bluuebunny/crossref_metadata_2025_split huggingface dataset:
N‐Oxyl Radicals in Oxidative C−O Coupling: Free‐Radical Hydrogen Substitution and Addition to C=C Bonds
Authors: Lopat'eva Elena R. , Krylov Igor B. , Yu Bing , Terent'ev Alexander O. 
Published: October 2024

AbstractN‐oxyl radicals occupy an important place in free‐radical oxidative CH‐functionalization being one of the most efficient redox‐organocatalysts for hydrogen atom abstraction (HAT). Their applications include aerobic radical chain autoxidation, CH‐functionalization with the formation of carbon‐carbon and carbon‐heteroatom bonds. The persistent nature of N‐oxyl radicals combined with their high reactivity in HAT results in their unique dual chemistry: the same radical can both propagate radical chain reaction (at low N‐oxyl concentrations) and effectively “terminate” carbon‐centered radicals (at higher N‐oxyl concentrations). The latter case opens a new synthetic application area of N‐oxyl radicals, in which they act as both hydrogen abstracting species and O‐reagents for cross‐coupling with carbon‐centered radicals thus produced. Apart from the C−H bond cleavage, reactive N‐oxyl radicals have been extensively used recently in C=C double bond functionalization via radical addition reactions. In this review, both free‐radical CH‐functionalization reactions with the introduction of N‐oxyl fragments and alkene difunctionalizations by N‐oxyls are covered with emphasis on the relationship between reaction conditions and selectivity.
Order‐Parameter‐Free Analysis of Soft Matter: Applications of Machine Learning via Image Recognition
Authors: Terao Takamichi , Kondo Masato 
Published: October 2024

AbstractVarious characteristic structures, with no long‐range spatial order, have often been observed in studies on the structural formation of soft materials. The order parameters, used to date, are not promising for computer detection of these types of structures. In this previous study, it is shown that machine‐learning analysis using convolutional neural networks is very effective for the structural formation of spherical colloidal particles. This method is applied to non‐spherical inverse patchy colloids and demonstrated that this order‐parameter‐free analysis method is effective for non‐spherical soft matter, which often exhibits complex structures. A recent development in the structural formation of colloidal particle systems corresponds to the problem of monolayers of core‐corona particle systems that exhibit a variety of structures. Monte Carlo simulations are performed for core‐corona particles, confined between parallel plates, to clarify the conditions for the appearance of the bilayer and its in‐plane structure formation. Parameter‐free analysis is performed using image‐based machine learning. The bilayer formation of the Jagla fluids is performed, and the phase diagram is clarified.
Tuning the controller gains using sensitivity analysis
Authors: Pal Anil Kumar , Kumar Sunil , Kamal Shyam , Leung Henry , Xiong Xiaogang 
Published: October 2024

AbstractThis paper tries to solve the general problem of controller gain tuning. To that end, sensitivity analysis has been utilized. The study provides vital results to extend the usage of sensitivity analysis for the class of finite‐time stable dynamics. The controller gain tuning procedure is elaborated by considering the examples of state feedback control and predefined time control. An insight into the selection of the gains or system parameters for these class of systems is presented with the help of sensitivity analysis. The sensitivity of the solution for these class of systems with the variation in the gains or system parameters is studied. Having know‐how about the adjustment of these system gains or parameters will be beneficial from the point of view of practical applications. Thus, the proposed approach finds utility in controller gain tuning, which is an important aspect of control design.
Therapeutic Effects of Puerarin Loaded Bone Marrow Mesenchymal Stem Cell‐Derived Exosomes in a Rat Model of Osteoarthritis
Authors: Zhang Yifei , Liu Kang , Ma Xuejing , Su Xiangchen , Zhao Liang , Wu Yi , Shi Yijie 
Published: October 2024

AbstractOsteoarthritis (OA) is the most prevalent chronic degenerative joint disease among the aged population. The primary objective of this study was to assess the therapeutic potential of puerarin loaded bone marrow mesenchymal stem cell‐derived exosomes (Pue@BMSC‐Exo), and reveal their inflammatory regulating mechanisms through affecting the nuclear factor kappa‐B (NF‐κB) signaling pathway. In this study, exosomes derived from BMSCs were isolated and identified. Cell proliferation and migration were evaluated by CCK‐8 and scratch methods. Furthermore, histological and micro‐computed tomography analysis were performed to assess alterations of articular cartilage in OA rats. Results showed that BMSC‐Exo and Pue@BMSC‐Exo conformed with the basic characteristics of exosomes. BMSC‐Exo increased the solubility of Pue and enhanced drug uptake by chondrocytes. In addition, Pue@BMSC‐Exo stimulated proliferation and migration of chondrocyte, and also promoted cartilage repair by reducing matrix metalloproteinase MMP13 production and increasing type II collagen (Col2) synthesis. Furthermore, Pue@BMSC‐Exo, by effectively inhibiting the NF‐κB signaling pathway, reduced the production of inflammatory mediators and attenuated the release of the inflammatory marker nitric oxide (NO), ultimately ameliorating the damage of chondrocyte. These findings exhibited the potential therapeutic significance of Pue@BMSC‐Exo in OA and warranted further exploration in clinical applications.
Production of Phenyldiazene Derivatives Using the Biosynthetic Pathway of an Aromatic Diazo Group‐Containing Natural Product from an Actinomycete
Authors: Kawai Seiji , Ning Jiayu , Katsuyama Yohei , Ohnishi Yasuo 
Published: October 2024

AbstractThe diazo group is an important functional group in organic synthesis because it confers high reactivity to the compounds and has been applied in various chemical reactions, such as the Sandmeyer reaction, Wolff rearrangement, cyclopropanation, and C−N bond formation with active methylene compounds. Previously, we revealed that 3‐diazoavenalumic acid (3‐DAA), which is potentially produced by several actinomycete species and contains an aromatic diazo group, is a biosynthetic intermediate of avenalumic acid. In this study, we aimed to construct a production system for phenyldiazene derivatives by adding several active methylene compounds to the culture of a 3‐DAA‐producing recombinant actinomycete. First, acetoacetanilide and its derivatives, which have an active methylene and are raw materials for arylide yellow dyes, were individually added to the culture of a 3‐DAA‐producing actinomycete. When their metabolites were analyzed, each expected compound with a phenyldiazenyl moiety was detected in the culture extract. Moreover, we established a one‐pot in vitro enzymatic production system for the same phenyldiazene derivatives using a highly reactive diazotase, CmaA6. These results showed that the diazo group of natural products is an attractive tool for expanding the structural diversity of natural products both in vivo and in vitro.
Regulating Zn Deposition Manner by Confining the Reactivity of Free Water in the Electric Double Layer
Authors: Liao Guoli , Zhang Yufei , Ye Minghui , Tang Yongchao , Wen Zhipeng , Du Wencheng , Liu Xiaoqing , Chao Li Cheng 
Published: October 2024

AbstractAqueous Zn ion batteries (AZIBs) are promising candidates of next‐generation energy storage devices with high safety and theoretical capacity. However, the irreversibility of metallic Zn anode, attributed to dendrite growth and water decomposition, severely limits the cycling durability of AZIBs and restricts their further development. Herein, a facile surface engineering strategy is put forward to tackle the issue of poor reversibility of the Zn anode. Benzotriazole (BTA) is employed as a functional additive of ZnSO4 electrolyte to confine the reactivity of free water situated in the electric double layer (EDL). Experimental results and theoretical simulation reveal that BTA can preferiencially adsorb onto the Zn surface to uniform Zn2+ ion distribution and alleviate H2O‐involved side reactions like hydrogen evolution, and surface passivation. Consequently, in BTA‐modulated aqueous electrolyte, the lifespan of the Zn anode is extended from 170 h–1092 h at 1 mA cm−2/1 mAh cm−2. The reversibility improvement of Zn anode also benefits the cycling durability of full devices including supercapacitors and batteries. Zn||I₂ batteries assembled in as‐designed electrolyte witness only 11.3 % capacity decay over 17000 cycles at 1 A g−1, far outstripping that observed in ZnSO4 counterpart (~4675 cycles). The design criteria proposed in this study offers a new concept for the development of regulation additives that confine the reactivity of free water in the electric double layer.
ACuGa6S10 (A = Rb, Cs): Design and Synthesis of Two New Cavity‐Chalcopyrite Chalcogenides Based on “Iterative Substitution” Strategy
Authors: Li Kaixuan , Zhang Xingyu , Chai Binqiang , Yu Hongwei , Hu Zhanggui , Wang Jiyang , Wu Yicheng , Wu Hongping 
Published: October 2024

AbstractTwo new non‐centrosymmetric chalcogenides, ACuGa6S10 (A=Rb, Cs) have been successfully synthesized by an “iterative substitution” strategy based on chalcopyrite CuFeS2 structural template. Benefiting from the substitution of Fe3+ cations by Ga3+ cations, ACuGa6S10 (A = Rb, Cs) exhibit wide suitable band gap of 2.48 and 2.40 eV, respectively, which is about five times higher than their structure template CuFeS2, and a large second harmonic generation response (1.5 and 1.8×AgGaS2). Combining theoretical calculation and structural analysis confirms that the [GaS4] tetrahedra make the main contribution on their good liner and nonlinear optical (NLO) performances. The “iterative substitution” strategy expands the design idea of materials and can lead to the discovery of a large number of IR NLO compounds.
A Bioequivalence Study of Azilsartan in Healthy Chinese Subjects
Authors: Liu Xiaobei , Dai Xiangrong , Yu Xiaohui , Zhou Huan , Xie Jing 
Published: October 2024

AbstractAzilsartan is an angiotensin II receptor blocker used for treating adult hypertension. It significantly improves cardiovascular outcomes in patients with high‐risk hypertension, heart failure, and diabetic nephropathy. A single‐center, randomized, open‐label, single‐dose, dual‐cycle, dual‐crossover clinical trial was conducted to evaluate the bioequivalence of azilsartan under fasting and postprandial conditions in 60 Chinese healthy volunteers. Thirty healthy subjects were enrolled in each test group, with random cross‐administration for fasting and postprandial tests. The concentration of azilsartan in human plasma was evaluated using liquid chromatography‐tandem mass spectrometry after a single oral administration of test and reference preparations, each at a dose of 20 mg (1 tablet). Pharmacokinetic parameters were determined using WinNonlin8.2 software, and bioequivalence was evaluated using SAS 9.4 software. The geometric mean ratios and 90% confidence intervals for maximum concentration, area under the plasma concentration‐time curve from time 0 to the time of last measurable concentration, and area under the plasma concentration‐time curve from time 0 to infinity of the test and reference preparations in the fasting and postprandial test groups were in the range of 80%‐125%. The incidence of adverse events in the fasting and postprandial test groups was 30% (9/30) and 33.3% (10/30), respectively. No serious adverse events or unexpected adverse drug reactions were observed. In conclusion, the test and reference preparations of azilsartan tablets demonstrate bioequivalence and good safety in healthy Chinese subjects under fasting and postprandial conditions.
Growth of YAG:Nd laser crystals by Horizontal Directional Crystallization in Protective Carbon‐Containing Atmosphere
Authors: Nizhankovskyi S. , Romanenko A. , Serdiuk O. , Vovk E. , Sidelnikova N. , Kozlovskyi A. , Kryvonohov S. , Lukienko O. , Skorik S. , Kovalenko N. , Bryliova K. , Pritula I. 
Published: October 2024

AbstractLaser‐quality yttrium‐aluminum garnet single crystals doped with neodymium (YAG:Nd) of a concentration up to 1 at. % is grown by the method of horizontal directional crystallization from a molybdenum crucible in the protective reducing atmosphere based on argon, СО, and hydrogen. It is found that the content of carbon impurity in the grown crystals does not exceed 5·10−3 wt %, the content of molybdenum being on the level of 1.5·10−3 wt %. The optical quality of the crystals depends on the composition of the growth atmosphere and annealing. It is shown that, besides the bands of neodymium ion absorption, the crystals are characterized by the intense absorption in the UV edge of the spectrum at 370 nm wavelength, and by the wide absorption band with a maximum at 580 nm caused by formation of F and F+‐centers. The absorption at 370 and 580 nm can be eliminated by annealing. The structure perfection of the crystals is characterized by the rocking curve half‐width (β) which value varies within the limits of 10–14 arc. sec for (001) plane. Laser testing demonstrates the parameters comparable with those of YAG:Nd crystals grown by the Czochralski method from iridium crucible.
Impact of environmental, social, and governance performance on cash holdings in BRICS: Mediating role of cost of capital
Authors: Chen Sisi , Farooq Umar , Aldawsari Salem Hamad , Waked Sami Sobhi , Badawi Mamoun 
Published: October 2024

AbstractAs businesses globally navigate the intricate landscape of environmental, social, and governance (ESG) practices, understanding their financial implications becomes paramount. The primary objective is to illuminate the impact of ESG performance on cash holdings (CHO) within the context of the BRICS nations. Additionally, the study aims to explore the mediating role of the cost of capital (COC) in shaping these relationships. The empirical analysis was conducted on comprehensive dataset over the period 2010–2022 of BRICS. We establish the regression analysis by utilizing a fixed effect and system GMM models. The empirical findings reveal a significant negative (−0.012 coefficient value) impact of ESG performance on CHO, indicating that a one‐unit increase in ESG can decrease the CHO by 1.2% and this effect is significant at 1%. This further highlights declining trend in cash reserves among companies embracing sustainability practices. Notably, the study documents the mediating role of the COC, showcasing its influence in reducing internal cash reserves in the presence of low external financing costs. The study highlights the financial benefits associated with robust ESG practices. Companies in the BRICS nations are encouraged to integrate sustainability considerations into their business strategies, recognizing the potential for reduced CHO and favorable COC outcomes. Beyond financial gains, the study underscores the societal and environmental contributions of ESG practices. This study contributes to the literature by uncovering the mediating role of the COC, providing a comprehensive understanding of how sustainability practices influence internal cash reserves in the context of diverse economic landscapes.
Efficient Hydrodeoxygenation of Lignin‐Derived Phenolic Compounds Over Ru‐Based Catalyst with Biochar and Al2O3 as Composite Support
Authors: Yin Tao , Ye Yichao , Jiang Hao , Lin Chengyin , Shu Riyang , Tian Zhipeng , Wang Chao , Shi Ning 
Published: October 2024

AbstractHydrodeoxygenation (HDO) is a common strategy for upgrading lignin‐derived phenolic compounds into high‐quality liquid fuels, and the support rational design of HDO catalysts is critical to achieve a good reaction performance. This work proposed a novel Ru‐based catalyst with biochar and Al2O3 as composite support. The addition of biochar can enlarge the porous structure, and the addition of Al2O3 can enhance the acid property of the support. By regulating the content of biochar and Al2O3 components, Ru/CA‐2 catalyst achieved the best HDO performance of lignin‐derived phenolic compounds, with the optimal component balance of 50 %C and 50 %Al2O3. This catalyst possesses the high Ru metal dispersion (1.38 nm particle size) to activate the hydrogen source, the moderate acid property to suppress carbon deposition and the abundant oxygen vacancy to promote substrate adsorption at the same time. 99.9 % conversion of guaiacol is obtained at 230 °C, with 99.9 % selectivity towards cyclohexane. Ru/CA‐2 catalyst also has a good recyclability, with no obvious activity loss after five runs. Furthermore, in the application of catalytic lignin‐oil HDO, the content of hydrocarbons increase from 10.7 % to 95.7 %, showing great potential on the industrial usage.
Recent Progress in External‐Field Enhanced Photo‐Electrochemistry
Authors: Wang Chengyi , Liu Zhifeng 
Published: October 2024

AbstractThe ever‐growing demands for energy supply have put great stress on environment protections. Photo‐electrochemistry (PEC) is a repaid developing technique which can directly transform solar energy into chemical compounds and have been regarded as a promising strategy to solve the energy and environmental problems. However, the biggest restriction is the fast recombination of photo‐generated charge carriers which greatly limits the PEC efficiency. In recent years, introducing external‐field into PEC system have been proved to be a powerful method to enhance the PEC performance and attracted more and more attentions. In this review, we summarized the remarkable progresses in external‐field enhanced PEC reactions including mechanical stress field, thermal field, electrical field, magnetic field and muti‐field coupling. The enhancing principles of different external‐fields have also been systemically discussed. Furthermore, the challenges and outlook of the external‐field enhanced PEC reactions are presented.
ON‐OFF Switching of Photocatalytic Hydrogen Evolution by Built‐in Pt‐Nitrogen‐Carbon Reticular Heterojunctions
Authors: Cognigni Leonardo , Gobbato Thomas , Benazzi Elisabetta , Paoloni Lorenzo , Vizio Biagio Di , Bonetto Ruggero , Rigodanza Francesco , Bonetto Alessandro , Agnoli Stefano , Bonchio Marcella , Costa Paolo 
Published: October 2024

AbstractCOF engineering with a built‐in, high concentration of defined N‐doped sites overcomes the “black‐box” drawback of conventional trial‐and‐error N‐doping methods (used in polymeric carbon nitride and graphene), that hamper a directed evolution of functional carbon interfaces based on structure‐reactivity guidelines. The cutting‐edge challenge is to dissect the many complex and interdependent functions that originate from reticular N‐doping, including modification of the material optoelectronics, band alignments, interfacial contacts and co‐localization of active‐sites, producing a multiple‐set of effectors that can all play a role to regulate photocatalysis. Herein, an ON‐OFF gated photocatalytic H2 evolution (PHE) is dictated by the Pt‐NPyridine‐carbon active sites and probed with a dual COF platform, based on stable β‐ketoenamine connectivities made of triformylphloroglucinol (Tp) as the acceptor knots and 1,4‐diaminonaphtalene (Naph) or 5,8‐diaminoisoquinoline (IsoQ) as donors. Our results showcase two novel COF‐Naph‐Tp and COF‐IsoQ‐Tp frameworks featuring quasi‐identical slip‐stacked microporous structure, and similar surface area, band gap, light harvesting envelope up to 700 nm, fluorescence emission profile/lifetime, and PEIS response at the surface/water interface (Rct=16–10±4 KΩ). A divergent behaviour is indeed observed for COF‐IsoQ‐Tp with record photoelectrochemical outputs (J=−16 μA cm−2, Rt=3 KΩ at 0.40 V vs RHE) and two orders of magnitude higher rate of PHE (11.3 mmol g−1 h−1, λ>400 nm, pH 5) compared to the inactive COF‐Naph‐Tp analogue. It turns out that PHE is regulated by the isoquinoline residues at the COF pores where emergent Pt‐NPyridine‐carbon functional heterojunctions are formed upon photo‐deposition of Pt nanoparticles as co‐catalysts, as probed by combined XPS and DFT calculations evidence. This work sets a key guideline to direct the design of carbon‐based materials encoding the installation of metal‐nitrogen‐carbon active sites within tailored coordination environments enabling the catalytic performance.
Evolution of and Perspectives on Differential‐Pair‐Based CMOS Variable Gain Amplifiers With Linear‐in‐Decibel Gain Control: A Tutorial
Authors: Wang Siqi , Lu Zhenghao , Tang Zhong , Yu Xiaopeng , Wu Hanming , Yeo Kiat‐Seng , Chen Yong 
Published: October 2024

ABSTRACTA variable gain amplifier (VGA) is an essential building block used in the automatic gain control (AGC) loop to provide a continuous, adjustable gain for the signal strength. To maintain the stability and consistency of the AGC loop, it is necessary to ensure that the gain of the VGA has an accurate dB‐linear characteristic. This tutorial provides a detailed overview of the development of dB‐linear VGAs based on differential pair structures over recent years. We categorize various VGA cells based on differential pair structures, analyze their operating principles, and explain the key features of each topology. Based on observation and extraction of the dB‐linear implementation schemes used by these VGAs, we summarize three basic methods for achieving dB‐linear gain control. We also discuss specific methods for realizing the exponential function, using a true exponential and a mathematical approximation, and present the different types of approximation functions adopted in the works described here. Considerations in regard to the tuning range, gain error, bandwidth, linearity, process‐temperature robustness, and circuit simplicity are also discussed. Finally, we draw comparisons and give perspectives for future dB‐linear VGAs.
A Case of Facultative Polygyny in an Enigmatic Monogamous Species, the European Nightjar (Caprimulgus europaeus)
Authors: Evens Ruben , Lathouwers Michiel , Creemers Jitse , Ulenaers Eddy , Eens Marcel , Kempenaers Bart 
Published: October 2024

ABSTRACTIn many socially monogamous bird species with biparental care, occasional social polygyny has been detected. We provide information about a case of facultative polygyny in the European Nightjar (Caprimulgus europaeus). The male nightjar (I96) formed a pair with two females (I95: the presumed primary female with whom he already bred since 2018; M042: the presumed secondary female, an inexperienced yearling). GPS and accelerometer data demonstrate how the male only sang in proximity of the primary nest, while assisting both females during incubation, as well as during the nestling period. When the male came to the nest, the primary and/or secondary female went foraging, but the secondary female received less assistance during incubation than the primary female, and her eggs were often left unattended. However, once the chicks of the secondary female hatched, male assistance suddenly increased, presumably at a cost to the primary female. Being only the second record of social polygyny in the European Nightjar, we do not have a direct explication for the occurrence of this polygynous event. We note that male density at the study site was lower than that observed in previous seasons. The male may have taken over the female that was initially paired to a neighbouring territory holder that then died. Alternatively, the inexperienced female might have mated with an already paired male, either because she was not aware of the mating status of the male, or because she could not find an unpaired male, or because mating with this paired male was better than mating with another unpaired male. In any case, the breeding ecology and mating behaviour of this crepuscular bird species remains little understood.