bluuebunny/crossref_metadata_2025_split huggingface dataset:
Quantifying Overdiagnosis for Multicancer Detection Tests: A Novel Method
Authors: Baker Stuart G. 
Published: November 2024

ABSTRACTMulticancer detection (MCD) tests use blood specimens to detect preclinical cancers. A major concern is overdiagnosis, the detection of preclinical cancer on screening that would not have developed into symptomatic cancer in the absence of screening. Because overdiagnosis can lead to unnecessary and harmful treatments, its quantification is important. A key metric is the screen overdiagnosis fraction (SOF), the probability of overdiagnosis at screen detection. Estimating SOF is notoriously difficult because overdiagnosis is not observed. This estimation is more challenging with MCD tests because short‐term results are needed as the technology is rapidly changing. To estimate average SOF for a program of yearly MCD tests, I introduce a novel method that requires at least two yearly MCD tests given to persons having a wide range of ages and applies only to cancers for which there is no conventional screening. The method assumes an exponential distribution for the sojourn time in an operational screen‐detectable preclinical cancer (OPC) state, defined as once screen‐detectable (positive screen and work‐up), always screen‐detectable. Because this assumption appears in only one term in the SOF formula, the results are robust to violations of the assumption. An SOF plot graphs average SOF versus mean sojourn time. With lung cancer screening data and synthetic data, SOF plots distinguished small from moderate levels of SOF. With its unique set of assumptions, the SOF plot would complement other modeling approaches for estimating SOF once sufficient short‐term observational data on MCD tests become available.
Palladium‐Catalyzed 2‐Aminoacetophenone Oxime Directed β‐sp2 and γ‐sp3 C─H Bond Functionalization of Aryl Carboxamides
Authors: Sankar Rathinam , Gnanasambandam Vasuki 
Published: November 2024

AbstractPd(II)‐catalyzed 2‐aminoacetophenone oxime‐assisted sp2 and sp3 C─H arylation of aryl carboxamides is disclosed. The 2‐aminoacetophenone oxime is an N,N‐bidentate auxiliary that proceeds C─H activation through a six‐membered palladacycle intermediate, and the activation/functionalization on C(sp3)─H bond by the six‐membered ligand palladacycle is novel and achieved. This auxiliary facilitates the subsequent sp3 and sp2 C─H bond activation/functionalization in one step. The optimized protocol enables access to various aryl groups at the β‐sp2‐ and γ‐sp3‐centers of aryl carboxamides. The bidentate auxiliary is easy to synthesize on a gram scale, and we also described deoximination procedure after C─H functionalization.
Green Corrosion Inhibition of Mild Steel in 1.0 M HCl Using Myrtus Communis Essential Oil: Experimental and Theoretical Investigations
Authors: Chaouche Rajae , Tiskar Malika , Amri Abdeslam El , Ihamdane Rachid , Dagdag Omar , Kim Hansang , Salghi Rachid , Berdimurodov Elyor , Berisha Avni , Chaouch Abdelaziz , Habsaoui Amar 
Published: November 2024

AbstractThis study investigates the green corrosion inhibition of mild steel in 1.0 M HCl using Myrtus communis essential oil (EOMC). Experimental and computational methods were combined to evaluate the corrosion inhibition effectiveness of EOMC. Weight loss measurements and electrochemical techniques, demonstrated that EOMC achieves a maximum corrosion inhibition efficiency of 94.81% at a concentration of 400 ppm of MCEO extract. The icorr significantly decreased from 983 µA/cm2 in the 1.0 M HCl solution to 51 µA/cm2 at 10−3 M, demonstrating the inhibitor's effectiveness. Polarization studies suggested mixed‐type inhibition, affecting both anodic and cathodic reactions, supported by changes in Tafel slopes. The Rct reached 462 Ω cm2 at 400 ppm of EOMC, enhancing the steel's protective capability. Higher temperatures increased the corrosion rate, with icorr values rising from 51 µA/cm2 at 298 K to 501 µA/cm2. Surface analysis using scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM‐EDX) confirmed the formation of a protective layer on the steel surface in the presence of EOMC. Additionally, density functional theory (DFT) calculations and molecular dynamics (MD) simulations provided further insights into the adsorption behavior of the EOMC molecules on the MS surface, revealing that the inhibition process involves both physisorption and chemisorption mechanisms.
Simulating High‐Efficiency, Lead‐Free Inorganic‐Organic Perovskite Tandem Solar Cells with over 46% Efficiency
Authors: Sultana Basra , Islam A. T. M. Saiful , Mamoon Iqra , Haque Md. Dulal , Badi Nacer , Irfan Ahmad , Rahman Md. Ferdous 
Published: November 2024

AbstractPerovskite‐based tandem solar cells (SCs) show significant potential for improving efficiency. In this study, three configurations were designed and optimized: a top cell (ITO/ZnSe/CH3NH3GeI3/CuSCN/Ni), a bottom cell (ITO/ZnSe/CH3NH3SnI3/CuI/Ni), and a tandem cell combining both. Using SCAPS‐1D, the study evaluated how the absorber layer thickness, doping concentration, and defect density affected photovoltaic (PV) performance. It also explored the influence of doping in the back surface field (BSF), interface defect densities, temperature, and back contact work function. The top cell achieved a power conversion efficiency (PCE) of 28.47%, with an open‐circuit voltage (VOC) of 1.21 V, a short‐circuit current density (JSC) of 27.17 mA/cm2, and a fill factor (FF) of 86.24%. The bottom cell reached a PCE of 18.46%, with a VOC of 0.83 V, a JSC of 27.17 mA/cm2, and an FF of 81.839%. The optimized tandem structure demonstrated a notably higher efficiency of 46.89%, with a JSC of 27.17 mA/cm2, a VOC of 2.04 V, and an FF of 84.31%. These results suggest the proposed CH3NH3GeI3/CH3NH3SnI3 tandem design could pave the way for efficient, eco‐friendly, and cost‐effective PV cells in a near future.
Efficient Synthesis of Dihydropyrimidine Hybrids via Guanidine‐Based Biginelli Reaction
Authors: Ramasamy Duraisamy , I Asharani , Dhakshanamurthy Thirumalai 
Published: November 2024

AbstractA versatile method has been developed for the synthesis of morpholine‐dihydropyrimidine hybrids, 3‐benzyl‐6‐methyl‐5‐(morpholine‐4‐carbonyl)‐4‐phenyl‐3,4‐dihydropyrimidin‐2(1H)‐one, through the construction of dihydropyrimidine (DHPM) via the guanidine‐based Biginelli reaction followed by sodium tertiary butoxide mediated substitution of the benzyl group at the 3rd position of DHPM ring. This substitution approach represents a novel method for obtaining N‐substituted Biginelli products in good yields (72%–84%). Further, the ester group was subjected to intergroup conversion by morpholine using in situ generated diisobutyl(morpholino)aluminum. Notably, this reaction exhibited tolerance to various functional groups, resulting in the corresponding derivatives of dihydropyrimidine–morpholine hybrids in excellent yield (62%–82%).
Comparison Investigation on the Photocatalytic Conversion of 5‐Hydroxymethylfurfural on g‐C3N4 and S‐doped g‐C3N4: Performance and Mechanism
Authors: Zheng Anqi , Li Kewang , Duan Hui , Shi Huijie 
Published: November 2024

AbstractPhotocatalytic oxidation was a green and sustainable method for conversing the biomass derived platform molecule 5‐hydroxymethylfurfural (HMF) to high value‐added 2,5‐diformyfuran (DFF). In this work, both graphitized carbon nitride (g‐C3N4) and sulfur doped g‐C3N4 (S‐g‐C3N4) were fabricated, characterized and applied in the photocatalytic conversion of HMF. Accelerated separation of the photogenerated charge carriers was obtained on S‐g‐C3N4 with higher production of reactive oxygen species (ROS) including singlet oxygen (1O2) and superoxide radicals (⋅O2−), whereas relative higher HMF conversion rate and DFF selectivity were achieved on g‐C3N4. The mechanism investigation suggested that the contradictory phenomena may be caused by the stronger binding affinity of HMF on S‐g‐C3N4 compared with g‐C3N4 based on the temperature‐programmed desorption (TPD) measurement and theoretical calculation. The strong adsorption of HMF on the catalyst surface was unfavorable for desorption of the intermediates, and led to the accumulation of large number of carbon‐centered radicals. Part of these radicals may react with each other to generate polymerization products and block the active sites of the catalyst, resulted in the low conversion efficiency of HMF and DFF selectivity finally. This work provided a new sight and valuable theoretical and experimental basis for developing efficient photocatalysts for biomass conversion.
Balancing Surface Chemistry and Flake Size of MXene‐Based Electrodes for Bioelectrochemical Reactors
Authors: Kolubah Pewee. D. , Mohamed Hend Omar , Hari Ananda Rao , Ping Yue , Hassine Mohamed Ben , Dally Pia , Obaid M. , Xu Xiangming , El‐Demellawi Jehad K. , Saikaly Pascal E. , Lanza Mario , Ghaffour Noreddine , Castaño Pedro 
Published: November 2024

AbstractMXenes have excellent properties as electrode materials in energy storage devices or fuel cells. In bioelectrochemical systems (for wastewater treatment and energy harvesting), MXenes can have antimicrobial characteristics in some conditions. Here, different intercalation and delamination approaches to obtain Ti3C2Tx MXene flakes with different terminal groups and lateral dimensions are comprehensively investigated. The effect of these properties on the energy harvesting performance from wastewater is then assessed. Regardless of the utilized intercalant molecules, MXene flakes obtained using soft delamination approaches are much larger (up to 10 µm) than those obtained using mechanical delamination methods (<1.5 nm), with a relatively higher content of ─O/─OH surface terminations. When employed in microbial fuel cells, electrodes made of these large MXene flakes have demonstrated a power density of over 400% higher than smaller MXene flakes, thanks to their lower charge transfer resistance (0.38 Ω). These findings highlight the crucial role of selecting appropriate intercalation and delamination methods when synthesizing MXenes for bioelectrochemical applications.
PEO‐Based Solid‐State Polymer Electrolytes for Wide‐Temperature Solid‐State Lithium Metal Batteries
Authors: Song Yunxuan , Su Meng , Xiang Hengying , Kang Junbao , Yu Wen , Peng Zhaozhao , Wang Hang , Cheng Bowen , Deng Nanping , Kang Weimin 
Published: November 2024

AbstractDeveloping solid‐state lithium metal batteries with wide operating temperature range is important in future. Polyethylene oxide (PEO)‐based solid‐state electrolytes are extensively studied for merits including superior flexibility and low glass transition temperature. However, ideal usage temperatures for conventional PEO‐based solid‐state electrolytes are between 60 and 65 °C, and unequable temperature degrades their electrochemical performances at low and high temperatures (≤25 °C and ≥80 °C). Herein, modification methods of PEO electrolytes for low, high especially wide‐temperature applications are reviewed based on detailed analyses of mechanisms involved in its modification at different temperatures. First, shortcomings of PEO solid electrolytes due to influence of temperature are pointed out. Second, existing modification strategies are summarized in detail from three aspects of high, low especially wide temperatures, including application of PEO derivatives or chain segment modification treatment of PEO, addition of fillers, and other modification methods such as reasonable regulation of lithium salts, introduction of functional layers and addition of metal‐organic frameworks (MOFs) or covalent organic frameworks (COFs). Finally, a summary and description of PEO‐based solid electrolyte research and development trends for wide‐temperature applications are provided. The review aims to offer some guidance for the creation of PEO solid batteries with wider working temperature ranges.
Evidence of Directional Structural Superlubricity and Lévy Flights in a van der Waals Heterostructure
Authors: Le Ster Maxime , Krukowski Paweł , Rogala Maciej , Dabrowski Paweł , Lutsyk Iaroslav , Toczek Klaudia , Podlaski Krzysztof , Menteş Tefvik Onur , Genuzio Francesca , Locatelli Andrea , Bian Guang , Chiang Tai‐Chang , Brown Simon A. , Kowalczyk Paweł J. 
Published: November 2024

AbstractStructural superlubricity is a special frictionless contact in which two crystals are in incommensurate arrangement such that relative in‐plane translation is associated with vanishing energy barrier crossing. So far, it has been realized in multilayer graphene and other van der Waals (2D crystals with hexagonal or triangular crystalline symmetries, leading to isotropic frictionless contacts. Directional structural superlubricity, to date unrealized in 2D systems, is possible when the reciprocal lattices of the two crystals coincide in one direction only. Here, directional structural superlubricity a α‐bismuthene/graphite van der Waals system is evidenced, manifested by spontaneous hopping of the islands over hundreds of nanometers at room temperature, resolved by low‐energy electron microscopy and supported by registry simulations. Statistical analysis of individual and collective α‐bismuthene islands populations reveal a heavy‐tailed distribution of the hopping lengths and sticking times indicative of Lévy flight dynamics, largely unobserved in condensed‐matter systems.
Pseudo‐Nanostructuring and Grain Refinement Enhance the Near‐Room‐Temperature Thermoelectric Performance in n‐type PbSe
Authors: Xie Yin , Deng Qian , Yang Yuxuan , Luo Yuange , Ou Wenxin , Zhao Zhilong , Luo Jiaxing , Wu Haijun , Ang Ran 
Published: November 2024

AbstractPbSe, a promising Te‐free thermoelectric material for medium‐temperature applications, has garnered considerable attention due to its substantial thermoelectric potential and relatively low cost. However, the vast majority of research on polycrystalline PbSe thermoelectrics has focused primarily on improving its medium‐temperature performance, often neglecting the enhancement of near‐room‐temperature performance and effective module design. Here, an n‐type polycrystalline PbSe material (Cu0.01Pb0.85Ge0.15Se) is presented that exhibits a room‐temperature zT of ≈0.6 and an average zT of 0.86 from 303 to 523 K. This superior performance is realized through the incorporation of a high‐concentration Ge into n‐type Cu0.01PbSe, which induces a novel pseudo‐nanostructure and grain refinement, promoting electron‐phonon decoupling. Based on this, seven‐pair module devices are fabricated, achieving a record‐high conversion efficiency of up to 5.1% at a temperature difference of only 228 K, and an unprecedented maximum cooling temperature difference of 47.2 K when the hot‐side temperature is 350 K. The findings provide a strong foundation for advancing Te‐free polycrystalline PbSe‐based materials for thermoelectric cooling and low‐temperature power generation.
Porous Amorphous‐Crystalline Heterostructured CoNiP Nanowire Arrays for Enhanced Hydrogen Evolution Performance under Acid‐Base Conditions
Authors: Huang Linyin , Yu Yuan , Qu Yanning , Sun Dongfeng , Fan Yuhao , Qiang Pengpeng , Wei Xinyue , Su Qingmei , Hao Xiaodong , Du Gaohui , Xu Bingshe , Wang Kai 
Published: November 2024

AbstractA novel porous amorphous‐crystalline heterostructured CoNiP nanowire arrays ((a‐c)CoNiP/CC) is presented. TEM observations and compositional calculations revealed ≈14.5% of the amorphous regions (a‐CoNiP) are interleaved in the crystalline regions (c‐(Co3.6Ni0.4)P4), forming massive amorphous‐crystalline heterogenous interfaces composed of the same elements. Only 38 and 64 mV overpotentials for the (a‐c)CoNiP/CC catalyst are required to reach the current density of −10 mA cm2 in acid and alkaline electrolyte, respectively, which is very close to the overpotentials (35 and 55 mV) of the commercial Pt/C HER catalyst. The theoretical calculation revealed that the (a‐c)CoNiP/CC has a completely different enhancement mechanism of HER reaction in acid‐base electrolytes. In particular, due to the natural corrosion resistance of the amorphous interface, the HER performance of this catalyst under the high current density condition is much better than that of the Pt/C catalyst either in acidic or in alkaline, suggesting its prospect for commercial applications.
Identification and Structural Characterization of Novel Process‐Related Impurities Present in Oseltamivir Phosphate Drug Substance and Its Precursor
Authors: Srinivas Torati , Reddy K. V. N. Suresh , Ramu Sigilipalli , Reddy M. Kiranmai , Reddy Maddireddy Srinivasa 
Published: November 2024

ABSTRACTThis article describes the identification, synthesis, and characterization of unknown impurities present in the oseltamivir phosphate drug substance and its precursor. Four unknown impurities were identified in the drug substance using high‐performance liquid chromatography analysis: Relative retention times of 1.05 and 2.50 azide impurities were found in the drug substance's precursor, and their corresponding impurities were found in the drug substance in amine form. Initially, the LC‐MS method was used to screen these impurities by identifying the mass of the impurities. Based on the impurities' mass and the drug substance's synthesis route, possible ways to form impurities were predicted. All these impurities were synthesized as predicted and characterized through infrared spectroscopy, nuclear magnetic resonance, and high‐resolution mass spectrometry techniques. It was found that these impurities are new and the synthesis method for these impurities is novel and has not been documented in the literature. The azido‐impurities found in this study are categorized as genotoxic impurities by Class 3 of the International Council for Harmonisation M7(R2) criteria, and these impurities must be regulated below certain thresholds.
A Note on Confidence Intervals for a Binomial p: Andersson–Nerman vs. Wilson
Authors: Andersson Per Gösta 
Published: November 2024

ABSTRACTNumerous approximate confidence intervals in closed form have been suggested over the years for the parameter in the binomial distribution. One of the oldest and still most advocated is the Wilson (score) interval, which in this article will be compared with the less well‐known Andersson–Nerman (henceforth AN) interval. These intervals are quite closely related, but it will be shown analytically and illustrated by examples that the coverage probability of the AN interval always equals or exceeds that of the Wilson interval, while also having uniformly larger expected length. Asymptotic expressions for the coverage probability and expected length of the AN interval are provided, using Edgeworth and Taylor expansions, respectively. The well‐behaved Wilson and AN pivots are furthermore contrasted with the problematic Wald pivot. The latter gives rise to the Wald interval, which is probably one of the best known and most used procedures altogether in the history of statistical inference. Unfortunately, this interval performs poorly, but even to this day it is to be found in many current textbooks. Therefore, it is still of relevance to search for attractive alternatives based on sound statistical principles.
MRGS‐ART: Metamorphic Relation and Group Selection Based on Adaptive Random Testing
Authors: Ying Zhihao , Towey Dave , Graham Bellotti Anthony , Quan Zhou Zhi 
Published: November 2024

ABSTRACTMetamorphic testing (MT) is effective in detecting software failures; it detects failures by examining the metamorphic relations (MRs) among source test cases (STCs), follow‐up test cases (FTCs) and their respective outputs. The STCs together with the corresponding FTCs, considered as a whole, are called metamorphic groups (MGs). MT performance relies heavily on the MRs and MGs. Previous studies have mainly focused on improving MT performance by identifying effective MRs, or through generation of MGs with high quality, but have somewhat neglected the selection of MRs and MGs from existing ones. In this paper, we address this issue by introducing a new metric for guiding the selection of effective MR‐MG pairs from a new perspective: The MR‐MG pair is chosen such that the MR makes the current MG as far away as possible from the executed MGs. We design an MR‐MG pair selection algorithm, named metamorphic relation and group selection based on adaptive random testing (MRGS‐ART), to implement our metric. The intuition behind MRGS‐ART is that we attempt to improve MT performance by achieving an even distribution of STCs and FTCs in their corresponding input domains for all the MRs used. Experimental results indicate that MRGS‐ART can enhance MT performance. We believe that this is the first comprehensive and systematic demonstration, from the perspective of both MRs and MGs, that making STCs and FTCs evenly distributed in their corresponding input domains can improve MT performance. Finally, by analysing the experimental results, we provide guidance on how to most effectively implement MRGS‐ART.
Health Risk Assessment and Heavy Metal Contamination Estimation in Date Palm Fruit Grown in Sindh, Pakistan: Multivariate Study
Authors: Bhatti Maira , Khan Humaira , Jalbani Nusrat Begum , Bhutto Shahid , Nawaz Hafiz Rub , Solangi Shakeel Haider , Ahsan Hina , Ismail Sarwat , Karim Arif , Imad Saima , Sultana Razia , Choudhry Ahsan , Tunio Nazir , Ho Soon Min 
Published: November 2024

ABSTRACTCadmium (Cd) and lead (Pb) are commonly found in the environment due to human activities like industrialization and development. These metals are toxic and often contaminate water, food, and edible plants, leading to human exposure. This study investigates Cd and Pb levels in 68 date samples from supermarkets across various regions of Sindh, Pakistan, including 30 samples provided by companies that export date palm fruits globally. Electrothermal atomic absorption spectrometry (ETAAS) with conventional wet acid digestion (CAD) was used for metal determination. Optimization was carried out by Plackett–Burman design (PBD), central composite design (CCD), and response surface methodology (RSM). Results indicated that Cd levels in export samples ranged from 0.012 ± 0.001 to 0.061 ± 0.004, with an average value of 0.031 ± 0.002 mg/kg. Lead levels in these samples varied from 0.028 ± 0.001 to 0.079 ± 0.03, averaging 0.055 ± 0.004 mg/kg. These levels were within the safety limits. However, local market samples exhibited slightly higher Pb levels, ranging from 0.15 ± 0.01 to 0.32 ± 0.03, with an average of 0.26 ± 0.02 mg/kg, exceeding the recommended safety limits. In contrast, the Cd content in local market samples ranged from 0.12 ± 0.01 to 0.16 ± 0.02 mg/kg, remaining below the WHO/FAO. These contaminants may originate from cultivation, water, air, transportation, processing, and so forth. The method was validated by standard addition recovery test, triplicate analysis, procedure blanks, and standard reference material (SRM). The average daily intake (ADI) values for TMs, along with the hazard index (HI) and target hazard quotients (THQs) were calculated to assess potential health risks.