bluuebunny/crossref_metadata_2025_split huggingface dataset:
Insights into the Distinct Behaviors between Bifunctional and Binary Organoborane Catalysts through Terpolymerization of Epoxide, CO2, and Anhydride
Authors: Xie Rui , Wang Yuhui , Li Shuai , Li Bo , Xu Jie , Liu Jinqian , He Yuchen , Yang Guan‐Wen , Wu Guang‐Peng 
Published: April 2024

AbstractAlkyl borane compounds‐mediated polymerizations have expanded to Lewis pair polymerization, free radical polymerization, ionic ring‐opening polymerization, and polyhomologation. The bifunctional organoborane catalysts that contain the Lewis acid and ammonium or phosphonium salt in one molecule have demonstrated superior catalytic performance for ring‐opening polymerization of epoxides and ring‐opening copolymerization of epoxides and CO2 than their two‐component analogues, i.e., the blend of organoborane and ammonium or phosphonium salt. To explore the origin of the differences of the one‐component and two‐component organoborane catalysts, here we conducted a systematic investigation on the catalytic performances of these two kinds of organoborane catalysts via terpolymerization of epoxide, carbon dioxide and anhydride. The resultant terpolymers produced independently by bifunctional and binary organoborane catalyst exhibited distinct microstructures, where a series of gradient polyester‐polycarbonate terpolymers with varying polyester content were afforded using the bifunctional catalyst, while tapering diblock terpolymers were obtained using the binary system. The bifunctional catalyst enhances the competitiveness of CO2 insertion than anhydride, which leads to the premature incorporation of CO2 into the polymer chains and ultimately results in the formation of gradient terpolymers. DFT calculations revealed the role of electrostatic interaction and charge distribution caused by intramolecular synergistic effect for bifunctional organoborane catalyst.
Morphological diversity of saber‐tooth upper canines and its functional implications
Authors: Shelbourne Caitlin D. , Lautenschlager Stephan 
Published: April 2024

AbstractElongated upper canine teeth, commonly known as saber‐teeth, have evolved three times within the sub‐order Feliformia. The species that wielded them flourished throughout the Cenozoic and have historically been separated into two morphological groups: the dirk‐tooths with longer, flatter canines, and the scimitar‐tooths with shorter, serrated teeth. However, quantitative morphological analysis has not been conducted on these teeth to determine the true amount of diversity within the group, and how the upper canine morphology of extant feliforms compared to their extinct relatives has also not been explored. Using Geometric Morphometric analysis, it is shown that saber‐tooth upper canine morphology is exceptionally diverse, with no extant clade having all its members occupy the same morphospace based on tooth length and curvature. Instead, a neutral basal morphospace is observed for all groups and diversification from this basal position is seen as species become more derived. A distinct and consistent scimitar tooth morphology is also not observed within the morphospace. When compared with extant taxa, several saber‐tooth species are seen to be morphologically similar to extant feliforms, several of which exhibit novel dietary strategies in comparison to the obligate carnivore felids. Biomechanical analyses of different actual and theoretical tooth shapes demonstrate that saber‐teeth upper canines further represent a functional compromise between sharpness, curvature, and length on the one hand, and robustness and material investment on the other.
K2[(VOHPO4)2(C2O4)]·2H2O as a high‐potential cathode material for potassium‐ion batteries
Authors: Niu Xiaogang , Li Nan , Chen Yifan , Zhang Jianwen , Yang Yusi , Tan Lulu , Wang Linlin , Zhang Zhe , Fedotov Stanislav S. , Aksyonov Dmitry , Wu Jianghao , Guo Lin , Zhu Yujie 
Published: April 2024

AbstractPotassium‐ion batteries (KIBs) represent a promising energy storage solution owing to the abundance of potassium resources. The efficacy of KIBs relies significantly on the electrochemical attributes of both their electrode materials and electrolytes. In the current investigation, we synthesized a layered compound K2[(VOHPO4)2(C2O4)]·2H2O via a heterogeneous nucleation approach and assessed its viability as a cathode material for KIBs. When integrated with a salt‐concentrated electrolyte with oxidation stability over 6 V, the compounds exhibit a high discharge potential of 4.1 V (vs. K+/K) alongside a reversible capacity of 106.2 mAh g−1. Furthermore, there is no capacity decay after 500 cycles at 100 mA g−1. This study shows the promise of layered metal organic frameworks as high‐potential materials for KIBs.
New Perspectives of Pt−CeO2 System: Stabilization on MWCNTs for Boosting Activity and Water‐Resistance in CO Oxidation at Ambient Temperatures
Authors: Slavinskaya Elena , Stonkus Olga , Kibis Lidiya , Lashina Elena , Zadesenets Andrey , Kardash Tatyana , Korenev Sergey , Podyacheva Olga , Boronin Andrei 
Published: April 2024

AbstractThe present study elucidates new perspectives regarding the Pt−CeO2 system for CO oxidation. The successful deposition of highly dispersed Pt−CeO2 species onto the surface of multiwalled carbon nanotubes (MWCNTs) led to the formation of abnormally active and water‐resistant catalysts. The catalysts were investigated by structural (XRD, TEM), spectral (XPS), and kinetic (TPR‐CO+O2, TPR‐CO, TPR‐H2) methods. The application of TPR‐CO+O2 revealed the remarkably high activity of all Pt−CeO2/MWCNTs catalysts at temperatures below 0 °C. The study of the catalysts at ambient temperature demonstrated high CO conversion in the presence of water vapor at a concentration of 100 ppm CO. The experimental findings suggest that active sites, comprising platinum structures stabilized directly on the surface of MWCNTs, play a pivotal role in the oxidation of CO under humid conditions. A dual‐site approach was employed to develop a kinetic model that effectively describes the experimental data. This model provides valuable insights into the mechanism of wet CO oxidation.
Pathway Selection in Temporal Evolution of Supramolecular Polymers of Ionic π‐Systems: Amphiphilic Organic Solvent Dictates the Fate of Water
Authors: Kotha Srinu , Sahu Rahul , Chandrakant Yadav Aditya , Bejagam Karteek K. , Reddy Sandeep K. , Venkata Rao Kotagiri 
Published: April 2024

AbstractUnderstanding solvent‐solute interactions is essential to designing and synthesising soft materials with tailor‐made functions. Although the interaction of the solute with the solvent mixture is more complex than the single solvent medium, solvent mixtures are exciting to unfold several unforeseen phenomena in supramolecular chemistry. Here, we report two unforeseen pathways observed during the hierarchical assembly of cationic perylene diimides (cPDIs) in water and amphiphilic organic solvent (AOS) mixtures. When the aqueous supramolecular polymers (SPs) of cPDIs are injected into AOS, initially kinetically trapped short SPs are formed, which gradually transform into thermodynamically stable high aspect ratio SP networks. Using various experimental and theoretical investigations, we found that this temporal evolution follows two distinct pathways depending on the nature of the water‐AOS interactions. If the AOS is isopropanol (IPA), water is released from cPDIs into bulk IPA due to strong hydrogen bonding interactions, which further decreases the monomer concentration of cPDIs (Pathway‐1). In the case of dioxane AOS, cPDI monomer concentration further increases as water is retained among cPDIs (Pathway‐2) due to relatively weak interactions between dioxane and water. Interestingly, these two pathways are accelerated by external stimuli such as heat and mechanical agitation.
Photo/Mechanical/Acidic Multi‐Stimuli Responses and Information Encryption Design of Acylhydrazone Derivative
Authors: Ye Yang , Wang Dechen , Zhang Yaru , Zhou Xiaomeng , Du Haowen , Yang Sen , Bao Ying , Hao Hongxun , Xie Chuang 
Published: April 2024

AbstractStimuli‐responsive crystalline materials have received much attention for being potential candidates of smart materials. However, the occurrence of polymorphism‐driven stimuli responses in crystalline materials remains interesting but rare. Herein, three polymorphs of an acylhydrazone derivative, N′‐[(E)‐(1‐benzofuran‐2‐yl) methylidene] pyridine −4‐carbohydrazide (BFMP) were prepared. Form‐1 undergoes a photomechanical response via E→Z photoisomerization under UV irradiation, accompanied by a decrease in fluorescence intensity and a change from colorless to yellow. Two types of Z→E thermal isomerization mechanisms with significant differences in conversion rate were observed at different temperatures in form‐1. The solid‐melt‐solid transition has a faster conversion rate compared to the solid‐solid transition due to freedom from lattice confinement. The transition from form‐2 to form‐3 can be achieved under grinding, coupled with a significant decrease in fluorescence intensity. The similar molecular stacking pattern of form‐2 and form‐3 provides a structural basis for the grinding‐induced crystalline transition behavior. In addition, the presence of the pyridine moiety imparts an acidochromic property. The combination of photochromism and acidochromism explores the possible applications of acylhydrazone derivatives in information encryption.
Generation, Characterization and Reactivity of a High‐Valent Mononuclear Cobalt(IV)−Diazide Complex
Authors: Kayne Michael , Murphy Patrick S. , Kwon Yubin M. , Lee Yuri , Jackson Timothy A. , Wang Dong 
Published: April 2024

AbstractHigh‐valent Fe(IV)=O intermediates of metalloenzymes have inspired numerous efforts to generate synthetic analogs to mimic and understand their substrate oxidation reactivities. However, high‐valent M(IV) complexes of late transition metals are rare. We have recently reported a novel Co(IV)−dinitrate complex (1‐NO3) that activates sp3 C−H bonds up to 87 kcal/mol. In this work, we have shown that the nitrate ligands in 1‐NO3 can be replaced by azide, a more basic coordinating base, resulting in the formation of a more potent Co(IV)−diazide species (1‐N3) that reacts with substrates (hydrocarbons and phenols) at faster rate constants and activates stronger C−H bonds than the parent complex 1‐NO3. We have characterized 1‐N3 employing a combination of spectroscopic and computational approaches. Our results clearly show that the coordination of azide leads to the modulation of the Co(IV) electronic structure and the Co(IV/III) redox potential. Together with the higher basicity of azide, these thermodynamic parameters contribute to the higher driving forces of 1‐N3 than 1‐NO3 for C−H bond activation. Our discoveries are thus insightful for designing more reactive bio‐inspired high‐valent late transition metal complexes for activating inert aliphatic hydrocarbons.
Prevalence and impact of endocrine disorders in advanced metastatic cancer patients undergoing cancer‐directed therapy: A prospective observational study
Authors: Karna Gaurav , Sehrawat Amit , Karna Saurabh , Kant Ravi , Sundriyal Deepak , Karn Summi , Jha Dipesh 
Published: April 2024

AbstractBackgroundNoncommunicable diseases (NCDs) contribute significantly to global morbidity and mortality, with cancer being one of the leading causes. In this prospective observational study, we aimed to investigate the prevalence and impact of endocrine disorders, specifically diabetes and thyroid dysfunction, in patients with advanced metastatic cancer undergoing cancer‐directed therapy.MethodsOver 15 months, we recruited 100 histologically proven advanced metastatic cancer patients from the Department of Medical Oncology Haematology, All India Institute of Medical Sciences, Rishikesh, and conducted institutional‐based prospective observational study. All participants over 18 years of age, treatment‐naive, and potential candidates for systemic chemotherapy with an expected clinical survival of at least 6 months were included in the study. Patients with prior therapy, secondary neoplasms, and those unable to complete 3 months of palliative chemotherapy were excluded. Patients were assessed for diabetes and thyroid function at presentation, after 3 and 6 months of cancer‐directed standard therapy. These data were analyzed, processed, and presented as results.ResultsThe mean age of participants was 50.45 years, with a near‐equal distribution of males and females. At baseline, 10% of the study population had preexisting endocrine disorders (2% hypothyroidism, 8% diabetes). By the end of 6 months, the prevalence increased to 18%, with females being more affected. Notably, the prevalence of new‐onset endocrine disorders during cancer‐directed therapy was only 3% for diabetes and 4% for thyroid dysfunction.ConclusionAnalysis of sociodemographic and cancer‐related characteristics showed no significant association with changes in diabetic and thyroid status at 3 and 6 months. However, substance use, particularly smoking, was associated with an increased risk of diabetes development (p < .05). Cancer type and treatment regimen did not show statistically significant correlations with endocrine dysfunction.ImplicationsOur study highlights the importance of considering endocrine disorders in advanced metastatic cancer patients undergoing therapy. The prevalence of diabetes and thyroid dysfunction increased during cancer‐directed therapy, particularly in females. Careful monitoring and timely intervention are essential to improve the quality of life for these patients. Further research is warranted to explore the long‐term effects of cancer‐directed therapy on endocrine health and develop tailored management strategies for this vulnerable population.
The Separability Problem in Molecular Quantum Systems: Information‐Theoretic Framework for Atoms in Molecules
Authors: Esquivel Rodolfo O. , Carrera Edmundo 
Published: April 2024

AbstractEven though molecules are fundamentally quantum entities, the concept of a molecule retains certain classical attributes concerning its constituents. This includes the empirical separability of a molecule into its three‐dimensional, rigid structure in Euclidean space, a framework often obtained through experimental methods like X‐Ray crystallography. In this work, we delve into the mathematical implications of partitioning a molecule into its constituent parts using the widely recognized Atoms‐In‐Molecules (AIM) schemes, aiming to establish their validity within the framework of Information Theory concepts. We have uncovered information‐theoretical justifications for employing some of the most prevalent AIM schemes in the field of Chemistry, including Hirshfeld (stockholder partitioning), Bader's (topological dissection), and the quantum approach (Hilbert's space definition). In the first approach we have applied the generalized principle of minimum relative entropy derived from the Sharma‐Mittal two‐parameter functional, avoiding the need for an arbitrary selection of reference promolecular atoms. Within the ambit of topological‐information partitioning, we have demonstrated that the Fisher information of Bader's atoms conform to a comprehensive theory based on the Principle of Extreme Physical Information avoiding the need of employing the Schwinger's principle, which has been proven to be problematic. For the quantum approach we have presented information‐theoretic justifications for conducting Löwdin symmetric transformations on the density matrix to form atomic Hilbert spaces generating orthonormal atomic orbitals with maximum occupancy for a given wavefunction.
A case of needle tract seeding with endoscopic findings of progression over time
Authors: Sawai Go , Dainaka Katsuyuki , Juichiro Yoshida , Inada Yutaka , Fukui Akifumi , Nishimura Takeshi , Fujii Hideki , Tomatsuri Naoya , Okuyama Yusuke , Sato Hideki 
Published: April 2024

AbstractAn 83‐year‐old male underwent three transgastric punctures with endoscopic ultrasound‐guided fine‐needle aspiration for the examination of a pancreatic body tumor. After a diagnosis of resectable pancreatic cancer and undergoing distal pancreatectomy, the patient was administered postoperative adjuvant chemotherapy with oral S‐1 for 6 months, and carcinoembryonic antigen and carbohydrate antigen 19‐9 levels were bimonthly evaluated. Carbohydrate antigen 19‐9 levels continually increased to 4638.1 U/mL at 45 months post‐fine‐needle aspiration. Endoscopic ultrasound‐guided showed a 25 mm low‐echoic, irregularly shaped, and heterogeneous tumor with clear margins protruding from the mucosa outside the gastric wall, and biopsy confirmed adenocarcinoma. Since the immunostaining findings of the specimen matched those of the previously resected specimen, needle tract seeding (NTS) due to puncture of the pancreatic cancer was identified as the cause. After a pylorus‐preserving gastrectomy at 46 months post‐fine‐needle aspiration, postoperative chemotherapy initiation, comprising gemcitabine and nab‐paclitaxel, was initiated; however, the patient died despite these interventions as he developed multiple peritoneal dissemination. Although rare, the incidence of NTS will increase in the future owing to the expected extended survival in post‐pancreatic cancer resection cases. We suggest regular upper gastrointestinal endoscopy and endoscopic ultrasound‐guided evaluations for patients who are at risk for NTS can facilitate early detection. Furthermore, it is extremely relevant to share experiences of encountered NTS cases in practice and extend knowledge of its varying endoscopic appearances.
High genetic connectivity of two pollinating flies despite urban disturbance
Authors: Wittische Julian , Lippert Stéphanie , Luttringer Amanda , Ariey Hinatea , Cruz António , Andrasi Balint , Thissen Dylan , Schleimer Anna , Drygala Frank , Mehnert Joerg , Mengual Ximo , Cantú‐Salazar Lisette , Frantz Alain C. 
Published: April 2024

AbstractHoverflies (Syrphidae) are essential pollinators, and their severe decline jeopardizes their invaluable contribution to plant diversity and agricultural production. However, we know little about the dispersal abilities of hoverflies in urbanized landscapes, limiting our understanding of the spatiotemporal dynamics of plant–pollinator systems and reducing our ability to preserve biodiversity in the context of global change. Previous work has not addressed how urbanization affects the functional connectivity of hoverflies and whether dispersal is a limiting factor in their population dynamics. In this study, we investigated the spatial genetic structure of two nonmigratory species of hoverflies in two urban areas. We collected more than a thousand specimens of each Syritta pipiens and Myathropa florea, each, by hand netting in two western European urbanized study areas of 490 and 460 km2 in 2021, and we genotyped them at 14 and 24 microsatellite loci, respectively. Based on spatial and nonspatial Bayesian clustering methods, we failed to reject the null hypothesis of panmixia, suggesting that both species exhibited high genetic connectivity despite urbanization. The distribution of allele frequencies was not correlated with geographic distance, implying that isolation‐by‐distance was negligible at the investigated spatial scale in both species. Although anthropogenic land cover changes generally have dramatic consequences on biodiversity, these hoverfly species retain high connectivity, which suggests that dispersal is not a strong limiting factor in their metapopulational dynamics. However, high effective population size and its confounding effect on signals of genetic drift may limit our ability to conclude confidently about landscape effects on gene flow in those two species. Provided we maintain or restore habitat, recolonization may be prompt even in urban areas.
AOP report: Development of an adverse outcome pathway for deposition of energy leading to cataracts
Authors: Carrothers Emma , Appleby Meghan , Lai Vita , Kozbenko Tatiana , Alomar Dalya , Smith Benjamin J. , Hamada Nobuyuki , Hinton Patricia , Ainsbury Elizabeth A. , Hocking Robyn , Yauk Carole , Wilkins Ruth C. , Chauhan Vinita 
Published: April 2024

AbstractCataracts are one of the leading causes of blindness, with an estimated 95 million people affected worldwide. A hallmark of cataract development is lens opacification, typically associated not only with aging but also radiation exposure as encountered by interventional radiologists and astronauts during the long‐term space mission. To better understand radiation‐induced cataracts, the adverse outcome pathway (AOP) framework was used to structure and evaluate knowledge across biological levels of organization (e.g., macromolecular, cell, tissue, organ, organism and population). AOPs identify a sequence of key events (KEs) causally connected by key event relationships (KERs) beginning with a molecular initiating event to an adverse outcome (AO) of relevance to regulatory decision‐making. To construct the cataract AO and retrieve evidence to support it, a scoping review methodology was used to filter, screen, and review studies based on the modified Bradford Hill criteria. Eight KEs were identified that were moderately supported by empirical evidence (e.g., dose‐, time‐, incidence‐concordance) across the adjacent (directly linked) relationships using well‐established endpoints. Over half of the evidence to justify the KER linkages was derived from the evidence stream of biological plausibility. Early KEs of oxidative stress and protein modifications had strong linkages to downstream KEs and could be the focus of countermeasure development. Several identified knowledge gaps and inconsistencies related to the quantitative understanding of KERs which could be the basis of future research, most notably directed to experiments in the range of low or moderate doses and dose‐rates, relevant to radiation workers and other occupational exposures.
Dissecting unique and common variance across body and brain health indicators using age prediction
Authors: Beck Dani , de Lange Ann‐Marie G. , Gurholt Tiril P. , Voldsbekk Irene , Maximov Ivan I. , Subramaniapillai Sivaniya , Schindler Louise , Hindley Guy , Leonardsen Esten H. , Rahman Zillur , van der Meer Dennis , Korbmacher Max , Linge Jennifer , Leinhard Olof D. , Kalleberg Karl T. , Engvig Andreas , Sønderby Ida , Andreassen Ole A. , Westlye Lars T. 
Published: April 2024

AbstractAgeing is a heterogeneous multisystem process involving different rates of decline in physiological integrity across biological systems. The current study dissects the unique and common variance across body and brain health indicators and parses inter‐individual heterogeneity in the multisystem ageing process. Using machine‐learning regression models on the UK Biobank data set (N = 32,593, age range 44.6–82.3, mean age 64.1 years), we first estimated tissue‐specific brain age for white and gray matter based on diffusion and T1‐weighted magnetic resonance imaging (MRI) data, respectively. Next, bodily health traits, including cardiometabolic, anthropometric, and body composition measures of adipose and muscle tissue from bioimpedance and body MRI, were combined to predict ‘body age’. The results showed that the body age model demonstrated comparable age prediction accuracy to models trained solely on brain MRI data. The correlation between body age and brain age predictions was 0.62 for the T1 and 0.64 for the diffusion‐based model, indicating a degree of unique variance in brain and bodily ageing processes. Bayesian multilevel modelling carried out to quantify the associations between health traits and predicted age discrepancies showed that higher systolic blood pressure and higher muscle‐fat infiltration were related to older‐appearing body age compared to brain age. Conversely, higher hand‐grip strength and muscle volume were related to a younger‐appearing body age. Our findings corroborate the common notion of a close connection between somatic and brain health. However, they also suggest that health traits may differentially influence age predictions beyond what is captured by the brain imaging data, potentially contributing to heterogeneous ageing rates across biological systems and individuals.