bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractPrecious 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

SummaryWorldwide, 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

AbstractThe 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

AbstractPolycaprolactone (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

AbstractPrevious 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

AbstractMethane 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

AbstractAutism 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

AbstractContemporary 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

AbstractA 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

AbstractWhereas 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

AbstractDespite 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

AbstractOxidative 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

AbstractIn 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

AbstractThe 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

AbstractMetal‐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

AbstractSyntheses 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

AbstractInvited 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.