bluuebunny/crossref_metadata_2025_split huggingface dataset:
1H NMR chemometrics and mechanistic insights on the thermal degradation of coconut oil
Authors: Flores Annabelle C. , Camacho Drexel H. 
Published: September 2024

AbstractThe re‐use and prolonged heating of cooking oils is a common practice in preparing deep‐fried foods. However, this could be unsafe and pose a health threat to consumers. This work investigates the thermal degradation of edible coconut oil under prolonged heating using chemometrics analysis of proton nuclear magnetic resonance (1H NMR) data. Coconut oil samples were heated continuously without food matrix at three different temperatures (150, 175, and 200°C) for 12 h and the 1H NMR spectra were collected every hour. NMR data revealed the formation of aldehyde oxidation products. Partial least squares discriminant analysis (PLS‐DA) discriminated the samples based on temperature and heating time. The Variable Importance Projection revealed the discriminating peaks highlighting the spectral feature due to hydroperoxides and aldehydes in the oil degradation. A probe into the 1H NMR of the degradation products of saturated coconut oil confirmed the formation of a ketone as evidenced by a CH2 triplet in the chemical shift region of protons alpha to a ketone. The results showed that the thermal degradation of coconut oil was influenced by temperature, time, moisture, and oxygen in the air which can contribute to the advancement in the control and assessment of coconut oil quality.
The influence of viscosity buildup on the foaming dynamics of rigid polyurethane foams
Authors: Cimavilla‐Román Paula , Álvarez‐Zapatero Pablo , Barroso‐Solares Suset , Vananroye Anja , Moldenaers Paula , Rodriguez‐Pérez Miguel Ángel 
Published: September 2024

AbstractThe viscoelastic properties development during the reactive foaming of four standard polyurethane formulations was monitored using a flooded parallel plate rheometer. The measurements in situ demonstrated how foams of low catalyst content took longer than 10 min to increase their viscosity from 1 to 103 Pa s, while foams with higher catalysts reached this modulus in less than 4 min. This polymerization speed deeply impacted the evolution of the cellular structure during foaming, which was demonstrated through in situ x‐ray imaging and computer simulation. Foams with high catalyst stabilized in their final cell size in 4–5 min, concurring with the stage of largest viscosity buildup. In contrast, the foams of low catalyst content underwent strong degeneration as a result of the slow gelification and stiffening of the matrix. Simulation results also revealed that stabilization of the cellular structure happens faster when the catalyst and blowing agent contents are increased.
Design, synthesis, evaluation, pharmacophore modeling, and 3D‐QSAR of lappaconitine analogs as potential analgesic agents
Authors: Wu Jingchuan , Lai Xiaohong , Zhang Yinyong , Li Yuzhu , Huang Shuai , Chen Lin , Zhou Xianli 
Published: September 2024

AbstractAlleviating pain is crucial for patients with various diseases. This study aimed to enhance the analgesic properties of lappaconitine, a natural drug, through structural modifications. Specifically, carbamate analgesic active fragments were innovatively introduced at multiple sites on the benzene ring of lappaconitine. A total of 53 lappaconitine analogs were synthesized and evaluated. Compounds 5a, 5c, 5e, 6, and 15j addressed the narrow therapeutic window of lappaconitine, enhancing drug safety. Notably, carbamate analogs exhibited significantly enhanced analgesic activity, with compounds 5a and 5c having ED50 values of 1.2 and 1.6 mg/kg, respectively, indicating higher potency than lappaconitine (3.5 mg/kg). A metabolic analysis of compound 5e was conducted in mice, revealing its primary metabolic processes and metabolites, and providing preliminary exploration for the druggability. Given the multiple analgesic targets of lappaconitine, its analgesic mechanism remains inconclusive. This study, for the first time, analyzed the pharmacological activity characteristics of the lappaconitine analogs using a pharmacophore model and established a three‐dimensional quantitative structure–activity relationship (3D‐QSAR) to elucidate the quantitative relationship between the structures of the synthesized compounds and their analgesic activities. These findings provide valuable guidance for future structural modification and optimization of analgesic drugs.
Synergistic effects of biological stimuli and flexion induce microcavities promote hypertrophy and inhibit chondrogenesis during in vitro culture of human mesenchymal stem cell aggregates
Authors: Zhang Bo , Berilla Jim , Cho Sungwoo , Somoza Rodrigo A. , Welter Jean F. , Alexander Peter E. , Baskaran Harihara 
Published: September 2024

AbstractInterzone/cavitation are key steps in early stage joint formation that have not been successfully developed in vitro. Further, current models of endochondral ossification, an important step in early bone formation, lack key morphology morphological structures such as microcavities found during development in vivo. This is possibly due to the lack of appropriate strategies for incorporating chemical and mechanical stimuli that are thought to be involved in joint development. We designed a bioreactor system and investigated the synergic effect of chemical stimuli (chondrogenesis‐inducing [CIM] and hypertrophy‐inducing medium [HIM]) and mechanical stimuli (flexion) on the growth of human mesenchymal stem cells (hMSCs) based linear aggregates under different conditions over 4 weeks of perfusion culture. Computational studies were used to evaluate tissue stress qualitatively. After harvesting, both Safranin‐O and hematoxylin & eosin (H&E) staining histology demonstrated microcavity structures and void structures in the region of higher stresses for tissue aggregates cultured only in HIM under flexion. In comparison to either HIM treatment or flexion only, increased glycosaminoglycan (GAG) content in the extracellular matrix (ECM) at this region indicates the morphological change resembles the early stage of joint cavitation; while decreased type II collagen (Col II), and increased type X collagen (Col X) and vascular endothelial growth factor (VEGF) with a clear boundary in the staining section indicates it resembles the early stage of ossification. Further, cell alignment analysis indicated that cells were mostly oriented toward the direction of flexion in high‐stress region only in HIM under flexion, resembling cell morphology in both joint cavitation and hypertrophic cartilage in growth plate. Collectively, our results suggest that flexion and HIM inhibit chondrogenesis and promote hypertrophy and development of microcavities that resemble the early stage of joint cavitation and endochondral ossification. We believe the tissue model described in this work can be used to develop in vitro models of joint tissue for applications such as pathophysiology and drug discovery.
CRISPR/Cas9‐based genome engineering in the filamentous fungus Rhizopus oryzae and its application to L‐lactic acid production
Authors: Zhu Haodong , Wang Han , Wang Li , Zheng Zhiming 
Published: September 2024

AbstractThe filamentous fungus Rhizopus oryzae is one of the main industrial strains for the production of a series of important chemicals such as ethanol, lactic acid, and fumaric acid. However, the lack of efficient gene editing tools suitable for R. oryzae makes it difficult to apply technical methods such as metabolic engineering regulation and synthetic biology modification. A CRISPR‐Cas9 system suitable for efficient genome editing in R. oryzae was developed. Firstly, four endogenous U6 promoters of R. oryzae were identified and screened with the highest transcriptional activity for application to sgRNA transcription. It was then determined that the U6 promoter mediated CRISPR/Cas9 system has the ability to efficiently edit the genome of R. oryzae through NHEJ and HDR‐mediated events. Furthermore, the newly constructed CRISPR‐Cas9 dual sgRNAs system can simultaneously disrupt or insert different fragments of the R. oryzae genome. Finally, this CRISPR‐Cas9 system was applied to the genome editing of R. oryzae by knocking out pyruvate carboxylase gene (PYC) and pyruvate decarboxylase gene (pdcA) and knocking in phosphofructokinase (pfkB) from Escherichia coli and L‐lactate dehydrogenase (L‐LDH) from Heyndrickxia coagulans, which resulted in a substantial increase in L‐LA production. In summary, this study showed that the CRISPR/Cas9‐based genome editing tool is efficient for manipulating genes in R. oryzae.
Redesigning glycolaldehyde synthase for the synthesis of biorefinery feedstock D‐xylulose from C1 compounds
Authors: Yan Yue , Zhao Haodong , Liu Dingyu , Zhang Jie , Liu Yuwan , Jiang Huifeng 
Published: September 2024

AbstractGlobal climate deterioration intensifies the demand for exploiting efficient CO2 utilization approaches. Converting CO2 to biorefinery feedstock affords an alternative strategy for third‐generation biorefineries. However, upcycling CO2 into complex chiral carbohydrates remains a major challenge. Previous attempts at sugar synthesis from CO2 either produce mixtures with poor stereoselectivity or require ATP as a cofactor. Here, by redesigning glycolaldehyde synthase, the authors constructed a synthetic pathway for biorefinery feedstock D‐xylulose from CO2 that does not require ATP as a cofactor. The artificial D‐xylulose pathway only requires a three‐step enzyme cascade reaction to achieve the stereoselective synthesis of D‐xylulose at a concentration of 1.2 g L−1. Our research opens up an alternative route toward future production of chemicals and fuels from CO2.
Physics‐informed neural networks for biopharmaceutical cultivation processes: Consideration of varying process parameter settings
Authors: Adebar Niklas , Arnold Sabine , Herrera Liliana M. , Emenike Victor N. , Wucherpfennig Thomas , Smiatek Jens 
Published: September 2024

AbstractWe present a new modeling approach for the study and prediction of important process outcomes of biotechnological cultivation processes under the influence of process parameter variations. Our model is based on physics‐informed neural networks (PINNs) in combination with kinetic growth equations. Using Taylor series, multivariate external process parameter variations for important variables such as temperature, seeding cell density and feeding rates can be integrated into the corresponding kinetic rates and the governing growth equations. In addition to previous approaches, PINNs also allow continuous and differentiable functions as predictions for the process outcomes. Accordingly, our results show that PINNs in combination with Taylor‐series expansions for kinetic growth equations provide a very high prediction accuracy for important process variables such as cell densities and concentrations as well as a detailed study of individual and combined parameter influences. Furthermore, the proposed approach can also be used to evaluate the outcomes of new parameter variations and combinations, which enables a saving of experiments in combination with a model‐driven optimization study of the design space.
Masking level differences under two different measurement conditions: A normative study of young adults
Authors: Cekic Sule , Mujdeci Banu , Karakoc Kursad , Bas Banu 
Published: September 2024

AbstractObjectiveThe objective of this study was to determine the gender‐specific normative values of masking level difference (MLD) in healthy young adults for two different measurement conditions.MethodsOne hundred young adults between the ages of 19 and 25 were included. Tympanometry, pure tone audiometry, and MLD were performed. In the first MLD measurement condition, the threshold level where the signal was out of phase and the noise was in phase (SπNo) was subtracted from the threshold level where the signal and noise were in phase (SoNo). In the second MLD measurement condition, the threshold level where the signal was in phase and the noise was out of phase (SoNπ) was subtracted from the threshold level where the signal and noise were in phase (SoNo). The mean test scores were obtained in decibels. Comparisons were made in terms of gender and conditions.ResultsThe mean MLD for SoNo‐SπNo condition was 10.3 ± 1.99 dB. For SoNo‐SoNπ condition, the mean MLD was 6.72 ± 2.38 dB. A significant difference was determined between the MLD under two different measurement conditions (p <.05). There was no significant difference in terms of gender (p >.05).ConclusionMean normative values of MLD test scores in gender‐specific healthy young adults for two different measurement conditions are presented.
Causal relationship between insomnia and thyroid disease: A bidirectional Mendelian randomization study
Authors: Li Zhonghui , Jia Zonghang , Zhou Peng , He Qingqing 
Published: September 2024

AbstractObjectiveSome correlations between thyroid disorders and insomnia have been found in previous studies; however, the causal relationship between them is unclear. The aim of this study was to investigate the causal relationship between insomnia and five thyroid disorders (hyperthyroidism, hypothyroidism, thyroiditis, thyroid nodules, and thyroid cancer).MethodsWe assessed the causal relationship between insomnia and thyroid disorders using inverse variance weighted, weighted median, and Mendelian randomization (MR)‐Egger analyses in MR analyses and then used inverse MR analyses to assess the causal relationship between thyroid disorders and insomnia.ResultsMR analysis showed that insomnia did not increase the risk of hyperthyroidism, hypothyroidism, thyroiditis, thyroid nodules, and thyroid cancer. However, reverse MR analysis showed that thyroid cancer increased the risk of insomnia (OR = 1.01, 95%CI: 1.00–1.02, p = .01), and the other four thyroid disorders had no direct causal relationship with insomnia. Sensitivity analyses indicated that the results were robust and no pleiotropy or heterogeneity was detected.ConclusionThis study did not find evidence of a bidirectional causal relationship between genetically predicted insomnia and hyperthyroidism, hypothyroidism, thyroiditis, and thyroid nodules. However, we found that although insomnia does not increase the risk of thyroid cancer, thyroid cancer does increase the risk of insomnia.
The Pantropical Genus Rhynchosia Lour. (Fabaceae: Cajaninae): Diversity of Medicinal Uses, Phytochemistry, Pharmacology, and Toxicology
Authors: Ayokun‐nun Ajao Abdulwakeel , Calphonia Shilaluke Kolwane , Sonnyboy Mothogoane Mashiane , Ntsamaeeng Moteetee Annah 
Published: September 2024

AbstractThe pantropical genus Rhynchosia belongs to the family Fabaceae and consists of approximately 230 species distributed mainly in Africa, America, and Asia. Several species of the genus have been used ethnomedicinally since 300–400 AD. This review presents for the first time a global overview of the extent of ethnomedicinal uses of species in the genus in addition to their phytochemistry, pharmacological activities, and toxicology. Online databases such as NCBI, PubMed, Science Direct, Scopus, SpringerLink, Taylor and Francis Online, etc., were used to source for publications on Rhynchosia species. Based on this review, 30 species (19 %) are traditionally used for treating an array of ailments around the globe, most especially in Africa and Asia. Flavonoids are the most detected/isolated phytochemicals from the Rhynchosia species. Pharmacological activities such as anticancer, antidiabetic, anti‐hyperlipidemic, antifungal, antioxidant, anti‐inflammatory, antinociceptive, butyrylcholinesterase, as well as eye‐protective and melanogenic effects were elicited by the extracts and isolated compounds from Rhynchosia species. Toxicity tests have only been carried out on R. sublobata and R. elegans extracts. Future studies should focus on the toxicological evaluation and validation of ethnomedicinal claims on the traditional uses of Rhynchosia species that have not been pharmacologically tested.
Examining the reciprocal associations between symptoms of depression and anxiety and contact with the criminal justice system
Authors: Silver Ian A. , Schwartz Joseph A. , Allen Samantha L. 
Published: September 2024

AbstractBackgroundTaken together, prior publications on the association between symptoms of depression and anxiety and contact with the criminal justice system (CJS) suggest a bi‐directional relationship, but all the studies only focus on one direction in this relationship.AimsTo examine, in longitudinally collected data, period‐specific within‐individual change in anxiety and depression measures preceding arrest measurement and, separately, following arrest measurement.MethodsData were obtained from the National Longitudinal Study of Youth 1997, a nationally representative sample of people born between 1980 and 1984 and first interviewed between ages 12–17 and a publicly accessible database. Our focus was on data for the 11 years 2000–2010. Using whole sample data, we tested for a reciprocal association between depression and anxiety during each 2‐year period and arrests during the following year, and vice versa, allowing for relatively fixed characteristics such as sex, age and socio‐economic indicators. We used period‐specific change modelling to test relationships.ResultsWe found that within‐individual increases in depression and anxiety scores over short periods (2‐year periods) of time was associated with an increase in the number of arrests subsequent over the following year, consistently throughout the whole of the 10 years studies. The reciprocal association was also observed, albeit the magnitude of the effects was much smaller.ConclusionThis study adds to the literature on the association between mental health and CJS contact by showing that they may be reciprocally associated. This suggests that facilitating co‐working or even formal partnerships between community mental health services and justice‐related services could be beneficial.
Methods for treating coronary eruptive calcified nodules
Authors: Ashikaga Takashi , Lee Tetsumin , Miyazaki Ryoichi , Nagase Masashi , Misawa Toru , Kaneko Masakazu , Nozato Toshihiro 
Published: September 2024

AbstractEruptive calcified nodules (CNs) are a manifestation of severely calcified plaques, which exist in acute coronary syndrome (ACS), non‐ACS lesions. Optical coherence tomography is crucial for diagnosing and treating eruptive CNs in clinical practice. Management of eruptive CNs is still a challenge for interventional cardiologists. There have been significant advances in the treatment of eruptive CNs such as intravascular lithotripsy, excimer laser coronary atherectomy, rotational atherectomy, and orbital atherectomy. We find a range of treatment modalities to be effective under different conditions. The selection of these devices should be considered based on guidewire position, lesion characteristics, clinical manifestations, and operator's experiences.
Copper Catalyzed Fluoroalkyl‐Selenization of Olefins
Authors: Yu Jian‐Liang , Zhang Qing‐Qing , Zhang Yi‐Fan , Zuo Ya‐Wen , Jin Ruo‐Xing , Wang Xi‐Sheng 
Published: September 2024

AbstractAn efficient copper catalyzed fluoroalkyl‐selenization reaction of olefins has been developed, providing 1,2‐difluoroarylselenides in moderate to excellent yields. The readily available ethyl bromodifluoroacetate and diphenyl diselenide (Ph2Se2) have been employed as efficient radical precursor and selenization reagents to react with olefins. The reaction features a broad substrate scope, including substituted alkenes with various functional groups.
Chlorodefluorination Induced by Gallium‐Based Lewis Acids
Authors: Tölke Katharina , Neumann Beate , Stammler Hans‐Georg , Hoge Berthold 
Published: September 2024

AbstractThe reaction of [Ga(C2F5)3(FSiMe3)] with chlorotrimethylsilane leads to the selective substitution of the α‐fluorine atoms by chlorine atoms and thus to the formation of [Ga(CCl2CF3)3(FSiMe3)]. The corresponding chlorogallate ion, [Ga(CCl2CF3)3Cl]−, could be isolated and structurally characterized as its tetraphenylphosphonium salt. The catalytic potential of [Ga(CCl2CF3)3(FSiMe3)] was demonstrated via the chlorodefluorination of Me3SiCF3, 2,2‐difluoropropane and [PPh4][Ga(C2F5)4].
Steric hindrance and orientation polarization by a zwitterionic additive to stabilize zinc metal anodes
Authors: Wang Lu , Yu Huaming , Chen Dongping , Jin Youliang , Jiang Liangliang , He Hanwei , Zhou Gang , Xie Zeqiang , Chen Yuejiao 
Published: September 2024

AbstractZinc metal stands out as a promising anode material due to its exceptional theoretical capacity, impressive energy density, and low redox potential. However, challenges such as zinc dendrite growth, anode corrosion, and side reactions in aqueous electrolytes significantly impede the practical application of zinc metal anodes. Herein, 3‐(1‐pyridinio)‐1‐propanesulfonate (PPS) is introduced as a zwitterionic additive to achieve long‐term and highly reversible Zn plating/stripping. Due to the orientation polarization with the force of electric field, PPS additive with π–π conjugated pyridinio cations and strong coordination ability of sulfonate anion tends to generate a dynamic adsorption layer and build a unique water–poor interface. PPS with steric hindrance effect and strong coordination ability can attract solvated Zn2+, thereby promoting the desolvation process. Moreover, by providing a large number of nucleation sites and inducing zinc ion flow, the preferred orientation of the (002) crystal plane can be achieved. Therefore, the interfacial electrochemical reduction kinetics is regulated and uniform zinc deposition is ensured. Owing to these advantages, the Zn//Zn symmetrical cell with PPS additive exhibits remarkable cycling stability exceeding 2340 h (1 mA cm−2 and 1 mA h cm−2). The Zn//V2O5 full cell also delivers stable cycling for up to 6000 cycles.
Morphologically and Compositionally Controlled Cs2SbBr6 by Bi and Ag Substitution
Authors: Frebel Alexander , Yoon Songhak , Neguse Samuel Meles , Jöckel Dennis Michael , Widenmeyer Marc , Ebbinghaus Stefan G. , Balke‐Grünewald Benjamin , Weidenkaff Anke 
Published: September 2024

AbstractMorphology‐controlled Cs2SbBr6 crystals are synthesized by Bi‐ and Ag‐substitution of the precursor solution. X‐ray diffraction (XRD) together with Raman spectroscopy confirms the lattice tilting and symmetry changes with the dominant appearance of higher index facets by Bi substitution. Ag substitution does not induce crystal symmetry changes in the Cs2BBr6 (B = Sb or Bi) phase, but results in highly defective structures hindering the formation of a smooth surface during the crystal growth. Successful substitution of Bi and limited substitution of Ag into Cs2SbBr6 is also confirmed by energy dispersive X‐ray spectroscopy (EDX). This research provides design principles and practical examples of how to control the morphology of Cs2SbBr6 crystals with structural defects and multiphase formation.