bluuebunny/crossref_metadata_2025_split huggingface dataset:
Highly Strained, Fully π‐Conjugated Porphyrin Cyclophanes: Template‐free Synthesis and Global Aromaticity
Authors: Ren Longbin , Han Yi , Jiao Liuying , Zou Ya , Wu Jishan 
Published: October 2024

AbstractPorphyrin‐based nanohoops, nanorings, and cages with fully π‐conjugated structures are highly sought after, but their synthesis remains challenging. Herein, we report the template‐free synthesis of a highly strained, bithiophene‐bridged porphyrin cyclophane (1) from a porphyrin quinone via a stereoselective nucleophilic addition followed by intermolecular Yamamoto coupling strategy. X‐ray crystallographic analyses of 1 and its dication 12+ reveal significantly distorted cyclophane‐like geometries, with calculated strain energies of 51.2 and 80.7 kcal/mol, respectively. While the neutral compound 1 exhibits localized aromaticity, the dication 12+ is globally aromatic, with the porphyrin unit displaying weak antiaromaticity. Additionally, the dication 12+ undergoes nucleophilic addition with chloride, relieving strain. This work presents a novel synthetic strategy for highly strained, fully π‐conjugated systems with intriguing electronic properties and chemical reactivity.
Functional Nucleic Acids as Bacterial Biosensors: A Focus on Clostridioides difficile Infection
Authors: Chow Kristie , Li Yingfu 
Published: October 2024

AbstractClostridioides difficile (CD) is a Gram‐positive, anaerobic, and spore‐forming bacillus that colonizes the human gut and causes a range of diseases, such as pseudomembranous colitis and antibiotic‐associated diarrhea, that are generally known as CD infection (CDI). Rapid and accurate detection of CDI with high sensitivity and specificity is crucial for patient treatment, infection control, and epidemiological monitoring. Current diagnostic methods for CDI have several limitations, such as high cost, long turnaround time, suboptimal sensitivity, and the need for specialized equipment. Hence, novel detection methods that can overcome these limitations are needed. Functional nucleic acids (FNAs) are a promising class of molecular recognition element (MRE) that can be incorporated into biosensors for detecting infectious pathogens. Several FNAs have been developed for detecting CD. In this review, an overview of CD, CDI, and current diagnostic methods for CDI and their drawbacks are provided. Furthermore, the design principles and working mechanisms of FNAs as well as their applications for the detection of pathogenic bacteria, including CD, are discussed. The potential for developing point‐of‐care paper sensors using currently available CD‐selective FNAs is also highlighted.
Electrocatalytic Applications in Hydrogen Evolution of Two Nitrogen Heterocyclic Cu(I) Coordination Polymer Modified Electrodes
Authors: Wu Huilu , Ma Yuanyue , Teng Junjie , Cai Quanlong , Gao Rongrong , Xie Yueyue 
Published: October 2024

ABSTRACTThe development of low‐cost, high‐efficiency, stable, and structurally adjustable electrocatalysts for hydrogen evolution reaction (HER) is of great significance for energy conversion. In this study, two new Cu(I) coordination polymers (CPs), formulated as {[Cu(L1)](PF6)·CH2Cl2}n (1) and {[Cu2(L2)1.5(PPh3)](PF6)2}n (2) (L1 = 1,3‐bis[1‐(pyridin‐3‐ylmethyl) ‐1H‐benzimidazol‐2‐yl]propane, L2 = 1,4‐bis[1‐(3‐pyridylmethyl)‐1H‐benzimidazol‐2‐yl]butane), were synthesized by interfacial diffusion method and characterized by single‐crystal x‐ray diffraction and IR and UV–Vis spectra. Structural analysis shows that the CP‐1 is a one‐dimensional chain structure, whereas the CP‐2 is a two‐dimensional layered structure, which is due to the different coordination modes of ligands L1 (bridging chelation) and L2 (bridging). The electrocatalytic activity for HER of Cu(I) CPs was studied by preparing modified glassy carbon electrodes (CP‐1/GCE and CP‐2/GCE). Electrochemical HER studies manifest that in 0.5 M H2SO4, the overpotential (η10298K) and Tafel slope (b 298K) are −769 mV and 173 mV dec−1 for CP‐1/GCE, −933 mV and 301 mV dec−1 for CP‐2/GCE, and −930 mV and 298 mV dec−1 for bare/GCE, respectively. The η10298K and b298K of CP‐1/GCE were significantly positive shifted and decreased compared with the bare/GCE, indicating that CP‐1/GCE has significant electrocatalytic activity and electrocatalytic HER activity order is CP‐1/GCE > CP‐2/GCE ≈ bare/GCE. This work provides an important reference for the application of non‐noble metal CPs in the field of electrocatalysis.
The Effects of a Minimal Length on the Kerr Metric and the Hawking Temperature
Authors: Hess Peter O. , Maghlaoui Leila 
Published: October 2024

ABSTRACTWe first resume the main properties of the pseudo‐complex General Relativity (pcGR). We show that the pcGR includes a generalized Mach's principle, namely that mass not only curved space–time but also changes vacuum properties. Then the Hawking temperature is determined within pcGR for a black hole, with varying the intensity of the dark energy around the central mass. In particular we investigate the effects of a minimal length, which is a consequence of pcGR. Three cases are studied: (i) The pc‐Schwarzschild case with zero minimal length; (ii) The pc‐Kerr case with zero minimal length; and finaly (iii) the pc‐Kerr‐case with a minimal length. We show that Hawking radiation can also be emitted in a curved space (the gravitational Schwinger effect), not necessarily at the surface of a star. When an event horizon is present, the theory predicts the occurrence of negative temperature, which generate negative pressure, stabilizing the star in this manner. We also show that the effects of a minimal length are only noticeable for very small black hole masses, showing that their formation is inhibited.
Spontaneous spinal epidural hematoma with hemiparesis: A stroke mimic
Authors: Suzuki Mio , Kano Yasuhiro , Watanuki Satoshi , Murata Kengo 
Published: October 2024

Key Clinical MessageSpontaneous spinal epidural hematoma (SSEH) is a rare cause of neck pain and hemiparesis. Clinicians should keep SSEH in mind as a rare stroke mimic presenting with hemiparesis to avoid needless and potentially hazardous thrombolytic therapy. Taking a careful history is useful for making a correct diagnosis.
Determination of Chain Transfer Constants of Alcohols for High‐Pressure Polyethylene Polymerization
Authors: Euler Bueno Laura , Zentel Kristina Maria , Busch Markus 
Published: October 2024

AbstractIn low‐density polyethylene (LDPE) production, low‐molecular‐weight species are used as chain transfer agents (CTAs). They reduce the degree of polymerization, which has an impact on the polymer properties, such as processability. To specifically adjust the product properties, a detailed understanding of the transfer kinetics to CTAs is indispensable. Thus, the transfer activity of various primary, secondary, and tertiary alcohols as well as diols was investigated experimentally between 120 °C and 250 °C at 2000 bar. The results were evaluated using the Mayo and chain length distribution (CLD) method, and the latter was found to give more reliable results. It was observed that the hydroxy group systematically increases transfer activity compared to alkanes. Additionally, a linear increase of transfer activity with the number of hydrogen atoms is found.
Phosphazene Tripeptide Conjugates: Design, Synthesis, In Vitro Cytotoxicity and Genotoxicity, Molecular Interactions in Binding Pockets on Human Breast and Colon Cancer Cell Lines
Authors: Çalışkan Eray , Yüksel Furkan , Çapan İrfan , Tekin Suat , Bouzidi Reda , Qaoud Mohammed T. , Biryan Fatih , Koran Kenan , Sandal Süleyman , Orhan Görgülü Ahmet 
Published: October 2024

AbstractThe biological activity of both cyclophosphazenes and peptides makes these compounds important for new studies in medicinal chemistry. For this purpose, five different phosphazene‐peptide conjugates synthesized from dichlorocyclotriphosphazene and tyrosine‐containing tripeptides. The synthesized compounds were evaluated for their in vitro cytotoxic activities against human breast (MCF‐7) and colon (Caco‐2) cancer cell lines using MTT assay. The derivatives induced cell death through DNA damage, with notable effects in Caco‐2 cell lines. Specifically, DTVV, DTVG, and DTVA were cytotoxic at 50 and 100 μM, while DTVP and DTVM were effective at 25, 50, and 100 μM. DTVM outperformed Tamoxifen at 50 μM in the MCF‐7 cell line. DNA damage studies of the compounds were performed using the comet assay method, evaluating tail length, tail density, olive tail moment, head length, and head density parameters. The findings indicated that cell death occurred via a DNA damage mechanism. The molecular intricacies of DTVA, DTVG, DTVM, DTVP and DTVV within the VEGFR2 kinase domain (3VHE) and Cyclophilin_CeCYP16‐Like Domain (2HQ6) binding pockets and various interactions, docking scores and potential activities of these derivatives were investigated. The differences in docking scores and interaction profiles highlight the potential efficacy and specificity of these compounds in targeting breast and colon cancer cells. These findings highlight the potential of phosphazene‐peptide derivatives as therapeutic agents in cancer treatment.
Effect of Electric Field on Carbon Encapsulation and Catalytic Activity of Pd for Efficient Formic Acid Decomposition
Authors: Guo Jiangnan , Hu Shuozhen , Zhang Xinsheng , Sun Shigang 
Published: October 2024

AbstractUtilizing carbon coated ferroelectric materials to introduce polarization‐induced electric field (PIEF) stimulates research of electric field‐assisted catalysts for various reactions. However, effect of PIEF on carbon coating mechanism has not been studied. Herein, tourmaline nanoparticles (TNPs) with spontaneous dipole moments were applied as the PIEF supplier and sucrose was utilized as the carbon precursor to synthesize carbon coated TNPs (TNP@SC) to uncover the influence of PIEF on the carbon coating and catalytic activity of Pd toward formic acid decomposition (FAD). PIEF enhanced the adsorption capacity of TNPs for the caramelized intermediate species and increased H+ concentration by facilitating water ionization. Polymerization of adsorbed caramelized intermediate species on TNPs was accelerated. Uniformly coated carbon layer with more defects, larger specific surface area, and higher porosity was coated on TNP. Such surface properties of the carbon layer were beneficial for strongly anchoring ultrafine Pd nanoparticles. Owing to the specific properties of carbon layer and existence of PIEF, Pd/TNP@SC exhibited higher FAD activity than the catalysts absent of PIEF. Stronger PIEF leaded to higher initial turnover frequency. This study provides guidance to supply electric field for catalysis.
Effects of Adding Tricalcium Silicate Nanoparticles to the Universal G2 Bond Adhesive as Self‐Etch Mode on the Shear Bond Strength to the Orthodontic Bracket
Authors: Al‐Labban Yasir R. , Alrubayee Mehdi , Zaidi Syed Jaffar Abbas , Kazmi Shakeel 
Published: October 2024

ABSTRACTObjectiveThis study investigated the effects of adding tricalcium silicate nanoparticles (TCSNp) to the universal G2 bond adhesive (G2BU) in self‐etch (SE) mode on shear bond strength (SBS) to orthodontic brackets, cytotoxicity, and degree of conversion (DC).Material and MethodsA total of 176 human teeth were divided into four groups based on TCSNp concentration in G2BU adhesive: 0% (control), 1%, 3%, and 5%. The G2BU adhesive consists of a hydrophilic primer (P) and a hydrophobic bonding agent (2B). TCSNp were added to the 2B component by mixing 0.1, 0.3, and 0.5 g of TCSNp with 9.9, 9.7, and 9.5 g of 2B, respectively. SBS was assessed after 24 h of water storage and 5000 thermocycles using a universal testing machine. Cytotoxicity was evaluated using the MTT assay on rat embryo fibroblast cells, and DC was measured using fourier‐transform infrared spectroscopy. Statistical analysis included one‐way ANOVA and Tukey's post‐hoc test, with significance set at p < 0.05.ResultsAfter 24 h, mean SBS values were 15.58 MPa (control), 13.66 MPa (1% TCSNp), 15.99 MPa (3% TCSNp), and 12.04 MPa (5% TCSNp). After 5000 thermocycles, SBS values decreased to 12.91 MPa (control), 12.42 MPa (1% TCSNp), 11.11 MPa (3% TCSNp), and 10.21 MPa (5% TCSNp). ANOVA showed significant differences between groups (p < 0.05), except between the control and 3% TCSNp groups. Cell viability increased with higher TCSNp concentrations, with significant differences at 72 h between control and 5% TCSNp groups (p = 0.014). Mean DC values were 51.66% (control), 49.33% (1% TCSNp), 49.66% (3% TCSNp), and 48% (5% TCSNp). ANOVA indicated no significant differences between groups.ConclusionsAdding TCSNp to G2BU in SE mode maintains clinically acceptable SBS levels and enhances cytocompatibility. Higher TCSNp concentrations may reduce SBS and DC slightly. Further studies are needed to evaluate long‐term effects.
Long‐term and landscape impacts of buffel grass on arid plant communities: Ecosystem shifts and acceleration by fire
Authors: Ryan‐Colton Ellen , French Kris , Wardle Glenda M. , Read John L. , Canty Peter D. , Lang Peter J. , Bickerton Doug C. , Schlesinger Christine A. 
Published: October 2024

AbstractPlant invasions drive biodiversity loss, transform ecosystems, and promote positive‐feedback cycles between invasion and fire. However, the long‐term impacts of invasive grasses across landscapes with diverse plant communities and interactions with fire are poorly known. Our objectives were to examine whether buffel grass (Cenchrus ciliaris), a globally significant plant invader, altered the abundance of understory and overstory plants, homogenized plant composition, and shifted ecosystems from woodlands to grassland and to explore interrelationships between invasion and fire. We combined two methodological approaches to assess invasion spread and impacts of buffel grass in the Aṉangu Pitjantjatjara Yankunytjatjara (APY) Lands of arid central Australia: a before‐after‐control‐impact (BACI) experiment over 25 years at 15 sites and a paired‐plot (randomized‐block) experiment at 18 sites. Both experiments spanned two geographic regions and multiple vegetation communities situated on flat plains and rocky hills. We used generalized linear mixed models to analyze predictions about plant abundance and permutational multivariate ANOVA (PERMANOVA) and permutational multivariate analysis of dispersion (PERMDISP) to examine changes in community composition. Fire and invasion interactions were explored using fire history or the relative fire tolerance of plant species as covariates, predictors, or responses. Fire interacted with the invasion process in multiple ways. Invaded sites had burnt more frequently and recently than native sites in one region, and where propagules were present in 1995, buffel grass abundance increased most when fires ensued. Abundance of understory plant functional groups (native grasses, ferns, and vines) decreased with invasion, and understory shrubs decreased due to frequent fires in invaded sites. Overstory composition shifted from fire‐sensitive species toward fire‐tolerant species, but this was not directly attributable to invasion. Partial evidence for ecosystem regime shifts included homogenization of understory communities in invaded rocky hills, and an increase in woody shrub cover at native but not invaded sites over 25 years, resulting in a 5% cover difference by 2019. Impacts were detected across heterogeneous ecological communities at a scale not previously tested amongst high background community variability. Although invasion is not dependent on fire, the acceleration of invasion spread and impacts with fire is a critical consideration for future research and management of grass invaders.
Soil climate underpins year effects driving divergent outcomes in semi‐arid cropland‐to‐grassland restoration
Authors: Mahood Adam L. , Barnard David M. , Macdonald Jacob A. , Green Timothy R. , Erskine Robert H. 
Published: October 2024

AbstractConverting croplands to grasslands can restore ecosystem functions and services, but there is uncertainty about why some restoration treatments succeed and others do not. One likely explanation for variation in restoration outcomes is that interannual variation in the drivers of community assembly, or “year effects,” is often overlooked in restoration planning. Existing restoration strategies tailor species compositions of seed mixes according to long‐term climate means and hardiness zones. However, individual years typically deviate from average climate norms such that restoration activities may be better informed by recent conditions than by climate averages. We monitored a 109‐ha field in northeastern Colorado that was converted from a winter wheat‐fallow rotation to native perennial grassland via seeding. The same seed mix was used to seed 6 of 12,120‐m strips in 2013 (drier) and 6 in 2014 (wetter). In the strips seeded in 2013, only one native grass and one shrub species from the seed mix established widely, whereas in 2014, all native grasses established. Higher soil moisture preceding seed application was positively associated with perennial grasses, while rhizomatous grasses, shrubs, and introduced annuals were associated with other variables. After seeding, high summer soil moisture was positively associated with a rhizomatous C3 grass, while the planted C4 bunchgrasses were negatively associated with high summer soil moisture and positively associated with high fall soil temperatures. We found evidence of facilitatory interactions between grasses and forbs, as well as antagonistic interactions between native perennial grasses and non‐native annuals. Our results suggest that the conditions immediately before and after planting govern community assembly and leave a lasting legacy and should be considered in planning treatments. We suggest composing seed mixes that are tailored to commonly encountered extremes of temperature and moisture availability. Land managers can also use split‐seeding or repeated seeding approaches, within or between years as bet‐hedging strategies. The development of more flexible funding mechanisms could allow for regional go/no‐go climate thresholds to avoid wasting resources.
CEO Age and Capital Structure Dynamics: The Moderating Effect of Overconfidence and Tenure
Authors: Ezeani Ernest , Bilal Bilal , Samuel Fulgence 
Published: October 2024

ABSTRACTThe Upper Echelons theory suggests that managerial characteristics will likely influence their financial decisions. Consistent with this theory, we examine CEO age's impact on Chinese firms' capital structure dynamics. We also investigate the moderating effects of overconfidence and tenure on the relationship between CEO age and capital structure. Using 18,235 firm‐year observations from Chinese listed firms, we document a positive relationship between CEO age and leverage. The results show that the CEOs' age‐overconfidence and age‐tenure relationship have an inverse relationship with leverage. Particularly, we find that CEO overconfidence and tenure impact market leverage more than book leverage. Our sensitivity analysis indicates that young CEOs use less debt, consistent with the market‐leaning hypothesis. We also find a positive relationship between CEO age and leverage in state‐owned enterprises. Our results are robust for decomposition analysis, selection bias test and endogeneity.
Exposure–Response Analysis of Tofacitinib in Active Psoriatic Arthritis: Results from Two Phase 3 Studies
Authors: Menon Sujatha , Shoji Satoshi , Tsuchiwata Shinichi , Fallon Lara , Kanik Keith 
Published: October 2024

AbstractTofacitinib is an oral Janus kinase inhibitor for the treatment of psoriatic arthritis (PsA). These post hoc exposure–response (E–R) analyses of pooled data from two Phase 3 studies (NCT01877668 and NCT01882439) characterized the relationships between tofacitinib exposure and efficacy (American College of Rheumatology [ACR] criteria), and changes in hemoglobin (Hgb) in patients with PsA. Efficacy data for the proportion of patients receiving tofacitinib 5 or 10 mg twice daily, or placebo, achieving ACR ≥20%, ≥50%, or ≥70% response criteria (ACR20, ACR50, and ACR70, respectively) at Month 3, were modeled jointly using a four‐category ordered categorical exposure–response model (ACR20 non‐responder, ACR20 responder but not ACR50 responder, ACR50 responder but not ACR70 responder, and ACR70 responder). A maximum drug effect (Emax) model (using average concentrations of tofacitinib at steady state [Cavg]) adequately described the exposure–ACR response rate relationship. Model‐predicted response rates for tofacitinib 5 and 10 mg twice daily were 51% and 58%, respectively, for ACR20; 29% and 36% for ACR50; and 15% and 20% for ACR70. The E–R relationship between tofacitinib exposure and changes in Hgb was assessed using an indirect response model, which generally predicted Hgb concentration–time profiles across treatments well. The proportions of patients experiencing a decrease in Hgb of >2 g/dL were similar with tofacitinib 5 mg twice daily or placebo. These results were generally consistent with previous analyses in rheumatoid arthritis and psoriasis, and support the use of tofacitinib 5 mg twice daily for active PsA.
An Assay on the Antibactericidal Functionality of Synthesized Mg‐Doped ZnO Nanoparticles on the Dental Microbes
Authors: Alhomaidi Eman A. , Saleh Ibrahim A. , Zomot Naser , Al‐Hawadi Jehad S. , Kha Mansour 
Published: October 2024

ABSTRACTWe succeeded in producing pure and magnesium‐doped zinc oxide nanoparticles (Mg‐Zn NPs) by making use of a Prosopis farcta leaf extract and subsequently distinguished the quality of our NPs with the use of field energy scanning electron microscopy (FESEM), energy‐dispersive X‐ray (EDX), powder X‐ray diffraction (PXRD), and UV–vis. In correlation to our observations, the particulates were spherically produced at a size of 20 nm with the ability to cause antimicrobial impacts on Streptococcus mutans bacteria and Candida albicans fungi. Inhibition zones of 18 ± 0.3 and 24 ± 0.3 mm were obtained for 5% Mg‐Zn NPs against bacteria and fungi, respectively. Based on these results, our work suggests a practicable proposition for our synthesized product to be considered as a worthy alternative for dental and oral utilizations.