bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photon–Dipole–Spin Interactions in M(TCNE)x/P(VDF‐TrFE) Multiferroic Heterostructure Available for Bimodal Control of Multistate Data‐Storage
Authors: Gao Mingsheng , Lu Xiangqian , Yang Yuying , Qin Wei 
Published: May 2024

AbstractOrganic multiferroic heterostructure is one of the most promising structures for the future design of high‐density flexible energy‐efficient data storage. Here, organic ferromagnetic metal(tetracyanoethylene) (M(TCNE))x/ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)) multiferroic heterostructures are fabricated, where the excited state in M(TCNE)x interacted with localized dipole in P(VDF‐TrFE) provides a key link for the interfacial coupling. Thus, aligned dipoles in P(VDF‐TrFE) by external electric field can affect the magnetization of Fe(TCNE)x effectively to result in a pronounced magnetization–voltage (M–V) hysteresis loop. Moreover, light‐induced electron‐hole pairs in Fe(TCNE)x with long lifetime effectively interact with the dipoles in P(VDF‐TrFE) to lead to an effect in external light control of electric polarization of P(VDF‐TrFE). Overall, the organic multiferroic heterostructure provides the possibility of realizing two storage modes, light control of dipole as well as electric field control of spin, which can broaden multifunctional applications of organic multiferroic materials in the area of multistate storage.
Fluorescence‐Enabled Colored Bilayer Subambient Radiative Cooling Coatings
Authors: Ma Xue , Fu Yang , Liu Danjun , Yang Ning , Dai Jian‐Guo , Lei Dangyuan 
Published: May 2024

AbstractPassive daytime radiative cooling has emerged as a promising green technology for the thermal management of buildings, vehicles, textiles, and electronics. Typically, both high solar reflectance and high thermal emissivity are prerequisites to achieve sufficient daytime cooling. However, colored radiative cooling materials are facing the dilemma of introducing visible light absorption, leading to challenges in balancing cooling and aesthetic demands. Here, three colored bilayer radiative cooling coatings, each comprised of a white base layer and a colored top layer with fluorescence enhancement are fabricated. Three phosphors (Sr2Si5N8:Eu2+, Y3Al5O12:Ce3+, and (Ba,Sr)SiO4:Eu2+) are employed with respective photoluminescence quantum yields (PLQYs) of 81%, 95.8%, and 91.0% as the colored pigment in the top layer. To mitigate the contradiction between coloration and solar reflectance, SiO2 microspheres are introduced into the top layer and utilize their Mie‐resonance‐based multiple scattering to increase the photoluminescent (PL) properties of the phosphors, which jointly boosts the effective solar reflectance (ESR) of the top layer. As a result, the three bilayer coatings exhibit soft colors while achieving subambient cooling with temperature drops of up to 1.5 °C. This fluorescence‐enhancement strategy may pave the way for preparing highly efficient radiative cooling coatings with tunable colors.
Hydration Sensitive Orthogonal Dual Emission of a DNA‐Stabilized Silver Nanocluster
Authors: Liisberg Mikkel Baldtzer , Rück Vanessa , Romolini Giacomo , Cerretani Cecilia , Vosch Tom 
Published: May 2024

AbstractDNA‐stabilized silver nanoclusters (DNA‐AgNCs) are a class of emitters that have primarily been studied for their molecular‐like photophysical properties with ns‐lived fluorescence. However, µs‐lived luminescence has recently been reported for an increasing number of DNA‐AgNCs, but little is still known about the origin of the long‐lived emission. To deepen the understanding of the long‐lived state, (DNA)2‐[Ag11]7+, an emitter with short‐ and long‐lived dual emission, is studied. By examining crystals of (DNA)2‐[Ag11]7+, it is found that the fluorescence and luminescence transitions are orthogonal to each other, which implies that components orthogonal to the long axis of the AgNC, such as the nucleobases, contribute significantly to the polarization character of the long‐lived luminescent state. The effect of the hydration level on the dual emission of dried (DNA)2‐[Ag11]7+ droplets is also investigated, and it is found that water drastically reduces emission from the long‐lived state and causes a redshift of the emission. Finally, an unusual excitation intensity‐dependent response of dried (DNA)2‐[Ag11]7+ droplets is noticed. This is ascribed to the heterogeneous local environment of the amorphous solid resulting in different conformations of (DNA)2‐[Ag11]7+ with different optically activated delayed fluorescence probabilities. The presented results provide new key insights into the nature of the long‐lived state of DNA‐AgNCs.
Inorganic Biomaterials Shape the Transcriptome Profile to Induce Endochondral Differentiation
Authors: Murali Aparna , Brokesh Anna M. , Cross Lauren M. , Kersey Anna L. , Jaiswal Manish K. , Singh Irtisha , Gaharwar Akhilesh 
Published: May 2024

AbstractMinerals play a vital role, working synergistically with enzymes and other cofactors to regulate physiological functions including tissue healing and regeneration. The bioactive characteristics of mineral‐based nanomaterials can be harnessed to facilitate in situ tissue regeneration by attracting endogenous progenitor and stem cells and subsequently directing tissue‐specific differentiation. Here, cellular responses of human mesenchymal stem/stromal cells to traditional bioactive mineral‐based nanomaterials, such as hydroxyapatite, whitlockite, silicon‐dioxide, and the emerging synthetic 2D nanosilicates are investigated. Transcriptome sequencing is utilized to probe the cellular response and determine the significantly affected signaling pathways due to exposure to these inorganic nanomaterials. Transcriptome profiles of stem cells treated with nanosilicates reveals a stabilized skeletal progenitor state suggestive of endochondral differentiation. This observation is bolstered by enhanced deposition of matrix mineralization in nanosilicate treated stem cells compared to control or other treatments. Specifically, use of 2D nanosilicates directs osteogenic differentiation of stem cells via activation of bone morphogenetic proteins and hypoxia‐inducible factor 1‐alpha signaling pathway. This study provides insight into impact of nanomaterials on cellular gene expression profile and predicts downstream effects of nanomaterial induction of endochondral differentiation.
Genetic variations of bread wheat varieties for bread‐making quality traits in moisture stressed areas of Wollo, Ethiopia
Authors: Tessema Agegnehu Mekonnen , Yimam Arega Gashaw , Hailemariam Firew Mekbib 
Published: May 2024

AbstractIn Ethiopia, wheat variety development has traditionally prioritized yield and disease resistance over bread‐making quality. To address this gap, our study evaluated 22 Ethiopian bread wheat varieties across six locations during the 2015/2016 season, utilizing a randomized complete block design with three replications. Various quality traits, including 1000‐kernel weight (TKW), hectoliter weight (HLW), Perten hardness index (HI), single kernel weight (SKW), single kernel diameter (SKD), grain protein content (PC), wet gluten (WG), Zeleny value (ZV), and starch content (SC), were analyzed. Significant effects of varieties, locations, and their interactions on these traits were observed (p < 0.01). Madawalabu, Danda'a, and Mekelle‐4 displayed superior TKW (>40 g), while Menze and Bolo exhibited higher HLW. HI values ranged from 82.8% in Sofumar to 35.5% in Mekelle‐3, indicating diverse grain hardness. Favorable milling traits were observed with SKW values exceeding 30 mg and SKD surpassing 2.5 mm. Genotype and location influenced PC (9.5%–11.0%) and WG content (21.6%–25.2%), meeting bread‐making requirements. ZV ranged from 21.9% to 31%, and SC varied from 64% to 68%, reflecting changes in starch concentration between varieties. Varietal performance varied, with Madawalabu, Menze, and Bolo showing promise. Correlation analysis revealed positive associations among HLW, SKD, SKW, TKW, PC, WG, and ZV, and a negative correlation with SC. These insights provide a foundation for targeted breeding strategies to enhance specific attributes crucial for optimal bread quality, contributing valuable information to wheat breeding programs.
Lenvatinib‐resistant hepatocellular carcinoma promotes malignant potential of tumor‐associated macrophages via exosomal miR‐301a‐3p
Authors: Waki Yuhei , Morine Yuji , Saito Yu , Teraoku Hiroki , Yamada Shinichiro , Ikemoto Tetsuya , Tominaga Tatsuya , Shimada Mitsuo 
Published: May 2024

AbstractBackgroundThe interactions between cancer cells and tumor‐associated macrophages (TAMs) via microRNAs (miRNAs) play crucial roles in malignant potential and drug resistance. However, it remains unclear how lenvatinib‐resistant hepatocellular carcinoma (LR HCC) promotes TAM tumor biology. Here we investigated the crosstalk between LR HCC cells and TAMs for cancer progression and lenvatinib resistance, focusing on an exosomal miRNA.MethodsWe used two bioinformatics software programs to identify miRNAs that target PTEN in gastrointestinal cancers, then investigated exosomal miRNA expression in LR HCC conditioned medium (CM). After modifying TAMs with LR HCC CM (LR TAM), macrophage phenotype and PTEN‐Nrf2 signaling pathway component expression were analyzed in LR TAMs. The malignant potential and drug resistance were investigated in naïve HCC cells cultured with LR TAM CM.ResultsLR HCC cells highly induced M2‐like properties in macrophages compared with naïve HCC cells. Exosomal miR‐301a‐3p expression was increased in LR HCC CM, with higher activation of the PTEN/PI3K/GSK3β/Nrf2 signaling pathway in LR TAMs. Naïve HCC cells were educated with LR TAM CM to promote malignant potential and lenvatinib resistance. Inhibition of exosomal miR‐301a‐3p prevented the malignant potential of LR TAMs. Activation of Nrf2 signaling by LR HCC cell‐derived exosomal miR‐301a‐3p skewed the transformation of macrophages to the M2 phenotype.ConclusionOur study provides new findings on the role of miR‐301a‐3p, suggesting it is a promising therapeutic target to improve HCC lenvatinib resistance.
Special RCA based sensitive point‐of‐care detection of HPV mRNA for cervical cancer screening
Authors: Long Yi , Tao Shurui , Shi Dongni , Jiang Xingyu , Yu Tian , Long Yingxi , Song Libing , Liu Guozhen 
Published: May 2024

AbstractDeveloping the sensitive point‐of‐care testing (POCT) of oncogenic nucleic acids from human papillomavirus (HPV) infection is essential in preventing cervical cancer, especially in resource‐limited settings. Rolling circle amplification (RCA) is attractive in achieving POCT via nucleic acid‐based aggregation under isothermal conditions. However, the influence of RCA product structure on the aggregation remains unexplored resulting in limited sensitivity. Here, a minimum secondary structured RCA technique (MSS‐RCA) is developed by designing a unique circular template, demonstrating significantly enhanced detection sensitivity with only one amplification step and one primer under isothermal conditions. The amplification efficiency of MSS‐RCA could be kinetically manipulated by controlling the secondary structure of the circular template. Introducing the invertase probe to MSS‐RCA, HPV16 E6/E7 nucleic acid target was detected with a personal glucose meter (PGM) with a sensitivity of 5 fm (50 zmol in 10 µL). This integrated MSS‐RCA‐PGM detection system was successfully applied to detect HPV16 E6/E7 mRNA extracted from 54 cervical swab samples reaching a positive predictive value of 100.00% and negative predictive values of 96.00% (77.77% to 99.40%, 95% CI). MSS‐RCA‐PGM provides a sensitive POCT platform for the detection of nucleic acid biomarkers for screening of cervical cancer or other diseases.
Eating through time: Understanding dietary practices across late prehistory in the northeastern Iberian Peninsula
Authors: Hernando R. , Moreno‐Ibáñez M. Á. , Carbonell E. , Cebrià A. , Daura J. , Díez‐Canseco C. , Edo M. , Fullola J. M. , Morales J. I. , Oms F. X. , Ramírez‐Pedraza I. , Sanz M. , Subirá M. E. , Tornero C. , Vergès J. M. , Lozano M. 
Published: May 2024

AbstractObjectiveThis study seeks to contribute to the current understanding of dietary variation in the late Prehistory of the northeastern Iberian Peninsula by examining buccal dental microwear patterns alongside archeological data from the same populations.Materials and MethodsTeeth from 84 adult individuals from eight distinct samples spanning the Middle‐Late Neolithic to the Middle Bronze Age (Cova de l'Avi, Cova de Can Sadurní, Cova de la Guineu, Cova Foradada, Cova del Trader, Roc de les Orenetes, Cova del Gegant, Cova dels Galls Carboners) were analyzed using optical microscopy to examine buccal dental microwear patterns.ResultsThe analysis did not reveal clear chronological contrasts in the dietary habits of these samples. Nevertheless, significant differences emerged among the samples, leading to their classification into two distinct sets based on the abrasiveness of the diet informed by the microwear patterns. These findings offer similarities and differences among samples in the Iberian Peninsula, shedding light on the diverse lifestyles of these individuals.DiscussionIntegrating our new results with other available proxies points to a multifaceted specialization in dietary patterns among these samples, influenced by factors such as habitat, resource selection, and available technology. By contextualizing the results within the broader context of the Iberian Peninsula, this research discerns shared characteristics and distinctive adaptations in the dietary practices and subsistence strategies of these groups. Ultimately, this study contributes to a deeper understanding of the intricate interplay between culture and environment in shaping human diets throughout late Prehistory.
Influence of Ti‐incorporated Zeolite Topology and Pore Condensation on Vapor Phase Propylene Epoxidation Kinetics with Gaseous H2O2
Authors: Kwon Ohsung , Zeynep Ayla E. , Potts David S. , Flaherty David W. 
Published: May 2024

AbstractVapor‐phase propylene (C3H6) epoxidation kinetics with hydrogen peroxide (H2O2) strongly reflects the physical properties of Ti‐incorporated zeolite catalysts and the presence of spectating molecules (“solvent”) near active sites even without a bulk liquid phase. Steady‐state turnover rates of C3H6 epoxidation and product selectivities vary by orders of magnitudes, depending on the zeolite silanol ((SiOH)x) density, pore topology (MFI, *BEA, FAU), and the quantity of condensed acetonitrile (CH3CN) molecules nearby active sites, under identical reaction mechanisms sharing activated H2O2 intermediates on Ti surfaces. Individual kinetic analyses for propylene oxide (PO) ring‐opening, homogeneous diol oxidative cleavage, and homogeneous aldehyde oxidation reveal that secondary reaction kinetics following C3H6 epoxidation responds more sensitively to the changes in zeolite physical properties and pore condensation with CH3CN. Thus, higher PO selectivities achieved in hydrophilic Ti‐MFI at steady‐state reflect the preferential stabilization of transition states for C3H6 epoxidation (a primary reaction) relative to PO ring‐opening and oxidative cleavage (secondary reactions) that solvation effects that reflect interactions among condensed CH3CN within pores and the extended pore structure.
An Asymmetric Coumarin‐Anthracene Conjugate as Efficient Fullerene‐Free Acceptor for Organic Solar Cells
Authors: Niharika Bhuyan Nirmala , Shankar S Shyam , Jyoti Panda Subhra , Shekhar Purohit Chandra , Singhal Rahul , Sharma Ganesh D. , Mishra Amaresh 
Published: May 2024

AbstractAsymmetric wide‐band gap fullerene‐free acceptors (FFAs) play a crucial role in organic solar cells (OSCs). Here, we designed and synthesized a simple asymmetric coumarin‐anthracene conjugate named CA‐CN with optical band gap of 2.1 eV in a single‐step condensation reaction. Single crystal X‐ray structure analysis confirms various multiple intermolecular non‐covalent interactions. The molecular orbital energy levels of CA‐CN estimated from cyclic voltammetry were found to be suitable for its use as an acceptor for OSCs. Binary OSCs fabricated using CA‐CN as acceptor and PTB7‐Th as the donor achieve a power conversion efficiency (PCE) of 11.13 %. We further demonstrate that the insertion of 20 wt % of CA‐CN as a third component in ternary OSCs with PTB7‐Th : DICTF as the host material achieved an impressive PCE of 14.91 %, an improvement of ~43 % compared to the PTB7‐Th : DICTF binary device (10.38 %). Importantly, the ternary blend enhances the absorption coverage from 400 to 800 nm and improves the morphology of the active layer. The findings highlight the efficacy of an asymmetric design approach for FFAs, which paves the way for developing high‐efficiency OSCs at low cost.
Highly Efficient Acidic Electrosynthesis of Hydrogen Peroxide at Industrial‐Level Current Densities Promoted by Alkali Metal Cations
Authors: Cao Peike , Zhao Xueyang , Liu Yanming , Zhang Haiguang , Zhao Kun , Chen Shuo , Yu Hongtao , Dong Fan , Nichols Nathaniel N. , Chen Jingguang G. , Quan Xie 
Published: May 2024

AbstractAcidic H2O2 synthesis through electrocatalytic 2e− oxygen reduction presents a sustainable alternative to the energy‐intensive anthraquinone oxidation technology. Nevertheless, acidic H2O2 electrosynthesis suffers from low H2O2 Faradaic efficiencies primarily due to the competing reactions of 4e− oxygen reduction to H2O and hydrogen evolution in environments with high H+ concentrations. Here, we demonstrate the significant effect of alkali metal cations, acting as competing ions with H+, in promoting acidic H2O2 electrosynthesis at industrial‐level currents, resulting in an effective current densities of 50–421 mA cm−2 with 84–100 % Faradaic efficiency and a production rate of 856–7842 μmol cm−2 h−1 that far exceeds the performance observed in pure acidic electrolytes or low‐current electrolysis. Finite‐element simulations indicate that high interfacial pH near the electrode surface formed at high currents is crucial for activating the promotional effect of K+. In situ attenuated total reflection Fourier transform infrared spectroscopy and ab initio molecular dynamics simulations reveal the central role of alkali metal cations in stabilizing the key *OOH intermediate to suppress 4e− oxygen reduction through interacting with coordinated H2O.
Unraveling Stoichiometry Effect in Nickel‐Tungsten Alloys for Efficient Hydrogen Oxidation Catalysis in Alkaline Electrolytes
Authors: Wang Ye‐Hua , Yang Yu , Gao Fei‐Yue , Zhang Xiao‐Long , Zhu Lei , Yan Hui‐Kun , Yang Peng‐Peng , Gao Min‐Rui 
Published: May 2024

AbstractAnion‐exchange membrane fuel cells provide the possibility to use platinum group metal‐free catalysts, but the anodic hydrogen oxidation reaction (HOR) suffers from sluggish kinetics and its source is still debated. Here, over nickel‐tungsten (Ni−W) alloy catalysts, we show that the Ni : W ratio greatly governs the HOR performance in alkaline electrolyte. Experimental and theoretical studies unravel that alloying with W can tune the unpaired electrons in Ni, tailoring the potential of zero charge and the catalytic surface to favor hydroxyl adsorption (OHad). The OHad species coordinately interact with potassium (K+) ions, which break the K+ solvation sheath to leave free water molecules, yielding an improved connectivity of hydrogen‐bond networks. Consequently, the optimal Ni17W3 alloy exhibits alkaline HOR activity superior to the state‐of‐the‐art platinum on carbon (Pt/C) catalyst and operates steadily with negligible decay after 10,000 cycles. Our findings offer new understandings of alloyed HOR catalysts and will guide rational design of next‐generation catalysts for fuel cells.
Highly Efficient Self‐Assembly of Heterometallic [2]Catenanes and Cyclic Bis[2]catenanes via Orthogonal Metal‐Coordination Interactions
Authors: Feng Qian , Ding Rui , Hou Yali , Zhang Zeyuan , Zhang Yafei , Liu Haifei , Guo Chenxing , He Gang , Zheng Bo , Zhang Yanmin , Zhang Mingming 
Published: May 2024

AbstractAlthough catenated cages have been widely constructed due to their unique and elegant topological structures, cyclic catenanes formed by the connection of multiple catenane units have been rarely reported. Herein, based on the orthogonal metal‐coordination‐driven self‐assembly, we prepare a series of heterometallic [2]catenanes and cyclic bis[2]catenanes, whose structures are clearly evidenced by single‐crystal X‐ray analysis. Owing to the multiple positively charged nature, as well as the potential synergistic effect of the Cu(I) and Pt(II) metal ions, the cyclic bis[2]catenanes display broad‐spectrum antibacterial activity. This work not only provides an efficient strategy for the construction of heterometallic [2]catenanes and cyclic bis[2]catenanes but also explores their applications as superior antibacterial agents, which will promote the construction of advanced supramolecular structures for biomedical applications.
Quantification of Native Lignin Structural Features with Gel‐Phase 2D‐HSQC0 Reveals Lignin Structural Changes During Extraction
Authors: Bourmaud Claire L. , Bertella Stefania , Bosch Rico Anna , Karlen Steven D. , Ralph John , Luterbacher Jeremy S. 
Published: May 2024

AbstractOur ability to study and valorize the lignin fraction of biomass is hampered by the fundamental and still unmet challenge of precisely quantifying native lignin's structural features. Here, we developed a rapid elevated‐temperature 1H−13C Heteronuclear Single‐Quantum Coherence Zero (HSQC0) NMR method that enables this precise quantification of native lignin structural characteristics even with whole plant cell wall (WPCW) NMR spectroscopy, overcoming fast spin relaxation in the gel phase. We also formulated a Gaussian fitting algorithm to perform automatic and reliable spectral integration. By combining HSQC0 measurements with yield measurements following depolymerisation, we can confirm the combinatorial nature of radical coupling reactions during biosynthesis leading to a random sequential organization of linkages within a largely linear lignin chain. Such analyses illustrate how this analytical method can greatly facilitate the study of native lignin structure, which can then be used for fundamental studies or to understand lignin depolymerization methods like reductive catalytic fractionation or aldehyde‐assisted fractionation.
Efficient Enzymatic Synthesis of Carbamates in Water Using Promiscuous Esterases/Acyltransferases
Authors: Meinert Hannes , Oehlschläger Florian , Cziegler Clemens , Rockstroh Jan , Marzuoli Irene , Bisagni Serena , Lalk Michael , Bayer Thomas , Iding Hans , Bornscheuer Uwe T. 
Published: May 2024

AbstractBiocatalysis provides an attractive approach to facilitate synthetic reactions in aqueous media. Motivated by the discovery of promiscuous aminolysis activity of esterases, we exploited the esterase from Pyrobaculum calidifontis VA1 (PestE) for the synthesis of carbamates from different aliphatic, aromatic, and arylaliphatic amines and a set of carbonates such as dimethyl‐, dibenzyl‐, or diallyl carbonate. Thus, aniline and benzylamine derivatives, aliphatic and even secondary amines could be efficiently converted into the corresponding benzyloxycarbonyl (Cbz)‐ or allyloxycarbonyl (Alloc)‐protected products in bulk water, with (isolated) yields of up to 99 %.