bluuebunny/crossref_metadata_2025 huggingface dataset:
Event‐Triggered Distributed Resilient State Estimator for Nonlinear Cyber‐Physical Systems Under Hybrid Cyberattacks
Authors: Wu Zhenwei , Zhang Langwen
Published: December 2024

This article investigates the problem of event‐triggered distributed resilient state estimator (ET‐DRSE) for nonlinear cyber‐physical systems (NCPSs) under hybrid cyberattacks. A stochastic model for hybrid cyberattacks is constructed by considering both false data injection (FDI) and Denial‐of‐Service (DoS) attacks. By proposing an event‐triggered mechanism, the network burden is reduced by decreasing the transmission rate of measurement information. To improve the flexibility, a detector‐based distributed resilient state estimator framework is derived. Coupled Riccati‐like difference equations (CRDEs) are proposed to obtain an upper bound (UB) of the estimation error covariance (EEC) of every subsystem. An estimation gain is designed to minimize the UB upon the error covariance of the resilient estimator by recursively solving the CRDEs. It is proved that the estimation error is probabilistically bounded through the application of random analytic theory. Finally, the performance of the proposed ET‐DRSE is verified through a numerical example and a chemical process example.
Charge Transfer‐Driven Conversion of Molecular Oxygen to Doublet State on Vanadium Diselenide (VSe2) Surface at Room Temperature
Authors: Boukhvalov Danil W. , Stefan Mariana , Joita Alexandra C. , Kuo Chia‐Nung , Shan Lue Chin , Politano Antonio
Published: December 2024

Oxygen in the excited state is essential for organic synthesis and medical treatment. Herein, a novel phenomenon is reported in which the magnetic ground state of molecular oxygen undergoes a transition at room temperature from S = 1 to S = 1/2, corresponding to the transition of O2 from a triplet to a doublet state after stable physical adsorption on the defect‐free surface of bulk VSe2. This density functional theory (DFT) calculations demonstrate the stable physical adsorption of O2 on both 1T‐ and 2H‐VSe2 surfaces without further decomposition. Electron spin resonance (ESR) measurements confirm the spin state transition. Theoretical simulations reveal the charge transfer from entangled V‐3d and Se‐4p bands to oxygen as the leading cause of the spin state transition. This mechanism has not been previously proposed and offers multiple potential applications, from organic synthesis to medicine. Moreover, this approach can be extended to reveal new aspects of known catalytic materials and to design novel catalysts.
La2Hf2O7 Based TBC Materials with Near‐Infrared Ultra‐Low Transmittance for Thermal Radiation Shielding
Authors: Zhao Qingyuan , Wang Shuqi , Chen Guoliang , Sun Yifan , Zou Yongchun , Xie Enyu , Peng Zijian , Yao Junteng , Jiahu Ouyang , Wang Yaming , Jia Dechang , Zhou Yu
Published: December 2024

As the thrust‐weight ratios of aero‐engines increase, the severe thermal radiation emitted by high‐temperature gases (≥1800 K) poses a significant challenge for thermal barrier coating (TBC) materials. Traditional TBC materials, despite their reliable thermal insulation properties, are nearly transparent to infrared radiation, which leads to direct radiative heating of the metallic substrate, consequently reducing its service life. In response, a La2Hf2O7‐based ceramic doped with a NiFe2O4 second phase is developed to prevent the penetration of thermal radiation and achieve exceptional thermal radiation shielding properties. The experimental results exhibit that 85%La2Hf2O7/15%NiFe2O4 possesses high absorptivity exceeding 0.85 across a broad wavelength range (0.2‐14 µm), and ultra‐low transmittance of 0.001 in the range of 0.4‐2.5 µm. It attributes to the presence of multi‐valent transition elements (Ni+/Ni2+ and Fe2+/Fe3+) in NiFe2O4, which significantly reduce the band gap width, enhancing photon absorption, scattering, and electron transition probability following infrared radiation absorption. These multifaceted contributions minimize radiative thermal conductivity to 1.55 W m−1 K−1, effectively shielding the radiative heat transfer. These advantages make this high‐temperature thermal shielding strategy highly competitive for the next generation of TBC materials development and application.
Insight into the Key Factors that Influence the Reaction Pathways in the Silyl‐Prins Cyclization of gem‐Vinylsilyl Alcohols
Authors: González‐Andrés Paula , Díez‐Poza Carlos , Peña Laura F. , Gónzalez‐Pinardo Daniel , Fernández Israel , Barbero Asunción
Published: December 2024

This work provides an in‐depth analysis of the factors governing the different reaction pathways in the acid‐catalyzed cyclization of gem‐vinylsilyl alcohols with aldehydes. The study evaluates the impact of both the ligands attached to silicon and the choice of the Lewis acid on the reaction outcome. Additionally, computational studies offer valuable insights into the mechanism that control these distinct pathways. The process enables the chemo‐ and stereocontrolled formation of a variety of structural frameworks, offering significant potential for the generation of a broad range of molecular architectures.
Inkjet Printed Multifunctional Graphene Sensors for Flexible and Wearable Electronics
Authors: Wang Feiran , Heaton Charles E. D. , Cottam Nathan D. , Austin Jonathan S. , Im Jisun , Fromhold T. Mark , Wildman Ricky D. , Hague Richard J. M. , Tuck Christopher J. , Makarovsky Oleg , Turyanska Lyudmila
Published: December 2024

The exceptional electrical properties of graphene with high sensitivity to external stimuli make it an ideal candidate for advanced sensing technologies. Inkjet printing of graphene (iGr) can provide a versatile platform for multifunctional sensor manufacturing. Here the multifunctional sensor enabled by combining the design freedom of inkjet printing with the unique properties of graphene networks is reported on. A fully inkjet printed multimaterial device consists of two layers of iGr stripes separated by a dielectric polymeric layer of tripropylene glycol diacrylate (TPGDA). In these devices, the bottom iGr layer, capped with TPGDA, provides temperature sensing, the top uncapped iGr is sensitive to the external atmosphere, while the capacitance between the two iGr layers is sensitive to the applied pressure. The fast, sensitive, and reproducible performance of these sensors are demonstrated in response to environmental stimuli, such as pressure, temperature, humidity, and magnetic field. The devices are capable of simultaneous sensing of multiple factors and are successfully manufactured on a variety of substrates, including Si/SiO2, flexible Kapton films and textiles, demonstrating their potential impact in applications compatible with silicon technologies as well as wearable and healthcare devices.
Enhancing H2 production from plasma‐assisted methanol steam reforming by catalyst engineering in a MXene membrane reactor
Authors: Chen Shaowei , Lu Zong , Niu Jiangqi , Shao Yan , Chen Yi , Ni Yaru , Liu Xiaoying , Wei Xiaoyang , Ou Xiaoxia , Fan Xiaolei , Wei Yanying , Chen Huanhao
Published: December 2024

Electrified methanol steam reforming (MSR) assisted by nonthermal plasma (NTP) is a pivotal enabler for clean hydrogen production at ambient conditions with several advantages. This study optimizes the NTP‐assisted MSR by catalyst engineering, as well as membrane technology (via a 2D MXene nanosheet membrane reactor). Our findings reveal that active‐phase engineering in catalyst design is crucial in regulating MSR pathways under NTP conditions with the bimetallic Ni–Cu alloys enhancing the H2 production via surface water–gas shift reaction (WGSR). Additionally, integrating a MXene membrane within a dielectric barrier discharge (DBD) NTP reactor enabled the reactive‐separation process, improving methanol conversion, H2 formation rate with higher purity, as well as showing a good stability.
Within‐leaf variation in embolism resistance is not a rule for compound‐leaved angiosperms
Authors: Rimer Ian M. , McAdam Scott A. M.
Published: December 2024

Premise

Hydraulic segmentation, caused by the difference in embolism resistance across plant organs, provides a sacrificial layer of cheaper plant organs, like leaves, to protect more costly organs, such as stems, during drought. Within‐leaf hydraulic segmentation has been observed in two compound‐leaved tree species, with leaflets being more vulnerable than the rachis or petiole. Many herbaceous species have compound leaves, and some species have leaflets that are associated with pulvini at the base of the lamina, which could provide an anatomical means of preventing embolism from spreading within a leaf because of the higher number of vessel endings in the pulvinus.

Methods

We used the optical vulnerability method to investigate whether differences in embolism resistance were observed across the leaf tissues of six herbaceous species and one deciduous tree species with compound leaves. Our species selection included both palmately and pinnately‐compound leaved species, one of each with a pulvinus at the base of the leaflets.

Results

We found considerable variation in embolism resistance across the species measured, but no evidence of variation in embolism resistance within the leaf. In two species with pulvini, we observed major embolism events crossing the pulvinus, spreading from the rachis or petiole into the lamina, and embolizing both tissues at the same water potential.

Conclusions

We conclude that within‐leaf hydraulic segmentation, caused by variation in embolism resistance, is not a universal phenomenon to compound‐leaved species and that the presence of a pulvinus does not provide a barrier to embolism spread in compound leaves.
qPCR‐based quantification reveals high plant host‐specificity of endophytic colonization levels in leaves
Authors: de Paula Caio César Pires , Bárta Jiří , Borovec Jakub , Frouz Jan , Rychtecký Pavel , Sirová Dagmara
Published: December 2024

Premise

Despite the high functional importance of endophytes, we still have limited understanding of the biotic and abiotic factors that influence colonization of plant hosts along major ecological gradients and lack quantitative estimates of their colonization extent. In this study, we hypothesized that the developmental stage of the ecosystem will affect the levels of bacterial and fungal endophytic assemblages in the foliar endosphere.

Methods

We quantified levels of bacterial and fungal endophytes in leaves of four plant hosts at four stages of vegetation succession using an optimized qPCR protocol with bacteria‐specific 16S and fungi‐targeting primers.

Results

(1) The ecosystem developmental stage did not have a significant effect on the colonization levels of bacterial or fungal endophytes. (2) Colonization levels by bacterial and fungal endophytes were governed by different mechanisms. (3) Endophytic colonization levels and their relationship to foliar tissue stoichiometry were highly host specific.

Conclusions

Quantifying colonization levels is important in the study of endophytic ecology, and the fast, relatively low‐cost qPCR‐based method can supply useful ecological information, which can significantly enhance the interpretation potential of descriptive data generated, for example, by next‐generation sequencing.
Regulating Crystalline Phase/Plane of Polymer Electrolyte for Rapid Lithium Ion Transfer
Authors: Wang Su , Li Chen , Ma Yue , Zhang Hongzhou , Shi Xixi , Zhang Lianqi , Song Dawei
Published: December 2024

Electronic‐rich functional groups and flexible segments have long been perceived to be the decisive factors influencing lithium‐ion transfer in polymer electrolytes, while crystallinity is regarded as the great scourge. Actually, the research on the influence of crystalline phase and crystalline plane is still in scarcity. Herein, taking poly(vinylidene fluoride)‐hexafluoropropylene (PVDF‐HFP) as an example, new (111/201) crystal planes (belonged to β‐phase) are regulated by dissolving process and clarified by Synchrotron radiation X‐ray diffraction and X‐ray diffraction. Density functional theory calculation indicates that the newly exposed (111/201) crystal planes provide higher binding energy with lithium ions and are conducive to provide more ion transport channels. 7Li nuclear magnetic resonance of new crystalline planes contained PVDF‐HFP based electrolyte shows lower field and sharper peak intensity, further proves the rapid lithium ion transfer. Therefore, a high ionic conductivity of 6.42×10−4 S cm−1 and a large lithium‐ion transfer number of 0.7 are achieved. This study offers a new insight into the influence of crystalline phase and crystalline plane on the transfer of lithium ion for polymer electrolytes.
Fabrication and Characterization of Amphotericin B Loaded Poly(Vinyl Alcohol)/Chitosan‐ZnO Biocomposite Films for Antimicrobial Wound Dressings
Authors: Tosyali Ozlem Ayse , Sahin Furkan , Cetin Yuksel , Karal‐Yilmaz Oksan
Published: December 2024

Developing efficient hydrogel‐based wound dressings has gained increasing attention in improved wound healing capabilities. In this study, the biocomposite hydrogel films consisting of polyvinyl alcohol (PVA), chitosan (CS), and zinc oxide nanoparticles (ZnO NPs) were prepared using the solvent casting method. The biocomposite hydrogel films were also loaded (5% w/w) with Amphotericin B (AmB) as a model drug to develop a new suitable material with potential application as high‐performance wound dressing with controlled drug release. The chemical nature, thermal properties, and morphology of the PVA/CS and PVA/CS‐ZnO biocomposite hydrogels were analyzed and compared by FTIR, TGA, and SEM–EDX analysis. The effect of ZnO NPs on swelling behavior in the PVA/CS films was studied. PVA/CS‐ZnO biocomposite hydrogels presented a lesser degree of swelling compared to ZnO‐free hydrogels. The AmB‐loaded hydrogel films exhibited a sustained release rate during 72 h in PBS at pH 7.4. Biocompatibility of all hydrogel types (with or without ZnO and AmB) using L929 and HaCaT cell lines was evaluated with high cell viability examined by MTT assay. The antimicrobial activity of the films was evaluated against
Escherichia coli
,
Staphylococcus aureus
, and
Candida albicans
using a modified AATCC 100 method, whereby the R value represents the log reduction in the number of surviving colonies. The mean R values for drug‐free PVA/CS‐ZnO hydrogel films were 6.81 for
E. coli
, 6.03 for
S. aureus
, and 6.82 for
C. albicans
. The addition of AmB further enhanced the antimicrobial activity, increasing the R values for
E. coli
to 7.16, for
S. aureus
to 6.38, and for
C. albicans
to 7.31, demonstrating a significant synergistic effect with maximum antimicrobial efficacy. The results showed that the AmB‐loaded biocomposite hydrogel films (PVA/CS‐ZnO‐AmB) can be used as a new wound dressing material.
Preparation and Characterization of an Environmentally Friendly Dust Suppressant for Crust in a Nondisturbance Area of an Open Limestone Mine
Authors: Sun Qi , Sun Weize
Published: December 2024

To solve problems caused by dust pollution in open limestone mines, environmental dust suppressants were prepared with natural polymer extracts as raw materials. The proportion range of guar gum (GG), sodium carboxymethyl cellulose (CMC), and sodium dodecyl sulfate (SDS) as the single components of the composite dust suppressant (CDS) was determined by a single‐factor test. Response surface methodology (RSM) was used to optimize the mix design, and the weather resistance, compressive strength, and cost of CDS were tested and compared with many commercial dust suppressants. Microscopic tests were used to analyze the structural properties and functional group changes in CDS. The results showed that the optimal concentration of the CDS agent was 0.192% GG, 0.3% CMC, and 0.351% SDS. Under the optimal ratio, the viscosity of CDS was 119.56 mPa∙s, the pH was 7.62, the surface tension was 30.3 mN/m, and the price was 83.3 RMB/t. The dust hardness after 7 days of spraying CDS was 87 HA. CDS exhibits good resistance to rain erosion, pressure resistance, freeze–thaw resistance, and wind erosion. CDS formed a cross‐linked structure by linking the amide and carboxyl groups, which can significantly reduce porosity, and form a compact and flat solidified layer, which has good dust suppression performance.
Action execution and observation in autistic adults: A systematic review of fMRI studies
Authors: Stillesjö Sara , Hjärtström Hanna , Johansson Anna‐Maria , Rudolfsson Thomas , Säfström Daniel , Domellöf Erik
Published: December 2024

Motor impairments are common in individuals with autism spectrum disorder (ASD) although less is known about the neural mechanisms related to such difficulties. This review provides an outline of functional magnetic resonance imaging (fMRI) findings associated with execution and observation of naturalistic actions in autistic adults. Summarized outcomes revealed that adults with ASD recruit similar brain regions as neurotypical adults during action execution and during action observation, although with a difference in direction and/or magnitude. For action execution, this included higher and lower activity bilaterally in the precentral cortex, the parietal cortex, the inferior frontal gyrus (IFG), the middle temporal gyrus (MTG), the occipital cortex, and the cerebellum. For action observation, differences mainly concerned both higher and lower activity in bilateral IFG and right precentral gyrus, and lower activity in MTG. Activity overlaps between action execution and observation highlight atypical recruitment of IFG, MTG, precentral, and parieto‐occipital regions in ASD. The results show atypical recruitment of brain regions subserving motor planning and/or predictive control in ASD. Atypical brain activations during action observation, and the pattern of activity overlaps, indicate an association with difficulties in understanding others' actions and intentions.
Surface Decoration of Cellulose With Trifluoromethylphenyl Substituted Thiourea: A Robust Hydrogen‐Bonding Catalyst in Conjunction With L‐Proline for the Asymmetric Direct Mannich Reaction
Authors: Poslu Ayşe Haliç , Koz Gamze
Published: December 2024

Cellulose is one of the most abundant biopolymers in nature. Despite being the subject of research in various fields, it is not as famous as chitosan in catalyst design. Herein, a novel thiourea‐functionalized cellulose (CTU‐6) was synthesized as a robust hydrogen bonding catalyst with the degree of substitution (DS) of 0.84. CTU‐6 was characterized using Fourier transform infrared spectroscopy (FT‐IR), scanning electron microscope (SEM), x‐ray powder diffraction (XRD), proton nuclear magnetic resonance spectroscopy (1HNMR), solid‐state cross‐polarization magic angle spinning carbon‐13 nuclear magnetic resonance (CP/MAS 13C‐NMR), thermal gravimetric analysis (TGA) and elementel analysis. CTU‐6 catalyzed the direct asymmetric Mannich reaction between acetone, aniline, and various aromatic aldehydes in cooperation with L‐proline. The reaction exhibited excellent enantioselectivity, achieving up to 98% enantiomeric excess (ee) at room temperature. Incorporating trifluoromethylphenyl‐substituted thiourea into the cellulose framework leverages its ability to form hydrogen bonds, thereby enabling precise control over the asymmetric induction. This study highlights the potential of cellulose‐based catalysts in advancing asymmetric synthesis and their versatility in various organic reactions in cooperation with small chiral ligands. This synergy not only facilitates the efficient catalytic process but also improves the stereochemical outcomes of the reactions. This method underscores the importance of utilizing renewable and versatile cellulose materials in combination with chiral auxiliaries to achieve high levels of enantioselectivity.
Exploring student acceptance of learning technologies in anatomy education: A mixed‐method approach
Authors: Lee Jason Wen Yau , Ong Dennis Wenhui , Soh Reuben Chee Chong , Rao Jai Prashant , Bello Fernando
Published: December 2024

Anatomical education is transitioning from the time‐honored cadaveric dissection to a blend of learner‐centered and technology‐enhanced learning approaches. In view of the increased use of various technologies for teaching and learning human anatomy, the aim of this study is to explore students' acceptance of four learning technologies using the technology acceptance model (TAM). This work was conducted at a graduate medical school in Singapore with first‐year MD Program students. The acceptances of the four learning technologies were compared in two studies. In Study 1 (n = 46), we compared a 3D‐printed (3DP) model with Primal Pictures to answer a clinical question in a Spine Anatomy Tutorial; in Study 2 (n = 55), we compared the Anatomage Table and Primal VR for a Brain Anatomy tutorial. There was a statistically significant preference (p < 0.05) for 3DP models over Primal Pictures for learning Spine Anatomy, and for Primal VR over Anatomage for learning Brain Anatomy. The perceived ease of use of any technology does not appear to influence the behavioral intention to use it. Qualitative feedback suggests that visualization and spatial relationships were among the most important facilitators of learning. Technology should be an enabler in learning but some technologies have a steeper learning curve than others. Therefore, to increase its perceived usefulness, educators must leverage the affordances of the technology when designing learning activities.
Screening of an Antibacterial and Coagulation Multifunctional Peptide and Its Application in Wound Healing
Authors: Zhang Shengjie , Zhang Rong , Li Chunxiao , Cong Hailin , Yu Bing
Published: December 2024

As a new type of drug developed in the era of antibiotics, antimicrobial peptides (AMPs) have great potential in antibacterial, antiviral and antitumor aspects. Different from the principle of action of antibiotics, AMPs have a better effect on resisting drug‐resistant bacteria. We synthesized a peptide library using solid‐phase synthesis and successfully screened the antimicrobial peptide RKGAK. AMPs provide effective defense against both bacteria and fungi. Research has found that the lowest inhibitory concentrations of RKGAK against S. aureus, E. coli, and C. albicans are 75 μg/mL, 100 μg/mL, and 300 μg/mL. Not only that, this antibacterial peptide also has certain antiviral and coagulation effects. It is a multifunctional peptide that has great potential in many biomedical fields. It also has the advantages of being less likely to develop drug resistance, low hemolytic activity and low cytotoxicity. Loading the peptide into hydrogels has achieved good results in applications that promote wound healing.
Dehydrocoupling of Phosphine‐Borane Adducts Under Ambient Conditions Using Aminoboranes as Hydrogen Acceptors
Authors: Wiebe Matthew A. , Staubitz Anne , Manners Ian
Published: December 2024

We report on the reactivity of aminoboranes (R2N=BH2; R = iPr, Et, Me) with phosphine‐borane adducts (PhR′PH ⋅ BH3; R′ = H, Ph): Sufficiently sterically unencumbered aminoboranes can accept hydrogen from phosphine‐borane adducts. The hydrogen transfer results in the formation of amine‐borane adducts (R2NH ⋅ BH3) and transient phosphinoboranes (PhR′P−BH2) in situ. These phosphinoboranes undergo subsequent reactivity to yield either polyphosphinoborane, [PhPH−BH2]n, or the linear dimer, Ph2PH ⋅ BH2−Ph2P ⋅ BH3. Unlike metal catalyzed phosphine‐borane dehydrocoupling, which occurs at elevated temperatures (2 M, toluene, ≥100 °C, ≥24 h), these dehydrocoupling reactions occur under ambient conditions (2 M, Et2O or C6D6, 20 °C, ≤24 h). We performed a computational mechanistic study in which we identified that this transformation potentially occurs via a P‐to‐N and B‐to‐B hydrogen transfer through a 6‐membered transition state.
Advances in Chiral Macrocycles: Molecular Design and Applications
Authors: Sun Zhihong , Tang Hao , Wang Lingyun , Cao Derong
Published: December 2024

Chiral macrocycles have recently emerged as promising materials for enantioselective recognition, asymmetric catalysis, and circularly polarized luminescence (CPL) due to their terminal‐free structure, preorganized chiral cavities, and unique host‐guest and self‐assembly properties. This review summarizes recent advances in the design and synthesis of chiral macrocycles with central, axial, helical, and planar chirality, each imparting distinct structural and chiroptical characteristics. We highlight key strategies for constructing these macrocycles and their applications in optoelectronic and catalytic systems. Emphasis is placed on the balance between rigidity and flexibility in macrocycle design, essential for effective molecular recognition, adaptable catalysis, and CPL. We conclude with perspectives on future opportunities, anticipating ongoing developments in chiral macrocycle research.
On the Reactivity of (S)‐Indoline‐2‐Carboxylic Acid
Authors: Cordella Fabiana , Faure Sophie , Taillefumier Claude , Pescitelli Gennaro , Martinelli Elisa , Alonci Giuseppe , Liu Zhengming , Angelici Gaetano
Published: December 2024

(S)‐Indoline‐2‐carboxylic acid (H‐(2S)‐Ind‐OH) possesses the ability to influence the conformation of peptide bonds towards the cis amide isomer in polar solvents. However, its potential utilization as a conformational switch within long peptide sequences poses challenges due to its low reactivity and strong inclination to form diketopiperazines. The present study explores its reactivity under various conditions and proposes synthetic strategies to overcome these limitations. A series of H‐(2S)‐Ind‐OH containing di‐ and tri‐peptides have been efficiently synthesized and characterized, ready to be inserted in more complex and longer sequences.
Robust Encoding of Precise Addressing Information on AuNPs to Direct Their Heritable Positioning on DNA Origami†
Authors: Li Yuxi , Jiang Chu , Zhou Yanyu , Liu Huajie , Zhang Yinan
Published: December 2024

Comprehensive Summary

The programmability of DNA assembly allows for the creation of gold nanostructures with custom shapes and tailored optical properties, holding promise for applications including single‐molecule sensing and imaging. While DNA origami provides addressable site information for structure construction, there have been few studies on encoding information onto gold nanoparticles (AuNPs) to guide the assembly of Au‐DNA origami structures, especially for encoding extensive information onto large AuNPs (e.g., 30 nm). In this work, we introduce a strategy that encodes extensive information onto versatile AuNPs ranging in size from 5 nm to 30 nm using a DNA origami template (parent origami). This encoded information serves to direct the positioning of the AuNPs within a regenerated DNA origami structure (daughter origami). Our findings demonstrate the successful assembly of AuNPs ranging from 5 nm to 30 nm on the same site of the daughter DNA origami as the parent DNA origami, with yields of up to 80%. This approach offers new possibilities for achieving precise control over AuNPs assembly and functionality.
Fluorenyl Radicals Stabilized by Donor‐π‐Radical Conjugation between Nitrogen Atoms and Carbon Radicals
Authors: Zhang Xinfang , Tong Zekun , Dong Shaoqiang
Published: December 2024

Comprehensive Summary

A design strategy towards stable fluorenyl radicals (FRs) has been developed through introducing donor‐π‐radical (D‐π‐R) conjugation, facilitated by the linkage of amine N atoms and FR centers via phenyl or 9‐anthryl moieties. Four FRs, with or without N atom containing protecting groups, were designed and synthesized for comparative analysis. X‐ray crystallographic studies revealed the planar fluorenyl skeletons of CDP‐FR and MA‐FR, which exhibit significant dihedral angles relative to their protecting groups. Wiberg bond‐order analysis and natural bond orbital analysis conducted on the C‐C and C‐N bond between the radical center and N atoms in all FRs clearly demonstrated the presence of D‐π‐R conjugation. Furthermore, time‐dependent DFT calculations, based on frontier molecular orbital analysis, highlighted the contribution of D‐π‐R structures as donor‐acceptor effect on the lowest energy absorptions of carbazole and diphenylamine substituted CDP‐FR and DPAA‐FR, which would promote charge transfer process and inhibit the photodegradation reaction. Consequently, beneficial from D‐π‐R conjugations, CDP‐FR and DPAA‐FR exhibited superior photostability compared to TP‐FR and MA‐FR. Our study offers a new strategy for the design and synthesis of persistent stable monoradicals.
Synthesis and Properties of Naphtho‐fused Fluorenyl Radical
Authors: Shi Dan , Tian Xiaoqi , Wu Shuai , Huang Yanxia , Xu Jindong , Zhai Ziang , Xie Lili , Li Yuanming , Sun Zhe
Published: December 2024

Comprehensive Summary

Open‐shell graphene fragments (OGFs) with non‐benzenoid topologies are attracting increasing attention due to their potential applications in organic light‐emitting diodes (OLEDs) and organic radical conductors. Herein, we report the synthesis of an air‐stable fluorenyl radical derivative (AR1) containing a seven‐membered ring, achieving thermodynamic stabilization through the fusion of a naphthalene ring around its periphery and anthracene substituent. The half‐life times (τ1/2) of AR1 in air‐saturated solution is 71.9 h. The high stability was ascribed to kinetic blocking of reactive sites with high spin densities. The geometric and electronic structures of AR1 were systematically studied by combining various experimental methods and density functional theory (DFT) calculations, which include X‐ray crystallographic analysis, electron spin resonance (ESR), cyclic voltammetry, and UV−vis−NIR measurements.
Promoting rapeseed yield: Improving canopy structure and formation of large pod via adjusting planting density
Authors: Wang Long , Li Yiyang , Qian Chen , Li Jing , Lin Guobing , Qu Wenting , Wang Yan , Lin Yaowei , Huang Yihang , Zheng Jingdong , You Jingjing , Zuo Qingsong
Published: December 2024

Increasing planting density is a common practice to enhance rapeseed (Brassica napus L.) yield via an increase in pod quantity. However, excessive density may lead to a deterioration in pod quality. Therefore, we hypothesized that improving pod quality based on a certain level of pod quantity could further increase seed yield. A randomized block experiment was conducted with five density levels (2.4, 3.6, 4.8, 6.0, and 7.2 × 105 plants ha−1, referred to as D1, D2, D3, D4, and D5) using two hybrid varieties of Qinyou10 and Ningza1838. The plot seed yield reached the maximum value in D2 or D3, and there was no significant difference between these two density levels. An increase in planting density resulted in a decrease in canopy thickness, but an increase in lodging angle and pod density. According to the number of seeds per pod, the pods were categorized into low‐productive pod (≤14), middle‐productive pod (15‒17), and high‐productive pod (≥18). The number of high‐productive pod in D2 and D3 ranged from 48.15 × 106 to 54.22 × 106 ha−1, accounting for 53.76%‒63.28% of the total pod number and 76.89%‒82.83% of the total seed yield. With the planting density increasing from D3 to D5, there was a significant transition from high‐productive pod to middle‐productive and low‐productive pods, causing a decrease in seed yield. Therefore, when the seed yield was targeted as 4500 kg ha−1, the suitable planting density ranged from 3.6 × 105 to 4.8 × 105 plants ha−1, and the optimal number of pods in population ranged from 83.0 × 106 to 94.0 × 106 ha−1, and the quantity proportion of high‐productive pod maintained >50%. This study provides a guide for high‐yield cultivation of rapeseed in China and presents a novel approach to promoting a potential yield of rapeseed.
Genomic prediction of metabolic content in rice grain in response to warmer night conditions
Authors: Bi Ye , Walia Harkamal , Obata Toshihiro , Morota Gota
Published: December 2024

It has been argued that metabolic content can be used as a selection marker to accelerate crop improvement because metabolic profiles in crops are often under genetic control. Evaluating the role of genetics in metabolic variation is a long‐standing challenge. Rice, one of the world's most important staple crops, is known to be sensitive to recent increases in nighttime temperatures. Quantification of metabolic levels can help measure rice responses to high night temperature (HNT) stress. However, the extent of metabolic variation that can be explained by regression on whole‐genome molecular markers remains to be evaluated. In the current study, we generated metabolic profiles for mature grains from a subset of rice diversity panel accessions grown under optimal and HNT conditions. Metabolite accumulation was low to moderately heritable, and genomic prediction accuracies of metabolite accumulation were within the expected upper limit set by their genomic heritability estimates. Genomic heritability estimates were slightly higher in the control group than in the HNT group. Genomic correlation estimates for the same metabolite accumulation between the control and HNT conditions indicated the presence of genotype‐by‐environment interactions. Reproducing kernel Hilbert spaces regression and image‐based deep learning improved prediction accuracy, suggesting that some metabolite levels are under non‐additive genetic control. Joint analysis of multiple metabolite accumulation simultaneously was effective in improving prediction accuracy by exploiting correlations among metabolites. The current study serves as an important first step in evaluating the cumulative effect of markers in influencing metabolic variation under control and HNT conditions.
Simulating sagebrush–cheatgrass plant community biomass production in the Great Basin using ALMANAC
Authors: Schantz Merilynn C. , Kiniry James R. , Williams Amber S. , Thorp Kelly R. , Newingham Beth , Hardegree Stuart P. , Williams C. Jason , Davies Kirk W. , Sheley Roger L.
Published: December 2024

Cheatgrass (Bromus tectorum) is a widespread species of concern throughout the western US, as it dominates many low‐elevation rangelands and continues to spread annually. As a winter annual grass, however, cheatgrass can produce high‐quality and cheap protein forage for livestock early in the growing season. Estimating biomass can lead to better management in these western United States and Great Basin plant communities. The present study was designed to evaluate the accuracy of biomass simulations in Great Basin plant communities using the process‐based Agricultural Land Management Alternative with Numerical Assessment Criteria (ALMANAC) model as it simulates biomass production and competing species interactions. For this study, data were used from the Sagebrush Steppe Treatment Evaluation Project to simulate cheatgrass, perennial grass, forb, and sagebrush biomass across three community types: native, invaded, and a co‐dominated community of sagebrush, perennial grasses, cheatgrass, and forbs at six representative Great Basin sites from 2006 to 2018. Our results indicated a strong relationship between simulated and measured biomass of total cheatgrass and perennial grasses across the three plant communities. Sagebrush and forb biomass were poorly simulated across most plant community types. Model accuracy also varied by site, largely depending on elevation. We saw high variability in simulated biomass across years, likely because of the single point‐in‐time measurements at peak biomass and the low biomass values of cheatgrass and forbs. Collectively, ALMANAC shows potential for assessing biomass production and plant interactions but will require more data and model development to fully comprehend its utility.
Dynamic conditioning of porcine kidney grafts with extracellular vesicles derived from urine progenitor cells: A proof‐of‐concept study
Authors: Burdeyron Perrine , Giraud Sébastien , Lepoittevin Maryne , Jordan Nina , Brishoual Sonia , Jacquard Maïté , Ameteau Virginie , Boildieu Nadège , Lemarie Estelle , Daniel Jonathan , Martins Frédéric , Mélis Nicolas , Coué Marine , Thuillier Raphaël , Leuvenink Henri , Pellerin Luc , Hauet Thierry , Steichen Clara
Published: December 2024

Among strategies to limit ischemia/reperfusion (IR) injuries in transplantation, cell therapy using stem cells to condition/repair transplanted organs appears promising. We hypothesized that using a cell therapy based on extracellular vesicles (EVs) derived from urine progenitor cells (UPCs) during hypothermic and normothermic machine perfusion can prevent IR‐related kidney damage.

We isolated and characterized porcine UPCs and their extracellular vesicles (EVs). Then these were used in an ex vivo porcine kidney preservation model. Kidneys were subjected to warm ischemia (32 min) and then preserved by hypothermic machine perfusion (HMP) for 24 h before 5 h of normothermic machine perfusion (NMP). Three groups were performed (n = 5–6): Group 1 (G1): HMP/vehicle + NMP/vehicle, Group 2 (G2): HMP/EVs + NMP/vehicle, Group 3 (G3): HMP/EVs + NMP/EVs.

Porcine UPCs were successfully isolated from urine and fully characterized as well as their EVs which were found of expected size/phenotype. EVs injection during HMP alone, NMP alone, or both was feasible and safe and did not impact perfusion parameters. However, cell damage markers (LDH, ASAT) were decreased in G3 compared with G1, and G3 kidneys displayed a preserved tissue integrity with reduced tubular dilatation and inflammation notably. However, renal function indicators such as creatinine clearance measured for 5 h of normothermic perfusion or NGAL perfusate's level were not modified by EVs injection. Regarding perfusate analysis, metabolomic analyses and cytokine quantification showed an immunomodulation signature in G3 compared with G1 and highlighted potential metabolic targets. In vitro, EVs as well as perfusates from G3 partially recovered endothelial cell metabolic activity after hypoxia. Finally, RNA‐seq performed on kidney biopsies showed different profiles between G1 and G3 with regulation of potential IR targets of EVs therapy.

We showed the feasibility/efficacy of UPC‐EVs for hypothermic/normothermic kidney conditioning before transplantation, paving the way for combining machine perfusion with EVs‐based cell therapy for organ conditioning.

Highlights

UPCs from porcine urine can be used to generate a cell therapy product based on extracellular vesicles (pUPC‐EVs).

pUPC‐EVs injection during HMP and NMP decreases cell damage markers and has an immunomodulatory effect.

pUPC‐EVs‐treated kidneys have distinct biochemical, metabolic, and transcriptomic profiles highlighting targets of interest.

Our results pave the way for combining machine perfusion with EV‐based cell therapy for kidney conditioning.
Searching the Crystal Ball for Tailored GLP‐1 Receptor Agonists Treatment in Type 2 Diabetes and Obesity
Authors: Saturnino Asia , Maddaloni Ernesto , Zampetti Simona , Buzzetti Raffaella
Published: December 2024

Background

Glucagon‐like peptide 1 receptor agonists (RA) are novel agents used in the management of type 2 diabetes (T2D) and obesity. Although highly effective, the response to treatment may vary significantly among patients.

Objective

This perspective review aims to summarise the current knowledge about markers of poor or good response to GLP‐1 RA, highlighting the possibility of tailoring treatment strategies and reducing costs associated with T2D and obesity treatment.

Methods

A comprehensive literature search was conducted using PubMed, NCBI, and Scopus databases, focussing on studies published between 2016 and 2024 that evaluated factors influencing treatment outcomes with GLP‐1 RA.

Results

Several markers, including baseline HbA1c levels, ghrelin and glucose‐dependent insulinotropic polypeptide (GIP) levels, specific gut microbiome composition, b‐cell function, and genetic markers, were identified as factors associated with treatment response.

Conclusion

Understanding predictive markers of response to therapy can enhance precision‐based medicine for the selection of patients eligible for GLP‐1 RA, improving clinical outcomes and optimising diabetes management.
The transformative potential of environmental governance integration for sustainable land use: The case of subsidence in the Dutch peatlands
Authors: van den Ende Mandy A. , Driessen Peter P. J. , Hegger Dries L. T. , Mees Heleen L. P.
Published: December 2024

Transformations of existing systemic structures are needed to address the root cause of many environmental land‐use (ELU) problems: unsustainable land use. One policy principle that can help achieve such transformation entails integrating cross‐cutting ELU problems with non‐environmental policy domains, also known as environmental policy integration (EPI). Its transformative potential is disputed, however, because different forms of integration involve varying degrees of value attribution to environmental concerns vis‐à‐vis other policy goals. Since the EPI literature indicates this degree is greatly influenced by actors and institutions, we consider environmental governance integration (EGI) a more appropriate term for evaluations. Using the case of subsidence in the Dutch peatlands, we aim to provide insights into EGI's potential and scope for improvement in facilitating transformative change toward sustainable land use. Our study reveals generally low to moderate EGI, because ELU concerns were integrated within the boundaries of a land‐use system that prioritizes prevailing economic interests. This indicates EGI being a (business‐as‐usual) governance approach that merits the label economic governance integration, since (transformative) environmental governance integration would entail an exploration of a myriad of different sustainable land‐use options, irrespective of existing system structures. We recommend a cognitive shift as a precondition for institutional reform and politics favoring transformative governance.
Sex‐based differences in shot put, javelin throw, and long jump in 8‐and‐under and 9–10‐year‐old athletes
Authors: Brown Gregory A. , Shaw Brandon S. , Shaw Ina
Published: December 2024

There is an ongoing debate regarding the necessity for sex‐segregated sports particularly in youth. However, there has been minimal evaluation of prepubertal sex‐based differences in the events of shot put, javelin throw, and long jump. Therefore, the top eight performances from the USA Track and Field National Youth Outdoor Championships and National Junior Olympic Championships during the years 2016–2023 for shot put, javelin throw, and long jump in the 8‐and‐under and 9–10‐year‐old age groups were analyzed for sex‐based differences. The 8‐and‐under males threw the shot put farther (P < 0.0001 and Hedges’ g = 0.922) than females by 19.3% and the 9–10‐year‐old males threw the shot put farther (P = 0.016 and Hedges’ g = 0.332) than females by 6.5%. The 8‐and‐under males threw the javelin farther (P < 0.0001 and Hedges’ g = 1.269) than females by 32.6% and 9–10‐year‐old males threw the javelin farther (P < 0.0001 and Hedges’ g = 1.169) than females by 23.5%. The 8‐and‐under males long jumped farther (P = 0.010 and Hedges’ g = 0.359) than females by 4.7% and 9–10‐year‐old age males long jumped farther (P = 0.007 and Hedges’ g = 0.552) than females by 3.9%. The average between sex differences were larger than the within sex differences between the first through fourth place finishers in all but 9–10‐year‐old shot put. In all events, the greatest individual distance for a male exceeded that for a female. Therefore, the present data indicate that, in elite competition, males in the 8‐and‐under and 9–10‐year‐old age groups typically performed long jump and throw the shot put and javelin farther than females of the same age.
Application of machine learning for optimization and modeling of turbidity removal from aqueous solution
Authors: Dutta Neelanjan , Dey Pankaj , Pal Joy
Published: December 2024

Turbidity affects the aesthetic and overall quality of water and therefore, its prediction and modeling are essential for designing treatment strategies. In the present research, the outcomes of altering parameters and optimizing the removal of turbidity using response surface methodology (RSM), artificial neural network (ANN), support vector machine (SVM), and K‐nearest neighbor (KNN) based on a statistically designed set of experiments are examined. pH, coagulant dose, and settling time are considered process variables. The optimum removal of turbidity was obtained at a pH range of 6–8, coagulant dosage of 20–35 mg/L, and settling time of 30–45 min for the coagulants. The best turbidity reduction (60%) was achieved using alum coagulant (30 mg/L), at a pH of 7.5 and settling time for 45 min. All the models proved to be effective in demonstrating how the operating variables being studied influence the removal of turbidity from the aqueous solution. In contrast to the RSM, SVM, and KNN models, the ANN more accurately characterized the parametric impact.
Long‐Term Outcomes of Reduced‐Toxicity Conditioning Using 8‐Gray Total Body Irradiation, Fludarabine, and Cyclophosphamide in Children, Adolescents, and Young Adults With Hematological Malignancies
Authors: Morokawa Hirokazu , Hirabayashi Koichi , Furui Yu , Okura Eri , Saito Shoji , Nakazawa Yozo
Published: December 2024

Recent studies have indicated that total body irradiation (TBI)‐based reduced‐toxicity conditioning (RTC) may be a potential treatment modality, especially in adults with leukemia. However, its efficacy and safety in children with hematological malignancies remain unclear. To investigate the long‐term outcomes and safety of allogeneic hematopoietic stem cell transplantation (allo‐HSCT) using an 8‐Gray (Gy) TBI/fludarabine (FLU)/cyclophosphamide (CY) RTC in children with hematological malignancies. We included 66 consecutive patients with leukemia, lymphoma, or myelodysplastic syndrome in this retrospective cohort study. Participants were < 25 years old and received an 8‐Gy TBI/FLU/CY RTC regimen followed by the first allo‐HSCT at Shinshu University Hospital between March 2004 and March 2021. The 5‐year overall and relapse‐free survival probabilities were 88.2% and 76.5%, respectively, in the lymphoid malignancy group. The myeloid malignancy group had probabilities of 72.4% and 58.6%, respectively. The 5‐year cumulative incidences of relapse and non‐relapse mortality were 20.6% and 2.9%, respectively, in the lymphoid malignancy group. These incidences were 37.9% and 3.4%, respectively, in the myeloid malignancy group. All patients had engraftment without early relapse and none developed grade 5 regimen‐related toxicity within 28 days after allo‐HSCT. Nonetheless, two patients had congenital abnormalities caused by chromosomal aberrations and died without relapse. 8‐Gy TBI/FLU/CY RTC was safe in children with hematological malignancies, regardless of the donor source. However, safety concerns were noted in cases of chromosomal aberration‐induced congenital abnormalities. Additionally, patients in the lymphoid and myeloid malignancy groups had favorable prognoses.