bluuebunny/crossref_metadata_2025 huggingface dataset:
Super‐Droplet‐Repellent Carbon‐Based Printable Perovskite Solar Cells
Authors: Mai Cuc Thi Kim , Halme Janne , Nurmi Heikki A. , da Silva Aldeliane M. , Lorite Gabriela S. , Martineau David , Narbey Stéphanie , Mozaffari Naeimeh , Ras Robin H. A. , Hashmi Syed Ghufran , Vuckovac Maja
Published: May 2024

Despite attractive cost‐effectiveness, scalability, and superior stability, carbon‐based printable perovskite solar cells (CPSCs) still face moisture‐induced degradation that limits their lifespan and commercial potential. Here, the moisture‐preventing mechanisms of thin nanostructured super‐repellent coating (advancing contact angle >167° and contact angle hysteresis 7°) integrated into CPSCs are investigated for different moisture forms (falling water droplets vs water vapor vs condensed water droplets). It is shown that unencapsulated super‐repellent CPSCs have superior performance under continuous droplet impact for 12 h (rain falling experiments) compared to unencapsulated pristine (uncoated) CPSCs that degrade within seconds. Contrary to falling water droplets, where super‐repellent coating serves as a shield, water vapor is found to physisorb through porous super‐repellent coating (room temperature and relative humidity, RH 65% and 85%) that increase the CPSCs performance for 21% during ≈43 d similarly to pristine CPSCs. It is further shown that water condensation forms within or below the super‐repellent coating (40 °C and RH 85%), followed by chemisorption and degradation of CPSCs. Because different forms of water have distinct effects on CPSC, it is suggested that future standard tests for repellent CPSCs should include rain falling and condensate formation tests. The findings will thus inspire the development of super‐repellent coatings for moisture prevention.
Coordination Confined Silver‐Organic Framework for High Performance Electrochemical Deionization
Authors: Wei Dun , Ouyang Baixue , Cao Yiyun , Yan Lvji , Wu Bichao , Chen Peng , Zhang Tingzheng , Jiang Yuxin , Wang Haiying
Published: May 2024

Silver (Ag) is deemed a promising anode material for capacitive deionization (CDI) due to its high theoretical capacity and efficient selectivity to Cl−. However, the strong volume change during the conversion reaction significantly undermines the cycling performance of the Ag electrode. Additionally, achieving well‐dispersed Ag in the active matrix is challenging, as Ag electrodes prepared by conventional thermal reduction tend to agglomerate. Herein, the organic linker confinement strategy is proposed, applying metal–organic framework (MOF) chemistry between Ag nodes and organic ligands to construct Ag‐based MOF. The uniform dispersion of Ag at the molecular level, confined in the organic matrix, efficiently enhances the utilization of active sites, and strengthens the interfacial stability of Ag. Consequently, the Ag‐MOF for the CDI anode exhibits an excellent Cl− removal capacity of 121.52 mg g−1 at 20 mA g−1 in 500 mg L−1 NaCl solution, and a high Ag utilization rate of 60.54%. After 100 cycles, a capacity retention of 96.93% is achieved. Furthermore, the Cl− capture mechanism of Ag‐MOF is elucidated through density functional theory (DFT) calculations, ex situ XRD, ex situ Raman and XPS. This ingenious electrode design can offer valuable insights for the development of high‐performance conversion electrodes for CDI applications.
Leaky Integrate‐and‐Fire Model and Short‐Term Synaptic Plasticity Emulated in a Novel Bismuth‐Based Diffusive Memristor
Authors: Zawal Piotr , Abdi Gisya , Gryl Marlena , Das Dip , Sławek Andrzej , Gerouville Emilie A. , Marciszko‐Wiąckowska Marianna , Marzec Mateusz , Hess Grzegorz , Georgiadou Dimitra G. , Szaciłowski Konrad
Published: May 2024

Memristors, being prospective work‐horses of future electronics offer various types of memory (volatile and nonvolatile) along with specific computational functionalities. Further development of memristive technologies depends on the availability of suitable materials. These materials should be easily available, stable, and preferably of low toxicity. Commonly used materials are lead halide perovskites, however, they are highly toxic and unstable under ambient conditions. Therefore a novel material is developed on the basis of bismuth iodide. In reaction with butylammonium iodide, it yields a novel compound, butylammonium iodobismuthate (BABI). Here, a diffusive memristor is introduced based on this compound and evaluates its memristive and neuromorphic properties. In contrast to nonvolatile memristors, the BABI memristors exhibit diffusive dynamics, which enable them to store the information only for short periods of time. This property is utilized to mimic the short‐term synaptic plasticity described by the leaky integrate‐and‐fire model of a biological neuron. Combined with high switching uniformity and self‐rectifying behavior, these devices show high classification accuracy for MNIST handwritten datasets, paving the way for their application in neuromorphic computing systems.
Dry Electrode Processing for High‐Performance Molten Salt Batteries
Authors: Wang Kuangyu , Wu Yulong , Yang Cheng , Yu Maosheng , Lei Chong , Zhang Yingchuan , Ding Tiezheng , Long Yuanzheng , Liu Kai , Li Meicheng , Wu Hui
Published: May 2024

Molten salt batteries (MSBs) are renowned for their rapid reaction kinetics, high safety, and cost‐effectiveness. However, their electrode design faces challenges due to polymer binder incompatibility in molten salt electrolytes (MSEs). To address this, an expanded graphite (EG) electrode is proposed through a dry electrode processing method for MSE‐based aluminum‐ion batteries. This method facilitates the fabrication of large‐area electrodes featuring high active material loadings of up to ≈60 mg cm−2. Notably, the EG electrode exhibits remarkable rate performance, achieving a specific capacity of 84.4 mAh g−1 in the AlCl3‐NaCl‐KCl MSE at 125 °C with a current density of 5 A g−1. This outstanding performance can be attributed to its rapid multi‐step intercalation reaction kinetics and well‐developed pore structure. Leveraging the chemical stability and fibrillization binding mechanism of the polytetrafluoroethylene binder, the electrode demonstrates longevity over 10,000 cycles, despite experiencing a three‐fold volume expansion. Additionally, a 100‐mAh‐scale Al‐EG full‐cell cycled 100 times with an energy efficiency of 78.7% at 500 mA underscores its potential for large‐scale applications. Considering the broad applicability of this approach, it can also provide crucial references and insights for electrode design across various MSB systems.
A 2D Metallic KCu4S3 Anode for Fast‐Charging Sodium‐Ion Batteries
Authors: Lu Chengyi , Liu Lei , He Song , Li Boxin , Du Zhuzhu , Du Hongfang , Wang Xuefei , Zhang Shaowei , Ai Wei
Published: May 2024

The search for advanced electrode materials to solve slow ion diffusion and poor conductivity issues has spurred the development of fast‐charging sodium‐ion batteries (SIBs). Herein, a 2D metallic anode, KCu4S3, is reported expertly crafted using a KSCN molten salt approach, laying the foundation for fast‐charging SIBs. It is found that the mixed metal‐valence states within this compound provide substantial advantages, particularly in enhancing the high‐rate capability and ensuring long‐term durability. The mechanism that appears to facilitate these benefits can be traced to the formation of NaCu2S2 intermediate, which assist in electron transfer during Na+ (de)intercalation. In situ observations confirm the sodiation products of NaCu2S2 and sodium polysulfide can recover to the original phase upon desodiation. Such distinctive characteristics endow KCu4S3 with remarkable electrochemical performances, including an impressive capacity of 355 mAh g−1 at 20 A g−1 and 100% capacity retention within 3000 cycles. Moreover, the full cell exhibits a high energy density of 332 Wh kg−1 and retains 92% of its capacity across 150 cycles at 1 A g−1. This work opens new horizons in the field of fast‐charging materials, making a significant step forward in shaping the future of SIBs.
An assessment of agroforestry as a climate‐smart practice: Evidences from farmers of northwestern region of Bangladesh
Authors: Ali Md. Manik , Ahmad Babor , Bari Md Shafiqul , Pal Abinash Chandra , Rahman Md. Lutfor , Sarmin Israt Jahan
Published: May 2024

Agroforestry systems have grown significantly in popularity in Bangladesh during recent years due to their favorable effects on the environment and human health. These systems are essential for supporting sustainable agriculture because they increase diversity, improve food security, and provide revenue. This study's main objective is to show how agroforestry is a widely used ecological and climate‐resilient practice in Bangladesh. The research explores investment analysis, adoption‐influencing factors, and a strength, weakness, opportunities, and threats (SWOT) analysis of agroforestry practices. A total of 340 respondents were chosen for this extensive study using a multistage random selection technique. The results showed a discrepancy in practice, with farmers exhibiting a high degree of awareness but limited application. Financial analysis employing metrics such as benefit‐cost ratio, net present value, and internal rate of return favored agroforestry, indicating its economic viability and potential benefits for adopters. Additionally, the adoption of agroforestry was found to be significantly influenced by a binary logistic regression model that highlighted several important features, including larger farm sizes, younger age groups, greater education levels, training experiences, frequent extension visits, and enhanced market access. The study also identified barriers to adoption, such as a lack of trained labor, poor technical assistance, and education. This thorough analysis clarifies the opportunities and constraints for agroforestry implementation in Bangladesh. It suggests broad adoption by means of focused training initiatives that empower farmers, provide observable advantages, and promote nationwide acceptance.
Gold‐Catalysierte Heck Reaktion: Wunschtraum oder Wirklichkeit? Korrespondenz zu “Unlocking the Chain Walking Process in Gold Catalysis”
Authors: Budzelaar Peter H. M. , Bochmann Manfred , Landrini Martina , Rocchigiani Luca
Published: May 2024

In zwei vielbeachteten Veröffentlichungen wurde vor kurzem über die Bildung von arylierten Heck‐Olefinen durch Katalyse mit MeDalPhosAuCl/AgOTf (J. Am. Chem. Soc. 2023, 145, 8810) und ihre Cyclisierung zu Tetralinen berichtet (Angew. Chem. Int. Ed. 2023, e202312786). Es wurde behauptet, es handle sich dabei um den erstmaligen Nachweis von Gold‐katalysierten Alken‐Insertionen in Au‐Aryl‐Bindungen, β‐H‐Eliminierung und Kettenwanderung durch Au−H. Wir zeigen hier, dass es sich dabei tatsächlich aber um einen Zweistufenprozess handelt, wobei nur der erste Schritt, die Bildung eines Alkyltriflat‐Esters als primäres organisches Produkt durch die wohlbekannte Alken‐Heteroarylierungssequenz, einen Gold‐Katalysator involviert. Die nachfolgende Umsetzung zu Heck‐Olefinen sowie deren Cyclisierung zu Tetralinen ist klassische, H+‐initiierte Carbokationenchemie. Diese Schritte finden auch unter Gold‐freien Bedingungen statt, mit identischen Resultaten. Literaturberichte über neuartige Reaktivität von Gold‐Katalysatoren, wie Kettenwanderung durch das hypothetische [LAuH]2+ Dikation, entbehren jeder faktischen Grundlage.
NETosis‐Inspired Cell Surface‐Constrained Framework Nucleic Acids Traps (FNATs) for Cascaded Extracellular Recognition and Cellular Behavior Modulation
Authors: Gong Hangsheng , Zhang Yihan , Xue Yuan , Fang Bowen , Li Yuting , Zhu Xudong , Du Yi , Peng Pai
Published: May 2024

Upon pathogenic stimulation, activated neutrophils release nuclear DNA into the extracellular environment, forming web‐like DNA structures known as neutrophil extracellular traps (NETs), which capture and kill bacteria, fungi, and cancer cells. This phenomenon is commonly referred to as NETosis. Inspired by this, we introduce a cell surface‐constrained web‐like framework nucleic acids traps (FNATs) with programmable extracellular recognition capability and cellular behavior modulation. This approach facilitates dynamic key chemical signaling molecule recognition such as adenosine triphosphate (ATP), which is elevated in the extracellular microenvironment, and triggers FNA self‐assembly. This, in turn, leads to in situ tightly interwoven FNAs formation on the cell surface, thereby inhibiting target cell migration. Furthermore, it activates a photosensitizer‐capturing switch, chlorin e6 (Ce6), and induces cell self‐destruction. This cascade platform provides new potential tools for visualizing dynamic extracellular activities and manipulating cellular behaviors using programmable in situ self‐assembling DNA molecular devices.
Elektrokatalytische formale C(sp2)−H Alkylierung via Nickel‐katalysierter elektrophiler Kreuzkupplung mit vielseitigen Arylsulfoniumsalzen
Authors: Michiyuki Takuya , Homölle Simon L. , Pandit Neeraj K. , Ackermann Lutz
Published: May 2024

Die Synthese sp3‐hybridsierter kohlenstoffreicher Moleküle ist aufgrund ihrer Bedeutung und ihres Erfolgs insbesondere in klinischen Studien von besonderem Interesse. In dieser Arbeit wurde das Einbringen von aliphatischen Ketten auf ein aromatisches Gerüst durch eine Nickel‐katalysierte C(sp2)−C(sp3) elektrophile Kreuzkupplungen mit Arylsulfoniumsalzen erreicht. So konnten einfach, nichtpräfunktionalisiere Arene durch die Bildung von Aryldibenzothiopheniumsalze alkyliert werden. Durch den elektrochemischen Ansatz können potenziell gefährliche chemische Redoxreagenzien vermieden werden. Insbesondere die Ein‐Topf Alkylierung erwies sich als praktikabel, was die Robustheit unseres Ansatzes unterstreicht.
Anion‐Reinforced Solvation Structure Enables Stable Operation of Ether‐Based Electrolyte in High‐Voltage Potassium Metal Batteries
Authors: Gu Mengjia , Zhou Xunzhu , Yang Qian , Chu Shenxu , Li Lin , Li Jiaxin , Zhao Yuqing , Hu Xing , Shi Shuo , Chen Zhuo , Zhang Yu , Chou Shulei , Lei Kaixiang
Published: May 2024

Electrolytes with anion‐dominated solvation are promising candidates to achieve dendrite‐free and high‐voltage potassium metal batteries. However, it's challenging to form anion‐reinforced solvates at low salt concentrations. Herein, we construct an anion‐reinforced solvation structure at a moderate concentration of 1.5 M with weakly coordinated cosolvent ethylene glycol dibutyl ether. The unique solvation structure accelerates the desolvation of K+, strengthens the oxidative stability to 4.94 V and facilitates the formation of inorganic‐rich and stable electrode‐electrolyte interface. These enable stable plating/stripping of K metal anode over 2200 h, high capacity retention of 83.0 % after 150 cycles with a high cut‐off voltage of 4.5 V in K0.67MnO2//K cells, and even 91.5 % after 30 cycles under 4.7 V. This work provides insight into weakly coordinated cosolvent and opens new avenues for designing ether‐based high‐voltage electrolytes.
Zeolitic Imidazolate Frameworks as Solid‐State Nanomachines
Authors: Nam Joohan , Kim Seokjin , Jin Eunji , Lee Soochan , Cho Hye Jin , Min Seung Kyu , Choe Wonyoung
Published: May 2024

Machines have continually developed with the needs of daily life and industrial applications. While the careful design of molecular‐scale devices often displays enhanced properties along with mechanical movements, controlling mechanics within solid‐state molecular structures remains a significant challenge. Here, we explore the distinct mechanical properties of zeolitic imidazolate frameworks (ZIFs)—frameworks that contain hidden mechanical components. Using a combination of experimental and theoretical approaches, we uncover the machine‐like capabilities of ZIFs, wherein connected composite building units operate similarly to a mechanical linkage system. Importantly, this research suggests that certain ZIF subunits act as core mechanical components, paving an innovative view for the future design of solid‐state molecular machines.
Alkene 1,3‐Difluorination via Transient Oxonium Intermediates
Authors: Dean Alice C. , Randle E. Harvey , Lacey Andrew J. D. , Marczak Giorio Guilherme A. , Doobary Sayad , Cons Benjamin D. , Lennox Alastair J. J.
Published: May 2024

The 1,3‐difunctionalization of unactivated alkenes is an under‐explored transformation that leads to moieties that are otherwise challenging to prepare. Herein, we report a hypervalent iodine‐mediated 1,3‐difluorination of homoallylic (aryl) ethers to give unreported 1,3‐difluoro‐4‐oxy groups with moderate to excellent diastereoselectivity. The transformation proceeds through a different mode of reactivity for 1,3‐difunctionalization, in which a regioselective addition of fluoride opens a transiently formed oxonium intermediate to rearrange an alkyl chain. The optimized protocol is scalable and shown to proceed well with a variety of functional groups and substitution on the alkenyl chain, hence providing ready access to this fluorinated, conformationally controlled moiety.
[2+1] Cycloadditions Modulate the Hydrophobicity of Ni‐N4 Single‐Atom Catalysts for Efficient CO2 Electroreduction
Authors: Shu Siyan , Song Tao , Wang Cheng , Dai Hao , Duan Lele
Published: May 2024

Microenvironment regulation of M‐N4 single‐atom catalysts (SACs) is a promising way to tune their catalytic properties toward the electrochemical CO2 reduction reaction. However, strategies that can effectively introduce functional groups around the M‐N4 sites through strong covalent bonding and under mild reaction conditions are highly desired. Taking the hydrophilic Ni‐N4 SAC as a representative, we report herein a [2+1] cycloaddition reaction between Ni‐N4 and in situ generated difluorocarbene (F2C:), and enable the surface fluorocarbonation of Ni‐N4, resulting in the formation of a super‐hydrophobic Ni‐N4‐CF2 catalyst. Meanwhile, the mild reaction conditions allow Ni‐N4‐CF2 to inherit both the electronic and structural configuration of the Ni‐N4 sites from Ni‐N4. Enhanced electrochemical CO2‐to‐CO Faradaic efficiency above 98 % is achieved in a wide operating potential window from −0.7 V to −1.3 V over Ni‐N4‐CF2. In situ spectroelectrochemical studies reveal that a highly hydrophobic microenvironment formed by the −CF2− group repels asymmetric H‐bonded water at the electrified interface, inhibiting the hydrogen evolution reaction and promoting CO production. This work highlights the advantages of [2+1] cycloaddition reactions on the covalent modification of N‐doped carbon‐supported catalysts.
Patterned Photonic Actuators with Dynamic Shape‐Morphing and Color‐Changing Capabilities Fabricated by Athermal Embossing Technology
Authors: Qian Nina , Hu Jun , Huang Shuai , Liu Zhiyang , Wang Meng , Keller Patrick , Yang Hong
Published: May 2024

Stimuli‐responsive patterned photonic actuators, characterized by their patterned nano/microscale structures and capacity to demonstrate synergistic color changes and shape morphing in response to external stimuli, have attracted intense scientific attention. However, traditional patterned photonic actuator systems still face limitations such as cumbersome and time‐consuming preparation processes and small‐scale deformations. Herein, we introduce a facile approach involving an athermal embossing technique to rapidly fabricate patterned photonic actuators based on near‐infrared (NIR) light‐responsive liquid crystal elastomers. The resulting patterned photonic actuators demonstrate remarkable features, including brilliant angle‐dependent structural color, complex three‐dimensional actuation, and good color durability under NIR light stimulation. As illustrative demonstrations of the proof‐of‐concept, we fabricate two light‐fuelled patterned photonic soft actuators: a butterfly‐inspired actuator that can produce wing‐flapping dynamic changes in structural color, and an origami crane‐shaped actuator with shape memory, structural color information storage, and dynamic display properties. This strategy provides distinct insights into the design and fabrication of various patterned photonic soft robotic devices and intelligent actuators.
Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex
Authors: Ahmed Hussayn , Ghosh Biki , Breitenlechner Stefan , Feßner Malte , Merten Christian , Bach Thorsten
Published: May 2024

In the presence of 1 mol % of a chiral iron porphyrin catalyst, various 3‐arylmethyl‐substituted 2‐quinolones and 2‐pyridones underwent an enantioselective amination reaction (20 examples; 93–99 % ee). The substrates were used as the limiting reagents, and fluorinated aryl azides (1.5 equivalents) served as nitrene precursors. The reaction is triggered by visible light which allows a facile dediazotation at ambient temperature. The selectivity of the reaction is governed by a two‐point hydrogen bond interaction between the ligand of the iron catalyst and the substrate. Hydrogen bonding directs the amination to a specific hydrogen atom within the substrate that is displaced by the nitrogen substituent either in a concerted fashion or by a rebound mechanism.
Stabilizing Few‐Atom Platinum Clusters by Zinc Single‐Atom‐Glue for Efficient Anti‐Markovnikov Alkene Hydrosilylation
Authors: Li Ruilong , Yu Ge , Lin Ze , Lin Xingen , Du Junyi , Gao Xiaoping , Su Chenliang , Wu Yuen
Published: May 2024

Few‐atom metal clusters (FAMCs) exhibit superior performance in catalyzing complex molecular transformations due to their special spatial environments and electronic states, compared to single‐atom catalysts (SACs). However, achieving the efficient and accurate synthesis of FAMCs while avoiding the formation of other species, such as nanoparticles and SACs, still remains challenges. Herein, we report a two‐step strategy for synthesis of few‐atom platinum (Pt) clusters by predeposition of zinc single‐atom‐glue (Zn1) on MgO nanosheets (Ptn−Zn1/MgO), where FAMCs can be obtained over a wide range of Pt contents (0.09 to 1.45 wt %). Zn atoms can act as Lewis acidic sites to allow electron transfer between Zn and Pt through bridging O atoms, which play a crucial role in the formation and stabilization of few‐atom Pt clusters. Ptn−Zn1/MgO exhibited a high selectivity of 93 % for anti‐Markovnikov alkene hydrosilylation. Moreover, an excellent activity with a turnover frequency of up to 1.6×104 h−1 can be achieved, exceeding most of the reported Pt SACs. Further theoretical studies revealed that the Pt atoms in Ptn−Zn1/MgO possess moderate steric hindrance, which enables high selectivity and activity for hydrosilylation. This work presents some guidelines for utilizing atomic‐scale species to increase the synthesis efficiency and precision of FAMCs.
Cobalt‐Mediated Photochemical C−H Arylation of Pyrroles
Authors: Märsch Julia , Reiter Sebastian , Rittner Thomas , Rodriguez‐Lugo Rafael E. , Whitfield Maximilian , Scott Daniel J. , Kutta Roger Jan , Nuernberger Patrick , de Vivie‐Riedle Regina , Wolf Robert
Published: May 2024

Precious metal complexes remain ubiquitous in photoredox catalysis (PRC) despite concerted efforts to find more earth‐abundant catalysts and replacements based on 3d metals in particular. Most otherwise plausible 3d metal complexes are assumed to be unsuitable due to short‐lived excited states, which has led researchers to prioritize the pursuit of longer excited‐state lifetimes through careful molecular design. However, we report herein that the C−H arylation of pyrroles and related substrates (which are benchmark reactions for assessing the efficacy of photoredox catalysts) can be achieved using a simple and readily accessible octahedral bis(diiminopyridine) cobalt complex, [1‐Co](PF6)2. Notably, [1‐Co]2+ efficiently functionalizes both chloro‐ and bromoarene substrates despite the short excited‐state lifetime of the key photoexcited intermediate *[1‐Co]2+ (8 ps). We present herein the scope of this C−H arylation protocol and provide mechanistic insights derived from detailed spectroscopic and computational studies. These indicate that, despite its transient existence, reduction of *[1‐Co]2+ is facilitated via pre‐assembly with the NEt3 reductant, highlighting an alternative strategy for the future development of 3d metal‐catalyzed PRC.
Combined thoracic erector spinae plane and inter‐transverse plane blocks for awake breast surgery
Authors: Marrone F. , Fusco P.F. , Paventi S. , Tomei M. , Failli S. , Fabbri F. , Pullano C.
Published: May 2024

Worldwide, breast cancer is the most commonly diagnosed cancer in women. Surgical procedures are typically performed using general anaesthesia, often complemented by regional anaesthesia to manage postoperative pain. However, avoidance of general anaesthesia for breast surgery may be desirable for clinical reasons or patient choice. It is theorised that the use of regional anaesthesia and the avoidance of volatile anaesthetics and opioid analgesia may have beneficial effects on oncological outcomes, and there is some evidence to support this. While many patients successfully undergo awake breast surgery, a limited number of anaesthetists possess direct experience of this approach, despite familiarity with regional anaesthesia techniques. Undertaking regional anaesthesia for awake breast surgery requires patient cooperation and excellent staff teamwork. Here, we present a case of a patient who underwent awake bilateral mastectomy with reconstruction. This was carried out under two ‘paravertebral‐by‐proxy’ blocks: the thoracic erector spinae plane and inter‐transverse plane blocks, with intravenous sedation.
Fluorinated graphite reinforced polytetrafluoroethylene/poly(butylene terephthalate) composites as friction materials for deep‐sea applications
Authors: Su Qiong , Wang Zhongxu , Liu Liang , Wang Hongling , Wang Jianzhang , Wang Yanbin , Liu Hao , Yan Fengyuan
Published: May 2024

The application of polymer composites is one of the most effective methods for preventing lubrication failure in deep‐sea engineering. In this study, fluorinated graphite (FGr) microsheets were incorporated into polytetrafluoroethylene (PTFE) microparticle‐filled poly(butylene terephthalate) (PBT) composites. The tribological performance in the simulated deep‐sea environment at elevated seawater pressure equivalent to 3000 m ocean depth was investigated. The results showed that FGr enhances the flexural and compressive strengths, thermal stability, and seawater resistance of the PTFE/PBT composite. The wear rate was decreased to 96% at the critical FGr content of 4% by improving the transfer onto the metallic counterfaces, preventing direct contact and shear between friction couples. Moreover, the seawater pressure impedes composite transfer, leading to a 29% increase in the wear rate.
Evaluation of the polycaprolactone hydrolytic degradation in acid solvent and its influence on the electrospinning process
Authors: Anaya‐Mancipe Javier Mauricio , de Figueiredo Agnes Chacor , Rabello Lucas Gomes , Dias Marcos Lopes , da Silva Moreira Thiré Rossana Mara
Published: May 2024

Polycaprolactone (PCL) is a pivotal biopolymer in biomedicine, especially in tissue engineering for scaffolds and biomaterials. Recognized for its effectiveness as a drug carrier with superior controlled release properties, PCL is commonly processed via electrospinning, typically employing chlorinated or fluorinated solvents known for cellular toxicity. As an environmentally conscious alternative, this study explores glacial acetic acid (AA) as a solvent for electrospinning solutions. Investigating PCL's molecular degradation through acid hydrolysis in acidic solvents (AA/formic acid) (FA), the study assesses the impact of storage time on resulting structures. Solutions containing 30% PCL in AA/FA (9:1) were stored at 35°C for up to 14 days, revealing a 50% molar mass reduction during solubilization through gel permeation chromatography, x‐ray diffraction, and Fourier‐transform infrared analyses. This reduction influenced chain packing, raising crystallinity indices from approximately 37% to 49% with prolonged storage. The reduced molar mass resulted in unstable Taylor cones, generating diverse mat morphologies. Intriguingly, this degradation enhanced water adsorption capacity, indicating exposed hydrogen bonds from acid hydrolysis as an advantageous trait for regenerative medicine. This underscores the hydrolyzed materials' potential for cell anchoring in tissue engineering.
Anatomy's missing faces: An assessment of representation gaps in atlas and textbook imagery
Authors: Beresheim Amy , Zepeda David , Pharel Marissa , Soy Tyler , Wilson Adam B. , Ferrigno Christopher
Published: May 2024

Previous research suggests that underrepresentation in medical curricula perpetuates inequities in healthcare. This study aimed to quantify the prevalence of human phenotypic diversity (e.g., skin tone, sex, body size, and age) across 11 commonly used anatomy atlases and textbooks in pre‐clerkship medical education, published from 2015 to 2020. A systematic visual content analysis was conducted on 5001 images in which at least one phenotypic attribute was quantifiable. Anatomy images most prevalently portrayed light skin tones, males, persons with intermediate body sizes, and young to middle‐aged adults. Of the 3883 images in which there was a codable skin tone, 81.2% (n = 3154) depicted light, 14.3% (n = 554) depicted intermediate, and 4.5% (n = 175) depicted dark skin tones. Of the 2384 images that could be categorized into a sex binary, 38.4% (n = 915) depicted females and 61.6% (n = 1469) depicted males. A male bias persisted across all whole‐body and regional‐body images, including those showing sex organs or those showing characteristics commonly associated with a specific sex (e.g. for males, facial hair and/or muscle hypertrophy). Within sex‐specific contexts, darker skin was underrepresented, but male depictions displayed greater overall skin tone variation. Although most images could not be assigned to a body size or age category, when codable, these images overwhelmingly depicted adults (85.0%; 482 of 567) with smaller (34.7%; 93 of 268) or intermediate (64.6%; 173 of 268) body sizes. Ultimately, these outcomes provide reference metrics for monitoring ongoing and future efforts to address representation inequalities portrayed in anatomical imagery.
Construction of Nanoflower Cobalt‐Based Catalyst for Methane‐Free CO Hydrogenation to Hydrocarbon Reaction
Authors: Liu Zhenxin , Wu Depeng , Liu Huiwen , Gao Yuji , Guo Xuehui , Zhao Chenxi , Xing Yu
Published: May 2024

Methane and its oxidation product (i. e., CO2) are both greenhouse gases. In the product chain of CO hydrogenation to hydrocarbon reaction, methane is also an unwanted product due to its poor added value. Herein we investigated the effect of structure‐directing agent urotropine on cobalt‐based catalyst supported on Al−O−Zn type carrier and achieved an initial and pioneering exploration of methane‐free CO hydrogenation to hydrocarbon reaction at mild CO conversion range. The catalyst modified by urotropine has a nanoflower micromorphology and can significantly change the reaction performance, almost completely eliminating the ability of the catalyst to inhibit C−C coupling within a mild CO conversion range, that is, it can produce no or less C1−C4 gaseous hydrocarbons, while rich in condensed hydrocarbons (i. e., C5+ hydrocarbon selectivity can reach as high as 92.8 %–100.0 %).
Prevalence of comorbidity of autism and ADHD and associated characteristics in school population: EPINED study
Authors: Canals Josefa , Morales‐Hidalgo Paula , Voltas Núria , Hernández‐Martínez Carmen
Published: May 2024

Autism and attention deficit hyperactivity disorder (ADHD) comorbidity in the school population have been understudied. This study estimates its prevalence considering both parents' and teachers' reports and clinical diagnosis. Sociodemographic, clinical, and cognitive data were compared by diagnostic groups: autism, ADHD, autism and ADHD, subthreshold autism spectrum disorder (ASD), subthreshold ADHD, and children without neurodevelopmental conditions. Following a two‐phase design, 3727 parents and teachers (1802 preschoolers, 1925 school‐age children) participated in the first phase. Subsequently, 781 participants underwent individual assessment for DSM‐5 diagnoses. The estimated prevalence of the comorbid diagnosis was 0.51% (0.28%–0.74%), with significant sex differences (0.16% girls, 0.89% boys). The cooccurrence of symptoms of autism and ADHD reported by parents or teachers was 3.2% and 2.6%, respectively. ADHD comorbidity was observed in 32.8% of autistic children and 31.4% of those with subthreshold ASD. ASD comorbidity was observed in 9.8% of children with ADHD and 5.7% of those with subthreshold ADHD. Comorbidity was reported by at least one informant in 95% of children. Only 15.8% of children with autism and ADHD had been previously diagnosed with both conditions. Early detection and accurate comorbidity diagnosis are crucial to address the clinical and socio‐educational needs of these children.
Influence of Grain Size on the Electrochemical Performance of Li7‐3xLa3Zr2AlxO12 Solid Electrolyte
Authors: Botros Miriam , Gonzalez‐Julian Jesus , Scherer Torsten , Popescu Radian , Loho Christoph , Kilmametov Askar , Clemens Oliver , Hahn Horst
Published: May 2024

Contemporary Li‐ion batteries are facing substantial challenges like safety and limited energy density. The development of all‐solid‐state battery cells mitigates safety hazards and allows the use of Li‐metal anodes increasing energy density. Garnet‐type solid electrolytes can be vital to achieving an all‐solid‐state cell and an understanding of the influence of its microstructure on the electrochemical performance is crucial for material and cell design. In this work the influence of grain size on the Li‐ion conductivity of Li7‐3xLa3Zr2AlxO12 (x=0.22) is presented. The synthesis and processing procedure allows changing the ceramic grain size, while maintaining the same synthesis parameters, eliminating influences of the synthesis on grain boundary composition. Field assisted sintering technology is a powerful method to obtain dense, fine‐grained ceramics with an optimal grain size of 2–3 μm, where the conductivity is double that of the counterpart (0.7 μm). A total Li‐ion conductivity of 0.43 mS cm−1 and an activation energy of 0.36 eV were achieved. The oxide‐based all‐solid‐state battery cell combining the garnet‐type electrolyte, a Li‐metal anode and a thin‐film LiCoO2 cathode was assembled and cycled at room temperature for 90 hours. This represents a proof of concept, for the application of oxide‐based electrolytes at ambient temperatures.
A fluorescent terbium‐metal–organic framework material for high‐sensitivity detection of vomitoxin and oxytetracycline hydrochloride in water
Authors: Huang Jia‐Yi , Liu Qiang , Zhu Hao , Lin Shuo‐Feng , Yang Ke‐Xin , He Hua‐Li , Gu Xun‐Gang , Shen Yong‐Hui , Qin Ling
Published: May 2024

A unique luminescent lanthanide metal–organic framework (LnMOF)–based fluorescence detection platform was utilized to achieve sensitive detection of vomitoxin (VT) and oxytetracycline hydrochloride (OTC‐HCL) without the use of antibodies or biomolecular modifications. The sensor had a fluorescence quenching constant of 9.74 × 106 M−1 and a low detection limit of 0.68 nM for vomitoxin. Notably, this is the first example of a Tb‐MOF sensor for fluorescence detection of vomitoxin. We further investigated its response to two mycotoxins, aflatoxin B1 and ochratoxin A, and found that their Stern–Volmer fluorescence quenching constants were lower than those of VT. In addition, the fluorescence sensor realized sensitive detection of OTC‐HCL with a detection limit of 0.039 μM. In conclusion, the method has great potential as a sensitive and simple technique to detect VT and OTC‐HCL in water.
Mixing customer ingratiation into evaluation: How service providers judge and evaluate rideshare experiences
Authors: Xiao Yazhen , Hasford Jonathan
Published: May 2024

Whereas consumer satisfaction is critical for the success of services, we research how providers evaluate customers in the sharing economy represented by the rideshare marketplace. We examine anticipated customer evaluation (ACE) as the underlying link and the provider's sense of power as a moderator for the relationship between customer ingratiation and provider evaluations. We first conducted a field pilot study and analyzed the content of rideshare trips described by drivers. Then, we tested the conceptual framework in four experiments that manipulated different rideshare customer behaviors (self‐presentation, other‐enhancement, and customer conformity). Our study contributes to the consumer research literature by examining provider evaluation and discovering the peer‐to‐peer (P2P) dynamic evaluation mechanisms that adopt a two‐way rating system.
State‐of‐the‐Art Review of Biomass Gasification: Raw to Energy Generation
Authors: Taqvi Syed Ali Ammar , Kazmi Bilal , Naqvi Salman Raza , Juchelková Dagmar , Bokhari Awais
Published: May 2024

Despite the increasing global need for sustainable energy, biomass gasification is becoming a highly promising method for transforming raw biomass into usable energy. The present review article analyzes the essential aspects of biomass‐based energy production, starting with an assessment of existing energy needs and the crucial contribution that biomass can make in fulfilling these demands. The research investigates recent advancements in several biomass gasification methods, explaining their mechanics and discussing the related difficulties. The research conducts a thorough evaluation of the efficiency, yield, and environmental consequences of biomass gasification, aiming to determine the feasibility of the technique. In addition, the study rigorously assesses the techno‐economic factors of energy generation from biomass, providing valuable information on the economic viability and scalability of various biomass gasification techniques. The present study is focused on providing a comprehensive understanding of biomass gasification by analyzing current improvements and conducting a techno‐economic comparison to make well‐informed decisions for a sustainable energy future.
Synthesis of New Bodipy Hydrazide Fluorescent Probes for the Detection of Carbonylated Proteins Generated by Oxidative Stress
Authors: Nina‐Diogo Anthony , Hyzewicz Janek , Hamon Marie‐Paule , Forté Jeremy , Thorimbert Serge , Friguet Bertrand , Botuha Candice
Published: May 2024

Oxidative stress is a cellular disorder implicated in various severe diseases and redox biology and represents an important field of research for the last decades. One of the major consequences of oxidative stress is the carbonylation of proteins, which is also a reliable marker to assess protein oxidative modifications. Accumulation of carbonylated proteins has been associated with aging and age‐related diseases and can ultimately causes cell death. Detection of these oxidative modifications is essential to understand and discover new treatments against oxidative stress. We describe the design and the synthetic pathway of new BODIPY fluorescent probes functionalized with hydrazide function for protein carbonyl labeling to improve existing methodologies such as 2D‐Oxi electrophoresis. Hydrazide BODIPY analogues show very good fluorescent properties such as NIR emission up to 633 nm and quantum yield up to 0.88. These new probes were validated for the detection and quantification of carbonylated proteins with 2D‐Oxi electrophoresis using mouse muscle protein extracts, as well as both flow cytometry and microscopy using oxidant stressed C2 C12 cells.
Synthesis of Zinc Oxide Nanoparticles Based on Coffee Husks Embedded on Mesoporous Silica for the Sensing of Acetaminophen
Authors: Vomo Lionnel Averie , Deffo Gullit , Fotsop Cyrille Ghislain , Djemmoe Lydiane Ghislaine , Tchieda Victor Kougoum , Eya'ane François Meva , Njanja Evangeline
Published: May 2024

In the present work, a green method improved by surface response methodology (SRM) has been used for the synthesis of zinc oxide nanoparticles (ZnONPs) from coffee husks extract, in which Santa Barbara‐15 (SBA‐15) mesoporous silica has been embedded. The composite formed has been drop coated on bare glassy carbon electrode and the resulting sensor (ZnONPs/SBA‐15/GCE) was used for the sensing of acetaminophen (ACT). Reaction factors such as pH, incubation time and precursor concentration were optimized during nanoparticles synthesis using SRM. The synthesized nanoparticles and the composite were characterized by ultraviolet‐visible spectrophotometry (UV‐Vis), Fourier transform infrared (FTIR) spectroscopy, powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X‐ray (EDX/EDX‐mapping) analysis, thermogravimetry analysis/differential thermogravimetry (TGA/DTG), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), showing the good elaboration of ZnONPs/SBA‐15/GCE. After optimization of parameters susceptible to affect the detection limit of ACT, the calibration curve was plotted from 4 μM to 32 μM, showing good linear response with a detection limit of 0.11 μM. The developed sensor shows good sensitivity, reproducibility, repeatability and storage stability at room temperature and was successfully applied for the determination of ACT in pharmaceutical sample.
Adaptive soft sensor modeling of chemical processes based on an improved just‐in‐time learning and random mapping partial least squares
Authors: Zhang Ke , Zhang Xiangrui
Published: May 2024

The just‐in‐time learning‐based partial least squares (JIT‐PLS) has been extensively applied to adaptive soft sensor modeling of complex nonlinear processes. However, it still has the problems of unreasonable relevant samples selection and unsatisfactory local modeling. Aiming at these problems, this paper proposes an improved just‐in‐time learning‐based random mapping partial least squares (IJIT‐RMPLS), including an improved relevant samples selection strategy and a random mapping PLS (RMPLS) model. On the one hand, considering the different correlation degrees between input variables and output variable, this method applies mutual information to evaluate the importance of each input variable and designs a variable‐weighted Euclidean distance to select relevant samples for local modeling. On the other hand, in order to prompt the prediction precision of local soft sensor models, this method combines the idea of nonlinear random mapping in extreme learning machines with PLS and builds a RMPLS with multiple activation functions. Applications on a numerical example and a real chemical process show that the proposed IJIT‐RMPLS has smaller prediction error compared with traditional JIT‐PLS.
Oriented Metal‐Organic Framework Membranes for Molecular Separations
Authors: Sun Yanwei , Liu Yi
Published: May 2024

Metal‐organic framework (MOF) membranes, which are recognized as state‐of‐the‐art platforms applied in various separation processes, have attracted widespread attention. Nonetheless, to overcome the trade‐off between permeability and selectivity, which is crucial for achieving efficient separation, it is important to rationally design and manipulate MOF membrane structure. Given remarkable advances in the past decade, a timely summary of recent advancement in this field has become indispensable. This review introduces major strategies for fabricating oriented MOF membranes, including in situ growth, contra‐diffusion method, interface‐assisted approach, and laminated nanosheet assembly. New insights into their updated progress and potential are elucidated. Of particular note, recent development and emerging applications of oriented MOF membranes, illustrating their potential to address environmental and energy challenges, are highlighted. Finally, remaining challenges facing their bath production and practical applications are discussed.
Synthesis of Indolines via Base‐Mediated C−H Activation and Defluorinative C−N Coupling, with no Need for Transition‐Metals
Authors: Weindl Christian , Hintermann Lukas
Published: May 2024

Syntheses of (partially) aromatic nitrogen heterocycles increasingly rely on transition‐metal catalyzed C−C‐ and C−N‐cross‐coupling reactions. Here we describe a different approach to the synthesis of indolines by a domino C(sp3)−H activation, 1,2‐addition, and defluorinative SNAr‐cyclization sequence to provide the target 1,2‐diarylindolines (1,2‐diaryl‐2,3‐dihydroindoles) from ortho‐fluorinated methyl‐arenes and N‐aryl imines (benzylidene anilines) in a cyclocondensation that is mediated by potassium hexamethyldisilazide (KHMDS) as base exclusively. This transition‐metal‐free process via C−H and C−F bond activation provides a one‐step entry into a wide array of indoline scaffolds (43 examples, up to 96 % yield). This privileged substructure is common in natural products and pharmaceuticals alike, and cannot be accessed by traditional condensation reactions.
Metal‐(Acyclic Diaminocarbene) Complexes Demonstrate Nanomolar Antiproliferative Activity against Triple‐Negative Breast Cancer
Authors: Katkova Svetlana A. , Bunev Alexander S. , Gasanov Rovshan E. , Khochenkov Dmitry A. , Kulsha Andrey V. , Ivashkevich Oleg A. , Serebryanskaya Tatiyana V. , Kinzhalov Mikhail A.
Published: May 2024

Invited for the cover of this issue are Tatiyana Serebryanskaya, Mikhail Kinzhalov and co‐workers at St. Petersburg State University, the Research Institute for Physical Chemical Problems, Belarusian State University, Togliatti State University and Blokhin National Medical Research Center of Oncology. The image depicts the shield of Pallas Athena with the structure of a palladium carbene complex that protects against triple‐negative breast cancer. Read the full text of the article at 10.1002/chem.202400101.
Adsorption, kinetic, and thermodynamic studies of natural curcumin dye on cotton and polyamide fabric and the liberation of its active principle
Authors: Schmidt Michele , Bierhalz Andréa Cristiane Krause , de Aguiar Catia Rosana Lange
Published: May 2024

The increasing emphasis on environmental sustainability and the demand for eco‐friendly practices have led to a surge in interest in natural products, particularly natural dyes, across industries, including textiles. Curcumin, extracted from the turmeric plant, has gained widespread application not only for its vibrant colour characteristics but also for numerous therapeutic properties, serving as an antioxidant, anti‐inflammatory agent, and promoting wound‐healing effects. This study aims to understand the physical and chemical phenomena associated with the adsorption and desorption of turmeric extract and its active principles on cotton and polyamide fibres through mathematical models, with the goal of expanding textile applications. Dyeing experiments revealed adsorption equilibrium times of less than 25 min for both fibres, with the pseudo‐second‐order model providing the best fit for dyeing kinetics, suggesting control through the chemisorption process. The Freundlich model better suited cotton adsorption isotherms (R2 = 0.778), while the Langmuir model fit well for polyamide (R2 = 0.981). Thermodynamic parameters indicated non‐spontaneous interactions between curcumin and cotton, with an endothermic process, and an exothermic and spontaneous process for polyamide. Friction and water tests indicated greater colour resistance for polyamide, with grades exceeding 4. Desorption tests in 100% ethanol solution showed a total release of only 0.88% and 0.97% for polyamide and cotton, respectively, sustained for 12 h, fitting the Higuchi mathematical model, indicating a purely diffusive release process. These results demonstrate the potential of curcumin dye for achieving high dye exhaustion percentages in natural and synthetic fabrics and sustained release properties.