bluuebunny/crossref_metadata_2025 huggingface dataset:
Forecasting Wholesale Electricity Market Prices Considering Bidding Conditions Using Price Sensitivity
Authors: Hirota Shinji , Cui Jindan , Fang Xue , Oozeki Takashi , Ueda Yuzuru
Published: October 2024

This article proposes a sophisticated forecasting model to predict significant price volatility on the Japan Electric Power Exchange (JEPX) due to the growing influence of solar photovoltaics (PV) in the energy mix. As solar power generation continues to grow, it significantly impacts the daily and seasonal price trends in the market. This method employs a neural network that integrates daily prices, net electricity demand (total demand minus PV output), and underlying time‐series data to determine the objective variable, defined as the deviation from the average price over the past week. Incorporating price sensitivity data from JEPX increases the accuracy of the model. These data reflect how prices respond to market‐specified bid adjustments, including a variety of bidding, providing a nuanced understanding of market responses. The results demonstrate that adding multiple price sensitivities significantly improves the model's ability to detect price spikes and provides a robust tool for transmission and distribution system operators to manage risk and optimize their market strategies in an increasingly renewable energy‐dominated landscape. This approach not only addresses daily and seasonal price fluctuations but also aligns with broader sustainability goals as the share of solar PV generation continues to grow.
Structures of a DNA Polymerase Caught while Incorporating Responsive Dual‐Functional Nucleotide Probes
Authors: Ghosh Pulak , Betz Karin , Gutfreund Cédric , Pal Arindam , Marx Andreas , Srivatsan Seergazhi G.
Published: October 2024

Functionalizing nucleic acids using DNA polymerases is essential in biophysical and biotechnology applications. This study focuses on understanding how DNA polymerases recognize and incorporate nucleotides with diverse chemical modifications, aiming to develop advanced nucleotide probes. We present the crystal structures of ternary complexes of Thermus aquaticus DNA polymerase (KlenTaq) with C5‐heterocycle‐modified environment‐sensitive 2′‐deoxyuridine‐5′‐triphosphate (dUTP) probes. These nucleotides include SedUTP, BFdUTP and FBFdUTP, which bear selenophene, benzofuran and fluorobenzofuran, respectively, at the C5 position of uracil, and exhibit high conformational sensitivity. SedUTP and FBFdUTP serve as dual‐app probes, combining a fluorophore with X‐ray anomalous scattering Se or 19F NMR labels. Our study reveals that the size of the heterocycle influences how DNA polymerase families A and B incorporate these modified nucleotides during single nucleotide incorporation and primer extension reactions. Remarkably, the responsiveness of FBFdUTP enabled real‐time monitoring of the binary complex formation and polymerase activity through fluorescence and 19F NMR spectroscopy. Comparative analysis of incorporation profiles, fluorescence, 19F NMR data, and crystal structures of ternary complexes highlights the plasticity of the enzyme. Key insight is provided into the role of gatekeeper amino acids (Arg660 and Arg587) in accommodating and processing these modified substrates, offering a structural basis for next‐generation nucleotide probe development.
Enantioselective Electrocatalysis for Cross‐Dehydrogenative Heteroarylation with Indoles, Pyrroles, and Furans
Authors: Liang Kang , Li Ning , Liu Minghao , Song Jin , Guo Chang
Published: October 2024

Oxidative cross‐dehydrogenative C−H/C−H functionalizations represent an exemplary approach for synthesizing carbonyl compounds via α‐heteroarylation. Here we present the development of a direct anodic oxidative coupling process between 2‐acylimidazoles and divergent heterocyclic systems including indole, pyrrole, and furan, facilitated by ferrocene‐assisted asymmetric nickel electrocatalysis with high levels of enantioselectivity. Mechanistic investigations indicate that the reaction initially involves the formation of a chiral Ni‐bound α‐carbonyl radical, which is then captured by the heteroarene radical cation via intermolecular stereoselective radical/radical cation coupling. The mild, scalable, and robust reaction conditions allow for a broad substrate scope and excellent functional group tolerance, enabling access to a wide range of chiral hetero‐compounds. The consequential α‐heteroaromatic carbonyl products can potentially be transformed into a plethora of synthetically valuable frameworks, as exemplified by their application in the asymmetric total synthesis of (−)‐COX‐2 inhibitor, (+)‐acremoauxin A, and (+)‐pemedolac.
Catalytic Dearomative [1,5]‐Sigmatropic Carbon Shift of Heterole‐Fused Norcaradienes Enabled Concise Helicenation
Authors: Bi Hongyan , Shen Chaoren , Wang Sunewang R.
Published: October 2024

In contrast to the locked fluxionality of norcaradienes fused by benzene, unexplored less aromatic heterole‐fused norcaradienes, creatively generated by intramolecular hydroarylation of heteroaryl alkynylcyclopropanes, reserve a balancing fluxionality that permits a dearomative [1,5]‐sigmatropic carbon shift of norcaradienes akin to the reduced aromaticity of heterole. This “walk” shift was confirmed by the isolation of a cycloheptatriene species derived from ring‐expansion of a dearomatized alkynylated heterole‐fused norcaradiene. A following ester‐directed ring‐opening rearomatization of these dearomatized heterole‐fused norcaradienes gives the products featuring migratory acylmethyls that are competent for helicenation with the neighboring (hetero) arenes via (formal) dehydrative alkenylation. Such balancing reactivity of heterole‐fused norcaradienes will open up the opportunity for the development of controllable reactions of fused norcaradienes.
Synthesis of reaction promoters for epoxy polymerization: Enhancing storage stability and mechanical properties of one‐pot epoxy systems
Authors: Lee Da Young , Kim Hye‐Jin , Kim Hyeon‐Gook , Tayebi Meysam , Kim Jong‐Hyun , Yu Seoyoon , Chung Ildoo , Lim Choong‐Sun , Seo Bongkuk
Published: October 2024

One‐pot epoxy formulations, containing uncured resin, curing agent, and promoter, require the promoter to be insoluble in the resin at room temperature to prevent premature polymerization. Here, we introduce three novel reaction promoters synthesized by reacting amino propyl imidazole (API) and various diisocyanates such as HMDI, IPDI, or MDI. We evaluate the impact of these promoters on the physical properties, storage stability, and curing kinetics of the resulting epoxy formulations. The results of the kinetic study showed that the compositions containing each synthesized promoter acted as reaction promoters, as evidenced by the lower activation energy in the differential scanning calorimetry (DSC) experiment. The results of the mechanical properties showed that HMDI‐API promoter improved both tensile and flexural strength, while exhibiting high storage stability. The findings provide valuable insights for selecting suitable promoters for specific applications in one‐pot epoxy systems.
Trends in New Use of Disease‐Modifying Antirheumatic Drugs for Juvenile Idiopathic Arthritis Among Commercially Insured Children in the United States from 2001 to 2022
Authors: Yalamanchili Priyanka , Lee Lydia Y. , Bushnell Greta , Mannion Melissa L. , Dave Chintan V. , Horton Daniel B.
Published: October 2024

Objective

The objective of this study is to describe recent trends in disease‐modifying antirheumatic drug (DMARD) use for children with juvenile idiopathic arthritis (JIA) in the United States.

Methods

We used commercial claims data (2000–2022) to perform a serial cross‐sectional utilization study of children aged 1 to 18 that were diagnosed with JIA. Initiations of conventional synthetic DMARDs (csDMARDs), biologic DMARDs (bDMARDs), or targeted synthetic DMARDs (tsDMARDs) were identified after a ≥12‐month baseline and expressed as a percentage of all new DMARD initiations per year, by category, class, and individual agent. Trends were evaluated using linear regression. We also examined the first bDMARDs and tsDMARDs initiated after csDMARD monotherapy.

Results

We identified 20,258 new DMARD use episodes among 13,696 individuals (median age 14 years, 67.5% female). csDMARDs, although most used overall, declined from 89.5% of new use episodes to 43.2% (2001–2022, P < 0.001 for trend). In contrast, bDMARD use increased (10.5–50.0%, P < 0.001). For tumor necrosis factor inhibitors (TNFi), etanercept peaked at 28.3% in 2006 and declined to 4.2% in 2022 (P = 0.002). Meanwhile, adalimumab use doubled (7.0–14.0%, 2007–2008) after JIA approval, increasing further following a less painful formulation release (20.5% in 2022, P < 0.001). However, overall TNFi use has declined with increasing use of other bDMARDs and tsDMARDs, particularly ustekinumab, secukinumab, and tofacitinib. By 2022, adalimumab was the most common b/tsDMARD initiated first after csDMARDs (77.8%).

Conclusion

Among commercially insured children with JIA in the United States, new b/tsDMARD use is rising and new csDMARD use is declining. For b/tsDMARDs, adalimumab is most used and is the predominant b/tsDMARD initiated first after csDMARDs. Patterns in DMARD use for JIA have evolved relative to multiple factors, including regulatory approvals and tolerability.
Voice‐over anatomy lectures created by AI‐voice cloning technology: A descriptive article
Authors: Mogali Sreenivasulu Reddy , Ng Olivia , Tan Jia Xin , San Thu Htet , Ng Kian Bee
Published: October 2024

The COVID‐19 pandemic revealed the pivotal role of digital learning and online lecture videos, leading a shift toward blended and flipped classrooms in the post‐pandemic era. This shift calls for development and (or) refreshment of novel online educational resources, such as Voice‐Over PowerPoint (VOPPT) presentations, specifically designed for asynchronous or synchronous learning methods. However, resource limitations often impede the timely delivery of high‐quality instructional materials. In this descriptive article, the use of AI‐voice cloning technology to automate the creation of VOPPT presentation has been explored. Descripts' Overdub tool, an AI‐voice cloning program, was trained on the 15‐min voice sample of an anatomy professor, and the synthesized voice was used to narrate presentations on inguinal canal and extrahepatic biliary anatomy. The educational use of this novel approach was evaluated based on the second‐year undergraduate medical students' qualitative feedback. Voice similarity analysis using Resemblyzer, an open‐source Python tool, showed a high similarity score of 0.92 between the cloned and original voices. Despite this, students raised concerns about the robotic voice, quick pace, punctuation problems, pronunciation difficulties, and expressed reservations about AI‐generated lecture narration. While the cloned voice closely matched the original, the AI‐generated narration fell short of capturing the nuanced details needed for an effective anatomy instruction. This uncovers AI's current limitations in the educational contexts but establishes a foundation for future progress in AI‐voice cloning technologies aimed at enhancing online educational resources for anatomy and medical education.
New delay‐dependent finite‐time stabilization of Takagi–Sugeno fuzzy approaches for delayed nonlinear systems
Authors: El Fezazi Nabil , Fahim Mohamed , Idrissi Said , Farkous Rashid , Alvarez Teresa , Tissir El Houssaine
Published: October 2024

In this paper, the finite‐time stability and stabilization of nonlinear systems with delays is studied, via a Takagi–Sugeno approach. By using a novel Lyapunov–Krasovskii functional and introducing some fuzzy free‐weighting matrices, sufficient conditions are derived, for bounded and differentiable time‐varying delays in terms of an upper bound of the delay derivatives. Then, we achieve closed‐loop stabilization in finite time through an efficient parallel distributed compensation design. The sufficient conditions are formulated as linear matrix inequalities to achieve the desired performance. Finally, the proposed methodology is applied to various case studies, highlighting its significance.
Implementierung von probabilistischen Baugrundmodellen in IFC 2x3 und 4.0
Authors: Wiegel Andreas , Peña‐Olarte Andrés , Cudmani Roberto
Published: October 2024

Die Prognose der Unsicherheiten in 3D‐Baugrundmodellen für BIM verbessert die Risikobewertung und Entscheidungsfindung und ermöglicht eine wirtschaftlichere und nachhaltigere Planung und Ausführung von Baumaßnahmen. Basierend auf Open‐Source‐Software wird ein Ansatz zur Implementierung probabilistischer Baugrundmodelle im Industry‐Foundation‐Classes‐ (IFC‐) Datenschema vorgeschlagen. Die Grundlagen von IFC, die für die Erstellung von Fachobjekt‐Geometrien sowie deren Georeferenzierung und Attribuierung erforderlich sind, werden erläutert. Zwei probabilistische 3D‐Modelle, die mit Bohrprofil‐ bzw. Cone‐Penetration‐Test‐ (CPT‐) Daten erstellt wurden, dienen als Anwendungsbeispiele; diese zeigen die prognostizierte Geometrie der Bodenschichten mit den zugehörigen Unsicherheiten basierend auf Volume Pixel (Voxel). Solange Voxel‐Modelle nicht in IFC integriert sind, bieten Isoflächen eine praktikable Zwischenlösung zur Darstellung von Bodenschichten und Unsicherheiten. Eine konsistente Georeferenzierung gewährleistet eine korrekte Positionierung im Koordinationsmodell. Die Modellierung von Baugrund‐ und geotechnischen Daten wird für verschiedene IFC‐Versionen gezeigt. Die aktuelle IFC‐Version 4 verbessert die Oberflächenmodellierung und reduziert die Datenredundanz. Der vorgestellte Ansatz ermöglicht eine maßgeschneiderte Implementierung probabilistischer Baugrundmodelle in IFC und eine effizientere Zusammenarbeit der an der Erstellung des BIM‐Modells beteiligten Experten.
Sustainable Fabrication of Luminescent Zinc Oxide Nanoparticles From Cucumis melo Fruit Peel Extract as Prospective Photocatalytic and Antigermicidal Agent
Authors: Murugesan Umamaheswari , Subramaniyan Vijayakumar , Subramaniyan Prathipkumar , Elavarasan Vidhya , Subramanian Sriram , Raja Mythili , Devanesan Sandhanasamy
Published: October 2024

The focus of current advances in nanotechnology has shifted significantly towards environmentally conscious methods that use harmless ingredients and moderated reaction circumstances to promote equitable development. Zinc oxide nanoparticles (NPs) currently grabbed attention of multiple medical fields owing to their unique ability to safeguard against cellular damage and alleviate serious human diseases via processes related to metabolism. This work focused on the generation of ZnO NPs using the peel of Cucumis melo fruit. The NPs were then analyzed and characterized using UV–Vis spectroscopy. The results indicated that at a wavelength of 352 nm, it was proven that the biosynthesis of ZnO NPs had occurred. The XRD pattern indicated the presence of dense crystal structures. The field emission scanning electron microscope (FE‐SEM) picture confirmed the existence of polygonal‐shaped ZnO NPs. The findings indicate that the produced ZnO NPs possess tough antibacterial properties against Gram‐positive and Gram‐negative microorganisms. When the ZnO NPs were exposed to direct sunshine for 80 min, they showed an 89% dye breakdown efficiency. This research specifically focused on the decomposition of reactivity dyes, with methylene blue dye being used as the target dye. The work demonstrates that the biosynthesis of ZnO NPs has a crucial and versatile role in the biological and environmental sectors.
Elevated endoplasmic reticulum pH is associated with high growth and bisAb aggregation in CHO cells
Authors: McFarland Kevin S. , Hegadorn Kaitlin , Betenbaugh Michael J. , Handlogten Michael W.
Published: October 2024

Chinese hamster ovary (CHO) bioprocesses, the dominant platform for therapeutic protein production, are increasingly used to produce complex multispecific proteins. Product quantity and quality are affected by intracellular conditions, but these are challenging to measure and often overlooked during process optimization studies. pH is known to impact quality attributes like protein aggregation across upstream and downstream processes, yet the effects of intracellular pH on cell culture performance are largely unknown. Recently, advances in protein biosensors have enabled investigations of intracellular environments with high spatiotemporal resolution. In this study, we integrated a fluorescent pH‐sensitive biosensor into a bispecifc (bisAb)‐producing cell line to investigate changes in endoplasmic reticulum pH (pHER). We then investigated how changes in lactate metabolism impacted pHER, cellular redox, and product quality in fed‐batch and perfusion bioreactors. Our data show pHER rapidly increased during exponential growth to a maximum of pH 7.7, followed by a sharp drop in the stationary phase in all perfusion and fed‐batch conditions. pHER decline in the stationary phase was driven by an apparent loss of cellular pH regulation that occurred despite differences in redox profiles. Finally, we found protein aggregate levels correlated most closely with pHER which provides new insights into product aggregate formation in CHO processes. An improved understanding of the intracellular changes impacting bioprocesses can ultimately help guide media optimizations, improve bioprocess control strategies, or provide new targets for cell engineering.
Late subsequent leukemia after childhood cancer: A report from the Childhood Cancer Survivor Study (CCSS)
Authors: Ghosh Taumoha , Hyun Geehong , Dhaduk Rikeenkumar , Conces Miriam , Arnold Michael A. , Howell Rebecca M. , Henderson Tara O. , McDonald Aaron , Robison Leslie L. , Yasui Yutaka , Ness Kirsten K. , Armstrong Gregory T. , Neglia Joseph P. , Turcotte Lucie M.
Published: October 2024

Background

Subsequent short‐latency leukemias are well‐described among survivors of childhood cancer. However, late (5–14.9 years from diagnosis, LL) and very late (≥15 years from diagnosis, VLL) subsequent leukemias have not been well studied. We assessed risk factors, prevalence, and outcomes for LL and VLL in the Childhood Cancer Survivor Study cohort.

Methods

Subsequent leukemias, among 25,656 five‐year survivors, were self‐reported and confirmed by pathology review. Standardized incidence ratios (SIR) and cumulative incidences were calculated, and relative risks (RR) were estimated using Cox regression for exposures.

Results

Seventy‐seven survivors developed subsequent leukemia, 49 survivors with LL (median time from diagnosis 7.8 years, range 5.0–14.5 years) and 28 with VLL (median time from diagnosis 25.4 years, range 15.9–42.8 years), with a cumulative incidence of 0.23% (95% CI 0.18%–0.30%) 20 years from diagnosis for all subsequent leukemias. The most common leukemia subtypes were acute myeloid leukemia, myelodysplastic syndrome, and chronic myeloid leukemia. Compared to the general population, survivors were at increased risk, for developing LL (SIR 9.3, 95% CI 7.0–12.1) and VLL (SIR 5.9, 95% CI 3.9–8.4). In multivariable relative risk analyses, cumulative epipodophyllotoxin dose >4000 mg/m2 was associated with increased risk for LL and VLL (RR 4.5, 95% CI 2.0–9.9).

Conclusions

In this large series of late subsequent leukemias, survivors of childhood cancer are at increased risk, with no evidence of plateau over time. We observed most risk among survivors who received high cumulative doses of epipodophyllotoxins. Ongoing consideration for this late effect should continue beyond 10 years.
In Vitro Antioxidant and Antifungal Activities of Extracts from Ocimum basilicum Leaves Validated by Molecular Docking and ADMET Analysis
Authors: Vijay Neha , Taleuzzaman Mohamad , Hudda Sharwan , Choudhary Nisha
Published: October 2024

The aim of study is to investigate the various mechanism‐based antioxidant and anti‐fungal properties of a hydroalcoholic extract of Ocimum basilicum L leaves. Additionally, conduct molecular docking to simultaneously validate in vitro activities. Also, perform ADMET analysis to know pharmacokinetic properties and its toxicity for its safety. Prior extract's qualitative analysis has been performed to identify the bioactive compounds by phytochemical tests and GC‐MS analysis. Different mechanism‐based in vitro antioxidant methods are studied; in different methods, different IC50 values have come, which revealed the extract's antioxidant potentials. The antifungal potential of the extract has been observed by performing a modified poison food assay and a time‐killing curve assay. In silico analysis with the human peroxiredoxin 5 enzyme (PDB ID: 1HD2) and secreted aspartic proteinase (PDB ID: 2QZX), which predict extract biological activity, has shown promising results of Ocimum basilicum L extract. In silico findings confirm the in vitro experimental outcome of the extract. The different IC50 values of extracts in different mechanisms indicate their therapeutic potential, and that encourages further research in formulation development. The time‐killing assay method gives information about a dynamic interaction between extract and microbial strain. Concentration‐dependent antifungal studies have significance in formulation development for dose determination. This study concludes by highlighting the antioxidant and antifungal properties of sweet basil as potential therapeutic benefits with an in‐silico approach.
Medicinal Chemistry Insights in Neuronal Nitric Oxide Synthase Inhibitors Containing Nitrogen Heterocyclic Compounds: A Mini Review
Authors: Bojovic Dijana , Nikolic Milos , Nedeljkovic Nikola , Vesovic Marina , Zivanovic Ana , Karovic Marko
Published: October 2024

Many scientific reports over the last two decades have focused on the discovery and development of novel nNOS inhibitors. The structural identity of isoforms, bioavailability, pharmacokinetic, and safety profile issues remain major obstacles in the discovery of more potent and selective nNOS inhibitors. This review aims to provide an in‐depth overview of the molecular interaction patterns between nNOS active site and inhibitors containing structurally diverse nitrogen heterocyclic compounds and highlight the structural properties needed to develop selective nNOS inhibitors. Previously published data allowed the usage of the structure‐driven approach in the designing of selective nNOS inhibitors, which relies on the specific structural features required to achieve isoform‐selectivity towards nNOS. The incorporation of chiral pyrrolidine ring, two aminopyridine heads, or a specific amino tail group, along with the inhibitor's capacity to adopt the curled conformation in the nNOS environment significantly strengthens the molecular interaction between the inhibitor and nNOS residues by forming specific electrostatic interactions and non‐bonded contacts that are vital for isoform selectivity. Additional structure‐activity relationship investigations are necessary to elucidate more structural characteristics that will ultimately resolve the exact structural basis required for isoform‐selective inhibition of nNOS.
SAICR‐CTO: Single Access Impella‐Guided Complete Revascularization in Chronic Total Occlusion—A Novel Approach to High‐Risk PCI
Authors: Sharma Vaibhav , Arokiadoss Abishek , Bhardwaj Anjali , Shamim Shariq
Published: October 2024

The Impella is a ventricular assist device (VAD) that provides circulatory assistance to patients with impaired heart function during percutaneous coronary intervention (PCI). It ejects blood from the left ventricle directly into the aorta. Although most cases of Impella‐assisted PCI are done using two access ports, the single access technique was described by Jason Wollmuth et al. An inherent drawback of multiple access is the heightened susceptibility to vascular complications like thrombosis, hematoma, pseudoaneurysm, and retroperitoneal bleeding. Single access for high‐risk PCI (SHiP) reduces complications from PCI access and is useful in patients with limited arterial access. This study presents a case of extension of SHiP technique used in a case of complex high‐risk intervention and CTO with dual access using an Impella single‐access sheath.
Emergent Behavior of a Photoswitchable Solute in a Biphasic Solvent System
Authors: Cvrtila Ivica , Otto Sijbren
Published: October 2024

Due to thermal E/Z isomerization, hydrazones in solution typically exist in thermodynamic equilibria between their isomers. Irradiation of such solutions leads to photostationary states that may differ from the equilibrium distribution. Operating such switchable hydrazones in a biphasic system of two immiscible solvents introduces three new degrees of freedom: the E/Z equilibrium in the second solvent and two equilibria for distribution of each of the isomers between the solvents. Irradiation of such a system can be performed in three different ways – the first solvent only, the second solvent only, and both solvents at once – all yielding distinct outcomes. Depending on the choice of materials and the mode of irradiation, such setup may lead to different emergent behaviors that are not immediately intuitive, including net cyclic transport or the accumulation of one photoswitched product in one of the phases, beyond what is reachable by irradiating a simple solution of the same photoswitch.
Application of Advanced Microscopy Techniques to the Characterization of Mixed Matrix Membranes
Authors: Poloneeva Daria , Gascon Jorge
Published: October 2024

Mixed matrix membranes (MMMs) have emerged as promising materials for various separation processes due to their tunable properties, enhanced separation performance and reproducibility. In this review paper, we provide a comprehensive overview of the methodologies, challenges, and applications associated with the characterization of MMMs using two advanced imaging techniques: Focused Ion Beam Scanning Electron Microscopy (FIB‐SEM) and Transmission Electron Microscopy (TEM). We begin by outlining the principles and capabilities of FIB‐SEM and TEM, emphasizing their suitability for studying the microstructure, morphology, and composition of MMMs at nanoscale resolution. Subsequently, we discuss the specific challenges and limitations encountered in the characterization of MMMs using these techniques, including sample preparation, image acquisition, and data interpretation. Furthermore, we review the diverse applications of FIB‐SEM and TEM in elucidating the structure‐property relationships of MMMs. Through illustrative examples, we highlight the valuable insights gained from these imaging techniques in optimizing MMMs for various separation applications. Finally, we propose future directions and emerging trends in MMM characterization, including the integration of lasers into FIB‐SEM and in situ characterization techniques, to address current challenges and push the boundaries of MMM design and performance. Overall, this review provides a comprehensive overview of the state‐of‐the‐art methodologies for characterizing MMMs using FIB‐SEM and TEM, identifies key challenges, and offers insights into future research directions aimed at harnessing the full potential of MMMs for sustainable separation technologies.
PnictogenIII Dications Supported by BZIMPY Ligands
Authors: Land Michael A. , Howlett William P. , Swidan Ala'aeddeen , Varga Ksenia , Robertson Katherine N. , Macdonald Charles L. B.
Published: October 2024

Two homologous series of pnictogen(III) dications, stabilized by 2,6‐bis(benzimidazole‐2‐yl)pyridine ligands have been prepared. Both series contain PnIII‐X moieties (Pn = P, As, Sb, Bi; X = Cl or Ph) and have been fully characterized using spectroscopic methods including X‐ray crystallography. The Lewis acidity of these compounds has also been probed by computational methods; the results suggest that the dictations are strong Lewis acids, with the PnCl2+ compounds being more acidic than the PnPh2+ compounds, and with Lewis acidity increasing from P to Bi, in both series. The PhP2+‐containing compound was also found to be a versatile PIII transfer reagent, leading to new synthetic routes for various PhP‐containing compounds. The redox chemistry of all compounds has also been probed using cyclic voltammetry and chemical reductions. In some cases the resulting PnI moieties could be trapped using diazabutadienes.
Modelling and optimization of amoxicillin degradation over ZnO and glucose oxidase modified TiO2 nanowire
Authors: Sohrabi Somayeh , Keshavarz Moraveji Mostafa
Published: October 2024

Recently, antibiotics posing threats to health and the environment have been highlighted. According to previous reports, amoxicillin is the most hazardous antibiotic in Tehran. In order to overcome the risks associated with the storage and contamination of oxidizing agents, a Janus structure of Ti/TiO2/FA/GOx/ZnO is introduced for in situ steady generation and consumption of H2O2. The most efficient nanowire structure of TiO2 is achieved at 140°C and 4.5 h. The footprints of GOx as the bioactive site to produce H2O2 and ZnO as the photoactive site to dope TiO2 have been proved by Raman, Fourier transform infrared (FTIR), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) analyses. For the first time, a Minimum Run Resolution V screening has been implemented for seven factors in an amoxicillin degradation process by the so‐called bio‐photo‐catalyst. According to analysis of variance (ANOVA), the significance of the three most important variables is as follows: amoxicillin concentration (C) > the area covered by TiO2 nanowires (E) > ZnO/GOx (F) ratio. The significance of the model over the 95% confidence interval is confirmed by R2 of 0.9970, F‐value of 108.10.
Association Between Family Income, Subclinical Myocardial Injury, and Cardiovascular Mortality in the General Population
Authors: Chebrolu Sneha , Kazibwe Richard , Soliman Elsayed Z.
Published: October 2024

Introduction

Both low family income and subclinical myocardial injury (SCMI) are risk factors for cardiovascular disease (CVD) mortality. However, the impact of their joint association on CVD mortality is unclear.

Methods

This analysis from the third National Health and Nutrition Examination Survey included 6805 participants (age 59.1 ± 13.4 years, 52.3% women, and 49.8% White) free of CVD at baseline. Family income was assessed using the poverty‐income ratio (PIR) and categorized into low (PIR < 1), middle (PIR = 1–4), and high (PIR > 4) income. A validated ECG‐based cardiac infarction injury score (CIIS) ≥ 10 was considered positive for SCMI. CVD mortality was determined using the National Death Index. Cox‐proportional hazard analysis was used to evaluate the associations of family income and SCMI, separately and jointly, with CVD mortality.

Results

A total of 1782 (26.2%) participants had SCMI at baseline. During a median follow‐up of 18.2 years, 856 (12.6%) events of CVD mortality occurred. In separate multivariable Cox models, SCMI (vs. no SCMI) and middle‐ and low‐income (vs. high‐income) were each associated with a higher risk of CVD mortality (HR [95% CI]: 1.34 [1.16–1.54], 1.44 [1.16–1.78], and 1.59 [1.22–2.07], respectively). Compared to high‐income participants without SCMI, those with low‐income and SCMI had an increased risk of CVD mortality (HR [95% CI]: 2.17 [1.53–3.08]). The multiplicative interaction between PIR and SCMI was not significant (p = 0.054).

Conclusion

Lower family income and SCMI are associated with CVD mortality, and their concomitant presence is associated with the highest risk. Family income and SCMI may help in the individualized assessment of CVD risk.
WSC: A Crowd‐Powered Framework for Mapping Decomposable Complex‐Task With Worker‐Set
Authors: Kumar Suneel , Pandey Sarvesh
Published: October 2024

The crowdsourcing platform serves as an intermediary managing the interaction between a requester who posts a decomposable task and a pool of workers who bid to solve it. Each worker intending to take up the task (partially or fully) decomposes it into multiple independent subtasks and submits it to the platform. Selection of a diverse set of workers (based on the bids received) to solve the decomposable task is challenging as it requires balancing factors like cost and quality while encouraging collaboration. We propose a Worker Set Computation (WSC) methodology to address these challenges by selecting a custom set of potential workers who can collaboratively complete the task with the optimal cost, in an efficient way. The aging technique is employed to dynamically update the weight of each worker, giving more weightage to the feedback received in the recent past. This, in turn, not only favors those workers who were rated well in the immediate past but also ensures that one odd feedback does not influence the overall rating heavily. We compare the performance of the proposed method against the state‐of‐the‐art methods, considering the computational (and budget) requirements, as well as the aging‐based worker rating.
Effect of Dapagliflozin on Measured vs. Panel‐Estimated Glomerular Filtration Rate
Authors: Iversen Esben , Nielsen Line Juel , Curovic Viktor Rotbain , Walls Anne Byriel , Eickhoff Mie Klessen , Frimodt‐Møller Marie , Persson Frederik , Rossing Peter , Houlind Morten Baltzer
Published: October 2024

Sodium–glucose cotransporter 2 (SGLT2) inhibitors can cause a reversible decline in glomerular filtration rate (GFR), which may influence dosing recommendations for renally excreted medications. In practice, GFR is typically estimated by serum creatinine concentration, but creatinine may not be a reliable indicator of GFR decline in the setting of SGLT2 inhibitor use. Alternative filtration markers such as cystatin C, β‐trace protein (BTP), and β2‐microglobulin (B2M) may be more appropriate, but little is known about how these markers are affected by SGLT2 inhibitor use. Therefore, we determined creatinine, cystatin C, BTP, and B2M concentration in a crossover study of 35 people with type 2 diabetes receiving 12 weeks of dapagliflozin treatment or placebo. Estimated GFR (eGFR) based on creatinine (eGFRcre), cystatin C (eGFRcys), their combination (eGFRcomb), or a panel of all four markers (eGFRpanel) was compared with measured GFR (mGFR) based on plasma clearance of chromium‐51 labeled ethylenediamine tetraacetic acid (51Cr‐EDTA). Dapagliflozin treatment was associated with a significant decrease in mGFR (−9 mL/min/1.73 m2, P < 0.001) but not a corresponding increase in concentration of any filtration marker. No eGFR equation accurately predicted change in mGFR between treatment periods, but eGFRcomb and eGFRpanel yielded the highest overall accuracy relative to mGFR across both treatment periods. These findings highlight the stability in performance gained by combining multiple filtration markers but suggest that eGFR in general is not an ideal metric for assessing short‐term GFR decline in people initiating SGLT2 inhibitor therapy.
Post‐Synthetic Modification of a MOF via Continuous Flow Methods for Gold E‐Waste Recycling
Authors: Roth Jocelyn , Trukhina Olga , Allouss Dalia , Stoian Dragos , Schertenleib Till , Felder Timo , Queen Wendy L.
Published: October 2024

This work represents a pioneering effort in utilizing continuous flow methods for the post‐synthetic modification of a nanoporous metal‐organic framework (Fe‐BTC or MIL‐100(Fe)) with short‐chain redox‐active oligomers (poly‐p‐phenylenediamine, PpPDA). The Fe‐BTC/PpPDA composite has been previously demonstrated to rapidly and selectively extract gold from complex liquids. Thus, in the present study, Fe‐BTC/PpPDA was synthesized on a 250 g scale and tested in eight industrially relevant solutions used for leaching metals from electronic waste. These leachates (e. g., cyanide, thiourea, and aqua regia) exhibited varying effectiveness, pH, and gold speciation, which led to significant differences in the composite′s performance during gold extraction. Notably, Fe‐BTC/PpPDA performed best in leaching solutions containing [AuCl4]− species. Subsequently, Fe‐BTC/PpPDA was structured into spherical beads using a novel microdroplet technique in continuous flow. These structured adsorbents were then placed in a column and assessed for gold recovery from real e‐waste solutions containing [AuCl4]− species. The composite reached a capacity of ~600 mg of gold per gram before breakthrough and a capacity of ~900 mg of gold per gram at a gold recovery rate of ~60 %. The selectivity of the composite was calculated to be 972, 262, and 193 for Au/Ni, Au/Co, and Au/Fe, respectively. Also, in situ X‐ray absorption near edge spectroscopy (XANES) was employed to monitor the gold oxidation state, providing the first evidence of gold reduction occurring on a timescale relevant to flow‐through experiments. It was confirmed that the redox‐active oligomers facilitate the reduction of Au3+ to metallic Au during extraction, enhancing the composite′s capacity and selectivity. Additionally, Fe‐BTC/PpPDA outperformed several commercial resins commonly used in gold recovery. Considering the scalability of the composite and its outstanding performance in realistic solutions, this work suggests a promising future for MOF/polymer composites in selective metal recovery from waste streams. Furthermore, the continuous flow methods used for post‐synthetic modification of the MOF may pave the way for more scalable production in the future.
Modulation of fatty acid profiles and turnover dynamics in jellyfish polyps through copepod diets: Insights into trophic interactions and nutrient flux
Authors: Chi Xupeng , Zhang Fang , Sun Song
Published: October 2024

Fatty acids (FAs) are vital biomolecules crucial for determining food quality for higher trophic levels. To investigate FA transfer and turnover time in predators, we conducted a diet switch experiment using jellyfish polyps. These polyps were fed food sources including Artemia sinica nauplii and FA‐manipulated copepod Pseudodiaptomus annandalei, maintained on distinct algal diets with varied FA compositions. Our findings reveal that copepods may have a strong potential to synthesize long‐chain polyunsaturated FA to maintain biochemical homeostasis when consuming low‐quality food. Consequently, the species‐specific fatty acid composition within plankton, combined with effects of seasonal environmental fluctuations and climate change, leads to changes in the FA composition of foundational food web components. These alterations create a complex “nutrient black box” effect as they propagate up trophic levels. Our study shows that jellyfish polyps fail to accumulate EPA and DHA but display high levels of ARA compared to their zooplankton and phytoplankton food sources, suggesting a potential association with dietary EPA and DHA through an unidentified pathway. Certain FA components indicate variations in the turnover time when polyps undergo a dietary shift. Understanding the trajectory of FA metabolism across the “phytoplankton–zooplankton” interface, along with its turnover time, provides crucial insights for modeling diet estimation of components within food webs.
Drivers of Wolf Activity in a Human‐Dominated Landscape and Its Individual Variability Toward Anthropogenic Disturbance
Authors: Ferreiro‐Arias Iago , García Emilio José , Palacios Vicente , Sazatornil Víctor , Rodríguez Alejandro , López‐Bao José Vicente , Llaneza Luis
Published: October 2024

Wolves (Canis lupus) exhibit contrasted activity patterns along their distribution range. The shift from diurnal to nocturnal habits within and among populations appears to be primarily driven by localized levels of human activity, with ambivalent responses toward such disturbance reported among populations. Yet, the drivers and the underlying individual variability of temporal avoidance patterns toward human remains unexplored. We equipped 26 wolves with GPS–GSM collars, obtaining 54,721 locations. We used step lengths, turning angles, and accelerometer data from recorded locations to infer activity through hidden Markov models (Conners, M. G., T. Michelot, E. I. Heywood, et al. 2021. “Hidden Markov Models Identify Major Movement Modes in Accelerometer and Magnetometer Data From Four Albatross Species.” Movement Ecology 9, no. 1: 1–16.). We further explored the probability of activity as a function of a set of proxies of anthropogenic disturbance at different spatial scales and its interaction with different periods of the day by fitting population‐level and individual‐based hidden Markov models. Wolves were predominantly active during dusk and night, yet variations in activity emerged among individuals across day periods. We did not find clear population‐level effects of anthropogenic disturbance predictors, as these were masked by a wide range of individual‐specific responses, which varied from positive to negative, with inter‐individual variability in responses changing according to different predictors and periods of the day. Our results suggest a non‐uniform strategy of wolves in adapting their behavior to human‐dominated environments, further underscoring the role of vegetation patches acting as functional refuge cover for buffering the effects of anthropogenic disturbance and boosting the persistence of the species in human‐dominated landscapes. This study, for the first time, reveals the individual variability in wolf responses to human disturbance. By fitting hidden Markov models to data from GPS–GSM collars deployed on 26 wolves, we found significant variation between individuals in their responses to different levels of anthropogenic pressure and across different times of day, highlighting a non‐uniform strategy for coping with perturbations in human‐dominated landscapes. Our findings underscore the diverse behavioral adjustments employed by wolves to persist in these environments and highlight the critical importance of vegetation patches serving as refuge cover.
Early Life History Divergence Mediates Elevational Adaptation in a Perennial Alpine Plant
Authors: Pålsson Aksel , Walther Ursina , Fior Simone , Widmer Alex
Published: October 2024

Spatially divergent natural selection can drive adaptation to contrasting environments and thus the evolution of ecotypes. In perennial plants, selection shapes life history traits by acting on subsequent life stages, each contributing to fitness. While evidence of adaptation in perennial plants is common, the expression of life history traits is rarely characterized, limiting our understanding of their role in adaptive evolution. We conducted a multi‐year reciprocal transplant experiment with seedlings from low and high elevation populations of the alpine carnation Dianthus carthusianorum to test for adaptation linked to contrasting climates and inferred specific contributions of early life stages to fitness. We assessed genotype by environment interactions in single fitness components, applied matrix population models to achieve an integrated estimate of fitness through population growth rates, and performed trade‐off analyses to investigate the advantage of alternate life history traits across environments. We found evidence of genotype by environment interactions consistent with elevational adaptation at multiple stages of the early life cycle. Estimates of population growth rates corroborated a strong advantage of the local genotype. Early reproduction and survival are alternate major contributors to adaptation at low and high elevation, respectively, and are linked by trade‐offs that underlie the evolution of divergent life history traits across environments. While these traits have a strong genetic basis, foreign populations express co‐gradient plasticity, reflecting the adaptive strategy of the local populations. Our study reveals that selection associated to climate has driven the evolution of divergent life histories and the formation of elevational ecotypes. While the high energy environment and strong competition favor investment in early reproduction at low elevation, limiting resources favor a more conservative strategy relying on self‐maintenance at high elevation. The co‐gradient plasticity expressed by high‐elevation populations may facilitate their persistence under warming climatic conditions.
Large, but Dispersal‐Limited Populations of the Marsh Fritillary Euphydryas aurinia Persist on Abandoned Military Training Areas Three Decades After the End of the Cold War
Authors: Schröer Cindy , Singer David , Kamp Johannes
Published: October 2024

Military training areas can host important biodiversity, due to the preservation of diverse, nutrient‐poor historical cultural landscapes and an insect‐friendly disturbance regime. In Europe, many training areas were abandoned after the end of the cold war in 1991 and the withdrawal of the Allied and Soviet forces. Many of these are now protected areas, and current management strategies vary from rewilding to active habitat management such as grazing or mowing. In a capture–release–recapture approach, marking 2418 individuals, we assessed the population size and movement patterns of the dry ecotype of the Marsh Fritillary Euphydryas aurinia Rottemburg 1775 on three former military training areas in Germany that varied in size and management (natural succession, mowing, and sheep‐/goat grazing). Euphydryas aurinia is a rare and declining butterfly species listed in Annex II of the European Union Habitats Directive. Jolly–Seber models revealed a large population of ca. 19,000 individuals on the largest study site and a smaller population at a second site, whereas recapture rates were too low to predict the population size reliably at a third site. Population densities were 190–194 butterflies ha−1 at the unmanaged, large site and 56–71 butterflies ha−1 at a smaller site grazed with sheep. Thirty‐nine percent of the recapture events occurred within the same 1‐ha‐study plot. The average minimum flight distance between the study plots was 313 m for males and 328 m for females. The maximum lifetime flight distance was 1237 m within 3 days. No dispersal was detected between study sites. Thirty years after cessation of the military use, the large former training site still held what likely is one of the largest populations of the species dry ecotype in Central Europe, including in areas where management ceased already in 1991. This suggests remarkable persistence of the species in areas without regular management, contrary to current opinion. However, regular flight distances seem not to be sufficient to connect the isolated habitat patches. It remains unknown how long the large population at the abandoned military area will persist without active habitat management. Careful, but active habitat management and restoration of habitat connectivity should thus be considered.
Copper‐Catalyzed Chemoselective Synthesis of Pyrazolo‐Sulfonamide: Impact of Solvent on Nitro‐Pyrazole Reactivity
Authors: Saha Rana , Dutta Swarnendu , Das Arka , Jana Rajarshi , Sonar Krutika , Gupta Sreya , Bhowmik Subhendu
Published: October 2024

This study presents a copper‐catalyzed, solvent‐dependent method for the rapid and efficient synthesis of N‐pyrazolo‐sulfonamides directly from nitro‐pyrazole and sulfonyl hydrazide under microwave conditions. The reaction exhibits notable solvent effects in pyrazole's reactivity. The ionic liquid DBU‐AcOH triggered the reactivity of 4‐nitro‐pyrazole, whereas the reaction in PEG proceeded selectively at the 3‐ & 5‐positions of pyrazole. Key applications of this method include the gram‐scale synthesis of pyrazolo‐sulfonamide, sulfaphenazole analogue and sulfonamide nucleoside.