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Estradiol and progesterone regulate secretion and metabolite content of extracellular vesicles from immortalized bovine uterine epithelial cells
Mild‐Condition Upcycling of Polyolefins Enabled by Micropore Confinement in Zeolites
Abstract The catalytic upcycling of polyolefin waste into valuable chemicals offers a sustainable strategy to mitigate plastic pollution and advance resource sustainability. Selectively cracking the inert C─C bonds in polyolefins under mild, co‐reactant‐free conditions remains a fundamental challenge due to their chemical stability and poor diffusivity. Herein, we report a co‐reactant‐free strategy for the selective cracking of polyolefin into C 2 –C 6 olefins at 240 °C under 1 atm N 2 , enabled by b ‐axis‐shortened HZSM‐5 nanosheet zeolites (s‐ZSM‐5) with tailored micropore confinement and acidity. Mechanistic investigations reveal an isomerization–oligomerization–scission (IOS) cycle confined within zeolite micropores, which arises from the synergistic interplay of controlled confinement and diffusion. This dynamic cycle is driven by the preferential diffusion of short‐chain olefins, which disrupts local reaction equilibrium and drives continuous cracking. The optimized s‐ZSM‐5 catalyst achieves up to 94.7% low‐density polyethylene (LDPE) conversion and 90.0% C 2 –C 6 olefin selectivity, while exhibiting exceptional coking resistance and compatibility with diverse post‐consumer plastics. These findings establish a novel mechanistic foundation for confined‐space effect and offer guiding principles for the rational design of solid catalysts for sustainable plastic upcycling.
Pre-trained multi-scale RWKV-GCN for multivariate time series forecasting
Harnessing Reversible 0D–1D Transformation in Chiral Mn(II) Halides for Smart Circularly Polarized Luminescence Switching and Multi‐Level Encryption
Abstract Circularly polarized luminescence (CPL) active materials with dynamically tunable properties are highly desirable for next‐generation photonics and encryption technologies, yet achieving this through predictable solid‐state structural transformations remains a formidable challenge. Herein, we demonstrate a novel dimensionality‐engineering strategy to realize stimuli‐responsive CPL in chiral hybrid Mn(II) halides. Employing a single chiral cation, R/S‐3‐methylmorpholine, we selectively synthesized two distinct phases: a red‐emissive 1D chain structure with octahedral Mn(II) centers and a green‐emissive 0D structure with tetrahedral coordination. Remarkably, the 0D phase undergoes a rapid and reversible ethanol‐assisted thermal transformation into the 1D phase, accompanied by a striking CPL color switch from green to red. This unique behavior stems from a stimulus‐induced recoordination of Mn–Cl units and reorganization of the hydrogen‐bonding network. Capitalizing on this reversible response and intrinsic chirality, we engineered a sophisticated multilevel photonic encryption platform, encompassing binary dot‐matrix coding, dual‐channel (photoluminescence/CPL) Morse code, and CPL‐based ASCII decryption. This work establishes structural dimensionality control as a powerful paradigm for creating intelligent, CPL‐active materials, opening new avenues for high‐security optical information technologies.
Adult age differences in the modulation of peripersonal space after tool use in virtual reality
Abstract Tool use has been shown to modulate the multisensory representation of the area surrounding our body known as peripersonal space (PPS). Yet, it remains unclear whether such effects extend to tool use in virtual reality (VR), and whether age may influence this modulation of PPS in VR. We investigated these questions in younger adults (YAs; 19–29 years) and older adults (OAs; 65–84 years). Participants completed a tool-use task in VR while viewing a virtual avatar from a first-person perspective. Tool-use effects on PPS were assessed using a visuo-tactile task before and after tool use, and participants rated their sense of ownership over the avatar at both time points. Results in YAs suggest a location-specific modulation of PPS after tool use. In contrast, OAs did not show a location-specific modulation but exhibited results suggesting a general enhancement of PPS within the VR environment. Interestingly, while both groups showed increased avatar ownership following tool use, only OAs demonstrated an association between this increase in ownership and increased overall multisensory facilitation in VR. These findings suggest that PPS remains responsive to VR environments in older age, but that the mechanisms underlying PPS modulation after tool use in VR differ with age.
Unexpected Dual Function of Plant YUCCA Enzymes Links Chlorophyll Catabolism to Auxin Homeostasis
Abstract Chlorophyll (Chl) metabolism is pivotal to both photosynthesis and plant senescence and represents one of the most fundamental biological processes on Earth with an estimated annual turnover of 1 billion tons. During Chl degradation, only early catabolites and corresponding enzymes are well characterized, whereas for late‐stage degradation products it remains often unclear if their formation involves specific enzymes. Here, we report that the ubiquitous YUCCA10 enzymes from the YUCCA flavin‐containing monooxygenase (FMOs) family in land plants, normally implicated in the biosynthesis of indole‐3‐acetic acid (IAA) as the primary form of auxin, surprisingly catalyze the production of several predominant Chl catabolites via mechanistically distinct Baeyer–Villiger oxidation and subsequent hydrolytic γ‐lactam‐forming deformylation reactions. These historically postulated but hitherto undiscovered Chl degradation steps on several high molecular weight chl catabolites were verified for YUCCA10 from Vitis vinifera and Coffea arabica , while YUCCA10 from Arabidopsis thaliana lacked this activity. In contrast, all three homologs were able to catalyze the rate‐limiting key step in IAA biosynthesis, akin to other YUCCA enzymes. Interestingly, Chl catabolites at physiological concentrations impaired IAA formation by YUCCA10 in vitro, suggesting a key role in leaf senescence through enzymatic feedback regulation of auxin levels.
Integrating GIS and AHP for sustainable ecotourism site suitability analysis: a case study of Bahir Dar, Ethiopia
Exposure-associated health implications of potentially toxic elements in maternal and umbilical cord blood at Ishaka adventist hospital, Bushenyi District, Uganda
High‐Efficiency Blue TADF Palladium(II) Complexes with Ligand‐to‐Ligand Charge Transfer Excited State
Abstract Electroluminescent complexes of the second‐row transition metals remain underdeveloped due to the challenge of simultaneously achieving fast radiative decay and slow nonradiative decay, particularly in the blue spectral region. Herein, we report a design strategy for strongly blue‐emitting pincer‐type Pd(II) complexes based on the thermally activated delayed fluorescence (TADF) mechanism. By paring a terdentate trifluoromethyl‐substituted bis‐ N ‐heterocyclic carbene (NHC) with a cyano‐substituted carbazolide ligand, the lowest‐lying singlet excited states of the resulting Pd(II) complexes exhibit dominant ligand‐to‐ligand charge transfer (LLCT) character. Electrochemical and theoretical calculations confirm that the oxidation and reduction processes are ligand‐controlled with minor metal involvement. Through tuning of the electron‐accepting strength and the triplet locally‐excited ( 3 LE) energy of the pincer bis‐NHC ligand via a subtle structural change, a blue emitting TADF Pd(II) complex ( PyPdCN ) is achieved, exhibiting an emission maximum of 472 nm and a quantum yield of 86% in doped film. The energy gap between 1 LLCT and 3 LE states proves crucial for regulating the excited state dynamics. Organic light‐emitting diodes employing PyPdCN as the emitter show blue electroluminescence with peaks ranging from 460 to 473 nm and maximum external quantum efficiencies exceeding 20%, representing a significant advancement in luminescent Pd(II) complexes.
Quantum transfer learning for cross-domain cybersecurity threat detection and categorization
Copper‐Catalyzed Regio‐ and Diastereoselective Dearomative Carbosilylation of Unactivated Arenes by Intercepting the Dienyl Radical
Abstract The radical‐mediated dearomatization of aromatic systems to generate cyclohexadienyl radical intermediates represents a crucial strategy for constructing three‐dimensional molecular architectures. Conventional approaches typically through ipso ‐addition and subsequent proton/oxygen/carbon dioxide trapping to suppress rapid re‐aromatization, significantly constraining product diversity. Furthermore, dearomative bifunctionalization reactions—which offer enhanced step‐ and atom‐economy—remain substantially underdeveloped. Herein, we disclose a copper‐catalyzed radical dearomative 1,4‐ and 1,2‐carbosilylation strategy applicable to diverse unactivated (hetero)aromatic substrates to selectively construct spiro‐ or fused‐cyclic products. The resulting vinyl and allylic silanes serve as versatile synthetic handles for downstream transformations, enabling the rapid construction of sp 3 ‐rich polycyclic scaffolds that are highly valuable in drug discovery. Mechanistic and DFT studies indicate that the reaction commences with copper(I)‐silicon‐mediated halogen atom transfer of readily available aryl iodides to generate aryl radicals. These reactive species exhibit dual pathways: direct ipso ‐addition to aromatic rings or 1,5‐hydrogen atom transfer followed by alkyl radical‐mediated ortho ‐addition. Subsequent trapping of the resulting dienyl radicals by copper(II)‐silicon species yields complex polycyclic systems containing cyclohexadienylsilicon frameworks with excellent chemo‐, regio‐ and diastereoselectivity. This methodology not only establishes a novel paradigm for copper‐catalyzed radical dearomative bifunctionalization but also provides an efficient radical ipso‐ and ortho ‐addition platform for synthesizing architecturally intricate polycyclic compounds.
Predefined-time tracking control for underwater robots
Floor Temperature‐regulated Poly(ether‐alt‐ester) With Thermal Stability and Chemical Recyclability Enabled by Polycondensation—Depolymerization−Repolymerization Strategy
Abstract Creating innovative poly(ether‐ alt ‐ester)s (PEAEs) with alternating ether and ester groups to address the trade‐offs between the polymer′s depolymerizability and thermostability is essentially important for advanced material applications and sustainable development. Current research efforts focus on modulating the ceiling temperature ( T c ) of monomers with small‐sized rings, to increase the thermostability of PEAEs at high temperature. Notably, floor temperature ( T f )−regulated PEAEs, obtained from entropy‐driven ring‐opening polymerization (ROP) of macrocyclic ether‐ester monomers, inherently exhibit enhanced thermodynamic stability as the temperature increases. However, high‐performance PEAEs regulated by T f remains long‐term underdeveloped owing to extremely low efficiency and selectivity in macrocyclic monomer synthesis. Herein, we developed a “polycondensation–depolymerization” strategy for macrocyclic ether‐ester monomer and presented the first example of T f ‐regulated PEAE with thermostability, melt processibility as well as chemical recyclability. The resulting PEAE is semi‐crystalline and ductile, and exhibits remarkable high decomposition temperature (with a T d,5% up to 378.3 °C) compared to the T c ‐regulated poly(1,4‐dioxan‐2‐one) (PPDO, T d,5% = 238.4 °C). This work corroborated the effectiveness of the T f ‐regulated PEAE in resolving the challenges associated with the T c ‐regulated analogs and provided a molecular‐level design principle for poly(ether‐ alt ‐ester) with high‐performance.
Sintered poultry-base waste as low-cost adsorbent for the uptake of Congo red: insight into kinetics, isotherms and thermodynamics
Bioinspired Backbone Editing Strategies for Rewriting Synthetic Polymers
Abstract The structure of a polymer backbone plays a central role in determining its physical properties, chemical reactivity, and function. In biological systems, biopolymers such as DNA, RNA, and proteins exhibit a remarkable degree of structural and functional adaptability, achieved through highly regulated post‐synthetic modifications of both side chains and backbones. By contrast, synthetic polymers have traditionally been designed with static, inert backbones, limiting post‐synthetic modulation of their core structures. Although post‐polymerization modification strategies have successfully enabled side chain and terminal group functionalization, precise editing of the polymer backbone remains underdeveloped. Inspired by the editing mechanisms of biological macromolecules, recent efforts have begun to explore chemical strategies for backbone editing in synthetic polymers. These emerging approaches offer transformative potential for generating functional polymeric materials for diverse applications. This Minireview highlights key backbone editing mechanisms in biological systems and discusses how these paradigms can inform the development of bioinspired backbone editing strategies to rewrite synthetic polymers.
Enhanced adaptive zebra optimization algorithm optimized kernel extreme learning machine for bankruptcy prediction problems
Novel Ferroelectric Mediated Dual S‐scheme Heterojunction with Multiple Built‐in Electric Fields for Enhanced Photoelectrochemical Seawater Splitting
Abstract Photoelectrochemical (PEC) seawater splitting is promising for direct utilization of solar energy and ocean resources for H 2 production, but encounters challenges like difficult separation and recombination between holes and electrons. Herein, a dual S‐scheme TiO 2 /SrTiO 3 /C 3 N 4 (TiO 2 /STO/CN) heterojunction is in situ synthesized to construct a self‐supporting three‐phase system for PEC seawater splitting. The dual S‐scheme heterojunction photoanode has high electron‐hole pair separation quality and low recombination efficiency, and exhibits excellent catalytic performance. It achieves a photocurrent density of 6.32 mA·cm −2 at 1.23 V and a high applied bias photon‐to‐current efficiency (ABPE) of 1.90%, which are much higher than that of the pristine TiO 2 photoelectrode and other reports. The remarkable PEC activity of TiO 2 /STO/CN is attributed to the effective charge separation driven by the multiple built‐in electric fields within the ferroelectric mediated dual S‐scheme heterojunction. The photogenerated carrier transfer pathways are discussed with multifarious methods such as band structure analysis, KPFM, EPR, and DFT calculations. It provides a perspective for constructing high‐performance photocatalysts.
Phytochemical analysis of green-branch bark extract and the brown gum exudates “kinos” from Eucalyptus camaldulensis by HPLC and GC–MS with their antifungal activity
Abstract Eucalyptus has been utilized in traditional Australian medicines for the treatment of various ailments and is also used in pharmaceutical and cosmetic products. Eucalyptus contains an important source of key bioactive volatile and nonvolatile compounds. With the increasing research interest in Eucalyptus extracts and their health properties as an eco-friendly treatment, the green-branch bark extract (GBE) and the brown gum exudates, known as “kinos,” from Eucalyptus camaldulensis Dehnh. grown in Egypt, were used as biofungicide agents applied to Pinus halepensis Mill. wood samples. The phytochemicals were analyzed using the chromatographic tools, HPLC and GC–MS. These extracts at concentrations of 125, 250, 500, and 1000 µg/mL were further tested for their antifungal activity against Fusarium circinatum and Pythium tardicrescens , which were isolated from the diseased roots of Pinus halepensis . HPLC analysis of GBE revealed that kaempferol (14043.15 µg/g extract), gallic acid (7021.37 µg/g extract), and ellagic acid (4983.92 µg/g extract) were the major compounds. In the kinos, the main compounds were chlorogenic acid (12511.35 µg/g extract), gallic acid (12443.92 µg/g extract), ellagic acid (8147.54 µg/g extract), and rutin (2025.87 µg/g extract). By the GC–MS, p -cymene (31.91%), spathulenol (26.56%), and crypton (11.60%) were detected as primary compounds in the GBE. In the kinos, the abundant identified compounds by GC–MS were spathulenol (19.61%), isoaromadendrene epoxide (9.13%), α -acorenol (4.71%), and patchoulane (4.68%). Both GBE and kinos showed potential antifungal activity at 1000 µg/mL, inhibiting F. circinatum growth with fungal inhibition percentage (FIP) values of 71.85% and 71.11%, respectively. The GBE at 1000 and 500 µg/mL exhibited the highest antifungal effects against P. tardicrescens , with FIP values of 39.62% and 35.55%, respectively. The primary uniqueness of research into green-branch bark extracts and kinos from Eucalyptus camaldulensis comes from the growing global problem of antifungal resistance and the pressing need to identify specific bioactive chemicals for innovative development and investigate their application in environmentally friendly wood-biofungicide applications.
Boosting the Nucleophilicity of the Diphenylphosphide Anion with Crown Ether Supported Heavy Alkali Metals to Facilitate Highly Efficient Catalytic Alkene Isomerisation
Abstract Caesium and rubidium have long experienced an interest drought in organoelement chemistry in comparison to the vast ocean of applications accomplished mainly by lithium and to a lesser extent, by sodium and potassium in this field. Here, we report a breakthrough study in catalytic alkene isomerisation using crown ether‐supported alkali metal phosphides in which the activity increases sequentially and significantly as Group One is descended with Cs(18‐crown‐6)PPh 2 performing best even at 1 mol% loadings with high turnover frequencies (TOFs) and good functional group tolerance. Elevating its profile further, Cs(18‐crown‐6)PPh 2 is also successful in a stepwise double catalysis on combining alkene isomerisation with its newly established hydrophosphination (HP) capacity to access challenging to make Markovnikov products. This remote functionalisation approach was also applied to alkynes with terminal alkynes preferentially producing allenes over internal alkynes in one‐pot reactions and then under HP, generating highly functionalised vinyl phosphines. Kinetic studies and DFT calculations have also been performed to shed light on mechanistic aspects of the Cs‐mediated isomerisation of model alkene allylbenzene.
Optimization of fuzzy logic controller in the converter of a standalone solar power system using the firefly algorithm
Abstract In single photovoltaic (PV) systems, inverters are highly important for transforming DC voltage into AC voltage with predetermined amplitude and frequency control. A good inverter must provide a stable output voltage and low harmonic distortion during potential load variation, and it must recover its stability in an efficient manner while maintaining the quality of power during disturbances. Fixed controllers usually do not provide satisfactory performance because of the inherent nonlinear characteristics of the systems, and this drives the adoption of intelligent control techniques. One area of interest is fuzzy logic controllers (FLCs), which can provide a good control measure of nonlinear dynamics and do not require use of a specific mathematical model. This study introduces the Firefly Algorithm to optimize fuzzy controller membership functions for improved voltage regulation, reduced MSE, and lower THD. The input and output membership functions are optimized in order to minimize the mean square error (MSE) of the output voltage. The proposed controller is tested for different load conditions including resistive loads, inductive loads, and non-linear loads; the performance is compared to a traditional fuzzy logic controller (FLC) as well as FLCs optimized using a Genetic Algorithm (GA) and Particle Swarm Optimization (PSO). Results from the simulation indicate the performance achieved from Firefly Algorithm (FA) is acceptable when compared with voltage regulation, harmonic distortion (THD), and dynamic responses for stand-alone photovoltaic systems. Simulation results indicate that the FA-optimized fuzzy logic controller produces a minimum total harmonic distortion of 2.89% and a mean square error of 0.0071, thus showing its superiority over the traditional PI and fuzzy logic controllers for various load conditions.