bluuebunny/crossref_metadata_2025_split huggingface dataset:
Partial‐Oxidation Enabling Homologous Ru/RuO2 Heterostructures With Proper d‐Dand Center as Efficient and Durable Cathode Catalysts for Ultralong Cycle Life in Li–O2 Batteries
Authors: Sun Chaoyang , Xiao Fenglong , Li Meiyan , Cui Deliang , Wang Qilong , Dang Feng , Yu Haohai , Lian Gang 
Published: October 2024

AbstractThe sluggish cycle kinetics is one of the major obstacles to the commercial application of Li–O2 batteries (LOBs), despite their large theoretical energy density. Efficient and long‐term durable cathode catalysts are urgently desired to strengthen their cycle stability and rate performance. Density functional theory calculations reveal that Ru/RuO2 Mott–Schottky heterostructures can manipulate the adsorption capacities of intermediates by modulating the d‐band center and redistribute interfacial charges, enabling efficient redox kinetics, reducing overpotentials, and optimizing the growth pathway of discharge products. Herein, a wet impregnation approach followed by partial oxidization of Ru nanodots to construct homologous Ru/RuO2 heterostructures as advanced cathode catalysts for boosting the electrochemical activities of LOBs is employed. They exhibit superior electrochemical performance, including high discharge specific capacity (17 120 mAh g−1 at 200 mA g−1), small overpotential (0.96 V), and ultralong cycle lifetime of 1209 cycles (>2400 h) at 500 mA g−1. Over 1260‐h stable cycle in air atmosphere at 500 mA g−1 demonstrates the potential application prospects of the Ru/RuO2 heterostructures in Li‐air batteries. Multiple ex/in situ measurements and theoretical calculation are conducted to investigate the optimizing mechanism of electrochemical performances.
Fertilizer nitrogen rate effects on broiler litter–fertilized corn: Grain yield and nutrient composition
Authors: Singh Rajveer , Prasad Rishi 
Published: October 2024

AbstractNitrogen (N) plays an important role in corn (Zea mays L.) production, but little is known of optimum fertilizer N rates for corn grain yield and nutrient composition when poultry manure such as broiler litter (BL) (Gallus gallus domesticus) is applied. Typically, farmers consider BL as a soil conditioner and often do not discount the N contribution from the BL application. Field experiments were conducted in 2020 and 2021 over three diverse environments across Alabama to determine the agronomic optimum nitrogen rate (AONR) for BL–fertilized dryland corn with five side dress fertilizer N rates (0, 84, 140, 196, and 252 kg N ha−1). The study utilized a yield response curve and evaluated the effect of fertilizer N rate on grain nutrient composition. BL (4.48 Mg ha−1 equivalent to 2‐ton acre−1) was applied to the study sites before planting each year. The AONRs for grain yield across these environments varied from 114 to 223 kg N ha−1 (0.013–0.027 kg of fertilizer N per kg of grain yield ha−1). The predicted grain yield at the AONRs ranged from 4.22 to 13.27 Mg ha−1. Grain N concentration increased with increasing fertilizer N rate. However, the weak to nonexistent correlation between fertilizer N and other grain nutrient elements suggests that raising the fertilizer N rate does not necessarily lead to higher nutrient levels in corn grain. Overall, these findings could be useful for developing N management guidelines for corn fields that receive BL in Alabama.
Circularity, Sustainability, and the Quality of Coffee Sold via Vending Machines: What Do Italian Consumers Prefer?
Authors: Bertossi Alberto , Troiano Stefania , Marangon Francesco 
Published: October 2024

ABSTRACTVending is an important sector in the daily lives of many people, and coffee is the most frequently consumed product in the European market. Like many other sectors, vending is responding to the challenge of sustainable development by taking various actions, such as offering increasingly ecologically sound coffee while maintaining/improving its quality. These are factors that consumers care greatly about. Although the scientific literature on coffee is vast, few studies have focused on the vending sector. The aim of the present study was to fill this gap by performing a choice experiment in Italy to understand which attributes (sustainable or nonsustainable) Italian consumers prioritized when purchasing coffee via vending machines. The results showed that the physical quality of coffee was paramount, while sustainability (although important) played a secondary role. The circularity of cups was the least considered aspect. The data obtained for this study contribute to academic knowledge of consumer behavior regarding the purchase of sustainable coffee at vending machines and can be used as a starting point for the development of strategies in line with sustainability principles.
Deep Learning‐Driven Modeling of Dynamic Acoustic Sensing in Biomimetic Soft‐Robotic Pinnae
Authors: Chakrabarti Sounak , Müller Rolf 
Published: October 2024

ABSTRACTBiological function often depends on complex mechanisms of a dynamic, time‐variant nature. An example is certain bat species (horseshoe bats—Rhinolophidae) that use intricate pinna musculatures to execute a variety of pinna deformations. While prior work has indicated the potential significance of these motions for sensory information encoding, it remains unclear how the complex time‐variant pinna geometries could be controlled to enhance sensory performance. To address this issue, this work has investigated deep neural network models as digital twins for biomimetic pinnae. The networks were trained to predict the acoustic impacts of the deformed pinna geometries. A total of three network architectures have been evaluated for this purpose using physical numerical simulations (boundary element method) as ground truth. The networks predicted the acoustic beampattern function from pinna shape or even directly from the states of actuators that were used to deform the pinna shapes in simulation. Inserting prior knowledge in the form of beam‐shaped basis functions did not improve network performance. The ability of the networks to produce beampattern predictions with low computational effort (in about three milliseconds each) should lend itself readily to supporting learning methods such as deep reinforcement learning that require many such functional evaluations.
Assessing Variance in Male Reproductive Skew Based on Long‐Term Data in Free‐Ranging Rhesus Macaques
Authors: Widdig Anja , Engel Lisa , Ruiz‐Lambides Angelina , Dubuc Constance , Weiß Brigitte M. 
Published: October 2024

ABSTRACTThe unequal share in male reproduction (male reproductive skew) has been reported across primate species. To explain the distribution of male reproduction within groups various skew models have been applied to primates, however the “dynamic tug‐of‐war” model first accounted for the specifics of primate sociality. This model assumes that an increase in the number of competing males, a high degree of female cycle synchrony and their interaction will result in a lower degree of male reproductive skew. Here, we first tested the predictors of this model in rhesus macaques (Macaca mulatta) using long‐term demographic and genetic data (up to 9 groups over 22 seasons) of the Cayo Santiago population (Puerto Rico). We also tested an extended version including group size and sex ratio and their interaction with female cycle synchrony. Finally, we investigated which male attributes determine the probability to become a top sire (highest paternity share per group and season). Confirming studies, male rhesus macaques exhibited low to medium degrees of reproductive skew based on the multinomial index, M. Unlike predicted, reproductive skew was higher in groups with more males. The extended analysis suggested that reproductive skew increased with group size in more male‐biased groups, but decreased with group size in female‐biased groups indicating that the numbers of male and female group members matter. We detected no effect of female cycle synchrony on the variance of reproductive skew. Finally, only maternal rank predicted the probability to become a top sire as long as males resided in their natal group. Together, our results did not support predictions by the dynamic skew model in rhesus macaques, but strengthen studies suggesting that other factors in addition to male‐male competition predict male reproductive output in rhesus macaques. Future skew studies should consider female choice and alternative male mating strategies.
Construction and Evaluation of pH‐Responsive Nitrogen‐Containing Metal–Organic Frameworks as Oral Drug Carriers
Authors: Qi Zhaorui , Li Xurui , Zhu Yueming , Li Li , Liu Yu 
Published: October 2024

ABSTRACTMetal–organic framework (MOF) is a porous material composed of metal ions/clusters and organic ligands. It has attracted much attention due to its high specific surface area, good biocompatibility, chemical modifiability, and diversity of components. Among many MOFs, zirconium‐based MOFs are particularly suitable for biological applications due to their optimal stability and low toxicity to hydrolysis. However, due to the weak coordination bonds between many metal clusters and organic ligands, most MOFs are prone to collapse in acidic environments, and the stability of MOFs as drug carriers cannot be guaranteed so that they cannot be widely used as oral drug carriers. This study synthesized the three MOFs using metal Zr ion clusters as the center and different nitrogen‐containing organic ligands, which are stable in gastric acid, namely, UiO‐66‐PDC, UiO‐66‐NH2, and UiO‐66‐NO2. The anionic drug loxoprofen (LOX) was loaded and characterized using scanning electron microscopy, infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and x‐ray diffraction. The adsorption and release behaviors of LOX and the three MOFs were studied from the molecular point of view by computer simulation. A series of behaviors and mechanisms of pH‐responsive nitrogen‐containing MOFs as oral drug carriers were further explored through rat pharmacokinetic experiments, the everted gut sac experiments, and intestinal absorption mechanism experiments. The experimental results show that there is a strong electrostatic interaction between anionic drug LOX and UiO‐66‐PDC under simulated gastric acid environment, which prolongs the half‐life of the drug, proving that LOX@UiO‐66‐PDC is a promising new oral drug delivery system.
Ruta Angustifolia Essential Oil: Behavioral and Insecticidal Effects Against Larvae and Adults of Tribolium castaneum
Authors: Annaz Houssam , Zerrad Hamass , Moullamri Mouna , Ajaha Ayoub , Kounnoun Ayoub , Cacciola Francesco , Altemimi Ammar B. , Laganà Vinci Roberto , Arakrak Abdelhay , Laglaoui Amin , Bouayad Noureddin , Rharrabe Kacem 
Published: October 2024

AbstractThe study aims to evaluate the behavioral and insecticidal effects of Ruta angustifolia EO (RAEO) against larvae and adults of a major pest insect, Tribolium castaneum. RAEO exhibited a strong repellency against both adults and larvae where percentages as high as 74 and 72 % of PR (Percentage of Repellency) were recorded respectively, at 0.47 μL/cm2 after 2 h. Regarding the antifeedant bioassay, no feeding deterrence was recorded in adults while an increase in appetite was registered in larvae exhibiting −80 % of FDI recorded at 0.2 μL/pellet. In terms of feeding preference, the response significantly depended on the developmental stage (F=97.19, P<0.05) and larvae were attracted to treated pellets recording percentages of 84 and 73 % of PI (Preference index) after 5 and 30 min at 0.05 μL/pellet; on the other hand, adults expressed a repulsive behavior at 0.2 μL/pellet with a PI of −81.1 (20 min), and −69.2 % (30 min). Regarding topical application toxicity, a significant difference was observed between larvae and adults (p<0.05 F=174.56). The study promotes the use of RAEO as a repellent and bioinsecticide for the control of larvae and adults of T. castaneum.
Polymer free biolimus coated stents to treat acute ST‐elevation myocardial infarction in Asian patients
Authors: Ong Paul J. L. , Chui Shing Fung , Tam Frankie Chor‐Cheung , Nguyen Quang Tuan , Tsai Cheng‐Ting , Kang Woong Chol , Nuruddin Amin Arif , Singh Ramesh , Chotinaiwattarakul Chunhakasem , Lee Michael 
Published: October 2024

AbstractBackgroundPatients undergoing primary percutaneous coronary intervention (PPCI) for ST‐segment‐elevation myocardial infarction (STEMI) have a high thrombotic burden and often have a high bleeding risk (HBR). Asian patients have different patterns of thrombotic and bleeding risk from other populations which may be particularly relevant in the setting of PPCI for STEMI.ObjectivesTo assess the safety and efficacy of the polymer free biolimus coated coronary stent (PF‐BCS, BioFreedomTM, Biosensors International) in Asian STEMI patients.MethodsPatients with acute STEMI who received at least one PF‐BCS were invited to participate after their index procedure. Follow‐up was performed at 1, 4, and 12 months. The primary endpoint was the rate of target lesion failure (TLF) at 1 year. A performance goal was derived from the biolimus eluting stent arm of the COMFORTABLE AMI study which was the only prior dedicated study of biolimus eluting stents in patients with STEMI.ResultsA total of 914 patients with STEMI were enrolled. Mean patient age was 60 ± 13 years, diabetes was present in 23.2% and 43% were active smokers. According to the ARC definition, 12.4% of the patients were HBR. TLF rate was 2.54% [95% CI: 1.52–3.56], p‐value for non‐inferiority <0.0001, p‐value for superiority = 0.0004). The rate of definite/probable stent thrombosis was 0.44% [95% CI: 0.16–1.16]. There was a trend toward more BARC 3 to 5 bleeding in ARC‐HBR patients (3.69% vs 1.46%, HR = 2.74, [95% CI: 0.87–8.62], p = 0.07).ConclusionsIn Asian patients undergoing PPCI for STEMI and treated with variable durations of DAPT, the use of a PF‐BCS was associated with low rates of TLF and stent thrombosis (NCT03609346).
Influence of Pnictogen and Ligand Framework on the Lewis Acidity and Steric Environment in Pnictogen Pincer Complexes
Authors: Kirsch Tamina Z. , Hannah Tyler J. , Chitnis Saurabh S. 
Published: October 2024

AbstractPnictogen pincer complexes are a fascinating class of compounds due to their dynamic molecular and electronic structures, and valuable stoichiometric or catalytic reactivity. As recognition of their unique chemistry has grown, so too has the library of pincer ligands employed and pnictogen centres engaged to prepare them. Here we computationally study how the choice of pincer ligand framework and pnictogen influence the electronic and steric outcomes within the complexes obtained. The most relevant electronic parameter is the pnictogen‐centred electrophilicity, which has been quantified by fluoride ion affinities and LUMO energies, while the most relevant steric parameter is the crowding around the central pnictogen, which has been quantified by the %Vbur values and visualized using steric maps. The resulting trends are analyzed with reference to binding pocket size, acceptor orbital type, electronic delocalization, π‐donor strengths, and heteroatom incorporation. Thus, considering 16 ligand frameworks and 4 heavy pnictogen centres, this study provides a broad‐spectrum view of stereo‐electronic variation in pnictogen pincer complexes, which, together with a recent study on geometric variation in the same family, provides a substantial dataset to guide future molecular design and reactivity studies.
Construction of a Fluorinated‐Anion Pillared Metal‐Organic Framework Exhibiting Dual‐Pore Architecture for Simultaneous Enhancement of C2H2 Adsorption Capacity and Selectivity
Authors: Li Liangjun , Li Fangru , Xu Wenli , Guo Mengwei , Zhu Peijie , Xing Tao , Li Zhi , Wang Mingqing , Wu Mingbo 
Published: October 2024

AbstractPhysisorption‐based separation processes represents a promising alternative to the conventional thermally driven methods, such as cryogenic separation. However, a significant challenge lies in balancing the trade‐off between adsorption capacity and selectivity of adsorbents. In this study, we introduce a novel fluorinated‐anion pillared metal‐organic frameworks (APMOFs) featuring a dual‐pore architecture, constructed using a pyridine‐oxazole bifunctional ligand. The inherent low symmetry of the ligand leads to significant distortion of the fluorinated‐anion pillars, resulting in a distinctive type of APMOFs characterized by dual‐pore architecture. On pore structure with constrict pore width is enriched with a high density of anion fluorinated pillars, offering numerous active sites advantageous for enhancing separation selectivity. Concurrently, the other pore structure exhibits larger dimensions, facilitating increased gas molecule accommodation and thereby augmenting adsorption capacity. Gas sorption studies reveal a substantial C2H2 adsorption capacity and a high C2H2/CO2 separation selectivity. Breakthrough experiments confirm its exceptional separation performance, while theoretical investigations elucidate a sequential adsorption process within these APMOFs, underscoring the efficacy of this strategy in overcoming trade‐off limits in adsorbents.
The Future is Bright: The Emergence of Glassy Organic Dots for Biological Applications
Authors: Primrose William L. , Sevilla‐Pym Angelica , Hudson Zachary M. 
Published: October 2024

AbstractGlassy organic dots (g‐Odots) are an emerging class of luminescent nanoparticles that offer enhanced photostability, superior brightness, and modular tunability compared to other commonly employed nanoparticles. In the last several years, they have been used as bioimaging probes for single‐ and multi‐photon cellular imaging, exhibiting low cytotoxicity even after several days. While they are emerging as promising materials for use in biological applications, g‐Odots face several key challenges before their use can become widespread. In this concept, we outline the state of the literature on g‐Odots and highlight a few ways in which their design and use can be improved upon.
C(sp2)‐Arylsulfones Directly from Arylsulfonyl Chlorides with Boronic Acids by Photoactivation of Boosted EDA Complexes
Authors: Yuan Nianting , Chen Sen , Liu Yuanxin , Chen Min 
Published: October 2024

AbstractDirectly with arylsulfonyl chlorides, a green and efficient deborylativesulfonylation of aryl(alkenyl)boronic acids has been developed to access both diarylsulfones and vinylarylsulfones in moderate to excellent yields at room temperature under visible‐light irradiation. This protocol features broad C(sp2)‐arylsulfone applicability, simple operation, accessibility of raw materials and ease of scale‐up. The key to the success of this photoredox transformation is introducing catalytic amounts of additives, naphthalen‐2‐ols, thus boosting the formed electron donor‐acceptor (EDA) complexes, which can dramatically improve not only the reaction efficiency but also the selectivity. This strategy was inspired and derived from specific substrates, representing a rare paradigm of how to exploit a more general reaction system. Moreover, extensive control experiments provide insights into the proposed mechanism.
Discovery of Truncated Cyclic Peptides Targeting an Induced‐Fit Pocket on PCSK9
Authors: Grosche Philipp , Flyer Alec N. , Gattlen Raphael , Xu Mei , Golosov Andrei A. , Vera Victoria , Pickett Stephanie , Brousseau Margaret E. , Chopra Rajiv , Clairmont Kevin B. , Koch Alexander , Liu Eugene , Reid Patrick , Perry Lauren , Yang Lihua , Yang Qing , Monovich Lauren G. 
Published: October 2024

AbstractProprotein convertase subtilisin/kexin type 9 (PCSK9) regulates plasma low‐density lipoprotein cholesterol (LDL−C) levels by promoting hepatic LDL receptor (LDL−R) degradation. We previously identified and optimized 13‐mer cyclic peptides that bind to a novel, induced‐fit pocket adjacent to the binding interface of PCSK9 and LDL−R and effectively disrupted the PCSK9/LDL−R protein‐protein interaction (PPI) both in vitro and in vivo. However this series of large cyclic peptides required charged groups for function and lacked oral bioavailability in rodents. We describe herein multiple structure‐based modifications to these original peptides to yield truncated, neutral molecules with full PPI function in both biochemical and cellular assays. In parallel, new mRNA‐peptide display screens identified non‐functional 8‐ and 9‐mer compounds which ligand the induced‐fit pocket in a distinct manner. Taken together, these studies indicate multiple directions to reduce the size and complexity of this peptide class toward a true small molecule oral agent.
Water as Solvent for the Dispersion of 2D Nanostructured Materials
Authors: Georgakilas Vasilios I. 
Published: October 2024

AbstractThe development of large number of two‐dimensional (2D) nanostructured materials that followed the success of graphene and the need for their handling and manipulation e. g., in inks, brought to the fore the study of solvents and substances that contribute to the stabilization of 2D nanomaterials in the liquid phase. The successful dispersion of 2D materials in solvents is combined with one of the most widespread preparation methods, that of liquid phase exfoliation. In this article, a review for the role of water in the preparation of different 2D nanostructures and their stable dispersions in the liquid phase is discussed. The use of water as a solvent or dispersant is instrumental in promoting materials with an ecological footprint, low cost, and sustainability.
Mechanism for the Indirect Photo‐Transformation of Molecular Switches using a Pyrrolo–Pyrrole Two‐Photon Absorbing Antenna
Authors: Bravo‐Romero Melissa , Guzmán‐Méndez Óscar , Reza Mariana M. , Peon Jorge 
Published: October 2024

AbstractElectron‐rich symmetric pull‐push‐pull molecules can act as efficient two‐photon absorbing units. When these chromophores are bonded directly to photo‐switchable molecules they can function as antenna systems to indirectly induce photochemical transformations in isomerizable groups after energy transfer. Recently, we developed an antenna–molecular switch system based on a pyrrolo–pyrrole two‐photon active chromophore. When this antenna section is functionalized with symmetrically situated azo‐sections as N,N’‐pyrrolic‐substituents, these azo molecular switches can be efficiently transformed from their E to their Z isomers after non‐linear light absorption by the antenna, followed by indirect excitation of the azo‐sections. In this contribution we present a case‐study of one of these systems through femtosecond‐resolved fluorescence to observe the dynamics involved in the excitation and relaxation steps within the antenna section, as well as the energy transfer pathways. By time‐resolving the emission signals we observed that the energy transfer can occur in parallel with the relaxation within the first singlet vibronic states localized at the pyrrolo–pyrrole antenna. In fact, the antenna‐to‐azo section energy transfer shows a biphasic nature. At early times, during the relaxation within the antenna, there is an initial population of azo‐section excited molecules. In addition, after the system has evolved to the fully relaxed S1 state at the antenna section, the energy transfer has components related to thermal fluctuations which increase the couplings with the receiver states at the azo‐switches giving transfer rates of the order of 1010 s−1 at room temperature. The characterization of these relaxation and energy transfer steps, as well as the role of the solvent in these processes, gives insights for the development of future molecules with indirect two‐photon isomerization properties using this kind of pull‐push‐pull two‐photon active antenna. Due to their two‐photon reactive properties, these systems can have applications in schemes where highly localized photo‐isomerization is required.