bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synergistic Effects of Silica‐Supported Iron−Cobalt Catalysts for CO2 Reduction to Prebiotic Organics
Authors: Belthle Kendra S. , Martin William F. , Tüysüz Harun 
Published: February 2024

AbstractTo test the ability of geochemical surfaces in serpentinizing hydrothermal systems to catalyze reactions from which metabolism arose, we investigated H2‐dependent CO2 reduction toward metabolic intermediates over silica‐supported Co−Fe catalysts. Supported catalysts converted CO2 to various products at 180 °C and 2.0 MPa. The liquid product phase included formate, acetate, and ethanol, while the gaseous product phase consisted of CH4, CO, methanol, and C2−C7 linear hydrocarbons. The 1/1 ratio CoFe alloy with the same composition as the natural mineral wairauite yielded the highest concentrations of formate (6.0 mM) and acetate (0.8 mM), which are key intermediates in the acetyl‐coenzyme A (acetyl‐CoA) pathway of CO2 fixation. While Co‐rich catalysts were proficient at hydrogenation, yielding mostly CH4, Fe‐rich catalysts favored the formation of CO and methanol. Mechanistic studies indicated intermediate hydrogenation and C−C coupling activities of alloyed CoFe, in contrast to physical mixtures of both metals. Co in the active site of Co−Fe catalysts performed a similar reaction as tetrapyrrole‐coordinated Co in the corrinoid iron‐sulfur (CoFeS) methyl transferase in the acetyl‐CoA pathway. In a temperature range characteristic for deeper regions of serpentinizing systems, oxygenate product formation was favored at lower, more biocompatible temperatures.
Influence of Defects and Charges on the Colloidal Stabilization of Graphene in Water
Authors: Vita Damasceno João Paulo , Picheau Emmanuel , Hof Ferdinand , Zarbin Aldo J. G. , Pénicaud Alain , Drummond Carlos 
Published: February 2024

AbstractMastering graphene preparation is an essential step to its integration into practical applications. For large‐scale purposes, full graphite exfoliation appears as a suitable route for graphene production. However, it requires overpowering attractive van der Waals forces demanding large energy input, with the risk of introducing defects in the material. This difficulty can be overcome by using graphite intercalation compounds (GICs) as starting material. The greater inter‐sheet separation in GICs (compared with graphite) allows the gentler exfoliation of soluble graphenide (reduced graphene) flakes. A solvent exchange strategy, accompanied by the oxidation of graphenide to graphene, can be implemented to produce stable aqueous graphene dispersions (Eau de graphene, EdG), which can be readily incorporated into many processes or materials. In this work, we prove that electrostatic forces are responsible for the stability of fully exfoliated graphene in water, and explore the influence of the oxidation and solvent exchange procedures on the quality and stability of EdG. We show that the amount of defects in graphene is limited if graphenide oxidation is carried out before exposing the material to water, and that gas removal of water before the incorporation of pre‐oxidized graphene is advantageous for the long‐term stability of EdG.
Expanding Chemical Frontiers: Approaches for Generating Diverse and Bioactive Natural Product‐Like Compounds Libraries from Extracts
Authors: Beato Aurélien , Haudecoeur Romain , Boucherle Benjamin , Peuchmaur Marine 
Published: February 2024

AbstractThe realms of natural products and synthetic compounds exhibit distinct chemical spaces that not only differ but also complement each other. While the convergence of these two domains has been explored through semisynthesis and conventional pharmacomodulation endeavours applied to natural frameworks, a recent and innovative approach has emerged that involves the combinatorial generation of libraries of ‘natural product‐like compounds’ (NPLCs) through the direct synthetic derivatization of natural extracts. This has led to the production of numerous NPLCs that incorporate structural elements from both their natural (multiple saturated rings, oxygen content, chiral centres) and synthetic (aromatic rings, nitrogen and halogen content, drug‐like properties) precursors. Through careful selection of extracts and reagents, specific bioactivities have been achieved, and this strategy has been deployed in various ways, showing great promise without reaching its full potential to date. This review seeks to provide an overview of reported examples involving the chemical engineering of extracts, showcasing a spectrum of natural product alterations spanning from simple substitutions to complete scaffold remodelling. It also includes an analysis of the accomplishments, perspectives and technical challenges within this field.
Microfluidic devices, materials, and recent progress for petroleum applications: A review
Authors: Betancur Stefanía , Quevedo Lina , Olmos Carol M. 
Published: February 2024

AbstractMicrofluidic devices are miniaturized systems that manipulate fluids on a small scale, typically at microlitre or nanolitre volumes. They have received significant attention in various industries, including petroleum applications. The recent advancements in microfluidic devices for petroleum applications have the potential to improve oil recovery efficiency, reduce costs, and provide valuable insights into fluid behaviour and reservoir characterization. This paper aims to provide a comprehensive overview of microfluidic devices, their materials, and their applications in the petroleum industry. The first section of the paper focuses on describing the materials used in microfluidic devices specifically tailored for energy sector applications. In the second section, the paper highlights relevant applications and discoveries in petroleum research, showcasing the innovative techniques and special features enabled by microfluidic devices. These applications include but are not limited to asphaltenes characterization, enhanced oil recovery (EOR), and water treatment. The versatility and customization of microfluidic devices have allowed researchers to accurately represent fractures, ensure chemical conformance, simulate high pressure–high temperature conditions and reservoir heterogeneity, and study geochemical interaction. Additionally, molecular tagging and machine learning techniques have been employed for image analysis, further enhancing the capabilities of microfluidic devices. Throughout the paper, the advantages and disadvantages of implementing microfluidic devices and utilizing specific materials are thoroughly discussed. This analysis provides valuable insights into the challenges and potential limitations associated with this technology. To conclude, the paper offers suggestions, ideas, and highlights for future research paths, pointing toward promising directions for further exploration in this field.
Dual Stabilization of a Tri‐Metallofullerene Radical Er3@C80: Exohedral Derivatization and Endohedral Three‐Center Bonding
Authors: Wu Yabei , Zhou Zhonghao , Xu Dan , Jiang Yuhang , Zhou Dingyi , Wang Zhiyong 
Published: February 2024

AbstractThe enclosed space within fullerene molecules, capable of trapping metal clusters, offers an opportunity to investigate the behavior of metal atoms in a highly confined sub‐nanometer environment. However, the studies on trimetallofullerenes M3@C80 have been very limited due to their difficult obtainability. In this paper, we present a new method for obtaining a tri‐metallofullerene Er3@C80 through exohedral modification of the fullerene cage. Our findings reveal that Er3@C80 exhibits a radical character and can react with the dichlorobenzene radical to generate a stable derivative Er3@C80PhCl2. Theoretical calculations demonstrate the presence of a three‐center two‐electron metal‐metal bond in the center of the fullerene cage. This bond serves to counterbalance the Coulomb repulsion between the Er ions. Consequently, both exohedral derivatization and endohedral three‐center bonding contribute to the substantial stability of Er3@C80PhCl2. Furthermore, molecular dynamics simulations indicate that the Er3 cluster within the molecule possesses a rigid triangle structure. The availability of M3@C80 derivatives opens avenues for future investigations into interactions among metal atoms, such as magnetic coupling, within fullerene cages.
A Theoretical‐Computational Study of Phosphodiester Bond Cleavage Kinetics as a Function of the Temperature
Authors: Nardi Alessandro Nicola , Olivieri Alessio , D'Abramo Marco , Amadei Andrea 
Published: February 2024

AbstractThe hydrolysis of the phosphodiester bond is an important chemical reaction involved in several biological processes. Here, we study the cleavage of this bond by means of a theoretical‐computational method in a model system, the dineopentyl phosphate. By such an approach, we reconstructed the kinetics and related thermodynamics of this chemical reaction along an isochore. In particular, we evaluated the kinetic constants of all the reaction steps within a wide range of temperatures, mostly corresponding to conditions where no experimental measures are available due to the extremely slow kinetics. Our results, in good agreement with the experimental data, show the robustness of our theoretical‐computational methodology which can be easily extended to more complex systems.
Performance and phenotypic stability of maize hybrids containing exotic introgressions in multi‐environment trials
Authors: Perkins Alden , Lima Dayane C. , Kaeppler Shawn M. , de Leon Natalia 
Published: February 2024

AbstractMaize (Zea mays L.) grown in the US Midwest contains only a small fraction of the genetic diversity present in the species. Maize populations from other parts of the world may contain genetic variation that could be used to improve or increase the diversity of US germplasm. This study was conducted to assess the performance and phenotypic stability of hybrids containing diverse exotic introgressions across North American environments. Doubled haploid (DH) lines were created by the Germplasm Enhancement of Maize project from backcross 1 families that used 27 open‐pollinated populations from Latin America as donor parents and PHZ51, a non‐Stiff Stalk inbred developed in Iowa, as the recurrent parent. DH lines were testcrossed with LH195, a Stiff Stalk inbred developed in Iowa, and hybrid field trials were performed at 24 environments in the United States and Canada. Experimental hybrids had variable flowering time, plant and ear height, and test weight, but none had significantly greater yield than the PHZ51 × LH195 hybrid. The slopes of linear reaction norm models were significantly lower for the experimental hybrids than the US‐adapted reference hybrids for three traits: yield, growing degree units (GDU) to anthesis, and GDU to silking. The results suggest that unfavorable alleles and phenotypic stability should be considered when exotic open‐pollinated populations are used in US maize breeding.
Recent Progress of Oligomeric Non‐Fullerene Acceptors for Efficient and Stable Organic Solar Cells
Authors: Qi Feng , Li Yanxun , Lin Francis R. , Jen Alex K.‐Y. 
Published: February 2024

AbstractOrganic solar cells (OSCs) have achieved remarkable power conversion efficiencies (PCEs) of over 19 % in the past few years due to the rapid development of non‐fullerene acceptors (NFAs). However, the operational stability remains a great challenge that inhibits their commercialization. Recently, oligomeric NFAs (ONFAs) have attracted great attention, which not only can deliver excellent device performance, but also improve the thermal‐/photo‐ stability of OSCs. This is attributed to the suppressed molecular diffusion of ONFAs associated with their high glass‐transition temperature (Tg) and improved thermodynamic properties of ONFAs. Herein, we focus on investigating the correction between the ONFA chemical structure, material properties, device performance, and stability. In addition, we also try to point out the challenges in synthesizing ONFAs and provide potential directions for future ONFA designs.
Recent Advances in Iridium‐based Electrocatalysts for Acidic Electrolyte Oxidation
Authors: Li Wanqing , Bu Yunfei , Ge Xinlei , Li Feng , Han Gao‐Feng , Baek Jong‐Beom 
Published: February 2024

AbstractOngoing research to develop advanced electrocatalysts for the oxygen evolution reaction (OER) is needed to address demand for efficient energy conversion and carbon‐free energy sources. In the OER process, acidic electrolytes have higher proton concentration and faster response than alkaline ones, but their harsh strongly acidic environment requires catalysts with greater corrosion and oxidation resistance. At present, iridium oxide (IrO2) with its strong stability and excellent catalytic performance is the catalyst of choice for the anode side of commercial PEM electrolysis cells. However, the scarcity and high cost of iridium (Ir) and the unsatisfactory activity of IrO2 hinder industrial scale application and the sustainable development of acidic OER catalytic technology. This highlights the importance of further research on acidic Ir‐based OER catalysts. In this review, recent advances in Ir‐based acidic OER electrocatalysts are summarized, including fundamental understanding of the acidic OER mechanism, recent insights into the stability of acidic OER catalysts, highly efficient Ir‐based electrocatalysts, and common strategies for optimizing Ir‐based catalysts. The future challenges and prospects of developing highly effective Ir‐based catalysts are also discussed.
A simplified model‐based nonlinear control with fast response and simple design flow for HB‐LLC resonant converter
Authors: Yang Yuhang , Chen Yanfeng , Zhang Bo 
Published: February 2024

SummaryLLC resonant converters have attracted much attention for its characteristics of high efficiency and high‐power density in recent years. Yet, with the diversity of application needs such as photovoltaic power generation and electric vehicles, traditional control solutions have gradually been unable to meet the increasing requirements, such as fast response to parameters perturbations. Besides, LLC converter is a high‐order nonlinear system, and it adds complexity to controller design. In order to solve these issues, taking the HB‐LLC converter as an example, this paper presents a simplified model‐based nonlinear control with fast response and simple design. The proposed controller is based on a second‐order model of LLC circuit, and the reverse design idea of the backstepping method is used to simplify the controller design. An experimental platform is built, and the results show that compared with PID control and linear active disturbance rejection control (LADRC), the proposed method has much smaller voltage undershoot (approximately 53.1% of PID and 68.4% of LADRC) and shorter settling time (approximately 27.8% of PID and 39.3% of LADRC) under input voltage change.
Are there specific cytologic features that can predict BRAFV600E mutational status of papillary thyroid carcinoma in fine‐needle aspiration specimens?
Authors: Mendes Juliann M. , Elsheikh Tarik M. , Di Marco Jessica , Russell Jennifer , Gladkaya Tatyana , Nicolas Marlo M. , Clapacs Elisha , Bena James F. , McAfee John L. , Policarpio‐Nicolas Maria Luisa C. 
Published: February 2024

AbstractBackgroundBRAFV600E mutation is the most common molecular alteration found in papillary thyroid carcinoma (PTC) and has been linked to recurrent disease or possibly more aggressive behavior. Some studies have reported sickle‐shaped nuclei (SSN) and plump pink cells (PPC) to be predictive markers of BRAF mutation in FNA cytology. We aimed to evaluate the reproducibility of the aforementioned cytologic features.MethodsA computerized search for diagnosed PTC surgical pathology cases tested for BRAFV600E mutation by Sanger DNA sequencing was performed. Blinded to BRAF results, the corresponding cytology was reviewed for presence of SSN and PPC. Classic nuclear PTC (CNPTC) features, cystic change, and psammoma bodies were also evaluated. The results were correlated with BRAFV600E mutational status and histologic subtypes.ResultsStudy cohort consisted of 113 cases (74 BRAFV600E mutated, 39 BRAFV600E wild type).SSN and combined CNPTC /SSN had positive predictive value of 74% and 75%, respectively. CNPTC showed 92% sensitivity and 20% specificity. Psammoma bodies had 92% specificity and 5% sensitivity. The presence of combined PPC/SSN showed 80% specificity, 27% sensitivity, and diagnostic accuracy of 45%. CNPTC was seen in 60/61 (98%) SSN and 45/45 (100%) PPC. There was no significant statistical association between SSN, PPC, and CNPTC with specific histologic subtypes and BRAF mutational status.ConclusionCNPTC is sensitive but not specific for BRAF mutational status. SSN, PPC, and CNPTC are not predictive markers for the presence of BRAF mutation or histologic subtypes. Additional studies may be needed to further corroborate these findings.
Routine application of SFC‐MS in doping control: Analysis of 3 × 1000 urine samples using three different SFC‐MS instruments
Authors: Gavrilović Ivana , Wüst Bernhard , Danaceau Jonathan , Braidman Emmanuelle , de la Torre Xavier , Botrè Francesco , Parr Maria Kristina , Cowan David 
Published: February 2024

AbstractSupercritical fluid chromatography‐mass spectrometry (SFC‐MS) has proved to be a beneficial tool for sample analysis for a wide variety of compounds and, as such, has recently gained the attention of the anti‐doping community. We have tested the applicability of SFC‐MS for routine doping control analysing approximately 3 × 1000 identical anti‐doping samples utilising SFC‐MS instruments from three different vendors: Agilent Technologies, Waters Corporation and Shimadzu Corporation. A ‘dilute and inject’ approach either without or after hydrolysis of glucuronide metabolites was applied. Most of the compounds included in our study demonstrated excellent chromatography, whereas some showed co‐elution with endogenous interferences requiring MS discrimination. Retention times typically were very stable within batches (%CV ≤ 0.5%), although this appeared to be analyte and column dependent. Chromatographic peak shape was good (symmetrical) and stable over the period of the testing without any change of column. Our results suggest that SFC‐MS is a sensitive, reproducible and robust analytical tool ready to be used in anti‐doping laboratories alongside the currently applied techniques such as gas and liquid chromatography coupled to mass spectrometry. Even if instruments are designed slightly differently, all three setups demonstrated their fitness for the purpose in anti‐doping testing.
Genetic diversity assessment of Helichrysum arenarium (Asteraceae) for the genetic restoration of declining populations
Authors: Van Rossum Fabienne , Godé Cécile , Baruca Arbeiter Alenka , Raspé Olivier , Simsek Melike , Barigand Benjamin , Hardy Olivier J. , Bandelj Dunja 
Published: February 2024

AbstractHelichrysum arenarium (L.) Moench (Asteraceae) is a self‐compatible, insect‐pollinated herb occurring in sand grasslands, and is declining and endangered in many parts of its European distribution range. A recovery plan of H. arenarium has been conducted in southern Belgium, involving plant translocations. We developed multiplex genotyping protocol for nine microsatellite markers previously published for Helichrysum italicum and two newly developed microsatellite markers for H. arenarium. Eleven polymorphic loci were associated (pooled) in two multiplex panels, to assess the genetic status of the only small remaining population in Belgium and of three large German populations used as seed source for propagating transplants. The small Belgian population was characterized by high clonality, with only two, however heterozygous, genets detected. The three large German populations showed high genetic diversity (He ranging from 0.635 to 0.670) and no significant inbreeding coefficient values, despite expectations of geitonogamous selfing. Management practices (grazing livestock) increasing seed dispersal distances, inbreeding depression at early stages of development, and mechanisms preventing or delaying selfing might be hypothesized to explain the observed patterns. The two Belgian genotypes remained within genetic variation range of German populations so that the high genetic differentiation between Belgian and German populations (FST values ranging from 0.186 to 0.206) likely resulted from genetic drift effects and small sample size. Transplants obtained from seeds sampled from the three large source populations from Germany constitute a highly diverse, noninbred gene pool, and are thus of high genetic quality for plant translocations.
Simultaneous species detection and discovery with environmental DNA metabarcoding: A freshwater mollusk case study
Authors: Vanderpool Daniel D. , Wilcox Taylor M. , Young Michael K. , Pilgrim Kristine L. , Schwartz Michael K. 
Published: February 2024

AbstractEnvironmental DNA (eDNA) sampling is a powerful tool for rapidly characterizing biodiversity patterns for specious, cryptic taxa with incomplete taxonomies. One such group that are also of high conservation concern are North American freshwater gastropods. In particular, springsnails of the genus Pyrgulopsis (Family: Hydrobiidae) are prevalent throughout the western United States where >140 species have been described. Many of the described species are narrow endemics known from a single spring or locality, and it is believed that there are likely many additional species which have yet to be described. The distribution of these species across the landscape is of interest because habitat loss and degradation, climate change, groundwater mining, and pollution have resulted in springsnail imperilment rates as high as 92%. Determining distributions with conventional sampling methods is limited by the fact that these snails are often <5 mm in length with few distinguishing morphological characters, making them both difficult to detect and to identify. We developed an eDNA metabarcoding protocol that is both inexpensive and capable of rapid, accurate detection of all known Pyrgulopsis species. When compared with conventional collection techniques, our pipeline consistently resulted in detection at sites previously known to contain Pyrgulopsis springsnails and at a cost per site that is likely to be substantially less than the conventional sampling and individual barcoding that has been done historically. Additionally, because our method uses eDNA extracted from filtered water, it is non‐destructive and suitable for the detection of endangered species where “no take” restrictions may be in effect. This effort represents both a tool which is immediately applicable to taxa of high conservation concern across western North America and a case study in the broader application of eDNA sampling for landscape assessments of cryptic taxa of conservation concern.