bluuebunny/crossref_metadata_2025_split huggingface dataset:
Optimization and validation of an HPLC‐HRMS method through semipreparative HPLC system for determining phytosterol oxidation products during refining processing and storage of vegetable oils
Authors: Calaminici Raffaele , Salgarella Nicolò Ivan , Cardenia Vladimiro , Forte Emanuele 
Published: February 2024

AbstractA semi‐preparative liquid chromatographic system (LC‐Prep) has been used to isolate and collect the main oxidation products generated from β‐sitosterol, campesterol, and stigmasterol, which represent the main sterols detected in vegetable oils. In less than 50 min, 15 different phytosterol oxidation products (POPs) were separated with a satisfactory resolution (R >1) and collected. From each pure phytosterol standard the 5,6α‐epoxy (α‐E), 5,6β‐epoxy (β‐E), 7‐keto (7‐K), 7α‐hydroxy (7α‐H), and 7β‐hydroxy (7β‐H) isomers were obtained. The purity of POPs was >90%. Then, the obtained pure POPs were used to validate an HPLC‐Orbitrap‐HRMS analytical method. The LOD and LOQ determined in medium chain triacylglycerols were >0.012 and >0.039 ng/mL, respectively; whereas the recoveries ranged between 82% and 98%. The suitability of the analytical method was evaluated on palm oil (PO), palm olein (POL), and high oleic sunflower oil (HOSO) during the whole refining processing (crude oil, neutralization and degumming, bleaching and deodorization) and under storage conditions (45°C, 16 days). In the refining steps, the total POPs content significantly increased (p < 0.05) by 29%, 20%, and 13% in PO, POL, and HOSO, respectively. The highest amount was found in HOSO (15.046 mg/kg), followed by POL (1.067 mg/kg) and PO (0.538 mg/kg). Under storage conditions, the content of POPs did not significantly (p > 0.05) change and was lower than 8.965 mg/kg. The developed semi‐preparative liquid chromatographic system coupled to the LC‐Orbitrap‐HRMS method demonstrated to be a useful and valid tool for a robust, precise, accurate, and sensitive determination of POPs in refined and stored vegetable oils.
Dielectric characterization of fiber‐ and nanofiller‐reinforced polymeric materials
Authors: Quader Raihan , Narayanan Lokesh Karthik , Caldona Eugene B. 
Published: February 2024

AbstractThis review provides an in‐depth analysis of the electrical responses and relaxation behaviors of various polymeric materials including fiber‐reinforced polymer composites, polymer nanocomposites (PNC), and nanofiller‐reinforced polymeric films and coatings using dielectric spectroscopy (DS). The underlying theory of DS, corresponding instrumentation, various dielectric parameters, relevant equations, interpretations, and polarization mechanisms are thoroughly explored. The impact of synthetic and natural fibers and a diverse range of nanofillers on the dielectric responses and relaxation mechanisms of fiber‐reinforced composites, and PNC and films, respectively, are also examined. For each summarized article, we provide an overview of the composite or film preparation, followed by concise explanations of the dielectric behaviors under diverse conditions, including variations in temperature, frequency, moisture levels, fiber/filler ratios, and chemical treatment. In essence, this review contributes to a nuanced understanding of the intricate relationship between material structure, properties, and performance via DS data interpretation across a spectrum of scenarios.
A review of methods for assessment of cognitive function in high‐altitude hypoxic environments
Authors: Fan Haojie , Meng Ying , Zhu Lingling , Fan Ming , Wang Du‐Ming , Zhao Yong‐Qi 
Published: February 2024

AbstractHypoxic environments like those present at high altitudes may negatively affect brain function. Varying levels of hypoxia, whether acute or chronic, are previously shown to impair cognitive function in humans. Assessment and prevention of such cognitive impairment require detection of cognitive changes and impairment using specific cognitive function assessment tools. This paper summarizes the findings of previous research, outlines the methods for cognitive function assessment used at a high altitude, elaborates the need to develop standardized and systematic cognitive function assessment tools for high‐altitude hypoxia environments.
Widening the net: Use of social media data in personal injury and disability evaluations
Authors: Drago Lisa M. , Giuliano Anthony J. 
Published: February 2024

AbstractA central tenet of forensic mental health assessment is the use of multiple sources of data. Traditionally, these sources have included clinical interviews with and observations of the examinee, written records review, psychological test data, and interviews with collateral sources. Data from social media and social networking sites (SNS) is now widely used in civil litigation. However, existing professional practice standards and guidelines do not specifically address the use of SNS data. This leaves forensic mental health evaluators with little guidance as to why, when and how to incorporate SNS data into their evaluations. We review the extant literature on the use of SNS and other social media data in personal injury and disability cases, including legal, ethical, and practical considerations, with the goal of providing forensic mental health practitioners with a framework for making decisions about when and how to incorporate these data into their evaluations and opinions. We advocate caution in conducting independent searches of social media and the Internet, and in making inferences about internal states based on SNS postings. To illustrate these points, we include a case study.
Alkaline Earth Metal Aluminate Support for Selective Oxidative Coupling of Methane
Authors: Wei Zenghao , Movick William J. , Obata Keisuke , Yu Yuhang , Takanabe Kazuhiro 
Published: February 2024

AbstractThe oxidative coupling of methane (OCM) provides a direct route to transform methane into higher value products. The alkali metal tungstate catalysts have demonstrated high selectivity towards C2 products, ethane (C2H6) and ethylene (C2H4). However, the severe sintering of the SiO2 support limits the reaction rate requiring active site densification to compete with unselective gas phase combustion reaction especially at high pressure operations. This work studies alkaline earth metal oxides as supports for K2WO4 catalysts to maintain comparatively high surface area under OCM conditions. Among Mg, Ca, and Sr aluminates, the K2WO4/MgAl2O4 catalyst exhibited the highest C2 yields. To achieve high C2 product selectivity, a relatively large loading of K2WO4 (20 wt %) was required likely to cover the unselective surface sites of MgAl2O4 support. The catalyst further showed high levels of stability when utilized at high pressures (0.9 MPa) for over 60 h, without any change in product selectivity. The Mn/K2WO4/MgAl2O4 showed multifold higher CH4 conversion rate, compared with the SiO2 counterpart. The findings showcase the potential of the MgAl2O4 support as a viable candidate for alkali metal tungstate catalysts for OCM, which introduces high density of active components in given volume in the reactor, which induces high contribution of the catalyst relative to the pure gas phase oxidation.
Ultrathin 2D Porphyrin‐Based Zr‐MOF Nanosheets as Heterogeneous Catalysts for Styrene Epoxidation and Benzylic C‐H Oxidation
Authors: Wang Haosen , Ren Yanwei , Feng Xiao , Jiang Huanfeng 
Published: February 2024

AbstractSelective oxidation of hydrocarbons using molecular oxygen as sole oxidant under mild conditions remains a challenging task. In this context, metal‐organic frameworks (MOFs) have been widely used in various oxidation reactions due to their porosity, high surface area and designability. However, the slow diffusion of substrates/products in micropores of three‐dimensional (3D) bulk MOFs hinders the efficient catalytic performance of such materials. Herein an ultrathin two‐dimensional (2D) porphyrin‐based Zr‐MOF nanosheet (Zr‐TCPP) is synthesized through modulator‐control strategy. Subsequently, various metal ions are anchored into the porphyrin ring by post synthesis modification to afford a series of 2D Zr‐TCPP(M) (M=Mn, Fe, Co, Ni, Cu and Zn). Various structural characterization techniques indicate Zr‐TCPP(M) is nanoflower structure with ultrathin nanoplate petals which provides fully exposed accessible active sites. Among them, Zr‐TCPP(Fe) shows excellent catalytic performance in styrene epoxidation reactions and benzylic C−H oxidation reactions using O2 as sole oxidant under ambient temperature and pressure. The remarkable activity arises from high density of exposed porphyrin‐Fe active sites, low diffusion barriers for substrates and products, as well as a similar homogeneous reaction space. Furthermore, Zr‐TCPP(Fe) nanosheet is easily recycled by centrifugation and reused at least five times without significant loss of catalytic activity.
Dehydrogenative Oxidation of Alcohols by Reusable Iridium Catalysts with a Cooperative Polymer Ligand
Authors: Maeda Hiroki , Kuno Taiki , Jeong Jaeyoung , Morisaki Yasuhiro , Fujita Ken‐ichi 
Published: February 2024

AbstractA series of iridium‐polymer complexes containing bipyridonate moieties were synthesized. The high catalytic performance of the iridium‐polymer complex for the dehydrogenative oxidation of alcohols was demonstrated. Notably, the bipyridonate moiety in the polymer structure acts as a chemically non‐innocent “functional ligand”, realizing the enhancement of dehydrogenation process. While numerous metal‐polymer catalysts have been reported so far, to our knowledge, introducing a “functional ligand” into a polymer chain that can operate cooperatively with transition metals by changing their structures during the catalytic processes is rare. The iridium‐polymer complex could be easily separated from the product and recovered by precipitation upon the addition of methanol after the catalytic reaction. Furthermore, the recovered catalyst could be reused without loss of catalytic efficiency at least ten times.
Development of Supercapacitors with 3D Porous Structures
Authors: Zhou Ruitao , Lam Kwok‐Ho 
Published: February 2024

AbstractThe pursuit of supercapacitors with simultaneous high power and energy densities has led to extensive research and successful outcomes through the integration of three‐dimensional (3D) electrodes, encompassing both 3D active materials and 3D porous current collectors. This mini review provides a summary of recent developments in supercapacitors featuring 3D structures. The incorporation of both 3D active materials and 3D current collectors proves effective in enhancing the mass loading of active materials without compromising their specific capacitance. The presence of pores in 3D porous current collectors contributes to additional double‐layer capacitance by offering a large surface area. Moreover, 3D porous transition metal current collectors can provide both double‐layer and faradic capacitances through the in‐situ surface oxidation mechanism. Beyond materials and geometries, this review also discusses synthesis strategies for electrodes, offering insights into the process‐structure‐property relationship crucial for supercapacitors. By combining 3D active materials with 3D current collectors, the energy density of supercapacitors could be substantially improved.
A personalized electronic textile for ultrasensitive pressure sensing enabled by biocompatible MXene/PEDOT:PSS composite
Authors: Li Yahua , Cao Wentao , Liu Zhi , Zhang Yue , Chen Ziyan , Zheng Xianhong 
Published: February 2024

AbstractFlexible, breathable, and highly sensitive pressure sensors have increasingly become a focal point of interest due to their pivotal role in healthcare monitoring, advanced electronic skin applications, and disease diagnosis. However, traditional methods, involving elastomer film‐based substrates or encapsulation techniques, often fall short due to mechanical mismatches, discomfort, lack of breathability, and limitations in sensing abilities. Consequently, there is a pressing need, yet it remains a significant challenge to create pressure sensors that are not only highly breathable, flexible, and comfortable but also sensitive, durable, and biocompatible. Herein, we present a biocompatible and breathable fabric‐based pressure sensor, using nonwoven fabrics as both the sensing electrode (coated with MXene/poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate [PEDOT:PSS]) and the interdigitated electrode (printed with MXene pattern) via a scalable spray‐coating and screen‐coating technique. The resultant device exhibits commendable air permeability, biocompatibility, and pressure sensing performance, including a remarkable sensitivity (754.5 kPa−1), rapid response/recovery time (180/110 ms), and robust cycling stability. Furthermore, the integration of PEDOT:PSS plays a crucial role in protecting the MXene nanosheets from oxidation, significantly enhancing the device's long‐term durability. These outstanding features make this sensor highly suitable for applications in full‐range human activities detection and disease diagnosis. Our study underscores the promising future of flexible pressure sensors in the realm of intelligent wearable electronics, setting a new benchmark for the industry.
Near‐IR Capturing N‐Methylbenzene Sulfonamide‐Phenothiazine Incorporating Strong Electron Acceptor Push‐Pull Systems: Photochemical Ultrafast Carrier Dynamics
Authors: Kumar Gupta Pankaj , Das Somnath , Misra Rajneesh , D'Souza Francis 
Published: February 2024

AbstractUnraveling the intriguing aspects of the intramolecular charge transfer (ICT) phenomenon of multi‐modular donor‐acceptor‐based push–pull systems are of paramount importance considering their promising applications, particularly in solar energy harvesting and light‐emitting devices. Herein, a series of symmetrical and unsymmetrical donor‐acceptor chromophores 1–6, are designed and synthesized by the Corey‐Fuchs reaction via Evano's condition followed by [2+2] cycloaddition retroelectrocyclic ring‐opening reaction with strong electron acceptors TCNE and TCNQ in good yields (~60–85 %). The photophysical, electrochemical, and computational studies are investigated to explore the effect of incorporation of strong electron acceptors 1,1,4,4‐tetracyanobuta‐1,3‐diene (TCBD) and dicyanoquinodimethane (DCNQ) with phenothiazine (PTZ) donor. An additional low‐lying broad absorption band extended towards the near‐infrared (NIR) region suggests charge polarization after the introduction of the electron acceptors in both symmetrical and asymmetrical systems, leading to such strong ICT bands. The electrochemical properties reveal that reduction potentials of 3 and 6 are lower than those of 2 and 5, suggesting DCNQ imparts more on the electronic properties and hence largely contributes to the stabilization of LUMO energy levels than TCBD, in line with theoretical observations. Relative positions of the frontier orbitals on geometry‐optimized structures further support accessing donor‐acceptor sites responsible for the ICT transitions. Eventually, ultrafast carrier dynamics of the photoinduced species are investigated by femtosecond transient absorption studies to identify their spectral characteristics and target analysis further provides information about different excited states photophysical events including ICT and their associated time profiles. The key findings obtained here related to excited state dynamical processes of these newly synthesized systems are believed to be significant in advancing their prospect of utilization in solar energy conversion and related photonic applications.
Interobserver agreement and risk of malignancy using the International Academy of Cytology Yokohama System for reporting breast FNA biopsy in a liquid‐based exclusive cohort
Authors: Folarin Olawunmi , Kim David , Gokozan Hamza N. , Heymann Jonas J. , Scarpa Carniello Jose V. , Rosado Lucelina , Siddiqui Momin T. , Patel Ami 
Published: February 2024

AbstractBackgroundPer the College of American Pathologist’s National Breast Fine Needle Aspiration Biopsy (FNAB) Practice Survey, ∼40% of laboratories use liquid‐based cytology (LBC) for breast FNAB. The reproducibility of the International Academy of Cytology Yokohama System (YS) for reporting breast FNAB on LBC was explored.DesignBreast FNAB specimens submitted as LBC only (all ThinPrep) between January 2017 and January 2021 were retrieved. Cases without histopathologic follow‐up were excluded. Clinical and radiologic information was collected. One cytologist and six cytopathologists rendered diagnoses per YS. All reviewers were blinded to the original diagnosis and histopathologic follow‐up. The risk of malignancy was calculated. Concordance rates were calculated by a weighted Cohen Kappa score (κ).ResultsReview of 110 cases demonstrated substantial to near‐perfect agreement between each reviewer (κ = 0.73–0.91) and follow‐up histopathology (κ = 0.66–0.85). The agreement was lowest in the inadequate (κ = 0.05) and atypical (κ = 0.04) categories. The lack of concordance in the atypical category was common in cases with low cellularity or incomplete structural features. The risk of malignancy for inadequate, benign, atypical, suspicious for malignancy, and malignant categories were 12.5% (2/16), 3% (2/65), 67%, (8/12) 100% (1/1), and 100% (16/16).ConclusionInterobserver agreement is excellent using the five YS categories in LBC. Lack of cellularity and incomplete architectural features were barriers to perfect agreement. Established pitfalls in the interpretation of LBC were cause for atypical diagnoses. Continuous training and education are recommended to avoid misdiagnosis because of the nonconventional cytomorphologic features of LBC and to improve inadequate and atypical rates within YS.
A real‐time patient‐specific treatment strategy for enhanced external counterpulsation
Authors: Li Bao , Liu Youjun , Li Guangfei , Zhang Zhe , Feng Yue , Mao Boyan 
Published: February 2024

AbstractDiastolic/systolic blood pressure ratio (D/S) ≥ 1.2 is the gold standard of enhanced external counterpulsation (EECP) treatment, but it does not show a clear clinical correspondence with the configuration of the EECP mode. As such, a single target results in different treatment effects in different individuals. The local haemodynamic effect (wall shear stress, WSS) of EECP on vascular endothelial cells is conducive to promote the growth of collateral circulation vessels and restore the blood supply distal to the stenosis lesion. Considering the haemodynamic effects of WSS on human arteries, this study developed a real‐time patient‐specific treatment strategy of EECP for patients with cardio‐cerebrovascular diseases. Based on patient‐specific haemodynamic data from 113 individuals, an optimization algorithm was developed to achieve the individualization of a 0D lumped‐parameter model of the human circulatory system, thereby simulating the patient‐specific global haemodynamic effects. 0D/3D coupled cardio‐cerebrovascular models of two subjects were established to simulate the local WSS. We then established statistical models to evaluate clinically unmeasurable WSS based on measurable global haemodynamic indicators. With the aim of attaining appropriate area‐ and time‐averaged WSS (ATAWSS, 4–7 Pa), as evaluated by global haemodynamic indicators, a closed‐loop feedback tuning method was developed to provide patient‐specific EECP treatment strategies. Results showed that for clinical data collected from 113 individuals, the individualized 0D model can accurately simulate patient‐specific global haemodynamic effects (average error <5%). Based on two subjects, the statistical models can be used to evaluate local ATAWSS (error <6%) for coronary arteries and for cerebral arteries. An EECP mode planned by the patient‐specific treatment strategy can promote an appropriate ATAWSS within a 16 s calculation time. The real‐time patient‐specific treatment strategy of EECP is expected to improve the long‐term outcome for each patient and have potential clinical significance.
The Importance of Spin‐Polarized Charge Reorganization in the Catalytic Activity of D‐Glucose Oxidase
Authors: Preeyanka Naupada , Zhu Qirong , Das Tapan Kumar , Naaman Ron 
Published: February 2024

AbstractThe reaction of D‐glucose oxidase (GOx) with D‐ and L‐glucose was investigated using confocal fluorescence microscopy and Hall voltage measurements, after the enzyme was adsorbed as a monolayer. By adsorbing the enzyme on a ferromagnetic substrate, we verified that the reaction is spin dependent. This conclusion was supported by monitoring the reaction when the enzyme is adsorbed on a Hall device that does not contain any magnetic elements. The spin dependence is consistent with the chiral‐induced spin selectivity (CISS) effect; it can be explained by the improved fidelity of the electron transfer process through the chiral enzyme due to the coupling of the linear momentum of the electrons and their spin. Since the reaction studied often serve as a model system for enzymatic activity, the results may suggest the general importance of the spin‐dependent electron transfer in bio‐chemical processes.
Thio‐Induced Organophosphate Breakdown Promoted by Methimazole: an Experimental and Theoretical Study
Authors: Campos Renan B. , Capato Lucas A. , Soares Patrícia M. , Tantillo Dean J. , Orth Elisa S. 
Published: February 2024

AbstractInvestigating the reactivity of small nucleophilic scaffolds is a strategic approach for the design of new catalysts aiming at effective detoxification processes of organophosphorus compounds. The drug methimazole (MMZ) is an interesting candidate featuring two non‐equivalent nucleophilic centers. Herein, phosphoryl transfer reactions mediated by MMZ were assessed by means of spectrophotometric kinetic studies, mass spectrometry (MS) analyses, and density functional theory (DFT) calculations using the multi‐electrophilic compound O,O‐diethyl 2,4‐dinitrophenyl phosphate (DEDNPP). MMZ anion acts primarily as an S‐nucleophile, exhibiting a nucleophilic activity comparable to that of certain oximes featuring alpha‐effect. Selective nucleophilic aromatic substitution was observed, consistent with the DFT prediction of a low energy barrier. Overall, the results bring important advances regarding the mechanistic understanding of nucleophilic dephosphorylation reactions, which comprises a strategic tool for neutralizing toxic organophosphates, hence promoting chemical security.
Enzymatic Formation of an Aminovinyl Cysteine Residue in Ribosomal Peptide Natural Products
Authors: Cheng Botao , Xue Yanqing , Duan Yuting , Liu Wen 
Published: February 2024

AbstractThe carboxyl‐terminal (C‐terminal) S‐[(Z)‐2‐aminovinyl]‐cysteine (AviCys) analogs have been identified in four families of ribosomally synthesized and post‐translationally modified peptides (RiPPs): lanthipeptides, linaridins, thioamitides, and lipolanthines. Within identified biosynthetic pathways, a highly reactive enethiol intermediate, formed through an oxidative decarboxylation catalyzed by a LanD‐like flavoprotein, can undergo two types of cyclization: a Michael addition with a dehydroamino acid or a coupling reaction initiated by a radical species. The collaborative actions of LanD‐like proteins with diverse enzymes involved in dehydration, dethiolation or cyclization lead to the construction of structurally distinct peptide natural products with analogous C‐terminal macrocyclic moieties. This concept summarizes existing knowledge regarding biosynthetic pathways of AviCys analogs to emphasize the diversity of biosynthetic mechanisms that paves the way for future genome mining explorations into diverse peptide natural products.