bluuebunny/crossref_metadata_2025_split huggingface dataset:
Boosting Electrochemical Performance via Extra‐Role of La‐Doped CeO2‐δ Interlayer for “Oxygen Provider” at High‐Current SOFC Operation
Authors: Nguyen Xuan Dong , Lee Sang Won , Kim Su Ji , Park Jungdeok , Koo Bonseok , Lee Seok Hee , Lee Shiwoo , Lim Hyung Tae , Irvine John T.S. , Shin Tae Ho 
Published: September 2024

AbstractUtilizing rare earth doped ceria in solid oxide cells (SOCs) engineering is indeed a strategy aimed at enhancing the electrochemical devices' durability and activity. Particularly, Gd‐doped ceria (GDC) is actively used for barrier layer and catalytic additives in solid oxide fuel cells (SOFCs). In this study, experiments are conducted with La‐doped CeO2 (LDC), in which the Ce sites are predominantly occupied by La, to prevent the formation of the Ce‐Zr solid solution. This LDC is comparably used as a functional interlayer between the electrolyte and cathode if sintered at lower temperatures to avoid La2Zr2O7 impurity. In addition, the high substitution of La3+ into the ceria lattice improves the oxygen non‐stoichiometry of LDC, leading to accelerated electrochemical high performance by the additional role of LDC for oxygen supplier capacitance at high current operation. Thus, it is confirmed that the improved SOFC high performance is achieved at the maximum power density (MPD) of ≈2.15 W cm−2 at 800 °C when the optimized LDC buffer layer is hired at the anode‐supported typed‐Samsung's SOFC by lowering the sintering temperature to prevent LDC's impurity reaction.
Economic evaluation of corn relative maturity hybrids in corn–pennycress–soybean rotations
Authors: Mohammed Yesuf Assen , Gesch Russ W. , Wells Samantha , Heller Nicholas J. , Lindsey Alexander J. , Hard Alexander W. , Phippen Winthrop B. 
Published: September 2024

AbstractThis manuscript is a follow‐up of previously published results that presented findings on pennycress (Thlaspi arvense L.) establishment and agronomics in response to previous corn (Zea mays L.) relative maturity (CRM) hybrids grown for grain and silage in the corn–pennycress–soybean [Glycine max (L.)] rotations. In this manuscript, we compared the economics of grain corn–pennycress–soybean rotations (grain rotation) with silage corn–pennycress–soybean rotations (silage rotation). The treatments were CRM hybrids ranging from 76 to 95 days (full season) at northern sites (Morris and Rosemount, MN) and 95 to 113 days (full season) at southern sites (Lexington, IL, and Custar, OH). Full‐season corn harvested for silage was included as a control treatment representing optimum conditions for sowing pennycress. A partial budget procedure was used for economic analysis. The results showed that the annualized net benefits (ANBs) ranged from $315 to $945 ha−1. The silage rotation produced greater ANBs than the grain rotation at all sites due to increased pennycress seed yield. In the grain rotation, the 105 days in the south, 95 days corn at Morris, and 86 days corn at Rosemount resulted in minimal ANB losses compared with silage rotation. Among grain corn treatments, some of the early CRM hybrids resulted in greater ANBs (up to 40%) than the full season hybrid. Results demonstrate potential to integrate pennycress into a grain rotation using early CRM hybrids. In addition, valuing the diverse ecosystem benefits that pennycress offers as a cash cover crop during the offseason between corn and soybean rotation may help to attract growers.
PHF6 mutations in chronic myelomonocytic leukemia identify a unique subset of patients with distinct phenotype and superior prognosis
Authors: Tefferi Ayalew , Fathima Saubia , Alsugair Ali Khalid A. , Aperna Fnu , Natu Anuya , Abdelmagid Maymona G. , Csizmar Clifford M. , Gurney Mark , Lasho Terra L. , Finke Christy M. , Mangaonkar Abhishek A. , Al‐Kali Aref , Pardanani Animesh , Reichard Kaaren K. , He Rong , Gangat Naseema , Patnaik Mrinal M. 
Published: September 2024

AbstractThe current study was inspired by observations from exploratory analyses of an institutional cohort with chronic myelomonocytic leukemia (CMML; N = 398) that revealed no instances of blast transformation in the seven patients with plant homeodomain finger protein 6 (PHF6) mutation (PHF6MUT). A subsequent Mayo Clinic enterprise‐wide database search identified 28 more cases with PHF6MUT. Compared with their wild‐type PHF6 counterparts (PHF6WT; N = 391), PHF6MUT cases (N = 35) were more likely to co‐express TET2 (89% vs. 45%; p < .01), RUNX1 (29% vs. 14%; p = .03), CBL (14% vs. 2%; p < .01), and U2AF1 (17% vs. 6%; p = .04) and less likely SRSF2 (23% vs. 45%; p < .01) mutation. They were also more likely to display loss of Y chromosome (LoY; 21% vs. 2%; p < .01) and platelets <100 × 109/L (83% vs. 51%; p < .01). Multivariable analysis identified PHF6MUT (HR 0.28, 95% CI 0.15–0.50) and DNMT3AMUT (HR 5.8, 95% CI 3.3–10.5) as the strongest molecular predictors of overall survival. The same was true for blast transformation‐free survival with corresponding HR (95% CI) of 0.08 (0.01–0.6) and 9.5 (3.8–23.5). At median 20 months follow‐up, blast transformation was documented in none of the 33 patients with PHF6MUT/DNMT3AWT but in 6 (32%) of 19 with DNMT3AMUT and 74 (20%) of 374 with PHF6WT/DNMT3AWT (p < .01). The specific molecular signatures sustained their significant predictive performance in the context of the CMML‐specific molecular prognostic model (CPSS‐mol). PHF6MUT identifies a unique subset of patients with CMML characterized by thrombocytopenia, higher prevalence of LoY, and superior prognosis.
An Association Between Left‐Hand Digit Ratio (2D:4D) and Anthropometric Indexes in Chinese Children and Adolescents Aged 8–15 Years in Bengbu City
Authors: Zhang Ya , Cao Ruiyao , Li Wenxiu , Fu Han , Zhu Jiamin , Xu Xuemo , Wang Rui , Peng Ziyu , Fu Lianguo 
Published: September 2024

ABSTRACTObjectivesThe digit ratio (2D:4D) is a possible marker of prenatal hormone exposure. The purpose of this study was to explore the relationships between digit ratio (2D:4D) and anthropometric indexes in Chinese children and adolescents.MethodsThis study is a cross‐sectional study. A school‐based survey among 685 children and adolescents aged 8–15 years were conducted by stratified cluster sampling. The length of index finger (2D) and ring finger (4D) of the left hand, height, sitting height (ST), weight, chest circumference (CC), waist circumference (WC), hip circumference (HC), and abdominal skinfold thickness (AST) were measured. Pearson correlation and multivariate linear regression were used to analyze associations between 2D:4D and above indexes.ResultsIn girls, 2D:4D was positively related to WC, AST, waist‐to‐height (WHtR), waist‐to‐hip ratio (WHR) after adjusting for ages (p < 0.05). The WC, AST, WHtR, and WHR among girls with 2D:4D ≥ 1 were significantly higher than those among girls with 2D:4D < 1, respectively (p < 0.05). However, there was no correlations between digit ratio (2D:4D) and above anthropometric indexes in boys (p > 0.05).ConclusionsThe 2D:4D was related to anthropometric indexes in girls, which suggests that the maternal prenatal hormone exposure might be related to the anthropometric indexes of their female offspring.
Heterogeneous Carbonylation of Alcohols on Charge‐Density‐Distinct Mo−Ni Dual Sites Localized at Edge Sulfur Vacancies
Authors: Yuan Qiao , Gu Yating , Chen Weimiao , Zhang Yue , Song Xiangen , Ding Yangming , Li Xingju , Zhu Lei , Jiang Zheng , Yan Li , Ma Jing , Ding Yunjie 
Published: September 2024

AbstractAlcohols carbonylation is of great importance in industry but remains a challenge to abandon the usage of the halide additives and noble metals. Here we report the realization of direct alcohols heterogeneous carbonylation to carbonyl‐containing chemicals, especially in methanol carbonylation, with a remarkable space‐time‐yield (STY) of 4.74 molacetyl/kgcat./h and a durable stability as long as 100 h on Ni@MoS2 catalyst. Mechanistic analysis reveals that the Mo−Ni dual sites localized at edge sulfur vacancies of Ni@MoS2 exhibit distinct charge density, which strongly activate CH3OH to break its C−O bond and non‐dissociatively activate CO. Density functional theory calculations further suggest that the low charge density in Mo−Ni, the Ni site, could significantly lower the barrier for CO migration and nucleophilic attack of methoxy species, and finally leads to the rapid formation of acetyl products. Ni@MoS2 catalyst could also effectively realize the carbonylation of ethanol, n‐propanol and n‐butanol to their acyl products, which may demonstrate its universal application for alcohols carbonylation.
In Situ Generation of 1‐Acetylpyrene as a Visible‐Light Photocatalyst for the Thia‐Paternò‐Büchi Reaction
Authors: Cormier Gabriel , Allain Clémence , Boddaert Thomas 
Published: September 2024

AbstractThe thia‐Paternò‐Büchi reaction represents a straightforward approach to build thietane cores. Unfortunately, the significant instability of thiocarbonyls, particularly thioketones and thioaldehydes, has hitherto rendered this photochemical [2+2]‐cycloaddition underexploited. To address this limitation, we report herein a visible‐light photochemical domino reaction including: the in situ generation of thiocarbonyls though a Norrish type II fragmentation of pyrenacyl sulfides, and the aforementioned thia‐Paternò‐Büchi reaction with various non‐volatile electron‐rich alkenes. The highly efficient synthesis of a wide range of unprecedented thietanes from intrinsically highly unstable thiocarbonyls, such as thioaldehydes and aliphatic thioketones, was made possible by the multitasking capability of pyrenacyl sulfides as a source of thiocarbonyl substrates and as precursors of 1‐acetylpyrene, which acts as the photocatalyst for the thia‐Paternò‐Büchi reaction. The photosensitizer properties of the latter have been experimentally established and a triplet‐triplet Dexter energy transfer based mechanism is proposed.
Unlocking Self‐antioxidant Capability and Processability of Additive‐free MXene Ink towards High‐performance Customizable Supercapacitors
Authors: Zheng Yuanchuan , Wang Yalei , Liu Dongqi , Zhao Jiupeng , Li Yao 
Published: September 2024

AbstractThe solution processing of MXene ink is the feasible strategy to realize its state‐of‐the‐art applications. Nevertheless, achieving high stability and processability of additive‐free MXene ink is particularly challenging. Herein, we propose an oxyanion‐terminated Ti3C2Tx MXene ink that exhibits excellent self‐antioxidant capability and processability. The vertex‐connected polyhedrons of oxyanions capping on the Ti3C2 host serve as an in situ antioxidative shield, effectively preventing the attack of free H2O molecules while increasing the robustness of the Ti−C bond and reducing the susceptibility of surface Ti atoms to oxidation. Consequently, the shelf life of MXene ink can be extended up to 5 months at room temperature. Moreover, the high electron accumulation of oxyanions enhances the interlayer interactions among MXene sheets through electrostatic binding, which enables the formation of stable and uniform MXene inks with controlled rheological properties and processability. Inspired by Chinese calligraphy, we utilize the oxyanion‐terminated MXene ink to fabricate high‐performance and customizable paper supercapacitors, which exhibit exceptional flexibility and stability, allowing them to be tailored to desired capacity, stretchability, and shapes. This in situ surface chemistry strategy of oxyanions can activate the self‐antioxidant capability and solution processability of MXene, paving the way for its widespread applications in flexible and wearable electronics.
Mn−Ce Symbiosis: Nanozymes with Multiple Active Sites Facilitate Scavenging of Reactive Oxygen Species (ROS) Based on Electron Transfer and Confinement Anchoring
Authors: Zhang Juan , Wang Zhihua , Lin Xingen , Gao Xiaoping , Wang Qiuping , Huang Rui , Ruan Yaner , Xu Haonan , Tian Lin , Ling Chen , Shi Ran , Xu Suowen , Chen Kong , Wu Yuen 
Published: September 2024

AbstractRegulating appropriate valence states of metal active centers, such as Ce3+/Ce4+ and Mn3+/Mn2+, as well as surface vacancy defects, is crucial for enhancing the catalytic activity of cerium‐based and manganese‐based nanozymes. Drawing inspiration from the efficient substance exchange in rhizobia‐colonized root cells of legumes, we developed a symbiosis nanozyme system with rhizobia‐like CeOx nanoclusters robustly anchored onto root‐like Mn3O4 nanosupports (CeOx/Mn3O4). The process of “substance exchange” between Ce and Mn atoms—reminiscent of electron transfer—not only fine‐tunes the metal active sites to achieve optimal Ce3+/Ce4+ and Mn3+/Mn2+ ratios but also enhances the vacancy ratio through interface defect engineering. Additionally, the confinement anchoring of CeOx on Mn3O4 ensures efficient electron transfer in catalytic reactions. The final CeOx/Mn3O4 nanozyme demonstrates potent catalase‐like (CAT‐like) and superoxide dismutase‐like (SOD‐like) activities, excelling in both chemical settings and cellular environments with high reactive oxygen species (ROS) levels. This research not only unveils a novel material adept at effectively eliminating ROS but also presents an innovative approach for amplifying the efficacy of nanozymes.
Can Deep Learning Search for Exceptional Chiroptical Properties? The Halogenated [6]Helicene Case
Authors: Uceda Rafael G. , Gijón Alfonso , Míguez‐Lago Sandra , Cruz Carlos M. , Blanco Víctor , Fernández‐Álvarez Fátima , Álvarez de Cienfuegos Luis , Molina‐Solana Miguel , Gómez‐Romero Juan , Miguel Delia , Mota Antonio J. , Cuerva Juan M. 
Published: September 2024

AbstractThe relationship between chemical structure and chiroptical properties is not always clearly understood. Nowadays, efforts to develop new systems with enhanced optical properties follow the trial‐error method. A large number of data would allow us to obtain more robust conclusions and guide research toward molecules with practical applications. In this sense, in this work we predict the chiroptical properties of millions of halogenated [6]helicenes in terms of the rotatory strength (R). We have used DFT calculations to randomly create derivatives including from 1 to 16 halogen atoms, that were then used as a data set to train different deep neural network models. These models allow us to i) predict the Rmax for any halogenated [6]helicene with a very low computational cost, and ii) to understand the physical reasons that favour some substitutions over others. Finally, we synthesized derivatives with higher predicted Rmax obtaining excellent correlation among the values obtained experimentally and the predicted ones.
Hydrogen Sulfide‐Triggered Artificial DNAzyme Switches for Precise Manipulation of Cellular Functions
Authors: Xie Xuan , Nan Hexin , Peng Jialong , Zeng Kaiqiang , Wang Hong‐Hui , Huang Yan , Nie Zhou 
Published: September 2024

AbstractThe development of synthetic molecular tools responsive to biological cues is crucial for advancing targeted cellular regulation. A significant challenge is the regulation of cellular processes in response to gaseous signaling molecules such as hydrogen sulfide (H2S). To address this, we present the design of Gas signaling molecule‐Responsive Artificial DNAzyme‐based Switches (GRAS) to manipulate cellular functions via H2S‐sensitive synthetic DNAzymes. By incorporating stimuli‐responsive moieties to the phosphorothioate backbone, DNAzymes are strategically designed with H2S‐responsive azide groups at cofactor binding locations within the catalytic core region. These modifications enable their activation through H2S‐reducing decaging, thereby initiating substrate cleavage activity. Our approach allows for the flexible customization of various DNAzymes to regulate distinct cellular processes in diverse scenarios. Intracellularly, the enzymatic activity of GRAS promotes H2S‐induced cleavage of specific mRNA sequences, enabling targeted gene silencing and inducing apoptosis in cancer cells. Moreover, integrating GRAS with dynamic DNA assembly allows for grafting these functional switches onto cell surface receptors, facilitating H2S‐triggered receptor dimerization. This extracellular activation transmits signals intracellularly to regulate cellular behaviors such as migration and proliferation. Collectively, synthetic switches are capable of rewiring cellular functions in response to gaseous cues, offering a promising avenue for advanced targeted cellular engineering.
A Smart Design of Non‐Noble Catalysts for Sustainable Propane Dehydrogenation
Authors: Smith Louise R. , Sun Zhao , Hutchings Graham J. 
Published: September 2024

AbstractPropane dehydrogenation (PDH), an important process for propylene synthesis, relies on expensive noble metals or highly toxic oxides as catalysts. In a recent publication, Gong and co‐workers report a breakthrough discovery for PDH by introducing a sustainable catalyst composed of titanium oxide overlayers encapsulating nickel nanoparticles, termed Ni@TiOx. This innovative catalyst showcases exceptional performance in PDH, exhibiting high propylene selectivity and stability under industrially relevant conditions. The study elucidates the role of defective TiOx overlayers and the electronic promotional effect of subsurface Ni in enhancing catalytic activity, translating a traditional model catalyst system into a sustainable industrial catalyst for low‐carbon energy and the chemical industry.
Unlocking Oxetane Potential: Modular Synthetic Platform for the Concise Synthesis of Acyclic Oligo‐Isoprenoids and Terpenoids
Authors: Albitz Krisztián , Tóth Sára , Csókás Dániel , Soós Tibor 
Published: September 2024

AbstractTerpenes occupy a unique place among the secondary metabolites due to their broad utility and extraordinary structural diversity. Their synthesis via polyene cyclization, either biomimetic or enzymatic, represents the cutting edge of modern synthetic chemistry. However, these endeavors have been inherently tied to the availability of natural and non‐natural acyclic polyene starting materials. Herein, we report an oxetane‐based platform for the modular construction of oxygenated polyolefins with precise geometric control. This “tail‐to head” iterative method leverages the site‐selective cross‐metathesis of terminal olefins to form an alkylidene oxetane moiety and the regioselective ring opening of alkenyl‐oxetanes for chain elongation. In addition, the unique and peculiar propensity of alkylidene oxetane fragment in various reactions was also revealed and exploited for site‐selective functionalization, cyclization, and as a protecting group in polyenes.
The Role of L‐Ligands in Silica‐Supported Ti Oxo/Imido Heterometathesis Catalysts
Authors: Bushkov Nikolai S. , Rumyantsev Andrey V. , Pichugov Andrey V. , Zhizhin Anton A. , Aleshin Dmitry Yu. , Gutsul Evgenii I. , Takazova Rina U. , Kitaeva Dinara Kh. , Dolgushin Fedor M. , Novikov Roman A. , Zhizhko Pavel A. , Zarubin Dmitry N. 
Published: September 2024

ABSTRACTWe report here the preparation and characterization of new well‐defined silica‐supported Ti imido complexes that present an L‐ligand variation in a structure of currently the most active oxo/imido heterometathesis catalyst (≡SiO)Ti(=NtBu)(Me2Pyr)(py)2 (1s), where py is replaced with stronger electron‐donating 4‐(N,N‐dimethylamino)pyridine (2s) or bidentate 2,2′‐bipyridine (3s). The materials were characterized with elemental and mass balance analyses and IR and solid‐state NMR that confirmed the selective formation of surface Ti species with terminal imido ligand. Evaluation of the catalytic oxo/imido heterometathesis activity of the obtained materials demonstrated that L‐ligands have a pronounced influence on the catalytic performance. In particular, the replacement of pyridine with stronger donating ligands resulted in a significant drop of activity. The catalytic results are discussed in view of the reaction mechanism and implications for further catalyst development.
Design of a bio‐based flame‐retardant epoxy/amine cross‐linked coatings
Authors: Mansouri Siavash , Hazra Raj Shankar , Swarup Shanti , Quadir Mohiuddin 
Published: September 2024

AbstractEpoxy cross‐linked coatings are widely used to protect and beautify many surfaces all around us. However, these coatings possess a dense carbonaceous structure, rendering them susceptible to ignition, spread, and propagation of flames. Therefore, flame‐retardant (FR) materials are added into these coatings as additives to improve flame resistance properties. Many of the commercially available FR additives are halogenated, metal oxide, and alkyl phosphate‐based compounds, often originating from nonrenewable resources. Some of these compounds produce undesirable toxic fumes and byproducts upon combustion. To overcome these challenges, we tested bio‐based phytic acid (PA) as an FR additive in epoxy resin, cross‐linked with bio‐based phenalkamine (NX)—a material derived from cashew oil nutshell. Our findings demonstrate that the incorporation of PA into an NX‐cross‐linked epoxy coating system significantly enhances the FR properties of the coatings while preserving their physico‐mechanical characteristics such as solvent resistance and hardness. Additionally, the inclusion of PA markedly enhances the FR performance of the coatings by reducing flame spread rate, minimizing dripping, and suppressing ignition temperature. Moreover, upon addition of 10% w/w PA increases the ignition time, decreases peak heat release rate (PHRR) by more than 25%, reduces total heat release (THR) by the similar amount, and suppresses total smoke production by >40% compared to the coatings containing FR‐ agents based on metal oxides and alkyl phosphates. Our work clearly demonstrates the feasibility of using PA as the FR additive for producing eco‐friendly and low‐flammable epoxy cross‐linked coatings.
The Impact of Parental Health Shocks on Child Schooling and Labour: Evidence From Thailand
Authors: Wongmonta Sasiwooth 
Published: September 2024

ABSTRACTThis paper uses household panel data from the Thai Socio‐Economic Surveys of 2012 and 2017 to examine the effects of parental health shocks on child education and labour. Three measures of parental health are analysed: chronic illness, hospitalisation, and functional health status. The results show that the parentʼs illness decreases school enrolment and leads to fewer years of education completed. Boys are less likely to have attended school if any parent was chronically ill or had any health problems. Parentsʼ chronic illness increases the probability of entering the labour force for youths aged 15 and over; however, only maternal illness increases their time spent at work. Additionally, parental illness significantly increases household health expenditures, but there is a significant decline in education expenditures. The results suggest that targeted government support to low‐income families affected by major illnesses of parents could help them to maintain their children in school.