bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Influence of Ions on the Electrochemical Stability of Aqueous Electrolytes
Authors: Sui Yiming , Scida Alexis M. , Li Bo , Chen Cheng , Fu Yanke , Fang Yanzhao , Greaney P. Alex , Osborn Popp Thomas M. , Jiang De‐en , Fang Chong , Ji Xiulei 
Published: March 2024

AbstractThe electrochemical stability window of water is known to vary with the type and concentration of dissolved salts. However, the underlying influence of ions on the thermodynamic stability of aqueous solutions has not been fully understood. Here, we investigated the electrolytic behaviors of aqueous electrolytes as a function of different ions. Our findings indicate that ions with high ionic potentials, i.e., charge density, promote the formation of their respective hydration structures, enhancing electrolytic reactions via an inductive effect, particularly for small cations. Conversely, ions with lower ionic potentials increase the proportion of free water molecules—those not engaged in hydration shells or hydrogen‐bonding networks—leading to greater electrolytic stability. Furthermore, we observe that the chemical environment created by bulky ions with lower ionic potentials impedes electrolytic reactions by frustrating the solvation of protons and hydroxide ions, the products of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. We found that the solvation of protons plays a more substantial role than that of hydroxide, which explains a greater shift for OER than for HER, a puzzle that cannot be rationalized by the notion of varying O−H bond strengths of water. These insights will help the design of aqueous systems.
Experimental Evidence for Non‐Fermi‐Contact J Coupling Across Chalcogen Bonds in Ionic Salt Cocrystal Polymorphs
Authors: Nag Tamali , Terskikh Victor V. , Bryce David L. 
Published: March 2024

AbstractA pair of novel polymorphic ionic cocrystals of 3,4‐dicyanotelluradiazole and tetraphenylphosphonium bromide are synthesized and are characterized by single‐crystal XRD. Strong and directional non‐covalent chalcogen bonds (ChB) between Te and Br are analyzed via solid‐state NMR to reveal large and anisotropic J(125Te,79/81Br) coupling tensors, providing unequivocal evidence for non‐Fermi contact contributions across ChBs. Along with large 79/81Br quadrupolar couplings for the Br− anions, these data provide new tools to characterize chalcogen bonds and to differentiate between ChB polymorphs.
The Stability of Hydrogen‐Bonded Ion‐Pair Complex Unexpectedly Increases with Increasing Solvent Polarity
Authors: Manna Debashree , Lo Rabindranath , Vacek Jaroslav , Miriyala Vijay Madhav , Bouř Petr , Wu Tao , Osifová Zuzana , Nachtigallová Dana , Dračinský Martin , Hobza Pavel 
Published: March 2024

AbstractThe generally observed decrease of the electrostatic energy in the complex with increasing solvent polarity has led to the assumption that the stability of the complexes with ion‐pair hydrogen bonds decreases with increasing solvent polarity. Besides, the smaller solvent‐accessible surface area (SASA) of the complex in comparison with the isolated subsystems results in a smaller solvation energy of the latter, leading to a destabilization of the complex in the solvent compared to the gas phase. In our study, which combines Nuclear Magnetic Resonance, Infrared Spectroscopy experiments, quantum chemical calculations, and molecular dynamics (MD) simulations, we question the general validity of this statement. We demonstrate that the binding free energy of the ion‐pair hydrogen‐bonded complex between 2‐fluoropropionic acid and n‐butylamine (CH3CHFCOO−…NH3But+) increases with increased solvent polarity. This phenomenon is rationalized by a substantial charge transfer between the subsystems that constitute the ion‐pair hydrogen‐bonded complex. This unexpected finding introduces a new perspective to our understanding of solvation dynamics, emphasizing the interplay between solvent polarity and molecular stability within hydrogen‐bonded systems.
The Celiac‐Disease Superantigen Oligomerizes and Increases Permeability in an Enterocyte Cell Model
Authors: Herrera Maria G. , Amundarain Maria J. , Dörfler Philipp W. , Dodero Veronica I. 
Published: March 2024

AbstractCeliac disease (CeD) is an autoimmune disorder triggered by gluten proteins, affecting approximately 1 % of the global population. The 33‐mer deamidated gliadin peptide (DGP) is a metabolically modified wheat‐gluten superantigen for CeD. Here, we demonstrate that the 33‐mer DGP spontaneously assembles into oligomers with a diameter of approximately 24 nm. The 33‐mer DGP oligomers present two main secondary structural motifs–a major polyproline II helix and a minor β‐sheet structure. Importantly, in the presence of 33‐mer DGP oligomers, there is a statistically significant increase in the permeability in the gut epithelial cell model Caco‐2, accompanied by the redistribution of zonula occludens‐1, a master tight junction protein. These findings provide novel molecular and supramolecular insights into the impact of 33‐mer DGP in CeD and highlight the relevance of gliadin peptide oligomerization.
Highly Selective Acetylene‐to‐Ethylene Electroreduction Over Cd‐Decorated Cu Catalyst with Efficiently Inhibited Carbon‐Carbon Coupling
Authors: Wang Zeping , Li Chengyu , Peng Gongao , Shi Run , Shang Lu , Zhang Tierui 
Published: March 2024

AbstractElectrochemical acetylene reduction (EAR) employing Cu catalysts represents an environmentally friendly and cost‐effective method for ethylene production and purification. However, Cu‐based catalysts encounter product selectivity issues stemming from carbon‐carbon coupling and other side reactions. We explored the use of secondary metals to modify Cu‐based catalysts and identified Cd decoration as particular effective. Cd decoration demonstrated a high ethylene Faradaic efficiency (FE) of 98.38 % with well‐inhibited carbon‐carbon coupling reactions (0.06 % for butadiene FE at −0.5 V versus reversible hydrogen electrode) in a 5 vol % acetylene gas feed. Notably, ethylene selectivity of 99.99 % was achieved in the crude ethylene feed during prolonged stability tests. Theoretical calculations revealed that Cd metal accelerates the water dissociation on neighboring Cu surfaces allowing more H* to participate in the acetylene semi‐hydrogenation, while increasing the energy barrier for carbon‐carbon coupling, thereby contributing to a high ethylene semi‐hydrogenation efficiency and significant inhibition of carbon‐carbon coupling. This study provides a paradigm for a deeper understanding of secondary metals in regulating the product selectivity of EAR electrocatalysts.
Enantioselective Hydrofunctionalization of Cyclobutenones: Total Synthesis of gem‐Dimethylcyclobutane Natural Products
Authors: Wang Shaowei , Zhong Changxu , Huang Yingchao , Lu Ping 
Published: March 2024

AbstractCyclobutanes with a gem‐dimethyl group are common motifs in natural products. However, strategies for constructing enantioenriched gem‐dimethyl cyclobutanes are still underdeveloped. Herein, we report an enantioselective approach to synthesize a broad group of chiral 2,3‐disubstituted cyclobutanones through sequential 1,4‐conjugate addition/trapping/cross‐coupling of readily available cyclobutenones. The intermediate 2‐bromocyclobutanone provides a valuable synthetic handle for further coupling transformations. In addition, this strategy was successfully utilized to synthesize gem‐dimethyl cyclobutane‐containing natural products, including (+)‐β‐caryophyllene, (−)‐raikovenal, (−)‐1β,9αH‐5‐linoleoyloxy‐4,5‐secocaryophyllen‐4‐one, and (−)‐rumphellanones A−C.
Dimethyl Carbonate Synthesis from CO2 over CeO2 with Electron‐Enriched Lattice Oxygen Species
Authors: Hou Guoqiang , Wang Qi , Xu Di , Fan Haifeng , Liu Kaidi , Li Yangyang , Gu Xiang‐Kui , Ding Mingyue 
Published: March 2024

AbstractDirect synthesis of dimethyl carbonate (DMC) from CO2 plays an important role in carbon neutrality, but its efficiency is still far from the practical application, due to the limited understanding of the reaction mechanism and rational design of efficient catalyst. Herein, abundant electron‐enriched lattice oxygen species were introduced into CeO2 catalyst by constructing the point defects and crystal‐terminated phases in the crystal reconstruction process. Benefitting from the acid‐base properties modulated by the electron‐enriched lattice oxygen, the optimized CeO2 catalyst exhibited a much higher DMC yield of 22.2 mmol g‐1 than the reported metal‐oxide‐based catalysts at the similar conditions. Mechanistic investigations illustrated that the electron‐enriched lattice oxygen can provide abundant sites for CO2 adsorption and activation, and was advantageous of the formation of the weakly adsorbed active methoxy species. These were facilitating to the coupling of methoxy and CO2 for the key *CH3OCOO intermediate formation. More importantly, the weakened adsorption of *CH3OCOO on the electron‐enriched lattice oxygen can switch the rate‐determining‐step (RDS) of DMC synthesis from *CH3OCOO formation to *CH3OCOO dissociation, and lower the corresponding activation barriers, thus giving rise to a high performance. This work provides insights into the underlying reaction mechanism for DMC synthesis from CO2 and methanol and the design of highly efficient catalysts.
Toward the production of biopolyethylene‐based ecocomposites with improved performance: The potential of eggshell particles as an ecological additive
Authors: Bezerra Elieber Barros , Wellen Renate Maria Ramos , Barreto Luna Carlos Bruno , da Silva Barbosa Ferreira Eduardo , do Nascimento Emanuel Pereira , Araújo Edcleide Maria 
Published: March 2024

AbstractLow‐density biopolyethylene (BioLDPE) ecocomposites added with particles of eggshell (ES) residue were produced using linear low‐density polyethylene grafted with maleic anhydride (LDPE‐g‐MA) as a compatibilizing agent. BioLDPE/ES and BioLDPE/ES/LDPE‐g‐MA compounds were processed in a twin‐screw extruder, and the specimens were injection molded. Torque rheometry increased and melt flow index reduced more prominently for the BioLDPE/LDPE‐g‐MA biocomposite with 20 phr ES, suggesting higher viscosity. Consequently, there was a higher level of ES particles breakdown, generating greater distribution and dispersion, as verified in optical microscopy and scanning electron microscopy images. This finding was supported by Fourier transform infrared spectroscopy, considering the intense absorption band at 871 cm−1 for BioLDPE/ES (20 phr)/LDPE‐g‐MA biocomposite, indicating a higher level of ES particles dispersion in BioLDPE matrix. Therefore, BioLDPE/ES (20 phr)/LDPE‐g‐MA biocomposite increased the elastic modulus, tensile strength, Shore D hardness, and heat deflection temperature by 51.4%, 16.9%, 16.4%, and 14, 6%, respectively, related to BioLDPE. Additionally, the flexibility was kept as seen in the elongation at break and impact strength, including not fractured during the impact test. Reported results for the biocomposites are valuable mainly for the polymer additive sector, since the ES has the potential to improve BioLDPE properties, expanding the range of applications.
Myeloablation Followed by Hematopoietic Stem Cell Transplantation and Long‐Term Normalization of Systemic Sclerosis Molecular Signatures
Authors: Wareing Nancy , Wang Xuan , Keyes‐Elstein Lynette , Goldmuntz Ellen A. , Lyons Marka A. , McSweeney Peter , Furst Daniel E. , Nash Richard A. , Crofford Leslie J. , Welch Beverly , Pinckney Ashley , Mayes Maureen D. , Sullivan Keith M. , Assassi Shervin 
Published: March 2024

ObjectiveIn the randomized Scleroderma: Cyclophosphamide or Transplantation (SCOT) trial, myeloablation, followed by hematopoietic stem cell transplantation (HSCT), led to the normalization of systemic sclerosis (SSc) peripheral blood cell (PBC) gene expression signature at the 26‐month visit. Herein, we examined long‐term molecular changes ensuing 54 months after randomization for individuals receiving an HSCT or 12 months of intravenous cyclophosphamide (CYC).MethodsGlobal PBC transcript studies were performed in study participants at pretreatment baseline and at 38 months and 54 months after randomization, as well as in healthy controls using Illumina HT‐12 arrays.ResultsThirty (HSCT = 19 and CYC = 11) participants had 38‐month samples available, and 26 (HSCT = 16 and CYC = 11) had 54‐month samples available. In the paired comparison to baseline, a significant down‐regulation of interferon modules and an up‐regulation of cytotoxic/natural killer module were observed at the 38‐month and 54‐month visits in the HSCT arm, indicating a long‐term normalization of baseline SSc gene expression signature. No differentially expressed modules were detected in the CYC arm. In comparison to samples from healthy controls, 38‐month visit samples in the HSCT arm showed an up‐regulation of B cell and plasmablast modules and a down‐regulation of myeloid and inflammation modules. Importantly, 54‐month HSCT samples did not show any differentially expressed modules compared to healthy control samples, suggesting completion of immune reconstitution. Participants in the CYC arm continued to show an SSc transcript signature in comparison to controls at both time points.ConclusionParalleling the observed clinical benefit, HSCT leads to durable long‐term normalization of the molecular signature in SSc, with completion of immune resetting to 54 months after HSCT.image
Robust estimation of dependent competing risk model under interval monitoring and determining optimal inspection intervals
Authors: Baghel Shanya , Mondal Shuvashree 
Published: March 2024

AbstractRecently, a growing interest is evident in modelling dependent competing risks in lifetime prognosis problems. In this work, we propose to model the dependent competing risks by Marshal‐Olkin bivariate exponential distribution. The observable data consists of a number of failures due to different causes across different time intervals. The failure count data is common in instances like one‐shot devices where the state of the subjects is inspected at different inspection times rather than the exact failure times. The point estimation of the lifetime distribution in the presence of competing risk has been studied through a divergence‐based robust estimation method called minimum density power divergence estimation (MDPDE) with and without constraint. The optimal value of the tuning parameter has been obtained. The testing of the hypothesis is performed based on a Wald‐type test statistic. The influence function is derived for the point estimator and the test statistic, reflecting the degree of robustness. Another key contribution of this work is determining the optimal inspection times based on predefined objectives. This article presents the determination of multi‐criteria‐based optimal design. Population‐based heuristic algorithm nondominated sorting‐based multiobjective Genetic algorithm is exploited to solve this optimization problem.
Methods comparison of two‐dimensional gel electrophoresis for host cell protein characterization
Authors: King Abigail , Zhao Yiwei , Lazar Alexandru , Capron Margeaux , Thiruvur Niranjan , Liu Xinrong 
Published: March 2024

AbstractTwo‐dimensional electrophoresis (2DE) is a gel‐based protein separation method based on size and charge which is commonly used for the characterization of host cell proteins (HCPs) during drug development in biotech and pharmaceutical companies. HCPs are a heterogenous mixture of proteins produced by host cells during a biologics drug manufacturing process. Different gel electrophoresis methods including traditional 2D SDS‐PAGE with silver and SYPRO Ruby fluorescent dye staining as well as two‐dimensional difference gel electrophoresis (2D‐DIGE) were compared for their relative abilities to characterize HCPs. SYPRO Ruby was shown to be more sensitive than silver stain in the traditional 2D gels both with and without product protein present. Silver stain also displayed a significant preference for staining acidic proteins over basic ones while SYPRO Ruby was more consistent in imaging proteins across different isoelectric points. The non‐traditional method of 2D‐DIGE provides high resolution and reproducibility when comparing samples with similar protein profiles but was limited in imaging HCP spots due to its narrow dynamic range. Overall, 2DE is a powerful tool to separate and characterize HCPs and is optimized by choosing the best stain or method for each specific application. Using a combination of two or more different 2DE staining methods, when possible, provides the most comprehensive coverage to support the characterization of a complex mixture like HCPs. However, in instances where only one staining method can be used, SYPRO Ruby is shown to be the more reliable, more sensitive, and easier to use traditional staining method for most HCP‐based applications.
The impact of multidisciplinary approaches on the outcomes of olfactory neuroblastoma treated with postoperative radiotherapy
Authors: Tsutsumi Yuki , Omura Kazuhiro , Kijima Yoshikazu , Kobayashi Masao , Fukasawa Nei , Takeda Teppei , Ebihara Teru , Aoki Satoshi , Otori Nobuyoshi , Kojima Hiromi , Aoki Manabu 
Published: March 2024

AbstractBackgroundWe investigated the outcomes of postoperative radiation therapy for olfactory neuroblastoma (ONB) and our cross‐departmental collaboration to enhance the effectiveness of cancer treatment.MethodsWe retrospectively evaluated 22 patients with ONB who underwent postoperative radiotherapy after tumor resection. En bloc resection was performed; pathology specimens were prepared in coronal sections; and irradiation fields were determined after discussion with radiation oncologists, head and neck surgeons, and pathologists.ResultsThe overall survival and local control rates were 95.5% and 100%, respectively, at a median 37‐month follow‐up. The 3‐ and 5‐year disease‐free survival (DFS) rates were 64.4% and 56.3%, respectively. Of the 22 patients, 9 (8 Kadish C and 1 Kadish B) had disease recurrence. Of the nine patients, five had positive margins and two had closed margins; cervical lymph node recurrence occurred in six, and distant metastasis with or without cervical lymph node recurrence occurred in three. DFS analysis of risk factors showed no statistically significant differences, but positive margins were a significant recurrence factor in multivariate analysis.ConclusionsThe local control rate of ONB treated with postoperative radiation therapy was 100%. This may be attributed to cross‐departmental cooperation between head and neck surgeons, pathologists, and radiation oncologists, which resulted in accurate matching of CT images for treatment planning with the location of the tumor and positive margins. Longer follow‐up periods are required to evaluate the effectiveness of our strategy.
Parenting attitudes, career adaptability, and bicultural acceptance perceived by multicultural youth
Authors: Choi Seokkyu , Kim Woohyoung , Choi Jungsuk 
Published: March 2024

AbstractThis study explores whether the development of career adjustment and biculturalism among multicultural adolescents in Korean society changes over a three‐year longitudinal period. To this end, a latent growth model (LGM) was adopted to examine the development of career adjustment and biculturalism among such adolescents. This study determines how the parenting attitudes in multicultural families affect the career adjustment and bicultural acceptance of multicultural children in a society with high educational expectations. This study tracks how permissive and authoritarian parents' attitudes change over time in terms of their relationship with their multicultural children, the networks of education and social stability that they establish for multicultural youths, and how they improve parental awareness of their children. For this purpose, taking into account the characteristics of the variables identified in the panel data, parenting attitudes are divided into two types: uninvolved and authoritarian. This study used the data from 2014 to 2016 of the Multicultural Adolescents Panel Study included indicators for bicultural acceptance, career adaptability, and parental nurturing attitudes. The results are as follows: First, this study found that authoritarian parenting attitudes and bicultural acceptance attitudes have positive outcomes, and permissive parenting attitudes, bicultural acceptance attitudes, and career adaptability showed no relationship. Second, career adaptability and bicultural acceptance had a positive (+) effect on career adaptability based on parenting attitudes and a negative (−) one on bicultural acceptance. In addition, authoritarian parental attitudes had a negative (−) impact on career adaptability. Third, authoritarian parental attitudes demonstrated significance for bicultural acceptance, and the rate of change in bicultural acceptance was negative (−) over time.
Determination of Physicochemical Characteristics, Phytochemical Profile and Antioxidant Activity of Various Clover Honeys
Authors: Sultana Sharmin , Foster Kevin , Bates Tiffane , Hossain Md Lokman , Lim Lee Yong , Hammer Katherine , Locher Cornelia 
Published: March 2024

AbstractThis paper reports on some physicochemical and phytochemical characteristics (i. e. pH, electrical conductivity, colour, moisture content, total phenolic content, sugar profile) and in vitro antioxidant activity of honeys harvested from five legume species, red clover (Trifolium pratense), balansa clover (T. michelianum), Persian clover (T. resupinatum), purple clover (T. purpureum) and sanfoin, also known as holy clover (Onobrychis viciifolia), that were grown in enclosed shade houses to ensure that the honeys’ characteristics are reflective of a truly monofloral honey. Glucose and fructose, determined via High‐Performance Thin‐Layer Chromatography (HPTLC) analysis, were found as the main sugars in all investigated honeys with the ratio of fructose to glucose ranging from 1 : 1.2 to 1 : 1.6. The honeys’ pH values ranged from 3.9 to 4.6 which met Codes Alimentarius (CA) requirements. The moisture content was found to be between 17.6 and 22.2 % which in some cases was slightly higher than CA requirements (≤20 %). The honeys’ colour values, prior and after filtration, were between 825.5–1149.5 mAU and 532.4–824.8 mAU respectively, illustrating golden yellow to deep yellow hues. The total phenolic content (TPC) of the honeys was determined using a modified Folin‐Ciocalteu assay. Their antioxidant activity was captured by the Ferric Reducing‐Antioxidant Power (FRAP) assay as well as HPTLC analysis coupled with 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) derivatisation. The highest total phenolic content was found in red clover honey (45.4 mg GAE/100 g) whereas purple clover honey showed the highest level of activity in the FRAP assay (7.3 mmol Fe2+/kg). HPTLC‐DPPH analysis of the honeys’ organic extracts demonstrated the presence of various bioactive compounds that contribute to their overall antioxidant activity. This study developed a methodology for producing monofloral clover honeys in a space limited, enclosed production system, which allowed to collate important baseline data for these honeys that can serve as the foundation for their potential future development into commercial honeys, including honeys that can be used for medicinal purposes.