bluuebunny/crossref_metadata_2025 huggingface dataset:
Selective Peroxygenase‐Catalysed Oxidation of Phenols to Hydroquinones
Authors: Brasselet Hugo , Schmitz Fabian , Koschorreck Katja , Urlacher Vlada B. , Hollmann Frank , Hilberath Thomas
Published: July 2024

An enzymatic method for the selective hydroxylation of phenols using a peroxygenase from Aspergillus brasiliensis (AbrUPO) is reported. A broad range of phenolic starting materials can be selectively transformed into the corresponding hydroquinones. Semi‐preparative syntheses of several hydroquinones were realised without further optimization pointing out the applicability of this enzyme as biocatalyst.
Molecular Dynamics‐Based Conformational Simulation Method for Analysis of Arrival Time Distributions in Ion Mobility Mass Spectrometry
Authors: Tashiro Keisuke , Ide Yuki , Taketsugu Tetsuya , Ohara Kazuaki , Yamaguchi Kentaro , Kobayashi Masato , Inokuma Yasuhide
Published: July 2024

Ion mobility‐mass spectrometry (IM‐MS) has recently contributed to the structural analysis of molecules, including supramolecules and proteins, by determining the ion arrival time distributions correlated with the collision cross sections (CCSs), as well as the mass‐to‐charge ratios. However, its application range is still limited owing to the lack of general CCSs simulation methods based on possible molecular conformations. Here, a molecular dynamics‐based conformational search method for simulating CCS distributions using projection approximation is reported. As a case study, the gas‐phase conformations of the sodium adducts of conformationally flexible polyketones with 3,3‐dimethylpentane‐2,4‐dione as the monomer are analyzed. The sodium adduct of the hexamer (m/z 781.4 for [1 + Na]+) showed a monomodal arrival time distribution, but that of the octamer sodium adduct (m/z 1033.5 for [2 + Na]+) is multimodal. The conformational analysis indicated an unimodal CCS distribution of simulated [1 + Na]+ conformations in which the sodium cation is mainly bound at the chain terminal. Conversely, four clusters of conformations are obtained for [2 + Na]+ based on the Na+‐coordination sites, which qualitatively reproduced the observed CCS distribution. This approach will extend the utility of IM‐MS for the conformational analysis of flexible molecules in the gas phase.
Diastereoselective Synthesis of Meso‐1,2‐Diarylethane‐1,2‐Diamines Via Sodium Reduction of Imidazolines
Authors: Bazanov Daniil R. , Lozinskaya Natalia A.
Published: July 2024

A facile method for the preparation of meso‐1,2‐diarylethane‐1,2‐diamines from aromatic aldehydes is disclosed. The stereoselectivity of the protocol is based on the disrotatory electrocyclic ring closure of readily generated diazopentadienes, followed by a SET reduction of the imidazoline fragment by sodium. The method is readily scalable to multi‐gram quantities and a wide range of alkoxy and alkyl‐phenyl substituents can be synthesized.
Work incentives in Australia: The distribution of effective marginal tax rates for working‐age Australians in 2023
Authors: Phillips Ben
Published: July 2024

Effective marginal tax rates are of interest to policymakers due to the concern that high rates lead to disincentives to work, particularly for secondary earners in couple families and single parents who pay personal income tax and lose government welfare payments as their private income increases. Hypothetical models of the tax and welfare system demonstrate the possibility of high effective marginal tax rates particularly for secondary earners in lower income families where personal income tax intersects with the loss of means‐tested welfare payment. This paper estimates effective marginal tax rates across the whole working‐age population, rather than for hypothetical families, using a microsimulation model based on a nationally representative sample of Australians. These distributional estimates suggest that high and very high effective marginal tax rates are relatively rare and that most persons of a working‐age face rates that are relatively modest. The paper extends previous work on distributional effective marginal tax rates to include the impact of formal childcare and the higher education loan program.
Amyloid and SCD jointly predict cognitive decline across Chinese and German cohorts
Authors: Shao Kai , Hu Xiaochen , Kleineidam Luca , Stark Melina , Altenstein Slawek , Amthauer Holger , Boecker Henning , Buchert Ralph , Buerger Katharina , Butryn Michaela , Cai Yanning , Cai Yue , Cosma Nicoleta Carmen , Chen Guanqun , Chen Zhigeng , Daamen Marcel , Drzezga Alexander , Düzel Emrah , Essler Markus , Ewers Michael , Fliessbach Klaus , Gaertner Florian C. , Glanz Wenzel , Guo Tengfei , Hansen Niels , He Beiqi , Janowitz Daniel , Kilimann Ingo , Krause Bernd J. , Lan Guoyu , Lange Catharina , Laske Christoph , Li Yuxia , Li Ruixian , Liu Lin , Lu Jie , Meng Fansheng , Munk Matthias H. , Peters Oliver , Perneczky Robert , Priller Josef , Ramirez Alfredo , Rauchmann Boris‐Stephan , Reimold Matthias , Rominger Axel , Rostamzadeh Ayda , Roy‐Kluth Nina , Schneider Anja , Spottke Annika , Spruth Eike Jakob , Sun Pan , Teipel Stefan , Wang Xiao , Wei Min , Wei Yongzhe , Wiltfang Jens , Yan Shaozhen , Yang Jie , Yu Xianfeng , Zhang Mingkai , Zhang Liang ,   DELCODE study group, SILCODE study group, Wagner Michael , Jessen Frank , Han Ying , Kuhn Elizabeth
Published: July 2024

INTRODUCTION

Subjective cognitive decline (SCD) in amyloid‐positive (Aβ+) individuals was proposed as a clinical indicator of Stage 2 in the Alzheimer's disease (AD) continuum, but this requires further validation across cultures, measures, and recruitment strategies.

METHODS

Eight hundred twenty‐one participants from SILCODE and DELCODE cohorts, including normal controls (NC) and individuals with SCD recruited from the community or from memory clinics, underwent neuropsychological assessments over up to 6 years. Amyloid positivity was derived from positron emission tomography or plasma biomarkers. Global cognitive change was analyzed using linear mixed‐effects models.

RESULTS

In the combined and stratified cohorts, Aβ+ participants with SCD showed steeper cognitive decline or diminished practice effects compared with NC or Aβ− participants with SCD. These findings were confirmed using different operationalizations of SCD and amyloid positivity, and across different SCD recruitment settings.

DISCUSSION

Aβ+ individuals with SCD in German and Chinese populations showed greater global cognitive decline and could be targeted for interventional trials.

Highlights

SCD in amyloid‐positive (Aβ+) participants predicts a steeper cognitive decline.

This finding does not rely on specific SCD or amyloid operationalization.

This finding is not specific to SCD patients recruited from memory clinics.

This finding is valid in both German and Chinese populations.

Aβ+ older adults with SCD could be a target population for interventional trials.
Incorporation of Pd Single‐Atom Sites in Perovskite with an Excellent Selectivity toward Photocatalytic Semihydrogenation of Alkynes
Authors: Yang Baoying , Liu Kunlong , Ma Yuhui , Ma Jian‐Jie , Chen Yi‐Yu , Huang Meirong , Yang Can , Hou Yidong , Hung Sung‐Fu , Yu Jimmy C. , Zhang Jinshui , Wang Xinchen
Published: July 2024

Semihydrogenation is a crucial industrial process. Noble metals such as Pd have been extensively studied in semihydrogenation reactions, owing to their unique catalytic activity toward hydrogen activation. However, the overhydrogenation of alkenes to alkanes often happens due to the rather strong adsorption of alkenes on Pd active phases. Herein, we demonstrate that the incorporation of Pd active phases as single‐atom sites in perovskite lattices such as SrTiO3 can greatly alternate the electronic structure and coordination environment of Pd active phases to facilitate the desorption of alkenes rather than further hydrogenation. Furthermore, the incorporated Pd sites can be well stabilized without sintering by a strong host–guest interaction with SrTiO3 during the activation of H species in hydrogenation reactions. As a result, the Pd incorporated SrTiO3 (Pd‐SrTiO3) exhibits an excellent time‐independent selectivity (>99.9 %) and robust durability for the photocatalytic semihydrogenation of phenylacetylene to styrene. This strategy based on incorporation of active phases in perovskite lattices will have broad implications in the development of high‐performance photocatalysts for selective hydrogenation reactions.
Bilateral Embedded Anchoring via Tailored Polymer Brush for Large‐Area Air‐Processed Blue Light‐Emitting Diodes
Authors: Wu Jiandong , Li Huixin , Yang Yang , Chen Yiling , Wang Zhongyu , Dong Fan , Liu Xinhao , Guo Yangyang , Yao Tanxi , Xu Yadong , Ye Qian , Wang Hongyue , Wang Hongqiang , Fang Yu
Published: July 2024

Perovskite light‐emitting diodes (PeLEDs) that can be air‐processed promises the development of displaying optoelectronic device, while is challenged by technical difficulty on both the active layer and hole transport layer (HTL) caused by the unavoidable humidity interference. Here, we propose and validate that, planting the polymer brush with tailored functional groups in inorganic HTL, provides unique bilateral embedded anchoring that is capable of simultaneously addressing the n phases crystallization rates in the active layer as well as the deteriorated particulate surface defects in HTL. Exemplified by zwitterionic polyethyleneimine‐sulfonate (PEIS) in present study, its implanting in NiOx HTL offers abundant nuclei sites of amino and sulfonate groups that balance the growth rate of different n phases in quasi‐2D perovskite films. Moreover, the PEIS effectively nailed the interfacial contact between perovskite and NiOx, and reduced the particulate surface defects in HTL, leading to the enhanced PLQY and stability of large‐area blue perovskite film in ambient air. By virtue of these merits, present work achieves the first demonstration of the air‐processed blue PeLEDs in large emitting area of 1.0 cm2 with peak external quantum efficiency (EQE) of 2.09 %, which is comparable to the similar pure‐bromide blue PeLEDs fabricated in glovebox.
Membrane‐Free Electrocatalytic Co‐Conversions of PBS Waste Plastics and Maleic Acid into High‐Purity Succinic Acid Solid
Authors: Zhou Bo , Shi Kai , Teng Xue , Li Zhenhua , Chen Lisong , Shi Jianlin
Published: July 2024

Plastic pollution, an increasingly serious global problem, can be addressed through the full lifecycle management of plastics, including plastics recycling as one of the most promising approaches. System design, catalyst development, and product separation are the keys in improving the economics of electrocatalytic plastics recycling. Here, a membrane‐free co‐production system was devised to produce succinic acid (SA) at both anode and cathode respectively by the co‐electrolysis of polybutylene succinate (PBS) waste plastics and biomass‐derived maleic acid (MA) for the first time. To this end, Cr3+‐Ni(OH)2 electrocatalyst featuring much enhanced 1,4‐butanediol (BDO) oxidation reaction (BOR) activity has been synthesized and the role of doped Cr has been revealed as an “electron puller” to accelerate the rate‐determining step (RDS) in the Ni2+/Ni3+ cycling. Impressively, an extra‐high SA production rate of 3.02 g h−1 and ultra‐high apparent Faraday efficiency towards SA (FEapparent=181.5 %) have been obtained. A carbon dioxide‐assisted sequential precipitation approach has been developed to produce high‐purity SA and byproduct NaHCO3 solids. Preliminary techno‐economic analysis demonstrates that the reported system is economically profitable and promising for future industrial applications.
Successively Controlling Nanoscale Wrinkles of Ultrathin 2D Metal–Organic Frameworks Nanosheets
Authors: Tang Wen‐Qi , Cheng Yue , Zhu Jian‐Ping , Zhou Ye‐Qin , Xu Ming , Gu Zhi‐Yuan
Published: July 2024

The wrinkles are pervasive in ultrathin two‐dimensional (2D) materials, but the regulation of wrinkles is rarely explored systematically. Here, we employed a series of carboxylic acids (from formic acid to octanoic acid) to control the wrinkles of Zr‐BTB (BTB=1, 3, 5‐(4‐carboxylphenyl)‐benzene) metal–organic framework (MOF) nanosheet. The wrinkles at the micrometer scale were observed with transmission electron microscopy. Furthermore, high‐angle annular dark‐field (HAADF) images showed lattice distortion in many nanoscale regions, which was precisely matched to the nano‐wrinkles. With the changes of hydrophilicity/hydrophobicity, MOF‐MOF and MOF‐solvent interactions were possibly synergistically regulated and wrinkles with different sizes were obtained, which was supported by HAADF, molecular dynamics, and density functional theory calculation. Different wrinkle sizes resulted in different pore sizes between the Zr‐BTB nanosheet interlayers, providing highly‐oriented thin films and the successive optimization of kinetic diffusion pathways, proved by grazing‐incidence wide‐angle X‐ray scattering and nitrogen adsorption. The most suitable wrinkle pore from Zr‐BTB‐C4 exhibited highly efficient chromatographic separation of the substituted benzene isomers. Our work provides a rational route for the modulation of nanoscale wrinkles and their stacked pores of MOF nanosheets and improves the separation abilities of MOFs.
Enhancing the Supercapacitive Behaviour of Cobalt Layered Hydroxides by 3D Structuring and Halide Substitution
Authors: Seijas‐Da Silva Álvaro , Oestreicher Víctor , Huck‐Iriart Cristián , Mizrahi Martín , Hunt Diego , Ferrari Valeria , Abellán Gonzalo
Published: July 2024

Among the two‐dimensional (2D) materials, layered hydroxides (LHs) stand out due to their chemical versatility, allowing the modulation of physicochemical properties on demand. Specifically, LHs based on earth‐abundant elements represent promising phases as electrode materials for energy storage and conversion. However, these materials exhibit significant drawbacks, such as low conductivity and in‐plane packing that limits electrolyte diffusion. In this work, we explore the synthetic flexibility of α‐CoII hydroxides (Simonkolleite‐like structures) to overcome these limitations. We elucidate the growth mechanism of 3D flower‐like α‐CoII hydroxyhalides by using in situ SAXS experiments combined with thorough physicochemical, structural, and electrochemical characterization. Furthermore, we compared these findings with the most commonly employed Co‐based LHs: β‐Co(OH)₂ and CoAl layered double hydroxides. While α‐CoII LH phases inherently grow as 2D materials, the use of ethanol (EtOH) triggers the formation of 3D arrangements of these layers, which surpass their 2D analogues in capacitive behavior. Additionally, by taking advantage of their anion‐dependent bandgap, we demonstrate that substituting halides from chloride to iodide enhances capacitive behavior by more than 40 %. This finding confirms the role of halides in modulating the electronic properties of layered hydroxides, as supported by DFT+U calculations. Hence, this work provides fundamental insights into the 3D growth of α‐CoII LH and the critical influence of morphology and halide substitution on their electrochemical performance for energy storage applications.
Dual credits and the community college pathway toward STEM degrees
Authors: Hu Xiaodan , Menees Jay
Published: July 2024

Community colleges are an important entry point and pathway for students to obtain a postsecondary degree in science, technology, engineering, and math (STEM) fields. To broaden STEM participation and increase STEM persistence, it is important to support community college students’ college‐level course completion and academic performance. This article explores whether earning dual credits in high school is related to community college students’ probability of completing any STEM/career and technical education (CTE) degree or persisting in a STEM program at a 4‐year institution. Using a nationally representative dataset, we find that earning dual credits, especially in the subject of math/science, is positively associated with community college students’ STEM/CTE success. We conclude the article with implications, recommending practitioners to highlight the benefits of dual credit on STEM success, streamline high school collaborations into STEM access and success strategy, and reimagine the role of CTE programs in STEM success for community college students.
Fe‐Catalyzed, Solvent‐Controlled, Switchable Routes for the Domino Construction of 2,4‐Disubstituted and 4‐Substituted Quinoline Scaffolds
Authors: Jagtap Prafull A. , Sawant Vaishnavi R. , Bhanage Bhalchandra M.
Published: July 2024

In this report, we unveil a highly efficient novel protocol for the domino synthesis of 2,4‐disubstituted and 4‐substituted quinoline scaffolds. The developed strategy involves earth‐abundant Fe‐catalyzed, solvent‐controlled, switchable routes for the selective construction of 2,4‐disubstituted and 4‐substituted quinoline frameworks, achieved by using either trifluoroethanol (TFE) or methanol (MeOH) as a solvent. By employing TFE as a solvent in Path A, the alkyne itself serves as a dual synthon through Fe‐catalyzed in situ C(sp)–C(sp) bond cleavage, enabling the synthesis of two important molecules: 2,4‐disubstituted and 4‐substituted quinolines. Later, upon switching the reaction medium from TFE to MeOH for Path‐B, only 4‐substituted quinolines were obtained extensively. In this Path‐B, Fe‐catalyzed oxidation of methanol was observed and here methanol functioned as both a solvent and an environmentally benign carbon source. Both of these strategies were utilized to prepare a broad range of mono‐ and di‐substituted quinoline derivatives. In the application section and for practical utility, the scale‐up studies, along with the photophysical properties of the synthesized quinoline moiety are also demonstrated.
Enhanced Degradation of Ciprofloxacin Hydrochloride Using Hybrid Advanced Oxidation Process of Hydrodynamic Cavitation and Ozonation
Authors: Bodawar Narendra , Shetty Rohit , Kamble Sanjay , Kulkarni Prashant
Published: July 2024

The degradation of ciprofloxacin hydrochloride (CFX), an extensively utilized antibiotic for bacterial infections, has been studied through the application of advanced oxidation processes (AOPs) including hydrodynamic cavitation (HC), ozonation (O3), the Fenton reaction, chemical oxidation, and hybrid AOPs such as HC/O3 and Fenton/O3. Among these, the hybrid combination of HC/O3 demonstrated the highest CFX degradation of 99.82 % within 180 min having an initial concentration of 1000 ppm. The optimization of the HC/O3 process was conducted by varying parameters including initial concentration, pH, ozone (O3) gas flowrate, and temperature. Throughout the degradation process, CFX underwent intermediate formation, which gradually degraded over time.
Effect of MnO2${\text{MnO}}_{2}$ doping on AC aging characteristics of varistor in arrester
Authors: Fu Zhengzheng , Zhang Zongxi , Fan Songhai , Cui Tao , Luo Donghui , Jiang Yiping , Meng Pengfei , Guo Jingke , Yin Yue
Published: July 2024

As the core component of lightning arrester, the performance of ZnO varistor directly affects the protection level of lightning arrester. Under the action of long‐term AC voltage, the varistors are prone to AC aging, which leads to the deterioration of its performance parameters and microstructure, resulting in the failure of the varistors. In this paper, the effects of doping on the voltammetry and double Schottky barrier characteristics of ZnO varistors under AC were studied by means of , scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy characteristic testing. The AC accelerated aging test was carried out for 168 h under 135 and 0.85 ratio of peak voltage. The results showed that the introduction of inhibited the migration of interstitial zinc ions to grain boundaries and decreased the AC aging rate. The aging rate was lowest when 1.5 mol% was doped.
Highly Selective Boron‐Wittig Reaction: A Practical Method to Synthesize Trans‐Aryl Alkenes
Authors: Guan Qitao , Ding Fupan , Zhang Chun
Published: July 2024

Olefins play an essential role in synthetic chemistry, serving not only as important synthons but also as key functional groups in numerous bio‐active molecules. Consequently, there has been considerable interest in the development of more powerful methods for olefins. While the Wittig reaction stands as a prominent choice for olefin synthesis due to its simplicity and the ready availability of raw materials, its limitation lies in the challenge of controlling cis‐trans selectivity, hampering its broader application. In this study, a novel Boron‐Wittig reaction has been developed utilizing gem‐bis(boryl)alkanes and aldehydes as starting materials. This method enables creating favourable intermediates, which possess less steric hindrance, and leading to trans‐olefins via intramolecular O−B bonds elimination. Notably, synthesis studies have validated its good efficacy in modifying bioactive molecules and synthesizing drug molecules with great trans‐selectivity. Furthermore, the reaction mechanism was elucidated based on intermediate trapping experiments, isotope labelling studies, and kinetic analyses.
Stacking Transformation‐Triggered Circularly Polarized Luminescence Reversion in γ‐Cyclodextrins‐Pyrene Co‐Assembly
Authors: Yang Shijie , Hu Fengqing , Xu Tianjing , Lin Fanjie , Han Jinsong , Li Fei
Published: July 2024

Considerable attention has been directed towards cyclodextrins (CDs) in the creation of co‐assembled CPL‐active materials, owing to their intrinsic chiral host cavities and synergistic host‐guest interactions. However, achieving reversed CPL emission regulation with single‐handedness CDs moiety poses a significant challenge. In this study, we have devised a series of γ‐CD‐based host‐guest complexes comprising dual pyrene imidazolium derivatives with multiple linkers, which exhibit reversed circularly polarized emission. We have uncovered that the transformation of excimer stacking within γ‐CD/pyrene complexes contributes to the inverted CPL emissions originating from a single‐handed chiral host. This research elucidates the phenomenon of (+)‐ and (−)‐circularly polarized excimer emission (CPEE) within γ‐CD, arising from right‐ and left‐handed stacking conformations, respectively.
[5]Molecular Necklaces Formed Through Zn2+‐Templated Binding of Macrocycles to Dynamically Formed Imines as Guest Recognition Sites
Authors: Wu Yi-Ju , Liu Yi-Hung , Chiu Sheng-Hsien
Published: July 2024

Herein we demonstrate an “in‐ring establishing” strategy for assembling interlocked molecules through dynamic imine formation, “establishing” the host recognition sites in situ. Using Zn2+ ions to template the assembly of a pyridine‐containing macrocycle with semidumbbell‐shaped triazole‐containing aldehyde and amine derivatives, we obtained the corresponding [2]rotaxane in high yield (85%) after subsequent imine reduction (NaBH4) and amine protonation (NH4PF6). We performed the same three steps (assembly, reduction, protonation) to prepare a stable and highly symmetrical [5]molecular necklace ([5]MN) from 12 components (two almost‐90°‐oriented dialdehydes, two almost‐90°‐oriented diamines, four macrocycles, four Zn2+ ions) in an overall yield of 69%.
Optimization design of supply chain network based on BP neural network performance evaluation and feedback mechanism
Authors: Wu Yao , Liu Weiwei
Published: July 2024

This paper proposes a supply chain network design method suitable for multi‐product and multi‐inventory models, and uses the improved BP neural network to evaluate and provide feedback on the collaborative performance of the supply chain, adjusting the supply chain network design scheme on time. In the context of the Internet of Things (IoT) in manufacturing, it has been found that supply chain operations are difficult to meet personalized customer needs with high precision and quality. Therefore, we adopted a dynamic library strategy, supply chain network optimization model, hybrid algorithm, and the improved BP neural network to solve the above problems. First, this paper designs a corresponding inventory strategy selection mechanism for the various ordering methods of retailers in the manufacturing IoT environment. Based on this, we have constructed a dual objective model for a sustainable supply chain network to minimize total cost and maximize customer satisfaction. Second, we have developed a hybrid improved Grey Wolf and Whale Algorithm (OLDGWOA) that can accurately solve the above model. The hybrid algorithm divides the population into two parts through opposition‐based learning, and then we use the improved grey wolf algorithm and whale algorithm to solve the two populations, and seek the optimal solution in the results, resulting in a hybrid algorithm. Finally, we constructed a supply chain performance evaluation model and feedback mechanism based on the improved BP neural network to adjust inventory strategies and network design at any time. We also validated the developed model and algorithm through numerical examples, and the results showed that: (1) the hybrid algorithm has certain advantages in search and solution speed, (2) the advantages of supply chain network design based on supply chain performance evaluation and feedback mechanisms, and (3) the trade‐off between ordering methods and inventory strategies, as well as the trade‐off between location and inventory strategies.
The Importance of Enhancing Donor–Donor and Acceptor–Acceptor Stacking Simultaneously for the Balance of Hole and Electron Mobility of Small Molecule Single‐Component Organic Solar Cells
Authors: Liu Kaikai , Zheng Shaohui
Published: July 2024

Single‐component organic solar cells (SCOSCs) have attracted extensive attention due to their simplified device manufacturing and excellent stability. However, the relationship between morphology and charge carrier mobility in the active layers of SCOSCs is not well understood. In this work, we present a comprehensive investigation on this issue by studying four dyads (fullerenes as acceptor units) used as materials of active layers in small‐molecule single‐component organic solar cells (SM‐SCOSCs), in which dyad 4 created the record of power conversion efficiency (PCE) of SM‐SCOSC until now. Utilizing a multiscale theoretical approach, the results identify that the acceptor–acceptor stacking is dominant in amorphous films, significantly improving electron mobility and lowering hole mobility. We also find the importance of achieving a balance between electron and hole mobility to further improve PCE of SM‐SCOSC because dyad 4 exhibits a more balanced electron/hole mobility than the other three molecules. These findings indicate the importance of tuning and enhancing donor–donor and acceptor–acceptor stacking simultaneously, offering insights for the design and optimization of future SM‐SCOSC.
Adjustment of Electronic (OMe and NO2) and Steric (CHPh2) Effects in Bis(imino)pyridinyliron Precatalysts for Producing High Molecular Weight Linear PE
Authors: Razzaq Ayesha , Ma Yanping , Mahmood Qaiser , Hu Zexu , Wang Yizhou , Zou Song , Zhou Aibo , Liang Tongling , Kong Shaoliang , Sun Wen‐Hua
Published: July 2024

Based on variations in steric and electronic substituents in the N‐aryl unit, a set of five 2‐[1‐(arylimino)ethyl]‐6‐[1‐(2‐benzhydryl‐4‐nitro‐6‐methoxyphenylimino)ethyl]pyridyliron dichloride complexes (where aryl=2,6‐dimethylphenyl (Fe‐Me2), 2,6‐diethylphenyl (Fe‐Et2), 2,6‐diisopropyl (Fe‐iPr2), 2,4,6‐trimethylphenyl (Fe‐Me3), 2,6‐diethyl‐4‐methylphenyl (Fe‐Et2Me)) were synthesized and investigated for ethylene polymerization. Their structures and compositions were confirmed by FTIR, elemental analysis, and X‐ray diffraction analysis (Fe‐Et2 and Fe‐iPr2), revealing a distorted square pyramidal geometry around the iron center. When activated in situ with MAO or MMAO, these iron complexes acted as highly active precatalysts, achieving activity levels up to 29.0×106 gPE molFe−1 h−1 for a 5‐min reaction at 60 °C. A notable characteristic of these precatalysts is their high thermal stability, maintaining significant activity (2.0×106 gPE molFe−1 h−1) at temperatures up to 100 °C. Importantly, the incorporation of strong electron‐withdrawing groups in the ligand structure favored the production of polyethylene with high molecular weights (up to 407.5 kg mol−1) across various reaction conditions, surpassing those of most previously reported iron complexes. Moreover, less hindered iron precatalysts showed higher activity compared to more hindered ones. However, the trend reversed when comparing the molecular weight of obtained polyethylene: more sterically hindered precatalysts yielded higher molecular weight polymers. The molecular weight distributions ranged from monomodal to bimodal with broad dispersity. DSC thermograms and 1H/13C NMR spectra of the polyethylene confirmed its highly linear microstructure, evidenced by sharp endothermic peaks and pronounced singlets for the −(CH2)n− repeating units.
A Macrocycle with a Pair of Endo‐Isocyanides and its Affinity to Gold(I)
Authors: Kress Charlotte , Häussinger Daniel , Zwick Patrick , Prescimone Alessandro , Mayor Marcel
Published: July 2024

A pair of isocyanides pointing towards each other are fixed in a macrocyclic scaffold. The arrangement not only increases their local concentration, it should also enable their linear arrangement in coordination compounds. The macrocyclic diisocyanide ligand 1 is synthesized and fully characterized. Its interaction with gold(I) ions is investigated. While IR‐ and 1H‐NMR‐based titration experiments unraveled a stoichiometry of 2 Au(I) ions per macrocycle 1, the corresponding association constants are studied by UV‐Vis titration experiments. However, the values are above the method's detection limits and only a lower boundary of an over‐all association constant is determined to be 3.0x107 m−1. The kinetics of the complex formation is further analyzed by NMR titration experiments and in spite of a change in the solvent, association constants about one order of magnitude larger than the lower limit determined by the UV‐Vis experiments are obtained.
Silver Thiophosphate (Ag3PS4) as a Multielectron Reaction Active Material for Lithium Solid‐State Batteries
Authors: Zhang Zhenggang , Wang Rongbin , Mazzio Katherine A. , Koch Norbert , Adelhelm Philipp
Published: July 2024

Beyond its Li‐ion conductivity, the solid electrolyte lithium thiophosphate (β‐Li3PS4) exhibits redox activity when its electrochemical stability window is exceeded. As this redox activity can be (partially) reversible, thiophosphates may be used as cathode active materials (CAM). Silver thiophosphate (Ag3PS4) is a well‐known Ag‐ion conductor, which has the same crystal structure and similar chemical composition as β‐Li3PS4. Here, Ag3PS4 is selected and studied as the CAM for Li solid‐state batteries (Li‐SSBs) with the configuration (In/InLi| β‐Li3PS4| Ag3PS4: β‐Li3PS4: C65 = 40: 50: 10 wt%). The cells provide a discharge capacity of 325 mAh g−1 at 10 mA g−1, but suffer from continuous capacity fading during cycling with an average Coulomb efficiency of 97% at 50 mA g−1. The reaction mechanism is studied using X‐ray diffraction, X‐ray photoelectron spectroscopy, Raman spectroscopy, and impedance spectroscopy. Overall, the reaction of Li with Ag3PS4 is found to be initially partially reversible, but over cycling Ag2S and S8 become the active materials along with the formation of other byproducts such as Ag2P2S6 and Li2P2S6.
A review of Leonureae – taxonomy, phylogeny and biogeography
Authors: Chen Yanyi , Wang Qiang
Published: July 2024

The tribe Leonureae (Lamioideae, Lamiaceae) is distributed in Eurasia and mainly in Central Asia, known as valuable herbal medicine. It comprises ca. 80 species in six genera: the Chaiturus, Lagochilus, Lagopsis, Leonurus, Loxocalyx, and Panzerina. Although the monophyly of Leonureae is well‐supported, the relationships within the tribe remain unclear, and the non‐monophyly of Lagopsis and Leonurus needs to be revised. Leonureae is particularly diverse in the arid regions of Central Asia, and it has been indicated that the diversification of Lagochilus and Panzerina was affected by the Qinghai‐Xizang Plateau's uplift and Quaternary climate oscillation. As the present understanding of Leonureae is deficient in taxonomy, phylogeny, and biogeography, this review aims to consolidate the current knowledge, hoping to promote the research progress.
Revolutionizing Energy: Tailored ZnOFe2O3/rGO for Glucose Oxidation in Fuel Cell Application
Authors: Razali Nur Afifah Mat , Yahya Norilhamiah , Ishak Nurul Atiqah Izzati Md , Karim Nabila A. , Kamarudin Siti Kartom
Published: July 2024

Metal‐based catalysts such as platinum and gold are frequently employed as electrocatalysts. However, they faced significant limitations, including high cost and susceptibility to poisoning and degradation, hindering their extensive utilization. To overcome these challenges, metal oxide offers promising alternatives for its fast electron transfer rate, large surface area, and high electrocatalytic activity in electrochemical oxidation materials. In this work, ZnO doped with Fe2O3 was scattered on reduced graphene oxide (rGO) to form a ZnOFe2O3/rGO hybrid by a hydrothermal method for glucose oxidation. The synthesized ZnOFe2O3/rGO composite was thoroughly characterized using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X‐ray diffraction (XRD), and X‐ray photoelectron spectra (XPS) analysis, and the electrochemical performance was evaluated using cyclic voltammetry. ZnO particles are highly uniform flowerlike particles interacting with uniform‐size spherical‐like particles of Fe2O3 in ZnO–Fe2O3 supported on the rGO. The result reveals that interaction between ZnO–Fe2O3 nanocomposites supported onto graphene sheets reduces agglomeration compared to parent nanoparticles. An increase in surface‐to‐volume ratio exhibits more surface‐active sites for electrooxidation and thus improved catalytic performance by a negatively shifted potential of −36.62 mV versus Ag/AgCl, representing appropriate electrocatalysts for use as the anode in glucose fuel cells. The maximum current density of 0.5201 mA cm−2 was achieved in the electrochemical glucose oxidation equipped with ZnOFe2O3/rGO, which was almost 20 and 3 times higher than ZnO and Fe2O3, respectively. The synergistic interaction of ZnO–Fe2O3 supported on rGO showed a vital role as an electrocatalytic mediator to facilitate the charge transfer for glucose oxidation.
New insights into trends of rainfall extremes in the Amazon basin through trend‐empirical orthogonal function (1981–2021)
Authors: Cerón Wilmar L. , Kayano Mary T. , Andreoli Rita V. , Canchala Teresita , Avila‐Diaz Alvaro , Ribeiro Igor O. , Rojas Juan D. , Escobar‐Carbonari Daniel , Tapasco Jeimar
Published: July 2024

Studies related to monitoring changes in frequency, intensity and duration of precipitation extremes are key to creating efficient climate change measures and forest conservation policies. This study describes new insights into rainfall precipitation extremes over the Amazon basin (AB) during the last four decades (1981–2021) from the Climate Hazards Group InfraRed Precipitation with Station data (CHIRPSv2). Here we analysed the trends of daily extreme precipitation indices proposed by the Expert Team on Climate Change Detection and Indices (ETCCDI) at the seasonal scale, using the trend‐empirical orthogonal function (TEOF). Our results indicate that the frequency of precipitation extremes increased over Peruvian Amazonia and northeastern Brazilian Amazonia, and reduced in the centre of AB, mainly during the first seasons of the year: December–January–February (DJF) and March–April–May (MAM). The cooling trend over the eastern and central tropical Pacific and the warming trend over the tropical and western subtropical Pacific could associate with the increase in frequency of precipitation extremes in DJF. Furthermore, during June–July–August (JJA) and September–October–November (SON), rainfall intensity indices showed a decrease in Colombia and the Bolivian Amazon; in contrast, northern and southern Peru delivered an increased pattern. The trend pattern in the JJA and SON seasons could be associated with a warming trend over most of the North Atlantic and a cooling in the 40°–60° S band. Our results demonstrate that the precipitation extremes over the AB have spatially varying trends. These heterogeneous trends over the space might be take into account for robust adaptation policies over the countries that are parts of the AB, such as Bolivia, Brazil, Colombia, Ecuador, Guyana, Perú, Surinam and Venezuela.
The role of cultural and personal values in authentication of tourist attractions: A quantitative investigation
Authors: Stepchenkova Svetlana , Dai Xiangyi , Guerrero‐Rodriguez Rafael , Belyaeva Veronika , Kim Minseong , Park Hyejin
Published: July 2024

This study investigates the role of personal and cultural values in the authentication of tourist attractions. An attitudinal value that an individual ascribes to attractions being genuine (indexically authentic) versus being staged (iconically authentic) is operationalized as primarily realist, constructivist, and postmodernist. Two dimensions of the Inglehart‐Welzel Cultural Map represent cultural values: secular‐traditional and self‐expression‐survival. We compared authentication outcomes of two indexical and two iconic attractions in five cultural contexts: China, Mexico, Russia, South Korea, and the U.S. Authenticity orientation affects authentication outcomes, especially in the context of recreated attractions. The effect of culture goes beyond the influence of demographics, familiarity, and personal attitudes toward authenticity. Tourists from cultures that are higher on self‐expression are more likely to accept staged attractions as authentic and express a higher propensity to visit. The relationship between personal values toward authenticity and authentication outcomes demonstrated cultural invariance in several national contexts.
The role of tourism in driving economic growth: An asymmetric augmented autoregressive distributed lag analysis of Singapore's experience
Authors: Karimi Mohammad Sharif , Karamelikli Huseyin , Naysary Babak
Published: July 2024

Tourism has long been recognized as a potential force for economic growth in various parts of the globe. This study revisits this causal relationship to demonstrate the consequences of long‐run and short‐run effects between tourism development and economic growth in the context of Singapore for the period 1983:1 to 2020:4. We employ an augmented autoregressive distributed lag (AARDL) to prevent degenerative results and ensure the robustness of findings. We also control for variables such as foreign direct investment, net export, gross fixed capital formation, labor, and government expenditure. The overall empirical results provide support for the positive implications of tourism development for economic growth in Singapore in the long run, and its elasticity is 0.14 in increasing and 0.08 in decreasing. This implies that tourism can be one of the important factors for Singapore's economic growth in the long run, but in the short run, the impact is either negative or insignificant. This study provides important policy implications and recommendations.
Negative emotions of industrial heritage tourists
Authors: Zhang Yinan , Shi Peihua , Liang Yanlu , Wang Liqin
Published: July 2024

Industrial heritage is a high‐quality tourism resource with distinctive landscapes, technological value, and regeneration potential, distinguishing it from other tourism resources. However, we note that industrial heritage itself has some negative attributes that cannot be ignored, such as environmental pollution, ecological damage, resource depletion, decay scenes, and historical attributes. We chose to focus on tourists' negative emotions and investigated whether these negative attributes trigger tourists' negative emotions through in‐depth interviews, a literature review, and questionnaire surveys. The results reveal that tourists experience negative emotions in response to the negative attributes of industrial heritage; tourists' strongest emotions were irritable, afraid and hostile; negative emotions experienced by tourists were related to their gender, age, occupation, and even the type of sites, and showed significant differences among different groups. We discuss the reasons for these results and propose several suggestions for management.
Presence of oxygen in diffusive equilibrium in thin films (DET) probes: Effect on phosphate and iron porewater profiles and advice for correct deoxygenation and handling procedures
Authors: Klamt Anna‐Marie , Kragh Theis , Glud Ronnie N. , Wagner Cecilie M. , Reitzel Kasper
Published: July 2024

Diffusive equilibrium in thin films (DET) probes are passive samplers that are designed to reflect in situ porewater concentrations. In this study, we show that the gel and the plastic housing of DET probes store a substantial amount of oxygen (O2) that affects the chemical composition of porewater. To ensure complete deoxygenation, DET probes need to be treated for 7 d with continuous nitrogen flow. Such fully deoxygenated probes can be handled in the air (exposure time: < 90 s) and deployed to sediments through oxic water (exposure time: < 2 s) without significant ad(b)sorption of O2. Furthermore, we deployed a set of untreated (i.e., in equilibrium with atmospheric O2) and a set of fully deoxygenated DET probes to lake sediments. The O2 present in untreated DET probes altered iron (Fe) and phosphate (P) porewater profiles significantly. This is caused by the oxidation, immobilization, and accumulation of redox‐sensitive Fe (oxyhydr)oxides in the probe over time. Since P has a high binding affinity to Fe (oxyhydr)oxides, it is not in equilibrium with the porewater and is overestimated as well. Our results highlight the importance of thorough deoxygenation of DET probes before deployment in sediments, especially when addressing redox‐sensitive porewater species.
Silicon Nitride Integrated Photonics from Visible to Mid‐Infrared Spectra
Authors: Buzaverov Kirill A. , Baburin Aleksandr S. , Sergeev Evgeny V. , Avdeev Sergey S. , Lotkov Evgeniy S. , Bukatin Sergey V. , Stepanov Ilya A. , Kramarenko Aleksey B. , Amiraslanov Ali Sh. , Kushnev Danil V. , Ryzhikov Ilya A. , Rodionov Ilya A.
Published: July 2024

Silicon nitride (Si3N4) photonic integrated circuits (PICs) are of great interest due to their extremely low propagation loss and higher integration capabilities. The number of applications based on the silicon nitride integrated photonics platform continues to grow, including the Internet of Things (IoT), artificial intelligence (AI), light detection and ranging (LiDAR), hybrid neuromorphic and quantum computing. It's potential for CMOS compatibility, as well as advances in heterogeneous integration with silicon‐on‐insulator, indium phosphate, and lithium niobate on insulator platforms, are leading to an advanced hybrid large‐scale PICs. Here, they review key trends in Si3N4 photonic integrated circuit technology and fill an information gap in the field of state‐of‐the‐art devices operating from the visible to the mid‐infrared spectrum. A comprehensive overview of its microfabrication process details (deposition, lithography, etching, etc.) is introduced. Finally, the limitations and challenges of silicon nitride photonics performance are pointed out in an ultra‐wideband, providing routes and prospects for its future scaling and optimization.
Efficient application of deep learning‐based elective lymph node regions delineation for pelvic malignancies
Authors: Wen Feng , Zhou Jie , Chen Zhebin , Dou Meng , Yao Yu , Wang Xin , Xu Feng , Shen Yali
Published: July 2024

Background

While there are established international consensuses on the delineation of pelvic lymph node regions (LNRs), significant inter‐ and intra‐observer variabilities persist. Contouring these clinical target volumes for irradiation in pelvic malignancies is both time‐consuming and labor‐intensive.

Purpose

The purpose of this study was to develop a deep learning model of pelvic LNRs delineation for patients with pelvic cancers.

Methods

Planning computed tomography (CT) studies of 160 patients with pelvic primary malignancies (including rectal, prostate, and cervical cancer) were retrospectively collected and divided into training set (n = 120) and testing set (n = 40). Six pelvic LNRs, including abdominal presacral, pelvic presacral, internal iliac nodes, external iliac nodes, obturator nodes, and inguinal nodes were delineated by two radiation oncologists as ground truth (Gt) contours. The cascaded multi‐heads U‐net (CMU‐net) was constructed based on the Gt contours from training cohort, which was subsequently verified in the testing cohort. The automatic delineation of six LNRs (Auto) was evaluated using dice similarity coefficient (DSC), average surface distance (ASD), 95th percentile Hausdorff distance (HD95), and a 7‐point scale score.

Results

In the testing set, the DSC of six pelvic LNRs by CMU‐net model varied from 0.851 to 0.942, ASD from 0.381 to 1.037 mm, and HD95 from 2.025 to 3.697 mm. No significant differences were founded in these three parameters between postoperative and preoperative cases. 95.9% and 96.2% of auto delineations by CMU‐net model got a score of 1–3 by two expert radiation oncologists, respectively, meaning only minor edits needed.

Conclusions

The CMU‐net was successfully developed for automated delineation of pelvic LNRs for pelvic malignancies radiotherapy with improved contouring efficiency and highly consistent, which might justify its implementation in radiotherapy work flow.
Patient Experience of Stiffness With Knee Osteoarthritis: An Interpretative Description Study
Authors: Reischl S. , Ziebart C. , Johnston Z. , Ma J. , Pham D. , Salloum J. F. , Sithganesan M. , Wikkerink S. , Munro K. , MacDermid J. C.
Published: July 2024

Introduction

Knee OA (KOA) can lead to pain, loss of muscle strength, and changes in gait. Knee stiffness is a classic feature of KOA that can increase the risk of falls but has been understudied.

Objective

To evaluate the impact of knee stiffness, the factors influencing the severity of stiffness, and the repercussions on participation for patients with KOA.

Methods

This qualitative study used an interpretive description approach. Purposeful sampling was used for patients with KOA over 45 years of age, fluent in English, diagnosed with KOA and reported KOA stiffness within the last 6 months. Participants were recruited through social media and Ontario clinics. Semi‐structured interviews were conducted over the phone or using zoom, recorded, and transcribed verbatim. Open, axial, and selective coding were used to identify clinically relevant themes.

Results

Twelve participants (5F, 7M) with a mean age of 60 years were included. The five themes identified include elusive and variable perceptions of joint stiffness, inactivity or too much activity exacerbates stiffness, adapting to the ebb and flow of symptoms, risk experiences and safety fears leads to reduced participation, and KOA stiffness impairs quality of life.

Conclusion

This study highlights characteristics of knee stiffness, consequences on participation, and quality of life for people with KOA. Monitoring knee stiffness for KOA is recommended for more appropriate treatment intensity, which could improve adherence to a home programme and potentially reduce the risk of falls.