bluuebunny/crossref_metadata_2025 huggingface dataset:
Transethosome‐Based Topical Administration Systems with Enhanced Penetration and Dual Actions for Treating EGFR‐Overexpressed Cutaneous Squamous Cell Carcinoma
Authors: Wang Wenyan , Tham Phoebe Huijun , Ding Chendi , Huang Ping , Li Tingxuan , Luo Jingjing , Xiang Huijing , Zeng Xiaowei , Chen Hongzhong , Zhao Yanli
Published: February 2024

Epidermal growth factor receptor (EGFR)‐overexpressing cutaneous squamous cell carcinoma (CSCC) necessitates more effective therapies due to its elevated metastasis risk compared to the conventional CSCC. While photodynamic therapy (PDT) is a promising way to treat CSCC, effectively administering photosensitizers to reach deeper skin malignancies remains a challenge. Herein, BE‐TEL is reported, a transethosome formulation designed to enhance skin and cutaneous tumor permeability, for targeted treatment of EGFR‐overexpressed CSCC. The formulation is co‐loaded with Erlotinib (Erb), a hydrophobic EGFR inhibitor, and BODIPY (BPY), a photosensitizer. Upon skin penetration and subsequent exposure to 660 nm light, BE‐TEL induces tumor cell apoptosis by reactive oxygen species (ROS) generation and EGFR pathway inhibition. ROS and Erb‐induced metabolic oxidative stress by upregulating the expression of NADPH oxidase 4 (NOX4) can enhance immunogenic cell death (ICD) and promote dendritic cell maturation for tumor‐specific immune response. Furthermore, the EGFR downregulation further mitigated the risk of metastasis and recurrence. In conclusion, BE‐TEL's superior penetration ability together with its combined PDT and EGFR targeted approach paves the way for an efficient strategy against EGFR‐overexpressed CSCC.
DNA Delivery to Intact Plant Cells by Casein Nanoparticles with Confirmed Gene Expression
Authors: Ben‐Haim Avital Ella , Feldbaum Reut Amar , Belausov Eduard , Zelinger Einat , Maria Raquel , Nativ‐Roth Einat , Mani Karthik Ananth , Barda Omer , Sionov Edward , Mechrez Guy
Published: February 2024

This research presents gene expression after DNA delivery into intact plant cells by protein nanoparticles. The DNA delivery is carried out by casein nanoparticles (CNPs). A plasmid harboring the red fluorescent protein DsRed sequence is absorbed to the CNPs surface by electrostatic interaction and served as a model DNA in this study, and its expression is monitored by the fluorescence of the DsRed protein. The zeta potential of the CNPs is tuned by altering the pH to obtain sufficient electrostatic interaction between the CNPs and the DsRed plasmid for successful DNA delivery into the cells of the model plant Nicotiana benthamiana. The CNPs are covalently modified with the green fluorescent dye 6‐Aminofluorescein (6‐AF) to determine their location in the plant. To assess the ability of the CNPs to deliver DNA into the cells, CNP/6‐AF/DsRed plasmid electrostatic conjugates are infiltrated into N. benthamiana leaves. Confocal fluorescence microscopy results showed successful intracellular and nucleus uptake of the conjugates at pH 4.5 and a concentration of 2 mg mL−1 at CNPs: DsRed plasmid ratio of 1:0.01. The successful gene expression is confirmed by RT‐PCR and qRT‐PCR. The first appearance of the emitted red signal of the DsRed protein is observed 24 h post‐infiltration.
Multifunctional Prosthesis Surface: Modification of Titanium with Cinnamaldehyde‐Loaded Hierarchical Titanium Dioxide Nanotubes
Authors: Mao Yi , Xie Xinru , Sun Guangxin , Yu Shiqi , Ma Mingqi , Chao Rui , Wan Tianhao , Xu Weifeng , Chen Xuzhuo , Sun Lei , Zhang Shanyong
Published: February 2024

Orthopedic prostheses are the ultimate therapeutic solution for various end‐stage orthopedic conditions. However, aseptic loosening and pyogenic infections remain as primary complications associated with these devices. In this study, a hierarchical titanium dioxide (TiO2) nanotube drug delivery system loaded with cinnamaldehyde for the surface modification of titanium implants, is constructed. These specially designed dual‐layer TiO2 nanotubes enhance material reactivity and provide an extensive drug‐loading platform within a short time. The introduction of cinnamaldehyde enhances the bone integration performance of the scaffold (simultaneously promoting bone formation and inhibiting bone resorption), anti‐inflammatory capacity, and antibacterial properties. In vitro experiments have demonstrated that this system promoted osteogenesis by upregulating both Wnt/β‐catenin and MAPK signaling pathways. Furthermore, it inhibits osteoclast formation, suppresses macrophage‐mediated inflammatory responses, and impedes the proliferation of Staphylococcus aureus and Escherichia coli. In vivo experiments shows that this material enhances bone integration in a rat model of femoral defects. In addition, it effectively enhances the antibacterial and anti‐inflammatory properties in a subcutaneous implant in a rat model. This study provides a straightforward and highly effective surface modification strategy for orthopedic Ti implants.
Intrinsic Defect‐Driven Synergistic Synaptic Heterostructures for Gate‐Free Neuromorphic Phototransistors
Authors: Deng Yao , Liu Shenghong , Ma Xiaoxi , Guo Shuyang , Zhai Baoxing , Zhang Zihan , Li Manshi , Yu Yimeng , Hu Wenhua , Yang Hui , Kapitonov Yury , Han Junbo , Wu Jinsong , Li Yuan , Zhai Tianyou
Published: February 2024

The optoelectronic synaptic devices based on two‐dimensional (2D) materials offer great advances for future neuromorphic visual systems with dramatically improved integration density and power efficiency. The effective charge capture and retention are considered as one vital prerequisite to realizing the synaptic memory function. However, the current 2D synaptic devices are predominantly relied on materials with artificially‐engineered defects or intricate gate‐controlled architectures to realize the charge trapping process. These approaches, unfortunately, suffer from the degradation of pristine materials, rapid device failure, and unnecessary complication of device structures. To address these challenges, an innovative gate‐free heterostructure paradigm is introduced herein. The heterostructure presents a distinctive dome‐like morphology wherein a defect‐rich Fe7S8 core is enveloped snugly by a curved MoS2 dome shell (Fe7S8@MoS2), allowing the realization of effective photocarrier trapping through the intrinsic defects in the adjacent Fe7S8 core. The resultant neuromorphic devices exhibit remarkable light‐tunable synaptic behaviors with memory time up to ≈800 s under single optical pulse, thus demonstrating great advances in simulating visual recognition system with significantly improved image recognition efficiency. The emergence of such heterostructures foreshadows a promising trajectory for underpinning future synaptic devices, catalyzing the realization of high‐efficiency and intricate visual processing applications.
Quantitative Assessment of Fungal Biomarkers in Clinical Samples via an Interface‐Modulated Optical Fiber Biosensor
Authors: Chen Pengwei , Wu Haotian , Zhao Yajing , Zhong Lv , Zhang Yujiao , Zhan Xundi , Xiao Aoxiang , Huang Yunyun , Zhang Hong , Guan Bai‐Ou
Published: February 2024

Invasive fungal infections pose a significant public health threat. The lack of precise and timely diagnosis is a primary factor contributing to the significant increase in patient mortality rates. Here, an interface‐modulated biosensor utilizing an optical fiber for quantitative analysis of fungal biomarkers at the early stage of point‐of‐care testing (POCT), is reported. By integrating surface refractive index (RI) modulation and plasmon enhancement, the sensor to achieve high sensitivity in a directional response to the target analytes, is successfully optimized. As a result, a compact fiber‐optic sensor with rapid response time, cost‐effectiveness, exceptional sensitivity, stability, and specificity, is developed. This sensor can successfully identify the biomarkers of specific pathogens from blood or other tissue specimens in animal models. It quantifies clinical blood samples with precision and effectively discriminates between negative and positive cases, thereby providing timely alerts to potential patients. It significantly reduces the detection time of fungal infection to only 30 min. Additionally, this approach exhibits remarkable stability and achieves a limit of detection (LOD) three orders of magnitude lower than existing methods. It overcomes the limitations of existing detection methods, including a high rate of misdiagnosis, prolonged detection time, elevated costs, and the requirement for stringent laboratory conditions.
Synthesis of Difluorocyclopropanes via Visible‐Light‐Mediated [1+2] Cycloaddition of Diazo Esters with gem‐Difluoroalkenes and Evaluation of their Antifungal Activity
Authors: Du Donghua , Ji Chang , Zheng Shaoying , Chen Yu , Cai Huanyu , Li Zhenghua , Yan Dingce , Teng Huailong
Published: February 2024

In this work, we reported a method for construction of difluorocyclopropanes through visible light‐promoted [1+2] cycloaddition reaction of aryl diazo esters with gem‐difluoroalkenes. The reaction proceeds under mild conditions, encompasses a wide range of substrates (36 examples), exhibits good tolerance to various substituents, and demonstrates a diastereoselectivity of >20:1. Additionally, antifungal activity evaluation revealed that these derivatives exhibited certain activity, the EC50 values for the products towards Botrytis cinerea and Rhizoctonia solani were measured to be 1.51 and 1.36 μM, respectively, which are significantly lower than those of commercial fungicides Hymexazol and Azoxystrobin. This work not only provides an efficient method for the synthesis of difluorocyclopropanyl derivatives, but reveals their potential applications in fungicide creation.
An Optical Neuromorphic Sensor with High Uniformity and High Linearity for Indoor Visible Light Localization
Authors: Zhong Shuai , Zhou Jiachao , Yu Fangwen , Xu Mingkun , Zhang Yishu , Yu Bin , Zhao Rong
Published: February 2024

The visible light localization system holds great promise as a highly accurate indoor positioning method. However, it still suffers deficiencies including high latency and power consumption, and large area cost. To address these issues, a high energy efficient spiking localization system inspired by the biological spatial representation system is presented. This system utilizes an optical neuromorphic sensor, consisting of a compact NbOx‐based threshold switching memristor and a photoresistor. The key lies in the system's ability to convert analog light information into electrical spikes, resembling the behavior of sensory neurons, which enables the encoding of light illuminance through spiking frequency. Consequently, the system achieves high uniformity, high linearity (≈10%), and high sensitivity (≈1.1 kHz Lux−1 and ≈72.7 kHz cm−1 for light illuminance and distance detection, respectively), indicating its potential suitability for visible light localizations. By leveraging a spiking neural network classifier, the system successfully distinguishes locations with different illuminances. After 150 epochs, it achieves an accuracy of 97%, showcasing the feasibility of using the spiking localization system in real‐world applications. The approach of spike‐based light positioning is a leap forward toward the development of future compact, highly energy‐efficient visible light localization systems.
Polymer Photocatalysts with Side Chain Induced Planarity for Increased Activity for Sacrificial Hydrogen Production from Water
Authors: Lyons Richard J. , Yang Ying , McQueen Ewan , Luo Liang , Cooper Andrew I. , Zwijnenburg Martijn A. , Sprick Reiner Sebastian
Published: February 2024

Conjugated polymers are promising materials for photocatalytic hydrogen evolution. However, most reported materials are not solution‐processible, limiting their potential for large‐scale application, for example as solution cast films. Flexible side‐chains are commonly introduced to provide solubility, but these often impart unfavorable properties, such as hydrophobicity, which lowers photocatalytic activity. Here, computational predictions are employed to aid in the design of chloroform soluble polymer photocatalysts that show increased planarity through favorable intramolecular interactions. Using this approach, three conjugated polymer photocatalysts with identical poly(benzene‐dibenzo[b,d]thiophene sulfone) backbones but different solubilizing side‐chains on the benzene‐ring are explored, i.e., tri(ethylene glycol), n‐decyloxy, and n‐dodecyl. These side‐chain variations significantly alterr the properties of the polymers, specifically energy levels, optical gap, and wettability. The hydrophobic n‐decyloxy functionalized polymer has a sacrificial hydrogen evolution rate of 17.0 µmol h−1 in suspension, while the hydrophilic tri(ethylene glycol) functionalized polymer is almost three times more active (45.4 µmol h−1). Conversely, no hydrogen evolution is observed for the purely alkyl side‐chain (n‐dodecyl) containing polymer due to the side‐chain induced torsion of the backbone. A thin‐film of the most active polymer exhibits a promising area‐normalized sacrificial hydrogen evolution rate of 7.4 ± 0.3 mmol h−1 m−2 under visible light irradiation.
Impact of Local Microenvironments on the Selectivity of Electrocatalytic Nitrate Reduction in a BPM‐MEA System
Authors: Huang Po‐Wei , Song Hakhyeon , Yoo Jaeyoung , Chipoco Haro Danae A. , Lee Hyuck Mo , Medford Andrew J. , Hatzell Marta C.
Published: February 2024

Electrochemical nitrate reduction reaction (NO3RR) has garnered increasing attention as a pathway for converting a harmful pollutant (nitrate) into a value‐added product (ammonia). However, high selectivity toward ammonia (NH3) is imperative for process viability. Optimizing proton availability near the catalyst is important for achieving selective NH3 production. Here, the aim is to systematically examine the impacts of proton availability on NO3RR selectivity in a bipolar membrane (BPM)‐based membrane electrode assembly (MEA) system. The BPM generates a proton flux from the membrane toward the catalyst during electrolysis. Thus, the BPM‐MEA system can modulate the proton flux during operation. The impact of interposer layers, proton scavenging electrolytes (CO32−), and catalyst configurations are also examined to identify which local microenvironments favor ammonia formation. It is found that a moderate proton supply allows for an increase in ammonia yield by 576% when compared to the standard MEA setup. This also results in a high selectivity of 26 (NH3 over NO2−) at an applied current density of 200 mA cm−2.
Electronegativity Induced d‐Band Center Offset for Pt‐Rh Dual Sites in High‐Entropy Alloy Boosts Liquid Fuels Electrooxidation
Authors: Lv Yipin , Lin Liangliang , Xue Ruixin , Zhang Pengfang , Ma Fengya , Gan Tao , Zhang Jiawei , Gao Daowei , Zheng Xiaobo , Wang Ligang , Qin Yuchen , Zhao Hui , Dong Yuming , Wang Yao , Zhu Yongfa
Published: February 2024

Investigating the catalytic behavior of the liquid fuels on well‐defined dual sites is crucial in understanding electrocatalytic reactions. Herein, concept holding bidirectional electronegativity dominant d‐band center regulation on Pt‐Rh dual sites is proposed to tailor the catalytic behaviors toward methanol oxidation reaction (MOR). The Pt‐Rh dual sites are engineered by introducing the low‐electronegativity Ga/Ni and high‐electronegativity W elements in PtRhGaNiW high‐entropy alloy (HEA), which can drive the electron cloud of Pt‐Rh dual sites redispersing over a wide orbit window. The optimized Pt‐Rh dual sites in PtRhGaNiW HEA nanowire achieve a high current density of 5.61 mA cm−2 toward MOR, which is 3.38 and 9.75 times than that of PtRh alloy (1.66 mA cm−2) and Pt/C (0.57 mA cm−2), as well as remarkably stability and COads poisonous resistance. The theoretical calculations further disclose that the redistribution of surface localized electron around Pt‐Rh dual sites can promote direct oxidation of ─OH, and accelerate the COads oxidation/removal. This work presents a breakthrough in designing advanced dual site electrocatalysts for complex catalytic reactions.
Severe epistaxis after posterior nasal nerve ablation requiring surgical intervention: A multi‐center case series
Authors: Khan Najm S. , Yoshiyasu Yuki , Wang Brian S. , Khoudari Antoine , Clerico Dean M. , King Jackson M. , Steele Toby O. , Dhanda Aatin K. , Takashima Masayoshi , Ahmed Omar G.
Published: February 2024

Key points

Severe epistaxis occurs in 2% of PNN ablation cases, independent of method or device type.

Major epistaxis requiring intervention after PNN ablation can occur on average 20 days post‐procedure.
In situ and Real‐time Monitoring the Chemical and Thermal Evolution of Lithium‐ion Batteries with Single‐crystalline Ni‐rich Layered Oxide Cathode
Authors: Zhang Qimeng , Wang Yuzhen , Deng Qiang , Chu Youqi , Dong Pengyuan , Chen Changdong , Wang Ziming , Xia Zhiguo , Yang Chenghao
Published: February 2024

High‐capacity Ni‐rich layered oxides are promising cathode materials for fabrication of lithium‐ion batteries (LIBs) with high energy density. However, thermal runaway of LIBs with these cathodes leads to great safety concerns. In this study, single crystalline LiNi0.9Co0.05Mn0.05O2 (NCM‐SC) has been prepared and a flexible optical fiber was buried inside the pouch‐type LIBs with NCM‐SC cathode to in situ study its real‐time temperature evolution during charge/discharge process. NCM‐SC exhibits an enhanced Li+ ions transportation efficiency and electrode reaction kinetics, which can effectively reduce the generation of polarization heat and mitigate the internal temperature rise of the pouch‐type battery. Meanwhile, solid‐electrolyte interface (SEI) film decomposition and gas accumulation are effectively alleviated, due to the enhanced thermal stability of SEI film formed on NCM‐SC. Moreover, the single crystal architecture can effectively retard layered to spinal and rock‐salt phase transition, mitigate the crack formation and structural collapse. Consequently, NCM‐SC exhibits an excellent electrochemical performance and enhanced thermal stability.
Photoelectron Migration Boosted by Hollow Double‐Shell Dyads Based on Covalent Organic Frameworks for Highly Efficient Photocatalytic Hydrogen Generation
Authors: Wang Meiying , Lv Haowei , Dong Beibei , He Wenhao , Yuan Daqiang , Wang Xinchen , Wang Ruihu
Published: February 2024

Photocatalytic hydrogen production based on noble metal‐free systems is a promising technology for the conversion of solar energy into green hydrogen, it is pivotal and challenging to tailor‐make photocatalysts for achieving high photocatalytic efficiency. Herein, we reported a hollow double‐shell dyad through uniformly coating covalent organic frameworks (COFs) on the surface of hollow Co9S8. The double shell architecture enhances the scattering and refraction efficiency of incident light, shortens the transmission distance of the photogenerated charge carriers, and exposes more active sites for photocatalytic conversion. The hydrogen evolution rate is as high as 23.15 mmol g−1 h−1, which is significantly enhanced when compared with that of their physical mixture (0.30 mmol g−1 h−1) and Pt‐based counterpart (11.84 mmol g−1 h−1). This work provides a rational approach to the construction of noble‐metal‐free photocatalytic systems based on COFs to enhance hydrogen evolution performance.
Azobenzene‐Based Linker Strategy for Selective Activation of Antibody–Drug Conjugates
Authors: Xiao Dian , Liu Lianqi , Xie Fei , Dong Jingwen , Wang Yanming , Xu Xin , Zhong Wu , Deng Hongbin , Zhou Xinbo , Li Song
Published: February 2024

Existing antibody–drug conjugate (ADC) linkers, whether cleavable or non‐cleavable, are designed to release highly toxic payloads or payload derivatives upon internalisation of the ADCs into cells. However, clinical studies have shown that only <1 % of the dosed ADCs accumulate in tumour cells. The remaining >99 % of ADCs are nonspecifically distributed in healthy tissue cells, thus inevitably leading to off‐target toxicity. Herein, we describe an intelligent tumour‐specific linker strategy to address these limitations. A tumour‐specific linker is constructed by introducing a hypoxia‐activated azobenzene group as a toxicity controller. We show that this azobenzene‐based linker is non‐cleavable in healthy tissues (O2 >10 %), and the corresponding payload derivative, cysteine‐appended azobenzene‐linker–monomethyl auristatin E (MMAE), can serve as a safe prodrug to mask the toxicity of MMAE (switched off). Upon exposure to the hypoxic tumour microenvironment (O2<1 %), this linker is cleaved to release MMAE and fully restores the high cytotoxicity of the ADC (switched on). Notably, the azobenzene linker‐containing ADC exhibits satisfactory antitumour efficacy in vivo and a larger therapeutic window compared with ADCs containing traditional cleavable or non‐cleavable linkers. Thus, our azobenzene‐based linker sheds new light on the development of next‐generation ADC linkers.
Mechanocatalytic Synthesis of Ammonia: State of the Catalyst During Reaction and Deactivation Pathway
Authors: Reichle Steffen , Kang Liqun , Demirbas Derya , Weidenthaler Claudia , Felderhoff Michael , DeBeer Serena , Schüth Ferdi
Published: February 2024

Ammonia synthesis holds significant importance for both agricultural fertilizer production and emerging green energy applications. Here, we present a comprehensive characterization of a catalyst for mechanochemical ammonia synthesis, based on Cs‐promoted Fe. The study sheds light on the catalyst‘s dynamic evolution under reaction conditions and the origin of deactivation. Initially, elemental Cs converts to CsH, followed by partial CsOH formation due to trace oxygen impurities on the surface of the Fe metal and the equipment. Concurrently, the mechanical milling process comminutes Fe, exposing fresh metallic Fe surfaces. This comminution correlates with an induction period observed during ammonia formation. Critical to the study, degradation of active Cs promoter species (CsH and CsNH2) into inactive CsOH emerged as the primary deactivation mechanism. By increasing the Cs content from 2.2 mol % to 4.2 mol %, we achieved stable, continuous ammonia synthesis for nearly 90 hours, showcasing one of the longest‐running mechanocatalytic gas phase reactions. Studies of the temperature dependence of the reaction revealed negligible bulk temperature influence in the range of −10 °C to 100 °C, highlighting the dominance of mechanical action over bulk thermal effects. This study offers insights into the complex interplay between mechanical processing, reactive species, and deactivation mechanisms in mechanocatalytic ammonia synthesis.
Light‐Triggered Disassembly of Molecular Motor‐based Supramolecular Polymers Revealed by High‐Speed AFM
Authors: van Ewijk Chris , Xu Fan , Maity Sourav , Sheng Jinyu , Stuart Marc C. A. , Feringa Ben L. , Roos Wouter H.
Published: February 2024

Photoresponsive supramolecular polymers have a major potential for applications in responsive materials that are externally triggered by light with spatio‐temporal control of their polymerisation state. While changes in macroscopic properties revealed the adaptive nature of these materials, it remains challenging to capture the dynamic depolymerisation process at the molecular level, which requires fast observation techniques combined with in situ irradiation. By implementing in situ UV illumination into a High‐Speed Atomic Force Microscope (HS‐AFM) setup, we have been able to capture the disassembly of a light‐driven molecular motor‐based supramolecular polymer. The real‐time visualisation of the light‐triggered disassembly process not only reveals cooperative depolymerisation, it also shows that this process continues after illumination is halted. Combining the data with cryo‐electron microscopy and spectroscopy approaches, we obtain a molecular‐level description of the motor‐based polymer dynamics reminiscent of actin chain‐end depolymerisation. Our detailed understanding of supramolecular depolymerisation will drive the development of future responsive polymer systems.
Low‐coordination Nanocrystalline Copper‐based Catalysts through Theory‐guided Electrochemical Restructuring for Selective CO2 Reduction to Ethylene
Authors: Fang Wensheng , Lu Ruihu , Li Fu‐Min , He Chaohui , Wu Dan , Yue Kaihang , Mao Yu , Guo Wei , You Bo , Song Fei , Yao Tao , Wang Ziyun , Xia Bao Yu
Published: February 2024

Revealing the dynamic reconstruction process and tailoring advanced copper (Cu) catalysts is of paramount significance for promoting the conversion of CO2 into ethylene (C2H4), paving the way for carbon neutralization and facilitating renewable energy storage. In this study, we initially employed density functional theory (DFT) and molecular dynamics (MD) simulations to elucidate the restructuring behavior of a catalyst under electrochemical conditions and delineated its restructuring patterns. Leveraging insights into this restructuring behavior, we devised an efficient, low‐coordination copper‐based catalyst. The resulting synthesized catalyst demonstrated an impressive Faradaic efficiency (FE) exceeding 70 % for ethylene generation at a current density of 800 mA cm−2. Furthermore, it showed robust stability, maintaining consistent performance for 230 hours at a cell voltage of 3.5 V in a full‐cell system. Our research not only deepens the understanding of the active sites involved in designing efficient carbon dioxide reduction reaction (CO2RR) catalysts but also advances CO2 electrolysis technologies for industrial application.
Highly Selective and Efficient Perdeuteration of n‐Pentane via H/D Exchange Catalyzed by a Silica‐Supported Hafnium‐Iridium Bimetallic Complex
Authors: Pichugov Andrey V. , Escomel Léon , Lassalle Sébastien , Petit Julien , Jabbour Ribal , Gajan David , Veyre Laurent , Fonda Emiliano , Lesage Anne , Thieuleux Chloé , Camp Clément
Published: February 2024

A Surface OrganoMetallic Chemistry (SOMC) approach is used to prepare a novel hafnium‐iridium catalyst immobilized on silica, HfIr/SiO2, featuring well‐defined [≡SiOHf(CH2tBu)2(μ‐H)3IrCp*] surface sites. Unlike the monometallic analogous materials Hf/SiO2 and Ir/SiO2, which promote n‐pentane deuterogenolysis through C−C bond scission, we demonstrate that under the same experimental conditions (1 bar D2, 250 °C, 3 h, 0.5 mol %), the heterobimetallic catalyst HfIr/SiO2 is highly efficient and selective for the perdeuteration of alkanes with D2, exemplified on n‐pentane, without substantial deuterogenolysis (<2 % at 95 % conversion). Furthermore this HfIr/SiO2 catalyst is robust and can be re‐used several times without evidence of decomposition. This represents substantial advance in catalytic H/D isotope exchange (HIE) reactions of C(sp3)−H bonds.
Preparation, shape memory properties and application research of PLA/PCL‐based shape memory polymers doped with Al2O3 and lignin
Authors: Liu Bei , Gu Xilong , Chen Xi , Yang Yawen , Zou Jiaqi , Yin Haibin , Cai Yongquan
Published: February 2024

In this paper, the influence of different material trademarks, mass ratios, the melt mass‐flow rate (MMFR) and molecular weights (MW), mold and injection temperatures, Al2O3 powder and lignin on the shape memory properties of PLA/PCL SMP material (PPSM) were then analyzed in detail by different characteristic methods. Besides, three promising applications (Origami metamaterials and variable‐stiffness grippers) are provided utilizing the PPSM doped with Al2O3/lignin. Eventually, a compensating strategy was discussed to improve the final configuration of the SMP after multi‐cycles. The shape memory recovery ratios could be improved by increasing the MMFR of PLA and the MW of PCL. The addition of 2 g‐Al2O3 could shorten the recovery time, while the addition of 2 g‐lignin could increase the thermal‐recovery force and mechanical performance. The shape memory rate under 20 g weights, initial peak forces at room and high temperatures of the origami metamaterials could reach 57%, 2027.29 N and 17.49 N, respectively. The tensile force of banding rebars could reach 150.29 N, which is promising to apply into the construction field.
Effect and mechanism analysis of matrix resin type on thermal aging characteristics of semi‐conductive shielding material for high voltage cable
Authors: Liu Tianyao , Liu Tianzhen , Li Xuejing , Wei Yanhui , Zhu Yuanwei , He Jinliang , Li Guochang
Published: February 2024

The type of matrix resin of the semi‐conductive shielding layer directly affects the thermal aging characteristics of the semi‐conductive shielding layer and the high‐voltage cable. In this paper, ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), and ethylene butyl acrylate (EBA) resins were used as matrix to prepare carbon black (CB) + EVA, CB + EEA, and CB + EBA shielding materials. The law of physicochemical, electrical, and mechanical properties of different matrix resin shielding materials with aging time was studied, and the influence mechanism of matrix resin on the aging characteristics of shielding materials was analyzed. The results show: with the increase of aging time, the crystallization area and the number of functional groups of the three shielding materials decreased to varying degrees. The number of functional groups in CB + EBA shielding materials decreased evenly with aging time, but that of CB + EVA and CB + EEA shielding materials changed significantly after 7 days of aging. After 60 days of aging, the crystallization area of CB + EBA shielding material changed slightly, but that of CB + EVA and CB + EEA shielding material decrease significantly. The electrical properties of the three shielding materials showed different decreasing trend with aging time. When the aging time is 7 days, the positive temperature coefficient (PTC) effect of CB + EEA shielding material decreases obviously. When the aging time is 30 days, the resistivity of CB + EVA and CB + EEA shielding material increases slowly (9 Ω cm–12 Ω cm) with the increase of temperature. When the aging time is 60 days, the resistivity of CB + EBA shielding material decreases obviously, and the PTC effect weakens obviously. Taking the mechanical properties of the shielding material as reference, the rapid deterioration stage of the mechanical properties of the three shielding materials is different. The CB + EVA and CB + EEA shielding material rapid deterioration time is 0–7 days, and the tensile strength and elongation of the shielding material are greatly reduced. The rapid deterioration stage of CB + EBA shielding material is 7–30 days, and the tensile strength and elongation decrease from 24.38 MPa and 499.5% to 14 MPa and 155.7%, respectively. This work can provide data support for the selection of matrix resin of shielding material and the fault analysis of shielding layer of high voltage cable.
Higher order structures and toughening mechanisms for simultaneously polymerized polymethacrylate/polyurethane
Authors: Kuwashiro Shiho , Hatanaka Yoshiro , Tao Kousaku , Higashi Seiji , Kago Keitaro , Hirano Hiroshi , Kishi Hajime
Published: February 2024

Amorphous polymer/crystalline polymer blends can be prepared via the simultaneous polymerization of polymethacrylate/polyurethane combinations. The relationship between higher order structures and fracture mechanisms in these blends must be uncovered to elucidate the source of the increased fracture toughness of such materials. The present work involves the production of blended polymethacrylate/polyurethane and assess the internal structures of these specimens using optical and electron microscopy. These observations reveal the presence of both spherulites and elastomeric phases. The spherulites consisting of the polyurethane and are several micrometers in diameter whereas the phase‐separated polyurethane elastomeric domains are approximately 100 nm in size. Multiple cracks, crack bridging and plastic deformation around the precrack tips of loaded specimens are evidently responsible for the increased toughness of these blends. The former two phenomena are attributed to the presence of spherulites while the plastic deformation of the methacrylate matrix is ascribed to cavitation of the polyurethane elastomeric phases in response to loading.
Groundtruthing cumulative impact assessments with biodiversity data: Testing indicators and methods for marine ecosystem condition assessments in South Africa
Authors: Smit Kaylee P. , Sink Kerry J. , Shannon Lynne J. , Bernard Anthony T. F. , Lombard Amanda T.
Published: February 2024

Accurate assessments of ecosystem condition are needed to inform management processes such as systematic conservation planning and protected area expansion, marine spatial planning and other effective area‐based conservation measures. Yet measuring the condition of dynamic and often largely inaccessible marine ecosystems is extremely difficult and presents a global challenge.

Broad‐scale cumulative impact assessments have been used in South Africa as a proxy for marine ecosystem condition in national assessments and reporting because the data are more readily available, and knowledge exists on the impacts of various human activities (or pressures) on marine ecosystems. While useful for national reporting, assessments based on in situ ecological data are also needed at finer scales relevant to management.

Applying the HELCOM BEAT approach, this study used in situ ecological data to identify potential methods and indicators that can be applied in South Africa to conduct integrated ecosystem assessments and to assess the suitability of current cumulative impact assessments as a proxy for condition.

Aggregated fish indicators demonstrated greater sensitivity to varying human pressures compared with benthic community indicators, with responsiveness differing by location. Notably, site‐level differences in empirical condition emerged that broad‐scale cumulative assessments often missed. The study thus highlighted the varying suitability of cumulative impact scores as proxies for condition, indicating their reliability for fish communities. However, this is also dependent on the pressure types included, the biotic indicators used and the area of focus.

Conservation decisions based solely on cumulative impact scores could misrepresent the actual condition of the environment, which makes it difficult to make management decisions, especially at finer scales. As such, conservation initiatives need to be regionally adapted to effectively address the unique pressures and conditions of each area and should be tailored to account for fine‐scale variability, instead of adopting a one‐size‐fits‐all approach.
The potential impact of aquaculture on the genetic diversity and conservation of wild fish in sub‐Saharan Africa
Authors: Sanda Mark K. , Metcalfe Neil B. , Mable Barbara K.
Published: February 2024

An increasing focus on aquaculture using introduced strains or species poses a serious threat to native wild species in sub‐Saharan Africa, yet almost no policies have been enacted or regulations put in place to address this environmental challenge. Aquaculture in these regions has traditionally been conducted on a relatively small scale but is currently expanding rapidly and is projected to continue increasing in the coming decades, with increasing use of genetically improved strains. This expansion is occurring in a region known for its high biodiversity, creating challenges for increasing fish production without damaging wild fish populations. However, few studies have yet assessed the impacts of changes in aquaculture practice on the genetic composition and diversity of wild populations. The use of non‐native improved strains for aquaculture could cause competition, gene introgression when there is interbreeding with native populations or species, displacement of species and possible extinction of the native wild populations.

After providing historical context on African aquaculture, this review describes the current methods of fish breeding and genetic improvement programmes for the main species of cultured fishes, focusing on the potential conservation impacts of the use of introduced (and selectively bred) farmed species. Existing aquaculture policies, legislation and regulations regarding the import and farming of fish are then compared across the main fish‐producing countries. We recommend a regional policy framework considering fish introduction, risk analysis and risk management, human resources development and genetic monitoring that could be drafted into the existing policies to strengthen conservation efforts.

We conclude by making recommendations for refining existing regulations and for future research aimed at minimizing the impacts of aquaculture on wild fish populations in sub‐Saharan Africa. Aquaculture in this region needs implementation of responsible guidelines to avoid genetic impacts on native populations of high conservation value.
BIM‐Integration von Sensordaten aus dem Monitoring von Eisenbahnbrücken im Betrieb
Authors: Brötzmann Jascha , Grunert Günther , Thiele Christian‐Dominik , Rüppel Uwe , Lorenzen Steven
Published: February 2024

Das Konzept des Building Information Modeling, kurz BIM, wird im AEC‐Sektor (Architektur, Ingenieurwesen, Bauwesen) v. a. in der Planung immer häufiger angewendet. Dies ist auf mehrere Faktoren zurückzuführen, darunter rechtliche Rahmenbedingungen sowie Fortschritte im Bereich der Softwareentwicklung und Datenverarbeitung. Dieser kontinuierliche Fortschritt führt zu einem breiten Spektrum an Anwendungsmöglichkeiten. So lässt sich das BIM‐Konzept daher auch für Anwendungen im Betrieb einsetzen, wie bspw. beim Monitoring von Eisenbahnbrücken. Hier werden Brückenbauwerke und Züge mit Sensoren ausgestattet, um die Brücken in Echtzeit überwachen und bewerten zu können. Die dabei aufgenommenen Sensordaten können in bestehende BIM‐Modelle integriert werden, um u. a. ein Update von Tragwerksmodellen durchzuführen und so realitätsnähere Tragwerksmodelle zu erhalten. Weiterhin ist auf der Grundlage der Auswertung der Sensordaten eine frühzeitige Schadenserkennung möglich und die aktualisierten Modelle können eine Abschätzung der Folgen erlauben. Diese Untersuchungen sind Teil des Forschungsprojekts ZEKISS, bei dem die Autoren hierfür Lösungsmöglichkeiten erarbeiten.
Transforming trash: strategies to develop waste into a feedstock for a circular bioeconomy
Authors: Ni Cynthia , Friedman Douglas C.
Published: February 2024

Organic by‐product and waste streams generated from agriculture and food production are important future feedstocks for manufacturing chemicals, polymers, and other materials in a circular bioeconomy. These waste streams are currently underutilized and under‐explored in the context of biomanufacturing though much funding and infrastructure have been made available for their use in energy generation. The natural ability of microorganisms to utilize compounds in organic wastes, coupled with advances in engineering biology that enable scientists to manipulate biological systems to produce chemicals, polymers, and materials, and improve upon those processes, present a promising technological approach to the utilization of these waste streams as feedstocks. However, the characteristics of waste streams make them challenging to incorporate into biomanufacturing processes. These challenges can be addressed with additional advances in engineering biology research and thoughtful approaches to process development. Research and process development around the use of existing, localized waste streams present distinct benefits and raise interesting considerations, and are important undertakings. These activities will be as complex as the waste streams targeted; as such, coordination of efforts across relevant agencies and organizations, and collaborations between researchers, waste generators, customers, and other stakeholders will be critical to their success. To make meaningful and rapid contributions towards utilization of organic wastes as biomanufacturing feedstocks we recommend: (1) The National Institute of Food and Agriculture (NIFA) at the US Department of Agriculture should incorporate into existing programs the development of organic waste conversion into chemicals, polymers, and other materials using engineering biology and, if possible, establish new programs focused on this area; and (2) NIFA should oversee, coordinate, and publicize collaborative efforts that include federal agencies, state and regional agricultural research centers and cooperatives, and program‐related infrastructure.
Listening to Hong Kong children's perspectives through pretend play
Authors: Leung Suzannie K. Y.
Published: February 2024

Quality in early childhood education and care (ECEC) has become an increasing concern in recent years. The issue has been regularly discussed by different stakeholders. However, the rising concern regarding quality in ECEC has not seriously taken into account children's perspectives. Hong Kong, with its academic‐driven education system, is no exception. Children's perspectives have been neglected under the impact of neoliberalism on education in Chinese society. Engaging with children's perspectives has thus become an important matter in Hong Kong society. In April 2019, a children's pretend‐play project was started in an open playground in Hong Kong. This project aimed to help children regain their subjectivities and share their thoughts through the process of pretend play. Children in this project were invited to create, pretend and imagine themselves in the role of superheroes so that they could express their perspectives. This alternative practice opened a space for children to liberate themselves through pretend‐play activities, while reworking the conventional pedagogies found in the neoliberal education system. The findings offer critical reflections on how to improve quality in ECEC by redeveloping trust and respect among adults and children through listening to children's perspectives.
How green human resource management can promote green competitive advantage: The role of green innovation
Authors: Zhang Shujie , Chen Mengyuan , Tang Guiyao
Published: February 2024

With growing public concerns about ecological issues, it has been increasingly critical for corporations to enhance their green competitive advantages. Utilizing a natural‐resource‐based view of firm and human resource management (HRM) perspective, we propose that green HRM (GHRM) promotes firms' green competitive advantages by facilitating two kinds of green innovation (i.e., green product/process innovation). Via a two‐wave survey study of chief human resources officers (CHOs) and chief financial officers (CFOs) from 69 companies in China, we find support that GHRM positively links to green product and process innovations, each of which will, in turn, have a positive correlation with a green competitive advantage. Moreover, an indirectly positive linkage between GHRM and green competitive advantage via two types of green innovation is also proved. Our study expands current research by demonstrating a positive effect of GHRM in building green competitive advantage and by revealing two parallel mechanisms of such effect.
New Azo Derivative of β‐Diketones and Its Cu(II), Co(II) Complexes: Synthesis, Theoretical Study and Biological Activity
Authors: Tahirli Shahla , Sadeghian Nastaran , Aliyeva Farqana , Sujayev Afsun , Günay Sevilay , Erden Yavuz , Shikhaliyev Namig , Kaya Savaş , Mehtap Özden Eda , Chiragov Famil , Berisha Avni , Taslimi Parham
Published: February 2024

The paper is focused on biological activity and theoretical study of the structure and properties of a new azo derivative of β‐diketones and its complexes with some metals. The aim of our work was to study the structure and properties of the newly synthesized compound as well as to theoretically determine the possibility of complex formation with the Cu(II) or Co(II) ions. A compound with the same substituents R1=R2=CH3 was chosen for the study. A synthesized azo compound based on 4‐amino antipyrine and its complexes with Cu(II), Co(II) in solution and solid phase is reported. The structures of these compounds have been testified by X‐ray, IR and  NMR spectroscopy. The combined experimental and theoretical approach was used. To study the structure and properties of the synthesized compound, as well as its possible complex formation with the Cu(II), quantum‐chemical calculations were carried out the 6‐31G basis set and the electron density functional theory (DFT) method. These 3‐(1‐phenyl‐2,3‐dimethyl‐pyrazolone‐5) azopentadione‐2,4 (PDPA) with Cu(II) and Co(II) complexes had effective inhibition against butyrylcholinesterase and acetylcholinesterase. IC50 values were found as 19.03, 3.64 μM for AChE and 28.47, 8.01 μM for BChE, respectively. Cholinesterase inhibitors work to slow down the acetylcholine‘s deterioration.
Bioactive 5/5/5/6 Four–Ring System Iridoids from Plumeria alba L.
Authors: Zhou Xin , Meng Xin‐Bin , Zhou Xue‐Ming , Zhu Zheng‐Tian , Yang Jing , Chen Hong‐Jie , Song Xin‐Ming
Published: February 2024

Two rare 5/5/5/6 four–ring system iridoids, allamancins A and B (1 and 2) together with one known biogenetically related iridoid derivative, 3‐O‐methyallamancin (3) were isolated from the flowers of Plumeria alba L. The structures of these iridoid derivatives were determined by comprehensive spectroscopic analyses. The absolute configuration of 1 was confirmed by X‐ray crystallographic analysis. The inhibitory activities of compounds 1–3 against nitric oxide (NO) production induced and three cancer cell lines were evaluated in vitro. Compounds 1 and 3 showed inhibitory activities on NO production with IC50 values of 18.3±0.12 and 22.1±0.14 μM, respectively. Compounds 1–3 showed moderate inhibitory activities against cancer cell lines of A549, Hela and MCF‐7.
A Facile Access to Green Fluorescent Albumin Derivatives
Authors: Saletti Mario , Paolino Marco , Venditti Jacopo , Bonechi Claudia , Giuliani Germano , Lamponi Stefania , Tassone Giusy , Boccia Antonella , Botta Chiara , Blancafort Lluís , Poggialini Federica , Vagaggini Chiara , Cappelli Andrea
Published: February 2024

A Morita‐Baylis‐Hillman Adduct (MBHA) derivative bearing a triphenylamine moiety was found to react with human serum albumin (HSA) shifting its emission from the blue to the green‐yellow thus leading to green fluorescent albumin (GFA) derivatives and enlarging the platform of probes for aggregation‐induced fluorescent‐based detection techniques. A possible interaction of MBHA derivative 7 with a lipophilic pocket within the HSA structure was suggested by docking studies. DLS experiments showed that the reaction with HSA induce a conformational change of the protein contributing to the aggregation process of GFA derivatives. The results of investigations on the biological properties suggested that GFA retained the ability of binding drug molecules such as warfarin and diazepam. Finally, cytotoxicity evaluation studies suggested that, although the MBHA derivative 7 at 0.1 μg/mL affected the percentage of cell viability in comparison to the negative control, it cannot be considered cytotoxic, whereas at all the other concentrations≥0.5 μg/mL resulted cytotoxic at different extent.
Functional and Mechanistic Characterization of the 4,5‐diepi‐Isoishwarane Synthase from the Liverwort Radula lindenbergiana
Authors: Xu Houchao , Köllner Tobias G. , Chen Feng , Dickschat Jeroen S.
Published: February 2024

The microbial type sesquiterpene synthase RlMTPSL4 from the liverwort Radula lindenbergiana was investigated for its products, showing the formation of several sesquiterpene hydrocarbons. The main product was structurally characterized as the new compound 4,5‐diepi‐isoishwarane, while the side products included the known hydrocarbons germacrene A, α‐selinene, eremophilene and 4,5‐diepi‐aristolochene. The cyclization mechanism towards 4,5‐diepi‐isoishwarane catalyzed by RlMTPSL4 was investigated through isotopic labeling experiments, revealing the stereochemical course for the deprotonation step to the neutral intermediate germacrene A, a reprotonation for its further cyclization, and a 1,2‐hydride shift along the cascade. The absolute configuration of 4,5‐diepi‐isoishwarane was determined using a stereoselective deuteration approach, revealing an absolute configuration typically observed for a microbial type sesquiterpene.