bluuebunny/crossref_metadata_2025 huggingface dataset:
On the Use of Recycled PVB to Develop Sustainable Separators for Greener Li‐Ion Batteries
Authors: Porporato Silvia , Darjazi Hamideh , Gastaldi Matteo , Piovano Alessandro , Perez Angelica , Yécora Beatriz , Fina Alberto , Meligrana Giuseppina , Elia Giuseppe A. , Gerbaldi Claudio
Published: October 2024

In this work, sustainable Li‐based battery separators are prepared starting from a waste material from the glass industry, viz. polyvinyl butyral (PVB) widely used as a sacrificial interlayer in high impact‐resistant windows. First, polymeric membranes are prepared via the phase‐inversion method using commercial PVB as the backbone and 4,4′‐methylenebis(cyclohexylisocyanate) as a crosslinking agent. They are characterized from a physicochemical viewpoint by thermomechanical analysis, infrared spectroscopy, and scanning electron microscopy, and are successfully tested as separators in Li‐metal cells with LP30 electrolyte. Electrical and electrochemical properties are evaluated by impedance spectroscopy and galvanostatic cycling, providing comparable results with commercial Celgard 25 µm monolayer microporous polypropylene separator. As a proof‐of‐concept, for the first time, recycled PVB‐based polymer membranes from wasted car glasses are prepared, adjusting the synthesis protocol to account for the presence of plasticizers and contaminants. They show a dense elastomeric appearance and proved to be compatible with Li metal and stable upon 600 h of Li plating/stripping. The electrochemical window is compatible with the LiFePO4 cathode, as demonstrated by prolonged galvanostatic cycling (250 cycles) in laboratory‐scale cells. Preliminary results are highly encouraging and pave the way to developing novel separators for safe, low‐cost, and sustainable energy storage devices.
AI‐assisted Field Plate Design of GaN HEMT Device
Authors: Xiang Xiaofeng , Palash Rafid Hassan , Yagyu Eiji , Dunham Scott T. , Teo Koon Hoo , Chowdhury Nadim
Published: October 2024

GaN High Electron Mobility Transistors (HEMTs) plays a vital role in high‐power and high‐frequency electronics. Meeting the demanding performance requirements of these devices without compromising reliability is a challenging endeavor. Field Plates are employed to redistribute the electric field, minimizing the risk of device failure, especially in high‐voltage operations. While machine learning is applied to GaN device design, its application to field plate structures, known for their geometric complexity, is limited. This study introduces a novel approach to streamlining the field plate design process. It transforms complex 2D field plate structures into a concise feature space, reducing data requirements. A machine learning‐assisted design framework is proposed to optimize field plate structures and perform inverse design. This approach is not exclusive to the design of GaN HEMTs and can be extended to various semiconductor devices with field plate structures. The framework combines technology computer‐aided design (TCAD), machine learning, and optimization, streamlining the design process.
Programmable Truncated Cuboctahedral Origami Metastructures Actuated by Shape Memory Polymer Hinges
Authors: Chen Yao , Shao Zerui , Feng Jian , Sareh Pooya
Published: October 2024

Over the past few decades, origami‐inspired structures have attracted great attention across various engineering fields due to their unique geometric and mechanical characteristics. Additionally, combining origami structures with active materials is employed to achieve programmable mechanical properties and self‐reconfigurability under external stimuli. In this work, a novel family of truncated cuboctahedral origami metastructures is proposed. These designs integrate shape memory polymers (SMPs) to actively achieve programmable mechanical properties and shape memory behavior. By utilizing SMPs for the creases and stiff materials for the panels, this approach enables deformation along the creases while enhancing the overall structural robustness. The mechanical properties and shape memory processes of these structures are investigated in detail. The proposed origami metastructures exhibit a negative Poisson's ratio and demonstrate excellent energy storage capabilities. Notably, their mechanical properties can be programmed by controlling both temperature and geometric parameters. More particularly, their Poisson's ratio can be tuned within a range of zero to −1. As a result, these truncated cuboctahedral origami metastructures hold significant potential for applications across various engineering domains, particularly in composite structures and active metamaterials.
Precision, quantitative measurement of sunflower capitulum inclination: A trigonometry‐based approach
Authors: DeValk Emily M. , Koehler Brady D. , Hulke Brent S.
Published: October 2024

Sunflower (Helianthus annuus) is a widely cultivated crop that exhibits a trait known as capitulum (or head) inclination at maturity. This trait is influenced by various structural factors, including head weight, stem traits, and plant height. A sunflower head should be at an angle at which the head faces the ground to avoid damage from the sun and birds. While this desired inclination range is known, current methods, including visual estimation and a model of measuring inclined length of the stem, fail to provide precise measurements of angle. This study introduces novel approaches to mathematically measure the head inclination angle. The research, which was conducted over the 2022 and 2023 growing seasons, involved an aluminum rod equipped with a ruler and a digital protractor to measure various height and angle components. Using the data collected, three methods were applied for measuring inclination: a previously published model as a control, a trigonometry‐based approach using angle and height measurements, and other model‐based approaches. A linear model resulted in a formula to calculate the head angle of any plant based solely on two height measurements, the highest point of the plant at both bloom (R5) and maturity (R9). Calculations of heritability and correlation suggest this method has created a precise alternative to existing estimation methods. The resulting formula has the potential to be paired with measurements from high‐throughput phenotyping methods, such as those facilitated with drones and ground robots, to fully automate the process of collecting head inclination data.
Drought response strategies of vascular epiphytes in isolated pasture trees in a Costa Rican tropical montane landscape
Authors: Vaughan Damon , Williams Cameron B. , Nadkarni Nalini , Dawson Todd E. , Draguljic Danel , Næsborg Rikke Reese , Gotsch Sybil G.
Published: October 2024

Premise

Vascular epiphytes of tropical montane cloud forests are vulnerable to climate change, particularly as cloud bases elevate and reduce atmospheric inputs to the system. However, studies have generally focused on epiphytes in contiguous forests, with little research being done on epiphytes on isolated pasture trees. We investigated water relations of pasture‐tree epiphytes at three sites located below and above the elevation of the average cloud base in Monteverde, Costa Rica.

Methods

We measured sap velocity and four microclimate variables in both the dry and wet season of 2018. We also measured functional traits, including pressure volume (PV) curves, predawn/midday water potential, and various lab‐based water relations traits. We used linear mixed models to assess the correlation between microclimate and sap velocity in both seasons and ANOVA to assess the variation in PV curve and water potential variables.

Results

The turgor loss point generally increased from the wettest to driest site. However, this trend was driven primarily by the increasing prevalence of leaf succulence at drier sites. Microclimatic variables correlated strongly with sap velocity in the wet season, but low soil moisture availability caused this correlation to break down during the dry season.

Conclusions

Our results emphasize the vulnerability of cloud forest epiphytes to rising cloud bases. This vulnerability may be more severe in pasture trees that lack the potential buffer of surrounding forest, but additional research that directly compares the canopy microclimate conditions between forest and pasture trees is needed to confirm this possibility.
Avatrombopag in immune thrombocytopenia: A real‐world study of the Spanish ITP Group (GEPTI)
Authors: Pascual‐Izquierdo Cristina , Sánchez‐González Blanca , Canaro‐Hirnyk Mariana‐Isabel , García‐Donas Gloria , Menor‐Gómez María , Gil‐Fernández Juan‐José , Monsalvo‐Saornil Silvia , de‐Laiglesia Almudena , Álvarez‐Román María‐Teresa , Jarque‐Ramos Isidro , Llácer María‐José , Pedrote‐Amador Begoña , Zafra‐Torres Denis , Caparrós‐Miranda Isabel , Ortúzar‐Pasalodos Ariana , Revilla‐Calvo Nuria , Bastida José‐María , Chica‐Gullón Esther , Alvarellos Montserrat , Jiménez‐Bárcenas Reyes , Bernat Silvia , Martínez‐Carballeira Daniel , Lakhwani Sunil , López‐Ansoar Elsa , Moreno‐Beltrán María‐Esperanza , Lorenzo‐Vizcaya Álvaro , Aguirre María‐Aránzazu , Lasa‐Eguialde Maialen , Canet Marta , González‐Gascón‐y‐Marín Isabel‐Teresa , Caballero‐Navarro Gonzalo , Cuesta Amalia , Díaz‐López Marta , Arquero Teresa , Moreno‐Carbonell Marta , Mingot‐Castellano María‐Eva ,   the Spanish ITP Group (GEPTI) of the Spanish Society of Hematology and Hemotherapy (SEHH)
Published: October 2024

Avatrombopag is the newest thrombopoietin receptor agonist (TPO‐RA) approved to treat immune thrombocytopenia (ITP). Real‐world evidence regarding effectiveness/safety is limited. The Spanish ITP Group (GEPTI) performed a retrospective study with patients starting avatrombopag for the first time. A total of 268 ITP patients were recruited. The median (interquartile range [IQR]) follow‐up time was 47.5 (30.4–58.9) weeks. Among the 193 patients with baseline platelet counts <50 × 109/L, 174 (90.1%) of them achieved response (PC ≥50 × 109/L), and 113 (87.6%) of the 129 who persisted on avatrombopag at last visit had platelet levels above such threshold. Results were similar when only those patients switching to avatrombopag due to previous treatment failure were considered (n = 104). Patients reached response in 13 (7–21) days. Among patients with baseline levels ≥50 × 109/L, 73/75 (97.3%) reported response, which was maintained by 53 (94.6%) of the 56 who continued on avatrombopag at the end of the study. Loss‐of‐response was always <10%. ITP duration did not influence response. Approximately 79% (34/43) of heavily pretreated (≥4 lines) patients with baseline platelet counts <50 × 109/L switching after previous failure achieved PC ≥50 × 109/L. Previous use of eltrombopag and/or romiplostim did not influence response, regardless of whether previous TPO‐RA(s) succeeded or failed. Avatrombopag allowed dose‐reduction/suspension of corticosteroids in 40/50 (80.0%) patients with baseline platelet counts <50 × 109/L. Overall, 40/268 (14.9%) thrombocytosis and 12/268 (4.5%) thromboembolic events were reported. Our real‐world cohort supports the use of avatrombopag to manage ITP, regardless of disease severity and treatment history.
A multilayer network analysis of Alzheimer's disease pathogenesis: Roles for p‐tau, synaptic peptides, and physical activity
Authors: Jones Andrea A. , Ramos‐Miguel Alfredo , Gicas Kristina M. , Petyuk Vladislav A. , Leurgans Sue E. , De Jager Philip L. , Schneider Julie A. , Bennett David A. , Honer William G. , Casaletto Kaitlin B.
Published: October 2024

INTRODUCTION

In the aging brain, cognitive abilities emerge from the coordination of complex pathways arising from a balance between protective lifestyle and environmental factors and accumulation of neuropathologies.

METHODS

As part of the Rush Memory and Aging Project (n = 440), we measured accelerometer‐based actigraphy, cognitive performance, and after brain autopsy, selected reaction monitoring mass spectrometry. Multilevel network analysis was used to examine the relationships among the molecular machinery of vesicular neurotransmission, Alzheimer's disease (AD) neuropathology, cognition, and late‐life physical activity.

RESULTS

Synaptic peptides involved in neuronal secretory function were the most influential contributors to the multilayer network, reflecting the complex interdependencies among AD pathology, synaptic processes, and late‐life cognition. Older adults with lower physical activity evidenced stronger adverse relationships among phosphorylated tau peptides, markers of synaptic integrity, and tangle pathology.

DISCUSSION

Network‐based approaches simultaneously model interdependent biological processes and advance understanding of the role of physical activity in age‐associated cognitive impairment.

Highlights

Network‐based approaches simultaneously model interdependent biological processes.

Secretory synaptic peptides were influential contributors to the multilayer network.

Older adults with lower physical activity had adverse relationships among pathology.

There was interdependence among phosphorylated tau, synaptic integrity, and tangles.

Network methods elucidate the role of physical activity in cognitive impairment.
Unveiling the Dual Role of Oxophilic Cr4+ in Cr−Cu2O Nanosheet Arrays for Enhanced Nitrate Electroreduction to Ammonia
Authors: Zhang Kai , Li Bo , Guo Fengchen , Graham Nigel , He Wenhui , Yu Wenzheng
Published: October 2024

Cuprous oxide (Cu2O)‐based catalysts present a promising activity for the electrochemical nitrate (NO3−) reduction to ammonia (eNO3RA), but the electrochemical instability of Cu+ species may lead to an unsatisfactory durability, hindering the exploration of the structure‐performance relationship. Herein, we propose an efficient strategy to stabilize Cu+ through the incorporation of Cr4+ into the Cu2O matrix to construct a Cr4+−O−Cu+ network structure. In situ and quasi‐in situ characterizations reveal that the Cu+ species are well maintained via the strong Cr4+−O−Cu+ interaction that inhibits the leaching of lattice oxygen. Importantly, in situ generated Cr3+−O−Cu+ from Cr4+−O−Cu+ is identified as a dual‐active site for eNO3RA, wherein the Cu+ sites are responsible for the activation of N‐containing intermediates, while the assisting Cr3+ centers serve as the electron‐proton mediators for rapid water dissociation. Theoretical investigations further demonstrated that the metastable state Cr3+−O−Cu+ favors the conversion from the endoergic hydrogenation of the key *ON intermediate to an exoergic reaction in an ONH pathway, and facilitates the subsequent NH3 desorption with a low energy barrier. The superior eNO3RA with a maximum 91.6 % Faradaic efficiency could also be coupled with anodic sulfion oxidation to achieve concurrent NH3 production and sulfur recovery with reduced energy input.
High‐Selectivity Tandem Photocatalytic Methanation of CO2 by Lacunary Polyoxometalates‐Stabilized *CO Intermediate
Authors: Zhu Qian , Li Zhaohui , Zheng Tao , Zheng Xingxing , Liu Si , Gao Shen , Fu Xionghui , Su Xiaofang , Zhu Yi , Zhang Yuanming , Wei Yongge
Published: October 2024

Stabilizing specific intermediates to produce CH4 remains a main challenge in solar‐driven CO2 reduction. Herein, g‐C3N4 is modified with saturated and lacunary phosphotungstates (PWx, x=12, 11, 9) to tailor the CO2 reduction pathway to yield CH4 in high selectivity. Increased lacuna of phosphotungstates leads to higher CH4 yield and selectivity, with a superior CH4 selectivity of 80 % and 40.8 μmol ⋅ g−1 ⋅ h−1 evolution rate for PW9/g‐C3N4. Conversely, g‐C3N4 and PWx alone show negligible CH4 production. The conversion of CO2 to CH4 follows a tandem catalytic process. CO2 is initially activated on g‐C3N4 to form *CO intermediates, meanwhile photogenerated electrons derived from g‐C3N4 transfer to PWx. Then the reduced PWx captures *CO, which is subsquently hydrogenated to CH4. With the injection of two photogenerated electrons, PW9 is capable of adsorbing and activating *CO. However, the reduced PW12 and PW11 are incapable of adsorbing *CO due to the small energy of occupied molecular orbitals, which is the reason for the poorer activity of PWx/g‐C3N4 (x=12, 11) compared with that of PW9/g‐C3N4. This work provides new insights to regulate highly selective CO2 photoreduction to CH4 by utilizing lacuna of polyoxometalates to enhance the interaction of metals in polyoxometalates with key intermediates.
Computational Stabilization of a Non‐Heme Iron Enzyme Enables Efficient Evolution of New Function
Authors: King Brianne R. , Sumida Kiera H. , Caruso Jessica L. , Baker David , Zalatan Jesse G.
Published: October 2024

Deep learning tools for enzyme design are rapidly emerging, and there is a critical need to evaluate their effectiveness in engineering workflows. Here we show that the deep learning‐based tool ProteinMPNN can be used to redesign Fe(II)/αKG superfamily enzymes for greater stability, solubility, and expression while retaining both native activity and industrially relevant non‐native functions. This superfamily has diverse catalytic functions and could provide a rich new source of biocatalysts for synthesis and industrial processes. Through systematic comparisons of directed evolution trajectories for a non‐native, remote C(sp3)−H hydroxylation reaction, we demonstrate that the stabilized redesign can be evolved more efficiently than the wild‐type enzyme. After three rounds of directed evolution, we obtained a 6‐fold activity increase from the wild‐type parent and an 80‐fold increase from the stabilized variant. To generate the initial stabilized variant, we identified multiple structural and sequence constraints to preserve catalytic function. We applied these criteria to produce stabilized, catalytically active variants of a second Fe(II)/αKG enzyme, suggesting that the approach is generalizable to additional members of the Fe(II)/αKG superfamily. ProteinMPNN is user‐friendly and widely accessible, and our results provide a framework for the routine implementation of deep learning‐based protein stabilization tools in directed evolution workflows for novel biocatalysts.
Access to Alkenyl Cyclobutanols by Ni‐Catalyzed Regio‐ and Enantio‐Selective syn‐Hydrometalative 4‐exo‐trig Cyclization of Alkynones
Authors: Li Xiao‐Lin , Deng Jiang‐Lian , Long Jian , Fu Yi‐Fan , Zheng Yu‐Qing , Liu Wen‐Bo
Published: October 2024

Enantioselective synthesis of (spiro)cyclobutane derivatives poses significant challenges yet holds promising applications for both synthetic and medicinal chemistry. We report here a nickel‐catalyzed asymmetric syn‐hydrometalative 4‐exo‐trig cyclization of 1,4‐alkynones to synthesize alkenyl cyclobutanols with a tetrasubstituted stereocenter. This strategy features a broad substrate scope, delivering a variety of trifluoromethyl‐containing rigid (spiro)carbocycle skeletons in good yields with high enantioselectivities (up to 84 % yield and 98.5 : 1.5 er). The synthetic utility is demonstrated through stereospecific transformations into fused spiro molecules. Experimental and computational mechanistic studies indicate that the reaction is initiated by an active Ni−H species, with carbonyl‐directed hydrometalation as the key for regioselective control. This catalytic method provides a general solution for regioselective hydrofunctionalization of alkynes and represents an efficient reaction pattern for assembling highly strained enantioenriched bioisosteres.
An Efficient CRISPR/Cas Cooperative Shearing Platform for Clinical Diagnostics Applications
Authors: Zhao Junhong , Kong Derong , Zhang Guanghui , Zhang Shen , Wu Yungen , Dai Changhao , Chen Yiheng , Yang Yuetong , Liu Yunqi , Wei Dacheng
Published: October 2024

The CRISPR/Cas system is a powerful genome editing tool and possesses widespread applications in molecular diagnostics, therapeutics and genetic engineering. But easy folding of the target sequences causes remarkable deterioration of the recognition and shear efficiency in the case of single Cas‐CRISPR RNA (crRNA) duplex. Here, we develop a CRISPR/Cas cooperative shearing (CRISPR‐CS) system. Compared with traditional CRISPR/Cas system, two CRISPR/Cas‐crRNA duplexes simultaneously recognize different sites in the target sequence, increasing recognition possibility and shearing efficiency. Cooperative shearing cuts more methylene blue‐ssDNA reporters on the electrode, enabling unamplified nucleic acid electrochemical assay in less than 5 minutes with a detection limit of 9.5×10−20 M, 2 to 9 orders of magnitude lower than those of other electrochemical assays. The CRISPR‐CS platform detects monkeypox, human papilloma virus and amyotrophic lateral sclerosis with an accuracy up to 98.1 %, demonstrating the potential application of the efficient cooperative shearing.
Toward mechanical recyclability of high barrier food packaging films through filler incorporation on the EVOH layer
Authors: Barros Carolina , Azevedo Ana G. , Cerqueira Miguel A. , Carneiro O. S. , Machado A. V.
Published: October 2024

To preserve food from moisture and oxygen, polymers, such as ethylene vinyl alcohol (EVOH) are used in multilayer structures to provide oxygen barrier, while low‐density polyethylene (LDPE) is used for a water vapor barrier. While this material combination is functionally ideal, it may not comply with the new packaging recycling guidelines. Some European markets have implemented rules that limit the weight percentage of EVOH in LDPE films. One way to increase recyclability is by reducing the amount of EVOH in the film structure while maintaining the packaging's oxygen barrier properties. To achieve this, it is necessary to improve the barrier properties of EVOH. With this objective in mind, this study evaluated the incorporation of nanoclays (NC), cellulose microcrystals (MCC), silicon dioxide nanoparticles (SiO2), and cellulose nanocrystals (CNC) into an EVOH matrix. The results indicate that NC and MCC facilitate a stable blown film extrusion process and have a better dispersion in the EVOH matrix. Based on this finding, three‐layer films (with an ABA configuration) consisting of LDPE (A) and EVOH (7 μm layer) with 0.5 or 1 wt.% MCC or NC (B) were produced to protect the EVOH from moisture and enable blown film processing. The oxygen transmission rate (OTR) values were lowest for 0.5 wt.% NC and 1 wt.% MCC incorporation. Although the films with micro and nanoparticles had increased haze, this did not affect the visibility of the packaged food.
Influence of functional group structures in nucleating agents on the crystallization behavior of poly(ethylene terephthalate)
Authors: Wu Jingbo , Lin Jianghua , Xiao Wenhao , Xu Ruijie , Lei Caihong
Published: October 2024

Nucleating agents are crucial for modifying semi‐crystalline polymers, but the impact of different end‐group structures on crystallization behavior remains unclear. This study synthesized succinic dihydrazide nucleating agents with various end groups (methyl, ethyl, and tert‐butyl) for PET composite materials. The tert‐butyl‐terminated nucleating agent showed the best performance, increasing the crystallization peak temperature to 203.8°C, crystallinity to 27.3%, and reducing half‐crystallization time to 2.8 min at 220°C. It also enhanced the impact strength to 47.2 kJ·m−2 and flexural modulus to 2623 MPa, while improving Vicat softening temperature and heat distortion temperature by 41 and 8°C, respectively. The results from FTIR and Raman Spectroscopy indicate that the interactions between the end groups of the nucleating agent and the CH bonds in the PET structure, the π–π interactions between the nucleating agent and the PET molecular structure, as well as the modulation of the PET chain conformation by the nucleating agent, are the primary factors contributing to the enhanced crystallinity of PET. This study provides a new approach for designing efficient nucleating agents for high‐performance materials.
Toward new applications of terpenes in polymeric materials: Synthesis and characterization of myrcene‐modified unsaturated polyester resins
Authors: Rodríguez‐Tobías Heriberto , Enríquez‐Medrano Francisco Javier , Salinas‐Hernández Myrna , Cabello‐Romero Judith Nazareth , Maldonado‐Textle Hortensia , Mendoza‐Carrizales Ricardo , Díaz‐Elizondo José , Olivares‐Romero José Luis , de León Ramón Díaz
Published: October 2024

β‐Myrcene, a terpenic monomer, holds potential for developing sustainable polymer‐based materials with enhanced properties. This study examines the synthesis of a myrcene‐based monomer and its incorporation into unsaturated polyesters, focusing on polymerization, curing, and final properties. Unsaturated polyesters were synthesized with varying myrcene‐based monomer content (6, 12, and 24 mol%), phthalic anhydride, maleic anhydride, propylene glycol, ethylene glycol, and diethylene glycol. Polymerization achieved conversion values of 0.92–0.93, resulting in polyesters with molar masses between 1400 and 1700 g mol−1 and dispersity indices of 2.0 to 2.3. Nuclear magnetic resonance (1H NMR) demonstrated short branch formation in myrcene‐modified polyesters and a high maleate‐to‐fumarate isomerization rate (92.66%–95.7%), affecting carbon–carbon double bonds per polyester mole (2.27 to 4.28) and final resin performance. Rheological analysis in a styrene solution (70/30 wt%) indicated shear‐thinning behavior, with viscosities ranging from 0.59 to 3.8 Pa·s, suggesting branching affects chain entanglement. Differential scanning calorimetry (DSC) revealed decreased curing enthalpy with increasing myrcene content, and it was inferred that myrcene's double bonds did not participate in curing. Glass transition temperatures of cured polyesters (70–107 °C) correlate with enthalpy trends. Thermal stability of myrcene‐modified polyesters is similar to the reference polyester, highlighting myrcene's potential as a sustainable monomer for customizable unsaturated polyesters.
FlowerMate: Multidimensional reciprocity and inaccuracy indices for style‐polymorphic plant populations
Authors: Simón‐Porcar Violeta , Muñoz‐Pajares A. Jesús , Arroyo Juan , Johnson Steven D.
Published: October 2024

Premise

Heterostyly in plants promotes pollen transfer between floral morphs, because female and male sex organs are located at roughly reciprocal heights within the flowers of each morph. Reciprocity indices, which assess the one‐dimensional variation in the height of sex organs, are used to define the phenotypic structure of heterostyly in plant populations and to make inferences about selection. Other reciprocal stylar polymorphisms (e.g., enantiostyly) may function in a similar manner to heterostyly. In‐depth assessment of their potential fit with pollinators requires accounting for the multidimensional variation in the location of sex organs.

Methods and Results

We have adapted the existing reciprocity indices used for heterostylous plant populations to incorporate multidimensional data. We illustrate the computation of the adapted and original indices in the freely available R package FlowerMate.

Conclusions

FlowerMate provides fast computation of reliable indices to facilitate understanding of the evolution and function of the full diversity of reciprocal polymorphisms.
Exploring the digital gray zone of online medicinal markets emerging from search
Authors: Söderström Kristofer Rolf , Sundin Olof
Published: October 2024

This explorative study investigates the emergence of gray zone markets from search engines amidst the global expansion of online markets. With the analytical approach of infrastructural inversion, we examine how the search infrastructure constructs access to a gray zone market including both authorized online pharmacies and unauthorized vendors. Using Sweden and Google Search as a case, we explore the online presence of three products (vitamin D, paracetamol, and Viagra), through search engine result page analysis, web crawling, and network analysis. Infrastructural inversion unveils the typically invisible mechanisms of search engines, considering user queries, algorithmic priorities, SEO practices, and pharmacy regulations. We find gray zones only emerge in searches for erectile disfunction medicinal products and information, where unauthorized vendors successfully competed for visibility in search engine rankings. A complex web of conditions can steer consumers toward gray zone markets, complicating the access to safe and regulated medicinal products. This can expose individuals to risks associated with unverified medicinal products, but also challenges the integrity of the online health information infrastructure.
Non‐Aqueous Liquid Electrolytes for Li‐O2 Batteries
Authors: Wang Shu , Yu Haohan , Fu Zerui , Liu Dapeng , Zhang Yu
Published: October 2024

Li‐O2 batteries (LOBs) have become a research hotspot of energy storage devices because of its high theoretical energy density. Practical applications require that non‐aqueous LOBs can deliver stable and high reversible capacity, which heavily depends on the appropriate electrolyte system. Therefore, it is very important to select electrolytes that are hard to decompose and conducive to modulating the growth kinetics of discharge products. Herein, we will review the current progress and challenges of non‐aqueous liquid electrolytes for LOBs by analyzing the influence factors on electrolyte stability and introducing the design and modification methods of electrolytes with different solvent types. At last, the possible research tactics have been proposed to develop advanced electrolytes for improving electrochemical performance of LOBs.
An analysis of attainment grouping policy in Singapore
Authors: Tan Charlene
Published: October 2024

This paper extends the scholarship on attainment grouping by focusing on the policy initiatives of streaming and subject‐based banding (SBB) in Singapore. The study is framed by the concept of pragmatic perfectionism, which refers to the continuous and ideals‐oriented drive to improve a system through practical, incremental and paradoxical measures. It is argued that SBB is aligned with setting by giving students the flexibility and choice to study different subjects at varying levels. Mixed‐attainment grouping is also evident, where students are grouped in mixed‐form classes for selected subjects. However, SBB may have inadvertently maintained between‐school segregation for elite and non‐elite schools by supporting the existing policy of school posting based on students' exam scores. This paper contributes to the diverse formulations, adaptations and justifications surrounding attainment grouping. The study also illustrates the usefulness of pragmatic perfectionism in foregrounding the potential and tensions in educational policymaking.
Establishing a multi‐method approach for unprecedented detection and quantification of 13 genotoxic impurities (GTIs) in Apixaban drug substance through ultra‐performance liquid chromatography (UPLC)
Authors: Ganta Sivaprasadu , Pamerla Muralidhar , Gunupuru Suresh Kumar , Salakolusu Suresh , Bevara Samatha , Padhy Harihara , Ganta Ravi Kumar
Published: October 2024

This groundbreaking study introduces a pioneering development of multi‐method approach for the first‐ever detection and quantification of 13 genotoxic impurities (GTIs) in Apixaban (Apx) drug substance using ultra‐performance liquid chromatography (UPLC) with ultraviolet (UV) detector. In this novel endeavor, two distinct UPLC‐UV methods, Method A (for impurities A to G) and Method B (for impurities H to M), were meticulously developed and validated as per International Council for Harmonization (ICH) guidelines to address the challenge of identification and control of 13 GTIs in Apx drug substance. The validation process included rigorous assessment of linearity, accuracy, specificity, precision, limit of quantification (LOQ), and limit of detection (LOD) for each impurity in each method which marks a significant advancement in pharmaceutical analysis. The developed methods address the regulatory requirements set forth by ICH M7(R2) guidelines by providing a reliable approach for quantifying GTIs in Apx drug substance at trace levels to minimize the potential carcinogenic risk to the patients.
Development of Chitosan‐Coated Graphene Oxide and Iron Oxide Nanocomposites for Targeted Delivery of Camptothecin to Liver Cancer Cells
Authors: Sukumar Kalpana , Bharathi Muruganantham , Hirad Abdurahman Hajinur , Alarfaj Abdullah A. , Hussein‐Al‐Ali Samer Hasan , Surya Parthasarathy
Published: October 2024

Innovative drug delivery platforms for selective, regulated, and sustained release of anticancer drugs are crucial in cancer treatment. This study presents nanoparticles developed from chitosan (CS), graphene oxide (GO), and magnetite (Fe3O4), and their nanocomposites to enhance the loading and release efficiency of camptothecin (CPT). Nanostructures were characterized using imaging microscopy, FT‐IR, and X‐ray diffraction, with an average crystallite size of 5.5 nm. Camptothecin binding proportions were 70 % for CS, 81 % for CS@Fe3O4, 58 % for CS@GO, and 74 % for CS@GO/Fe3O4. At pH 5.0, CPT release ratios were 87 %, 80 %, 88 %, and 90 %, respectively, and at pH 7.4, 84 %, 72 %, 89 %, and 87 %. Cytotoxicity was assessed using the MTT assay against HepG2 and SMMC‐7721 cancer cells. CPT‐CS@GO/Fe3O4 exhibited the highest survival at 5 μM and 12.5 μM concentrations, indicating it as the most effective nanocarrier for camptothecin delivery. The study demonstrates CS@GO/Fe3O4′s potential as a superior drug delivery system.
Boosting Enzyme Activity in an Anhydrous Gas Flux with Amphiphilic Polymers
Authors: Jian Yupei , Zhu Kaiyi , Han Yilei , Zhang Shuiwei , Xia Meng , Jiang Guoqiang , Liu Zheng
Published: October 2024

Gas‐phase enzymatic catalysis offers great potential for both green synthesis and the efficient degradation of volatile chemicals. However, solid enzymes often exhibit extremely low activity compared to their counterparts in native aqueous phase. Although a few immobilization methods have succeeded in increasing activity by preserving enzyme structure, approaches for boosting enzyme activity remain underdeveloped. In this study, we propose a general and facile method to boost enzyme activity in the gas phase, which utilizes amphiphilic polymers to energize enzyme conformational dynamics and thus enhance enzyme catalysis kinetics. The triblock copolymer Pluronics with low melting points were co‐lyophilized with Candida antarctica lipase B (CalB), yielding Pluronic/CalB powders that appeared a 70‐fold increase in activity compared to free CalB powder. Low‐field nuclear magnetic resonance (LF‐NMR), solid‐state nuclear magnetic resonance (ssNMR) and dielectric relaxation spectroscopy identified the enhancement of enzyme dynamics on the µs–ms timescale, whereas Fourier transform infrared spectroscopy (FTIR) detected structural perturbations of the native enzyme in Pluronic/CalB. The apparent activity of the enzyme/polymer powders correlated positively with both enzyme dynamics and polymer flexibility. These findings provide new molecular physical insights into gas‐phase enzyme catalysis, which are essential for advancing enzyme applications in nonnatural scenario.
Demonstrating Synergistic Activity of Magnetic Iron Oxide Nano Photocatalyst for C−H Activation in Heterogeneous Phase
Authors: Mandal Tanumoy , Kishor Paul Braja , Islam Malekul , De Sarkar Suman
Published: October 2024

This report describes a dual catalytic approach for the versatile C−H arylation of arenes under photo‐excitation at room temperature. The cooperative catalysis utilizes iron oxide magnetic nanoparticles (which mostly contain Fe3O4 along with some γ‐Fe2O3) as the potential photocatalyst, which merges with the Pd‐catalyzed C−H activation cycle for the reductive generation of aryl radical from aryl diazonium salt, revealing its photocatalytic activities. The method is applicable to a wide range of aryl coupling partners and different directing groups, demonstrating excellent productivity, nice co‐operativity and recyclability. Adequate control experiments and mechanistic studies assisted in establishing the radical‐based reaction mechanism for the C−H arylation occurring in the heterogeneous phase.
Acetic Acid‐Driven One‐Pot Synthesis of 4,7‐dihydro‐[1,2,3]thiadiazolo[5,4‐b]pyridine‐6‐carboxamides and Pharmacological Evaluations
Authors: Bhalodiya Savan S , Parmar Mehul P. , Patel Chirag D. , Patel Subham G. , Vala Disha P. , Suresh Nandhakumar , Jayachandran Bhuvaneshwari , Kumar Arumugam Madan , Narayan Mahesh , Patel Hitendra M.
Published: October 2024

A diverse set of 4,7‐dihydro‐[1,2,3]thiadiazolo[5,4‐b]pyridine‐6‐carboxamides 4(a–o) was synthesized via a one‐pot reaction of 5‐amino‐[1,2,3]thiadiazole, various aromatic aldehydes, and different acetoacetanilides, using glacial acetic acid. The resulting compounds were obtained in moderate to good yields. All the newly synthesized compounds were evaluated for their antimicrobial activity. Among them, compound 4 e demonstrated superior efficacy against the Salinivibrio proteolyticus strain of Gram‐negative bacteria compared to ciprofloxacin. Compound 4 d exhibited the highest potency against the fungal strain Candida albicans, surpassing amphotericin B. The physicochemical characteristics of 4 d and 4 e were assessed. According to docking analysis, DHTDAPy 4 e shows a higher binding affinity of −7.2 kcal/mol in the binding cavity of the receptor. These findings illustrate the safety, tolerability, and potency of the newly synthesized DHTDAPy compounds against fungal and bacterial infections.
RyuGuard—Combining Ryu and machine learning for proactive DDoS defense in software‐defined networks
Authors: Sendil Vadivu D. , Rajagopalan Narendran
Published: October 2024

Software defined network (SDN) is an experimental network design utilized by software companies, academia, and healthcare systems to provide adequate resource utilization, data management, superior network control, and administration. However, these networks face substantial risks, especially from distributed denial of service (DDoS) attacks, requiring robust cybersecurity measures. This article proposes RyuGuard, an intrusion detection and prevention system (IDPS) enhanced with machine learning (ML) capabilities, specifically designed to protect SDNs from DDoS attacks. A DDoS‐specific dataset was collected in the SDN environment through feature extraction from normal and malicious traffic. The evaluation of the dataset with the ML classifiers demonstrates that the decision tree (DT) was the most effective model, with a low false alarm rate (FAR), achieving an accuracy of 99.9%, and rapid execution time, which ensures timely detection and response, suitable for real‐time implementation. RyuGuard, with DT deployment and utilizing the programmability feature of SDN, is designed to predict and prevent the DDoS attack from the ongoing traffic of SDN. Compared with the other existing models, the presented IDPS, RyuGuard, enables early attack prediction, preventing the full impact of DDoS within the network while maintaining sustained throughput and performance with low CPU utilization.
Enhancing Edge Environment Scalability: Leveraging Kubernetes for Container Orchestration and Optimization
Authors: Aruna K. , Gurunathan Pradeep
Published: October 2024

Kubernetes is an open‐source container orchestration platform, offers a comprehensive suite of features for managing containerized applications effectively. These features encompass horizontal scaling, per‐node‐pool cluster scaling and automated resource request adjustments. This research endeavors to harness these capabilities to address the limitations experienced by fog servers in edge environments, particularly those arising from restricted network connectivity and scalability challenges. In this research paper, the primary focus is on Kubernetes role of enhancing scalability, providing a robust framework for managing containerized applications. The proposed approach involves creating a predefined number of pods and containers within a Kubernetes cluster, specifically designed to efficiently handle incoming requests while optimizing CPU and memory usage. This method implements a microservice architecture for the web tier, with separate pods for the front end, back end and database, ensuring modular and scalable design. All pods communicate and integrate through REST APIs, facilitating seamless interaction and data exchange between the services. When handling web requests, the approach enables and controls both internal and external networks, ensuring secure and efficient communication. The analysis then examines the CPU and memory utilization of the pods, as well as node bandwidth, to provide a comprehensive evaluation of container scalability and performance within the Kubernetes cluster. These findings effectively demonstrate Kubernetes' capability in managing container scalability and optimizing resource utilization, highlighting its efficiency and robustness in a microservice environment.
Nitrogen and Sulfur Doped Porous Carbon Sheet with Trace Amount of Iron as Efficient Polysulfide Conversion Catalyst for High Loading Lithium‐Sulfur Batteries
Authors: Sivaraj Jeevanantham , Dasari Bosubabu , Subramani Prakash , Pitchai Jayashree , Unni Sreekuttan M. , Ramesha K.
Published: October 2024

The major challenges in enhancing the cycle life of lithium‐sulfur (Li−S) batteries are polysulfide (PS) shuttling and sluggish reaction kinetics (S to Li2S, Li2S to S). To alleviate the above issues, the use of heteroatom‐doped carbon as a cathode host matrix is a low‐cost and efficient approach, as it works as a dual‐functional framework for PS anchoring as well as an electrocatalyst for faster redox kinetics. Here, the dual role of heteroatom‐doped carbon sheets (CS) in the chemisorption of Li2S6 and catalysis of its faster conversion to Li2S is established. To substantiate the catalytic effect, composite cathodes were prepared by encapsulating sulfur in CS which is further blended with carbon nanotubes (CNTs) to form a free‐standing cathode. The electrochemical performances of the three cathodes (S@Fe−N‐CS‐CNT, S@Fe−S‐CS‐CNT, and S@Fe‐NS‐CS‐CNT) were evaluated by constructing Li−S cells. The S@Fe‐NS‐CS‐CNT delivers a high initial discharge capacity of 1017 mAh g−1 at 0.5 C rate and sustains a capacity of 751 mAh g−1 after 260 cycles with a capacity retention of 73.8 %. Even at a high S loading (12 mg cm−2), it delivers an initial discharge capacity of 892 mAh g−1 and retained 575 mAh g−1 after 200 cycles.
Encapsulating Ammonia Borane in Cobalt Decorated Kaolinite Monolith Aerogel for Hydrogen Storage and Controllable Release
Authors: Mi Ang , Yun Rongping , Shang Huishan , Zhang Bing , Xiang Xu
Published: October 2024

Achieving the “on‐off” control of hydrogen release remains a huge challenge in efficiently harnessing hydrogen energy on demand. In this work, a controlled hydrogen production strategy is proposed. Hydrogen carrier ammonia borane (AB) and Co catalyst are loaded into kaolinite aerogel (KA) to obtain a composite AB@Co/KA monolith. The results show that Co particles with surface‐oxidized species are uniformly decorated on the surface of aerogel, and AB can fill the pores of aerogel to form a composite hydrogen storage material. Hydrogen generation is modulated on AB@Co/KA by tuning the amount of water added, which achieves an “on‐off” hydrogen release on demand. The Co‐modified KA (Co/KA) can be repackaged multiple times for recycling use after the AB is completely hydrolyzed. This work provides a promising approach for controlling the release of hydrogen neither the input of additional energy nor foreign reagents added to the reaction system.
Lumen‐apposing metal stents for anastomosis creation throughout the gastrointestinal tract: A large single‐center experience
Authors: Gökce Emine , Devisscher Lindsey , Rashidian Niki , Palmeri Enrico , Hindryckx Pieter
Published: October 2024

Objectives

The introduction of lumen‐apposing metal stents (LAMSs) has revolutionized the field of therapeutic endoscopic ultrasound. This study aims to evaluate the efficacy and safety of LAMS in creating an endoscopic ultrasound‐guided anastomosis between two segments of the gastrointestinal (GI) tract.

Methods

Data from all consecutive LAMS procedures for anastomosis creation between two segments of the GI, conducted between October 2019 and February 2024, were retrospectively analyzed for technical success (defined as correct deployment of the LAMS in the target), clinical success (defined as achievement of the intended clinical goal), and adverse events.

Results

A total of 145 LAMS procedures were performed in 136 patients. Indications for LAMS procedures included the need for endoscopic access to or reversal of surgically excluded segments of the GI tract (n = 73, 50.3%), and the alleviation of any GI outflow obstruction (n = 72, 49.7%). The overall technical and clinical success rates were very high (97.2% and 95.2%, respectively). Adverse events were observed in 20/145 (13.8%) cases, including 11 (7.6%) minor events (AGREE <3) and nine (6.2%) major events (AGREE ≥3). Major events included stent migration (n = 1), persisting fistula (n = 3), and bleeding (n = 4). All adverse events were successfully managed, and there were no procedure‐related deaths. Loss of LAMS patency occurred in 4/145 (2.8%) cases and could be endoscopically managed in all cases.

Conclusions

The creation of anastomoses with LAMS between two segments of the GI tract appears to be effective and safe, with a low reintervention rate due to loss of LAMS patency.
Impact of advanced endoscopy training on colonoscopy quality and efficiency
Authors: Watanabe Takashi , Murano Tatsuro , Ikematsu Hiroaki , Shinmura Kensuke , Wakabayashi Masashi , Minakata Nobuhisa , Maasa Sasabe , Mitsui Tomohiro , Yamashita Hiroki , Inaba Atsushi , Sunakawa Hironori , Nakajo Keiichiro , Kadota Tomohiro , Yano Tomonori
Published: October 2024

Objectives

Few reports have detailed improvements in the quality of colonoscopies with continuous training post‐fellowship completion. We examined the changes in colonoscopy performance among trainees during our advanced endoscopy training program.

Methods

Screening or surveillance colonoscopies performed by 11 trainees who participated in our 3‐year advanced endoscopy training program between April 2015 and March 2020 were retrospectively analyzed. Quality and efficiency metrics of colonoscopies were evaluated annually.

Results

Altogether, 297, 385, and 438 colonoscopies were enrolled in the first, second, and third training years, respectively. The mean insertion times were 8.6, 7.6, and 6.9 min in the first, second, and third training years, respectively, with significant improvement from the first to second year (p = 0.03) and from the first to third year (p < 0.01). The adenoma detection rate, proximal adenoma detection rate, and mean number of adenomas per patient exhibited a tendency to improve annually; however, the difference was not significant. Polypectomy efficiency was 10.5%, 11.2%, and 13.0%, with significant improvements from the first to third year (p < 0.01) and from the second to third year (p = 0.02). Insertion time and polypectomy efficiency showed significant improvements, especially among trainees experienced with <500 colonoscopies.

Conclusions

Through our advanced endoscopy training program, there has been an improvement in the quality and efficiency of colonoscopy for trainees who have completed their fellowships, particularly those with <500 colonoscopies.