0.31, 95% CI = 0.16–0.58; tumor necrosis factor superfamily member 12, OR per SD = 0.51, 95% CI = 0.31–0.85) were inversely associated whereas 13 proteins were positively associated with risk of HCC; positive ORs per SD ranged from 1.73 for interleukin (IL)‐10 to 2.35 for C‐C motif chemokine‐19. A total of 11 proteins were further replicated in the UK Biobank. Seven of the eight selected positively associated proteins also showed positive associations with HCC risk by enzyme‐linked immunosorbent assay, with ORs ranging from 1.56 for IL‐10 to 2.72 for hepatocyte growth factor. More studies are warranted to further investigate the roles of these observed inflammatory proteins in HCC etiology, early detection, risk stratification, and disease treatment.
Myelodysplastic syndrome occurring after enfortumab vedotin treatment for metastatic urothelial carcinoma
Authors: Yanagida Kazuki , Kawai Taketo , Seito Toyoshi , Matsumoto Kensuke , Kaneko Tomoyuki , Nakagawa Tohru
Published: June 2024

Introduction

Enfortumab vedotin is an antibody‐drug conjugate targeting Nectin‐4 for the treatment of advanced urothelial carcinoma in patients previously treated with platinum‐containing chemotherapy and immune checkpoint inhibitors. Common adverse events include rashes, peripheral neuropathy, and hyperglycemia. However, there are no reports on the development of myelodysplastic syndrome during enfortumab vedotin therapy in clinical settings.

Case presentation

A 72‐year‐old male patient experienced prolonged and severe thrombocytopenia 18 weeks after the start of enfortumab vedotin therapy for metastatic urothelial carcinoma, requiring daily platelet transfusions. Bone marrow examination and chromosomal analysis confirmed the diagnosis of myelodysplastic syndrome. Treatment with eltrombopag proved to be effective.

Conclusion

This is the first report of the development of myelodysplastic syndrome during enfortumab vedotin therapy in a clinical setting. Although rare, myelodysplastic syndrome can occur during enfortumab vedotin therapy.