bluuebunny/crossref_metadata_2025_split huggingface dataset:
Amylose Dimerization in Solution Can Be Studied Using a Model System
Authors: Nybro Dansholm Charlotte , Meier Sebastian , Beeren Sophie R. 
Published: January 2024

AbstractAmylose, the linear polymer of α‐1,4‐linked glucopyranose units, is known to crystallize as a parallel double helix, but evidence of this duplex forming in solution has remained elusive for decades. We show how the dimerization of short amylose chains can be detected in solution using NMR spectroscopy when the glucans are labeled at the reducing‐end with an aromatic moiety that overcomes chemical shift degeneracy leading to distinct signals for the single‐stranded and duplex amylose. A set of α‐1,4 glucans with varying lengths of 6, 12, 18, and 22 glucose units and a 4‐aminobenzamide label were synthesized, enabling the first systematic thermodynamic study of the association of amylose in solution. The dimerization is enthalpically driven, entropically unfavorable and beyond a minimum length of 12, each additional pair of glucose residues stabilizes the duplex by 0.85 kJ mol−1. This fundamental knowledge provides a basis for a quantitative understanding of starch structure, gelation and enzymatic digestion, and lays the foundations for the strategic use of α‐1,4‐glucans in the development of self‐assembled materials.
Chemical, physical, and sensory properties of nixtamalized oat tortillas
Authors: Aráuz Andrea B. , Jefferies Laura K. , Taylor Bradley J. , Dunn Michael L. 
Published: January 2024

AbstractBackground and ObjectivesWhile alkaline nixtamalization has historically been used for corn, this process may have application in other cereals. Drawbacks to wider use include the lengthy steep time, as well as the volume of alkaline wastewater produced. This study evaluated a novel, waste‐effluent‐free nixtamalization process for oat (Avena sativa) masa, and compared properties of oat masa and tortillas prepared with 1%, 1.5%, and 2% lime, with and without steeping.FindingsA minimal‐water‐addition, 45‐min simmering process, without steeping, was effluent‐free, and produced oat tortillas comparable to those produced using a traditional overnight steep. The pH increased significantly with increasing lime content (r = .982). Consumer overall‐liking scores did not significantly differ across treatments, though appearance scores were significantly higher for 2% lime samples (p < .05), which were significantly darker and more yellow, based on L* and b* values. Masa adhesiveness means ranged from 1.49 to 1.52 N, with no significant differences between the no‐steep treatments. Higher lime addition (1.5%–2%) in the no‐steep process significantly improved tortilla flexibility, based on extensibility and rollability scores, though tortilla rupture force did not vary significantly across treatments. Tortilla rollability scores at 3‐days were lowest ( = 1.1 + 0.31, indicating less cracking) for the 1.5%–2% lime no‐steep treatments, which were significantly better than the steeped treatment ( = 3.7 + 0.48). Consumers rated the steeped sample as significantly less flexible. B‐vitamins were negatively impacted by increasing lime, while calcium increased significantly with lime addition.ConclusionsThe no‐steep, effluent‐free nixtamalization process produced oat tortillas with good masa and tortilla texture, which were not significantly different in consumer liking than tortillas produced via a traditional process.Significance and NoveltyThis research suggests nixtamalization can be applied to other grains in a shorter, environmentally friendly process, with broader commercial applicability.
Incorporating Gadolinium Oxide (Gd2O3) as a Rare Earth Metal Oxide in Carbon Nanofiber Skeleton for Supercapacitor Application
Authors: Aydın Hamide , Üstün Burcu , Kurtan Ümran , Aslan Ayşe , Karakuş Selcan 
Published: January 2024

AbstractIn this study, we synthesized gadolinium oxide nanoparticles (Gd2O3 NPs) incorporated heteroatom‐doped microporous carbon nanofibers (CNF) to serve as electrode materials for enhancing supercapacitive energy storage. Our primary focus is on elucidating the impact of these hybrid electrode materials on key supercapacitor performance properties such as specific capacitance, specific energy, and specific power. To comprehensively assess the structural and chemical attributes of Gd2O3 NPs‐incorporated heteroatom‐doped microporous CNFs (CNF/Gd2O3) we employed an array of advanced characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy (RAMAN), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS). Our research has yielded impressive results, demonstrating a significant increase in supercapacitive performance. Specifically, the CNF/Gd2O3‐1 symmetric supercapacitor cell (SSC) has demonstrated a good specific capacitance of 162.3 F/g and a high specific energy of 8.12 Wh/kg at a specific power of 300 W/kg. These findings could be a new pathway to prepare composite electrodes for use in energy storage applications and promote further development for other rare‐earth nanostructures.
H2O ⋅ B(C6F5)3‐Catalyzed para‐Alkylation of Anilines with Alkenes Applied to Late‐Stage Functionalization of Non‐Steroidal Anti‐Inflammatory Drugs
Authors: Winfrey Laura , Yun Lei , Passeri Ginevra , Suntharalingam Kogularamanan , Pulis Alexander P. 
Published: January 2024

AbstractAnilines are core motifs in a variety of important molecules including medicines, materials and agrochemicals. We report a straightforward procedure that allows access to new chemical space of anilines via their para‐C−H alkylation. The method utilizes commercially available catalytic H2O ⋅ B(C6F5)3 and is highly selective for para‐C‐alkylation (over N‐alkylation and ortho‐C‐alkylation) of anilines, with a wide scope in both the aniline substrates and alkene coupling partners. Readily available alkenes are used, and include new classes of alkene for the first time. The mild reaction conditions have allowed the procedure to be applied to the late‐stage‐functionalization of non‐steroidal anti‐inflammatory drugs (NSAIDs), including fenamic acids and diclofenac. The formed novel NSAID derivatives display improved anti‐inflammatory properties over the parent NSAID structure.
Fluorogenic Rhodamine Probes with Pyrrole Substitution Enables STED and Lifetime Imaging of Lysosomes in Live Cells
Authors: Zhou Ying , Wang Qiuping , Chanmungkalakul Supphachok , Wu Xia , Xiao Hui , Miao Rong , Liu Xiaogang , Fang Yu 
Published: January 2024

AbstractFluorogenic dyes with high brightness, large turn‐on ratios, excellent photostability, favorable specificity, low cytotoxicity, and high membrane permeability are essential for high‐resolution fluorescence imaging in live cells. In this study, we endowed these desirable properties to a rhodamine derivative by simply replacing the N, N‐diethyl group with a pyrrole substituent. The resulting dye, Rh‐NH, exhibited doubled Stokes shifts (54 nm) and a red‐shift of more than 50 nm in fluorescence spectra compared to Rhodamine B. Rh‐NH preferentially exists in a non‐emissive but highly permeable spirolactone form. Upon binding to lysosomes, the collective effects of low pH, low polarity, and high viscosity endow Rh‐NH with significant fluorescence turn‐on, making it a suitable candidate for wash‐free, high‐contrast lysosome tracking. Consequently, Rh‐NH enabled us to successfully explore stimulated emission depletion (STED) super‐resolution imaging of lysosome dynamics, as well as fluorescence lifetime imaging of lysosomes in live cells.
Structure‐Activity Relationship Study to Develop Peptide Amphiphiles as Species‐Specific Antimicrobials
Authors: Pereira Aramis J. , Xing Huihua , de Campos Luana J. , Seleem Mohamed A. , de Oliveira Kelly M. P. , Obaro Stephen K. , Conda‐Sheridan Martin 
Published: January 2024

AbstractAntimicrobial peptide amphiphiles (PAs) are a promising class of molecules that can disrupt the bacterial membrane or act as drug nanocarriers. In this study, we prepared 33 PAs to establish supramolecular structure‐activity relationships. We studied the morphology and activity of the nanostructures against different Gram‐positive and Gram‐negative bacterial strains (such as Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa and Acinetobacter baumannii). Next, we used principal component analysis (PCA) to determine the key contributors to activity. We found that for S. aureus, the zeta potential was the major contributor to the activity while Gram‐negative bacteria were more influenced by the partition coefficient (LogP) with the following order P. aeruginosa>E. coli>A. baumannii. We also performed a study of the mechanism of action of selected PAs on the bacterial membrane assessing the membrane permeability and depolarization, changes in zeta potential and overall integrity. We studied the toxicity of the nanostructures against mammalian cells. Finally, we performed an in vivo study using the wax moth larvae to determine the therapeutic efficacy of the active PAs. This study shows cationic PA nanostructures can be an intriguing platform for the development of nanoantibacterials.
Photopharmacology of Protease Inhibitors: Current Status and Perspectives
Authors: Coene Jonathan , Wilms Simon , Verhelst Steven H. L. 
Published: January 2024

AbstractProteases are involved in many essential biological processes. Dysregulation of their activity underlies a wide variety of human diseases. Photopharmacology, as applied on various classes of proteins, has the potential to assist protease research by enabling spatiotemporal control of protease activity. Moreover, it may be used to decrease side‐effects of protease‐targeting drugs. In this review, we discuss the current status of the chemical design of photoactivatable proteases inhibitors and their biological application. Additionally, we give insight into future possibilities for further development of this field of research.
Boosting Energy‐Transfer Processes via Dispersion Interactions
Authors: Cerveri Alessandro , Scarica Gabriele , Sparascio Sara , Hoch Matteo , Chiminelli Maurizio , Tegoni Matteo , Protti Stefano , Maestri Giovanni 
Published: January 2024

AbstractThe generation of open‐shell intermediates under mild conditions has opened broad synthetic opportunities during this century. However, these reactive species often require a case specific and tailored tuning of experimental parameters in order to efficiently convert substrates into products. We report a general approach that can overcome these ubiquitous limitations for several visible‐light promoted energy‐transfer processes. The use of either naphthalene (5–20 equiv.) or simple binaphthyl derivatives (10–30 mol %) greatly increases their efficiency, giving rise to a new strategy for catalysis. The trend is consistent among different media, photocatalysts, light sources and substrates, allowing one to improve existing methods, to more easily optimize conditions for new ones, and, moreover, to disclose otherwise inaccessible reaction pathways.
Deconstructing Best‐in‐Class Neoglycoclusters as a Tool for Dissecting Key Multivalent Processes in Glycosidase Inhibition
Authors: Liang Yan , Schettini Rosaria , Kern Nicolas , Manciocchi Luca , Izzo Irene , Spichty Martin , Bodlenner Anne , Compain Philippe 
Published: January 2024

AbstractMultivalency represents an appealing option to modulate selectivity in enzyme inhibition and transform moderate glycosidase inhibitors into highly potent ones. The rational design of multivalent inhibitors is however challenging because global affinity enhancement relies on several interconnected local mechanistic events, whose relative impact is unknown. So far, the largest multivalent effects ever reported for a non‐polymeric glycosidase inhibitor have been obtained with cyclopeptoid‐based inhibitors of Jack bean α‐mannosidase (JBα‐man). Here, we report a structure‐activity relationship (SAR) study based on the top‐down deconstruction of best‐in‐class multivalent inhibitors. This approach provides a valuable tool to understand the complex interdependent mechanisms underpinning the inhibitory multivalent effect. Combining SAR experiments, binding stoichiometry assessments, thermodynamic modelling and atomistic simulations allowed us to establish the significant contribution of statistical rebinding mechanisms and the importance of several key parameters, including inhitope accessibility, topological restrictions, and electrostatic interactions. Our findings indicate that strong chelate‐binding, resulting from the formation of a cross‐linked complex between a multivalent inhibitor and two dimeric JBα‐man molecules, is not a sufficient condition to reach high levels of affinity enhancements. The deconstruction approach thus offers unique opportunities to better understand multivalent binding and provides important guidelines for the design of potent and selective multiheaded inhibitors.
Chiral measure of chiral polyhedrons
Authors: Kimura Tsunehisa , Kimura Ryoma , Mizukoshi Yuki , Furusawa Kazuya 
Published: January 2024

AbstractTo quantify chiral shape, a tensor describing the particle shape has been proposed. This tensor, named the shape tensor (S‐tensor), is an analog of the hydrodynamic tensor that relates the rotational and translational motions of particles in a liquid. The determinant of the S‐tensor, named chirality measure density (CMD), was calculated for chiral tetrahedrons and octahedrons. It was found that CMD is opposite in sign when the mirror images are chiral to each other and vanishes when they are achiral. Therefore, the CMD is a good measure to distinguish the mirror images. The interaction between chiral particles was discussed in terms of the CMD.
Transcatheter aortic valve replacement: Past, present, and future
Authors: Srinivasan Akash , Wong Felyx , Wang Brian 
Published: January 2024

AbstractTranscatheter aortic valve replacement (TAVR) has emerged as a ground‐breaking, minimally invasive alternative to traditional open‐heart surgery, primarily designed for elderly patients initially considered unsuitable for surgical intervention due to severe aortic stenosis. As a result of successful large‐scale trials, TAVR is now being routinely applied to a broader spectrum of patients. In deciding between TAVR and surgical aortic valve replacement, clinicians evaluate various factors, including patient suitability and anatomy through preprocedural imaging, which guides prosthetic valve sizing and access site selection. Patient surgical risk is a pivotal consideration, with a multidisciplinary team making the ultimate decision in the patient's best interest. Periprocedural imaging aids real‐time visualization but is influenced by anaesthesia choices. A comprehensive postprocedural assessment is critical due to potential TAVR‐related complications. Numerous trials have demonstrated that TAVR matches or surpasses surgery for patients with diverse surgical risk profiles, ranging from extreme to low risk. However, long‐term follow‐up data, particularly in low‐risk cases, remains limited, and the applicability of published results to younger patients is uncertain. This review delves into key TAVR studies, pinpointing areas for potential improvement while delving into the future of this innovative procedure. Furthermore, it explores the expanding role of TAVR technology in addressing other heart valve replacement procedures.
No Influence of Asundexian on Cardiac Repolarization
Authors: Brase Christine , Kanefendt Friederike , Loewen Stephanie , Himmel Herbert , Schmitz Sebastian 
Published: January 2024

AbstractInhibition of activated factor XI reduces thrombogenesis while maintaining physiological hemostasis, with the expectation of reduced bleeding risk compared with standard of care in the clinical setting. Asundexian (BAY 2433334), an activated factor XI inhibitor, is in clinical development for the prevention of thromboembolic events. The effect of asundexian and its plasma metabolite M10 on cardiac repolarization and potential interactions with the hNav1.5 sodium, hCav1.2 calcium, and human ether‐à‐go‐go‐related gene (hERG) potassium channels was investigated in vitro. Additionally, asundexian effects on cardiac parameters and electrocardiogram were examined in telemetered beagle dogs. A randomized, placebo‐controlled, 4‐way crossover, thorough QT study in healthy adults evaluated the influence of 50 and 150 mg of asundexian on the corrected QT interval, including 400 mg of moxifloxacin as positive control. Across all studies, asundexian and M10 were not associated with any effects on cardiac repolarization. The largest in vitro effects of asundexian (approximately 20% inhibition) were seen for hCav1.2 and hERG. Throughout the thorough QT study, the upper limits of the one‐sided 95% confidence interval of placebo‐corrected mean changes from baseline in Fridericia corrected QT for 50 and 150 mg of asundexian were below Δ = 10 milliseconds. Asundexian demonstrated favorable safety and tolerability profiles.
A Study on Thiol‐Michael Addition to Semi‐Synthetic Elastin‐Hyaluronan Material for Electrospun Scaffolds
Authors: Laezza Antonio , Pepe Antonietta , Solimando Nicola , Armiento Francesca , Oszust Floriane , Duca Laurent , Bochicchio Brigida 
Published: January 2024

AbstractThiol‐Michael addition is a chemical reaction extensively used for conjugating peptides to polysaccharides with applications as biomaterials. In the present study, for designing a bioactive element in electrospun scaffolds as wound dressing material, a chemical strategy for the semi‐synthesis of a hyaluronan‐elastin conjugate containing an amide linker (ELAHA) was developed in the presence of tris(2‐carboxyethyl)phosphine hydrochloride (TCEP ⋅ HCl). The bioconjugate was electrospun with poly‐D,L‐lactide (PDLLA), obtaining scaffolds with appealing characteristics in terms of morphology and cell viability of dermal fibroblast cells. For comprehending the factors influencing the efficiency of the bioconjugation reaction, thiolated amino acids were also investigated as nucleophiles toward hyaluronan decorated with Michael acceptors in the presence of TCEP ⋅ HCl through the evaluation of byproducts formation.
Exploring the role of companies and sustainability disclosure in achieving sustainable development goals: A focus on zero hunger and social inclusion
Authors: Damiano Rodolfo , Di Maria Chiara 
Published: January 2024

AbstractThe Agenda 2030 Sustainable Development Goals (SDGs) require collaboration between governments, individuals, and the business community. However, research is still needed to understand how companies should contribute to the SDGs. Notably, researchers acknowledge companies' reporting practices play a crucial role in connecting organizational behavior to sustainability, advocating for more inclusive and transparent reporting to enhance companies' contribution to sustainable development. Despite the extensive literature on sustainability disclosure, limited empirical studies focus on socially inclusive and dialogic reporting as a determinant of SDGs’ achievement. Focusing on the second SDG (“Zero hunger”), this study analyses 211 of the most relevant worldwide large public companies in achieving it. The results reveal that companies adopting more inclusive and dialogic reporting practices also make greater contributions to SDG2, thus underlining the significance of inclusive reporting in achieving SDGs.
Enhanced Electrocatalytic Conversion of Nitrates to Ammonia: Fuel from Waste
Authors: Metem Prattakorn , Toledo‐Carrillo Esteban , Ye Fei , Dutta Joydeep 
Published: January 2024

AbstractAmmonia (NH3) is globally one of the most produced chemicals. Despite being known for its use as a fuel and as a precursor of multiple chemicals, during its production, it is responsible for more than 1.2 % of the total global CO2 emission and consumes a large amount of energy. In this work, we studied a flow‐through membrane‐free electrocatalytic device (CMED) to produce continuous stream of NH3 from a common water contaminant, nitrate (NO3−). Indium‐palladium (In−Pd) nanoparticles were impregnated in activated carbon cloth (ACC) and used as a cathode in the electrochemical device. It is found that in the counter electrode, adding oxygen evolution reaction (OER) active catalysts like platinum (Pt) for the regeneration of hydrogen ions enhances the rate of ammonia conversion to 7.28 μmol min−1 cm−2, eliminate the production of toxic nitrite by‐products, as well as provide a platform for a stable energy consumption over long periods of time. This method for the conversion of NO3− into NH3 promises a way forward for sustainable resource utilization while generating fuel from waste and contributing to future circular economies, and managing the nitrogen cycle in water that is a major challenge of the 21st century society.
A Metallomicellar Catalyst for Controlled Oxidation of Alcohols and Lignin Mimics in Water using Open Air as Oxidant
Authors: Thiruvengetam Prabaharan , Sunani Pragyansmruti , Kumar Chand Dillip 
Published: January 2024

AbstractAlcohol groups and β‐O‐4 (C−C) linkages are widespread in biomass feedstock that are abundant renewable resource for value‐added chemicals. The development of sustainable protocols for direct oxidation or oxidative cleavage of feedstock materials in a controlled fashion, using open air as an oxidant is an intellectually stimulating task to produce industrially important value‐added carbonyls. Further, the oxidative depolymerization of lignin into fine chemicals has evoked interest in recent times. Herein, we report the first example of a catalyst system that could activate molecular oxygen from atmospheric air for controlled oxidation and oxidative cleavage/depolymerization of feedstock materials such as alcohols, β‐O‐4 (C−C) linkages and real lignin in water under open air conditions. The selectivity of carbonyl products is controlled by altering the pH between ~7.0 and ~12.0. The current strategy highlights the non‐involvement of any external co‐catalyst, oxidant, radical additives, and/or destructive organic solvents. The catalyst shows a wide substrate scope and eminent functional group tolerance. The upscaled multigram synthesis using an inexpensive catalyst and easily available oxidant evidences the practical utility of the developed protocol. A plausible mechanism has been proposed with the help of a few controlled experiments, and kinetic and computational studies.
Consequences of drought for grassland songbird reproduction
Authors: Smith Emma B. , Roe Austin J. , Silber Katy M. , Williams Emily J. , Winnicki Sarah K. , Boyle W. Alice 
Published: January 2024

AbstractAbiotic stressors can be major sources of selection, resulting in diverse demographic responses operating via multiple direct and indirect mechanisms. However, unusual weather events are notoriously difficult to study due to their spatial and temporal unpredictability. A severe drought affected the Flint Hills of Kansas in 2018, occurring during the ongoing population‐level studies of three species of declining grassland songbirds: Eastern Meadowlarks (Sturnella magna), Grasshopper Sparrows (Ammodramus savannarum), and Dickcissels (Spiza americana). We compared nest survival, nest initiation date, and potential behavioral drivers of reproductive differences (i.e., nest orientation, investment) between the 2018 drought year and 2–6 years of average‐to‐wet years. Nest initiation in the drought year was concentrated early in the season, suggesting that birds did not renest or attempt second broods. The two species that build domed nests shifted the orientation of nest entrances away from early morning sun and toward the direction of prevailing winds in the drought year. Multiple nest‐level metrics of investment and success were similar in drought and nondrought years. These results suggest that demographic changes during droughts can reflect both direct responses and may also involve biotically mediated trophic consequences.