bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tautomerization Makes Topological Phase Transition in 2D Organometallic Lattices
Authors: Li Junyao , Liu Zhao , Li Xingxing , Yang Jinlong 
Published: March 2024

AbstractThe investigation into approaches for achieving reversible control of topological phase transitions has attracted substantial research interest. So far, several system‐dependent physical control methods are developed, while a chemical strategy for efficient regulation of topological properties is still lack. Here, this study presents a chemical means to achieve reversible topological control in 2D organometallic lattices by introducing the lactam‐lactim tautomerization modules in the organic linkers. The strategy is validated in the theoretically designed 2D hexagonal framework with planar tricoordinated Co as nodes and 2,2′‐bithiazole derivatives as organic linkers, which transforms from a ferrimagnetic half metal with a local gap featuring Chern number of +1 to a ferromagnetic Chern insulator possessing Chern number of −1 after lactam‐lactim tautomerization. Simultaneously, a flip in the spin polarization of charge carriers between the two lattice tautomers is also observed.
Direct Catalytic Stereoselective Synthesis of C4′ Functionalized Furanoside and Nucleoside Derivatives with a Tetrasubstituted Stereocenter
Authors: Zhang Kaiheng , Wu Haibo , Inge A. Ken , Córdova Armando 
Published: March 2024

AbstractA direct catalytic stereoselective synthesis of C4’ functionalized furanoside and nucleoside derivatives with a tetrasubstituted stereocenter is disclosed. The amine‐catalyzed stereoselective α‐aminomethylation reactions on furanoside‐derived aldehyde derivatives gave the corresponding C4’ functionalized D‐ or L‐ribose derivatives in good to excellent yields (67−94%) with up to >20:1 dr.
Rim‐Based Binding of Perfluorinated Acids to Pillararenes Purifies Water
Authors: Gao Tu‐Nan , Huang Si , Nooijen Rick , Zhu Yumei , Kociok‐Köhn Gabriele , Stuerzer Tobias , Li Guanna , Bitter Johannes H. , Salentijn Gert I. J. , Chen Bo , Miloserdov Fedor M. , Zuilhof Han 
Published: March 2024

AbstractPer‐ and polyfluoroalkyl substances (PFAS) pose a rapidly increasing global problem as their widespread use and high stability lead worldwide to water contamination, with significant detrimental health effects.[1] Supramolecular chemistry has been invoked to develop materials geared towards the specific capture of PFAS from water,[2] to reduce the concentration below advisory safety limits (e.g., 70 ng/L for the sum of perfluorooctane sulfonic acid, PFOS and perfluorooctanoic acid, PFOA). Scale‐up and use in natural waters with high PFAS concentrations has hitherto posed a problem. Here we report a new type of host–guest interaction between deca‐ammonium‐functionalized pillar[5]arenes (DAF−P5s) and perfluoroalkyl acids. DAF−P5 complexes show an unprecedented 1 : 10 stoichiometry, as confirmed by isothermal calorimetry and X‐ray crystallographic studies, and high binding constants (up to 106 M−1) to various polyfluoroalkyl acids. In addition, non‐fluorinated acids do not hamper this process significantly. Immobilization of DAF−P5s allows a simple single‐time filtration of PFAS‐contaminated water to reduce the PFOS/PFOA concentration 106 times to 15–50 ng/L level. The effective and fast (<5 min) orthogonal binding to organic molecules without involvement of fluorinated supramolecular hosts, high breakthrough capacity (90 mg/g), and robust performance (>10 regeneration cycles without decrease in performance) set a new benchmark in PFAS‐absorbing materials.
Electrochemical Nickel‐Catalyzed Hydrogenation
Authors: Li Liubo , Wang Xinyi , Fu Niankai 
Published: March 2024

AbstractOlefin hydrogenation is one of the most important transformations in organic synthesis. Electrochemical transition metal‐catalyzed hydrogenation is an attractive approach to replace the dangerous hydrogen gas with electrons and protons. However, this reaction poses major challenges due to rapid hydrogen evolution reaction (HER) of metal‐hydride species that outcompetes alkene hydrogenation step, and facile deposition of the metal catalyst at the electrode that stalls reaction. Here we report an economical and efficient strategy to achieve high selectivity for hydrogenation reactivity over the well‐established HER. Using an inexpensive and bench‐stable nickel salt as the catalyst, this mild reaction features outstanding substrate generality and functional group compatibility, and distinct chemoselectivity. In addition, hydrodebromination of alkyl and aryl bromides could be realized using the same reaction system with a different ligand, and high chemoselectivity between hydrogenation and hydrodebromination could be achieved through ligand selection. The practicability of our method has been demonstrated by the success of large‐scale synthesis using catalytic amount of electrolyte and a minimal amount of solvent. Cyclic voltammetry and kinetic studies were performed, which support a NiII/0 catalytic cycle and the pre‐coordination of the substrate to the nickel center.
Asymmetric, Remote C(sp3)−H Arylation via Sulfinyl‐Smiles Rearrangement
Authors: Hu Yawen , Hervieu Cédric , Merino Estíbaliz , Nevado Cristina 
Published: March 2024

AbstractAn efficient asymmetric remote arylation of C(sp3)−H bonds under photoredox conditions is described here. The reaction features the addition radicals to a double bond followed by a site‐selective radical translocation (1,n‐hydrogen atom transfer) as well as a stereocontrolled aryl migration via sulfinyl‐Smiles rearrangement furnishing a wide range of chiral α‐arylated amides with up to >99 : 1 er. Mechanistic studies indicate that the sulfinamide group governs the stereochemistry of the product with the aryl migration being the rate determining step preceded by a kinetically favored 1,n‐HAT process.
Postsynthetically Modified Alkoxide‐Exchanged Ni2(OR)2BTDD: Synergistic Interactions of CO2 with Open Metal Sites and Functional Groups
Authors: Yu Sumin , Kim Namju , Choe Jong Hyeak , Kim Hyojin , Kim Dae Won , Youn Jeongwon , Lee Yong Hoon , Hong Chang Seop 
Published: March 2024

AbstractPostsynthetic modifications (PSMs) of metal–organic frameworks (MOFs) play a crucial role in enhancing material performance through open metal site (OMS) functionalization or ligand exchange. However, a significant challenge persists in preserving open metal sites during ligand exchange, as these sites are inherently bound by incoming ligands. In this study, for the first time, we introduced alkoxides by exchanging bridging chloride in Ni2Cl2BTDD (BTDD=bis (1H‐1,2,3,–triazolo [4,5‐b],–[4′,5′‐i]) dibenzo[1,4]dioxin) through PSM. Rietveld refinement of synchrotron X‐ray diffraction data indicated that the alkoxide oxygen atom bridges Ni(II) centers while the OMSs of the MOF are preserved. Due to the synergy of the existing OMS and introduced functional group, the alkoxide‐exchanged MOFs showed CO2 uptakes superior to the pristine MOF. Remarkably, the tert‐butoxide‐substituted Ni_T exhibited a nearly threefold and twofold increase in CO2 uptake compared to Ni2Cl2BTDD at 0.15 and 1 bar, respectively, as well as high water stability relative to the other exchanged frameworks. Furthermore, the Grand Canonical Monte Carlo simulations for Ni_T suggested that CO2 interacts with the OMS and the surrounding methyl groups of tert‐butoxide groups, which is responsible for the enhanced CO2 capacity. This work provides a facile and unique synthetic strategy for realizing a desirable OMS‐incorporating MOF platform through bridging ligand exchange.
Enhanced Proximity of Rh1,2‐Rhn Ensembles Encaged in UiO‐67 Boosting Catalytic Conversion of Syngas to Oxygenates
Authors: Yu Jun , Liu Tingting , Gu Qingqing , Wang Jia , Han Ying , Li Gonghui , Guo Qiangsheng , Gu Ye , Wu Xinping , Gong Xueqing , Yang Bing , Mao Dongsen 
Published: March 2024

AbstractMaintaining high conversion under the premise of high oxygenates selectivity in syngas conversion is important but a formidable challenge in Rh catalysis. Monometallic Rh catalysts provide poor oxygenate conversion efficiency, and efforts have been focused on constructing adjacent polymetallic sites; however, the one‐pass yields of C2+ oxygenates over the reported Rh‐based catalysts were mostly <20 %. In this study, we constructed a monometallic Rh catalyst encapsulated in UiO‐67 (Rh/UiO‐67) with enhanced proximity to dual‐site Rh1,2‐Rhn ensembles. Unexpectedly, this catalyst exhibited high efficacy for oxygenate synthesis from syngas, giving a high oxygenate selectivity of 72.0 % with a remarkable CO conversion of 50.4 %, and the one‐pass yield of C2+ oxygenates exceeded 25 %. The state‐of‐the‐art characterizations further revealed the spontaneous formation of an ensemble of Rh single atoms/dimers (Rh1,2) in the proximity of ultrasmall Rh clusters (Rhn) confined within the nanocavity of UiO‐67, providing adjacent Rh+‐Rh0 dual sites dynamically during the reaction that promote the relay of the undissociated CHO species to the CHx species. Thus, our results open a new route for designing highly efficient Rh catalysts for the conversion of syngas to oxygenates by precisely tuning the ensemble and proximity of the dual active sites in a confined space.
Supercritical foaming of novel poly(ether‐b‐amide) elastomer and compression property characterization
Authors: Qiu Chao , Zhu Ping , Dong Xia , Wang Dujin 
Published: March 2024

AbstractLightweight foam made of poly(ether‐b‐amide) (PEBA) elastomer has been widely used in sport shoes due to its superior rebounding and supporting properties. Novel PEBA with polyamide 1012 as hard segments and poly(tetramethylene oxide) (PTMO) as soft segments was foamed by supercritical CO2. The influence of foaming process parameters, that is saturation temperature, pressure on the morphology of cellular structure was systematically studied by scanning electron microscopy (SEM) and wide‐angle x‐ray diffraction (WAXD). By controlling the viscoelastic behavior of PEBA at certain temperatures and pressures, foams with low density and energy loss coefficient can be fabricated. The cell density of 4.5 × 109 cells/cm3and expansion ratio of 16.0 of the foams can be obtained respectively. Cyclic compression performance of foams was systematically studied. For the foams with the highest expansion ratio, the energy loss coefficient of 11.9% in the first cycle and 3.5% after equilibrium were observed, which were less than those of former reported PEBA foams. The relationship between the Young's modulus and expansion ratio is in line with the Gibson–Ashby relationship.
No place to call home: Distribution patterns of the tufted ghost crab, Ocypode cursor, populations in nature reserves, Israel, Eastern Mediterranean
Authors: Galil Bella S. , Goren Menachem , Gayer Kfir , Bronstein Omri 
Published: March 2024

Abstract
The once plentiful population of the tufted ghost crab, Ocypode cursor, a legally protected species, suffered a steep decline along the densely populated Mediterranean coast of Israel.
Here we assessed the effects of recreational disturbance on crab populations in three sandy shore nature reserves and adjacent bathing beaches with differing accessibility during the summers of 2020–2021, employing burrow counts and burrow opening diameter as proxies for population abundance and population size structure.
A total 6270 burrows were identified, counted and their opening diameter measured during the study period. The number of burrows was greatest close by the waterline and diminished landwards; this landwards decline was notable in the smallest burrows (<20 mm), representing the youngest population fraction. Comparison of population abundance between the surveyed nature reserves and adjacent bathing beaches revealed greater numbers in the former. However, a pronounced postweekend reduction in the number of burrows was apparent in nature reserves during both survey years, across sites and months and clearly indicates elevated recreational activity. The number of burrows in the nature reserve nearest to main population centres and abutting a popular bathing beach was smaller compared with the peripheral nature reserves.
We observed no postsunrise activity of adult crabs, though in strictly access‐restricted beaches, crabs were active diurnally. We thus suggest that the crabs shifted their diel activity patterns as avoidance response to chronic anthropogenic disturbance, enduring a forced curfew and a temporal habitat loss.
If the sandy nature reserves are to function as true refugia for the tufted ghost crab, restorative management is to include significant conservation and mitigation intervention measurements/actions.
The skull of Liolaemus huayra compared to other species of Liolaemus and Phymaturus (Squamata, Liolaemidae)
Authors: Assad Esteban Eduardo , Abdala Cristian Simón , Montero Ricardo 
Published: March 2024

AbstractDespite the extensive study of various aspects of the genus Liolaemus, there remains a scarcity of information regarding the osteology of species. In the last two decades, over 100 species have been described within the genus, but still less than 10% of the Liolaemus species includes any osteological data. In this study, we provide a description of the skull of Liolaemus huayra, a taxon closely related to the L. dorbignyi clade (a subset of the L. montanus group). The species was originally described in 2008 based on a few specimens from the Sierra de Quilmes, Tucumán. By obtaining new specimens from a nearby locality (La Ovejería, Catamarca), we were able to prepare the skulls of two males and two females specimens. Despite the limited sample size, we observed intra‐specific variability in characters such as postorbital and nasal shape, as well as mandibular curvature. We also document some inter‐specific differences based on the scarce osteological information available from other species within the genus. This description constitutes a significant contribution to the osteology of the Liolaemidae clade. We emphasize the importance of detailed descriptions that provide morphological characters suitable for inclusion in comprehensive phylogenetic analyses.
Brain atlas of the annual Garcialebias charrua fish
Authors: Torres‐Pérez Maximiliano , Herrera María Laura , Rosillo Juan Carlos , Berrosteguieta Inés , Casanova Gabriela , Olivera‐Bravo Silvia , Fernández Anabel Sonia 
Published: March 2024

AbstractAnnual fish have become attractive study models for a wide range of disciplines, including neurobiology. These fish have developed different survival strategies. As a result, their nervous system is under considerable selective pressure when facing extreme environmental situations. Fish from the Austrolebias group exhibit rapid neurogenesis in different brain regions, possibly as a result of the demanding conditions of a changing habitat. Knowledge of cerebral histology is essential for detecting ontogenic, anatomical, or cytoarchitectonic changes in the brain during the short lifespan of these fish, such as those reflecting functional adaptive plasticity in different systems, including sensory structures. The generation of an atlas of Garcialebias charrua (previously known as Austrolebias charrua) establishes its anatomical basis as a representative of a large group of fish that share similarities in their way of life. In this work, we present a detailed study of both gross anatomy and microscopic anatomy obtained through serial sections stained with the Nissl technique in three orientations: transverse, horizontal, and parasagittal planes. This atlas includes accurate drawings of the entire adult brain of the male fish Garcialebias charrua, showing dorsal, ventral, and lateral views, including where emergence and origin of cranial nerves. This brain atlas allows us to understand histoarchitecture as well as the location of neural structures that change during adult neurogenesis, enabling comparisons within the genus. Simultaneously, this atlas constitutes a valuable tool for comparing the brains of other fish species with different behaviors and neuroecologies.
Analysis of Solvent‐Free Intensive‐Dry‐Mixed NMC‐Based Lithium‐Ion Battery Cathodes: Numerical Investigations on Performance Determinants
Authors: Chauhan Anshuman , Lischka Clemens , Nirschl Hermann 
Published: March 2024

AbstractA numerical investigation on the implications of intensive‐dry mixing on the resulting cathode microstructure and hence, the electrochemical performance has been presented in this contribution. In this regard, characterization as well as scale‐resolving electrochemical performance simulations were carried out. The basis for these numerical investigations were computer generated cathode geometries, generated by means of a discrete element method simulation model, presented in our previous work. Consequently, three different stages of comminution of the conductivity additive during intensive dry mixing with nickel rich active material were incorporated into computational half cells and classified based on the simple quality parameter, bulk density. Furthermore, the possible coating phenomenon occurring during the process, to which the bulk density measurements are not susceptible, was modelled with the help of a numerical parameter called the coating factor. It was found that bulk density of cathode blends, which is a rather trivial parameter to measure from intensive dry mixed blends, could be strongly correlated to cathode performance under the consideration of solvent free manufacturing. The findings suggest that, while considering limited volume during cell design, higher bulk density of dry cathode components delivers the best performance under higher energy and low current conditions. At high power and high current condition however, a compromise between energy and power dictates the choice. Conversely, if the material mass is the constraining factor, the lower bulk density tends to perform the best due the best utilisation of the available energy.
Drying kinetics and mathematical modeling of seeds of two mango varieties at different temperatures and with different pretreatments
Authors: Gebre Getachew D. , Keneni Yadessa G. , Gebremariam Shemelis N. , Marchetti Jorge M. 
Published: March 2024

AbstractIncreasing global waste generation is not only a threat but also an opportunity to address energy insecurity and pollution using green valorization techniques. However, this requires pretreatment of waste and byproducts and optimization of drying to obtain high‐quality biofuels. Hence, this study aims to analyze the performance of currently used drying models, the influence of different drying temperatures, drying time, and seed pretreatment on the drying kinetics of two varieties of mango seed. Accordingly, whole seeds and crushed seeds were exposed to five drying temperatures (313–353 K) in a heating furnace. Weight loss was recorded systematically, converted into moisture ratio, and then fitted to four semitheoretical mathematical models, namely: (i) Lewis, (ii) Henderson and Pabis, (iii) Page, and (iv) Avhad and Marchetti models. The fitness of these models was compared using statistical parameters, such asR2,X2, root mean square error (RMSE), mean bias error (MBE), and mean absolute error (MAE). The results showed that seed pretreatment and increasing the drying temperature led to an increase in the rate of moisture evaporation and reduced the time required for drying. Among all models, the Avhad and Marchetti model provided higherR2values of 0.9994 and 0.9991 for local and hybrid mango at 313 K, and 0.9977, and 0.9970 for local and hybrid crushed mango seeds at 353 K and 313 K, respectively; hence, it showed the best performance. The activation energy (Ea) showed a slight differences for both varieties of mango seed and among pretreatments in all mathematical models. The mean Ea values for local and hybrid mango seeds were 41.18 kJ mol−1and 46.21 kJ mol−1, respectively. For whole and crushed local and hybrid mango varieties, the mean Ea values were 31.37 kJ mol−1, 40.80 kJ mol−1, 50.99 kJ mol−1, and 51.61 kJ mol−1. The likely reason for this variation might be differences in variety, chemical composition, growing conditions, and cellular structure of the seed varieties.
Conserved immuno‐collagenic subtypes predict response to immune checkpoint blockade
Authors: Mei Jie , Cai Yun , Xu Rui , Li Qing , Chu Jiahui , Luo Zhiwen , Sun Yaying , Shi Yuxin , Xu Junying , Li Di , Liang Shuai , Jiang Ying , Liu Jiayu , Qian Zhiwen , Zhou Jiaofeng , Wan Mengyun , Yang Yunlong , Zhu Yichao , Zhang Yan , Yin Yongmei 
Published: March 2024

AbstractBackgroundImmune checkpoint blockade (ICB) has revolutionized the treatment of various cancer types. Despite significant preclinical advancements in understanding mechanisms, identifying the molecular basis and predictive biomarkers for clinical ICB responses remains challenging. Recent evidence, both preclinical and clinical, underscores the pivotal role of the extracellular matrix (ECM) in modulating immune cell infiltration and behaviors. This study aimed to create an innovative classifier that leverages ECM characteristics to enhance the effectiveness of ICB therapy.MethodsWe analyzed transcriptomic collagen activity and immune signatures in 649 patients with cancer undergoing ICB therapy. This analysis led to the identification of three distinct immuno‐collagenic subtypes predictive of ICB responses. We validated these subtypes using the transcriptome data from 9,363 cancer patients from The Cancer Genome Atlas (TCGA) dataset and 1,084 in‐house samples. Additionally, novel therapeutic targets were identified based on these established immuno‐collagenic subtypes.ResultsOur categorization divided tumors into three subtypes: “soft & hot” (low collagen activity and high immune infiltration), “armored & cold” (high collagen activity and low immune infiltration), and “quiescent” (low collagen activity and immune infiltration). Notably, “soft & hot” tumors exhibited the most robust response to ICB therapy across various cancer types. Mechanistically, inhibiting collagen augmented the response to ICB in preclinical models. Furthermore, these subtypes demonstrated associations with immune activity and prognostic predictive potential across multiple cancer types. Additionally, an unbiased approach identified B7 homolog 3 (B7‐H3), an available drug target, as strongly expressed in “armored & cold” tumors, relating with poor prognosis.ConclusionThis study introduces histopathology‐based universal immuno‐collagenic subtypes capable of predicting ICB responses across diverse cancer types. These findings offer insights that could contribute to tailoring personalized immunotherapeutic strategies for patients with cancer.