bluuebunny/crossref_metadata_2025 huggingface dataset:
Essential Oil Components Incorporated Emulsion Hydrogels for Eradicating Dermatophytosis Caused by Pathogenic Fungi Trichophyton mentagrophytes and Microsporum canis
Authors: Preman Namitha K. , Amin Nikhitha , Sanjeeva Sandesh G. , Surya Suprith , Kumar B Sukesh , Shenoy Manjunath M. , Shastry Rajesh P. , Johnson Renjith P.
Published: August 2024

Dermatophytosis is a prevalent fungal infection and public health burden, majorly caused by the attack of zoophilic fungi genera of Trichophyton and Microsporum. Among them, T. mentagrophytes and M. canis are the dominating pathogens that cause dermatophytosis in humans. Though anti‐fungal treatments are available, the widespread drug resistance and minimal efficacy of conventional therapies cause recurring infections. In addition, prolonged anti‐fungal medications induce several systemic side effects, including hepatotoxicity and leucopenia. The anti‐dermatophytic formulation of biocompatible essential oil components (EOCs) is attractive due to their highly potent anti‐dermatophytic action. Herein, two EOCs, Eugenol (EU) and Isoeugenol (IU), incorporated emulsion hydrogel (EOCs‐EHG) synthesized from hydroxypropylmethyl cellulose and poly(ethylene glycol) methyl ether methacrylate. The cytocompatibility of the hydrogels is confirmed by treating them with fibroblast and keratinocyte cell lines. The EOCs‐EHG demonstrated pH and temperature‐responsive sustained release of entrapped EOCs and inhibited fungal spore germination. T. mentagrophytes and M. canis biofilms are eradicated at a minimal inhibitory concentration of 2 µg mL−1 each of EU and IU. The in vivo anti‐dermatophytic activity of EOCs‐EHG is confirmed in dermatophyte‐infected Wistar albino rat models. The topical application of EOCs‐EHG demonstrated complete infection eradication and facilitated skin regeneration, emphasizing the therapeutic potential of EOCs‐EHG against dermatophytosis.
Modified Titanium Implants Satisfy the Demands of Diabetic Osseointegration via Sequential Regulation of Macrophages and Mesenchymal Stem Cells
Authors: Ma Bo , Chen Fangye , Liu Xin , Zhang Yang , Gou Shuangquan , Meng Qianxiang , Liu Peng , Cai Kaiyong
Published: August 2024

The application of titanium (Ti) implants for patients with diabetes mellitus (DM) is still facing a significant challenge due to obstacles such as hyperglycemia, reactive oxygen species (ROS), and chronic inflammation, which hinders osseointegration. To address this issue, a Ti implant with dual functions of regulating polarization of macrophages and facilitating osseointergration is developed via hydrothermal reaction and hydrogel coating. The reactive oxygen species (ROS) and glucose (Glu) responsive hydrogel coating can locally deliver adenosine (ADO) in the early stage of implantation. The controlled release of ADO regulated the phenotype of macrophages, restored oxidative balance, and enhanced mitochondrial function during the early stages of implantation. Subsequently, strontium (Sr) ions will be released to promote osteogenic differentiation and proliferation of mesenchymal stem cells (MSCs), as the hydrogel coating degraded. It eventually leads to bone reconstruction during the late stages, aligning with the biological cascade of bone healing. The modified Ti implants showed effective osteogenesis for bone defects in DM patients, shedding light on the design and biological mechanisms of surface modification. This research offers promising potential for improving the treatment of bone‐related complications in diabetic patients.
Approaching 20% Efficiency in Ortho‐Xylene Processed Organic Solar Cells by a Benzo[a]phenazine‐Core‐Based 3D Network Acceptor with Large Electronic Coupling and Long Exciton Diffusion Length
Authors: Luo Zhenghui , Wei Weifei , Ma Ruijie , Ran Guangliu , Jee Min Hun , Chen Zhanxiang , Li Yuxiang , Zhang Wenkai , Woo Han Young , Yang Chuluo
Published: August 2024

High‐performance organic solar cells often rely on halogen‐containing solvents, which restrict the photovoltaic industry. Therefore, it is imperative to develop efficient organic photovoltaic materials compatible with halogen‐free solvents. Herein, a series of benzo[a]phenazine (BP)‐core‐based small‐molecule acceptors (SMAs) achieved through an isomerization chlorination strategy is presented, comprising unchlorinated NA1, 10‐chlorine substituted NA2, 8‐chlorine substituted NA3, and 7‐chlorine substituted NA4. Theoretical simulations highlight NA3's superior orbit overlap length and tight molecular packing, attributed to interactions between the end group and BP unit. Furthermore, NA3 demonstrates dense 3D network structures and a record electronic coupling of 104.5 meV. These characteristics empower the ortho‐xylene (o‐XY) processed PM6:NA3 device with superior power conversion efficiency (PCE) of 18.94%, surpassing PM6:NA1 (15.34%), PM6:NA2 (7.18%), and PM6:NA4 (16.02%). Notably, the significantly lower PCE in the PM6:NA2 device is attributed to excessive self‐aggregation characteristics of NA2 in o‐XY. Importantly, the incorporation of D18‐Cl into the PM6:NA3 binary blend enhances crystallographic ordering and increases the exciton diffusion length of the donor phase, resulting in a ternary device efficiency of 19.75% (certified as 19.39%). These findings underscore the significance of incorporating new electron‐deficient units in the design of efficient SMAs tailored for environmentally benign solvent processing of OSCs.
Anti−Reflection Metamaterials with Phase Gradient Index Generate Surface Waves for Radar Stealth in the Microwave Regime
Authors: Huang Lingxi , Zhao Rongzhi , Ji Lianze , Ruan Jiachang , Zhang Xuefeng
Published: August 2024

Although the conversion of propagating waves into surface waves is anticipated to introduce a novel degree of freedom for radar stealth materials, the manipulation of wavelength and traveling direction of surface waves at small phase gradients remains unclear. Here the aforementioned conversion is demonstrated utilizing a metamaterial composed of carbonyl iron powders, where the momentum mismatch is compensated by the material and the phase gradient index of the aligned meta−atoms. Surface waves are generated in the direction of the phase gradient within a phase span of 180°. The metamaterials with 5−level metastructure (5x:1x) generate surface waves with two wavelengths, and get the ξ/k0 value (ratio of the phase gradient index to the wave vectors of propagating wave) of 7.5 and 4.32, respectively. Furthermore, the dual phase gradient metastructure possesses the capability to alter the trajectory of the leaky microwave, converting it into a waveform resembling that of a vortex, while simultaneously preserving the integrity of surface waves. The sample achieves an effective absorption bandwidth of 5.67–7.96 and 20.19–21.10 GHz with an optimal absorption peak of −40.77 dB at 6.87 GHz. Present study develops a novel mechanism to improve the radar stealth properties of microwave absorption materials.
Structure‐Guided Engineering of a Short‐Chain Dehydrogenase LfSDR1 for Efficient Biosynthesis of (R)‐9‐(2‐Hydroxypropyl)adenine, the Key Intermediate of Tenofovir
Authors: Wang Qingyu , Cong Lin , Guo Jiyang , Wang Jiajun , Han Xu , Zhang Wenhe , Liu Weidong , Wei Hongli , You Song
Published: August 2024

(R)‐9‐(2‐hydroxypropyl) adenine ((R)‐HPA) is an important intermediate for the synthesis of tenofovir and its prodrugs. Herein, structure‐guided rational design of short‐chain dehydrogenase LfSDR1 was adopted to improve the catalytic performance for enantioselective synthesis of (R)‐HPA at high substrate loading. The crystal structures of LfSDR1 in its apo form as well as in complex with NADPH were solved, which were used for mutagenesis studies and illustration mechanism. Three residues (G92, E141 and V186) were identified as hotspots by structural analysis, and variants V186A/G92V and V186A/G92V/E141L with remarkably improved activity were obtained. By molecular dynamics (MD) simulation of WT and variants, G92V plays a key role in enzyme‐substrate interaction in the binding pocket. Whole cells expressing the mutant LfSDR1‐V186A/G92V and glucose dehydrogenase BsGDH from Bacillus subtilis were used as the catalyst, and up to 200 g L−1 substrate without cosolvent was completely converted to (R)‐HPA with 99.9% ee and a high space‐time yield (STY) of 800 g L−1 day−1. This study improves the understanding of the catalytic mechanism of LfSDR and provides a potential biocatalytic strategy for industrial synthesis of (R)‐HPA.
Bowl on the ring: Molecular crowns hosting fullerenes synergistically by buckybowl and nanohoop
Authors: Song Wenru , Liu Zhe , Hua Xinqiang , Yang Shaojie , Tang Xia , Yuan Chengshan , Liu Zitong , Zhang Hao‐Li , Shao Xiangfeng
Published: August 2024

Curved π‐electron systems show unique properties and assembly feature that enable the specific applications in materials science and supramolecular chemistry. Herein, fullerene, carbon nanohoop and π‐bowl are integrated by the coupling of covalent and supramolecular tactics. Firstly, π‐bowl trichalcogenasumanenes (TCSs) are fused with a carbon nanohoop [10]CPP via covalent joint to form molecular crowns 4a/4b, which show structural and electronic complementarity and accordingly strong binding affinity to C60/C70. Secondly, the supramolecular assemblies of 4a/4b with fullerenes afford the host‐guest complexes 4a/4b⊃C60/C70 in solution (molar ratio, 2:1) and solid state (molar ratio, 1:1). In the crystals of host–guest complexes, the intra‐cluster and inter‐cluster interactions are respectively dominated by the [10]CPP and TCSs moieties of 4a/4b. Additionally, it is found that 4a/4b are good photosensitizers for generating 1O2 and show structural adaptability in accordance to assembly conditions. 4a/4b take an endo‐conformation in their own crystals with TCSs and [10]CPP moieties being bowl‐shaped and elliptical, respectively. In contrast, the [10]CPP on 4a/4b changes into circular and the TCSs moiety becomes flat (for 4b) or shows bowl inversion to be exo‐conformation (for 4a) in 4a/4b⊃C60/C70.
Recent Advances in Scandium(III) Triflate Catalysis: A Review
Authors: Kumar Sumit , Arora Aditi , Sapra Shivani , Chaudhary Riya , Singh Brajendra K. , Singh Sunil K.
Published: August 2024

Over the past three decades, triflate salts have emerged as crucial Lewis acid catalysts in organic synthesis, playing a significant role in cyclization, C−H bond functionalization, and various other reactions. Among these, rare‐earth triflates have garnered attention due to their water compatibility, environmental friendliness, noncorrosive nature, and reusability. In particular, scandium(III) triflate [Sc(OTf)3] stands out as a water‐resistant Lewis acid with remarkable catalytic activity in aqueous environments. Unlike typical Lewis acids such as AlCl3, BF3, and SnCl4, which are decomposed or deactivated by water, Sc(OTf)3 remains stable and effective. Its exceptional Lewis acidity, resilience against hydrolysis, and recyclability make it a prominent green catalyst. The unique stability of Sc(OTf)3 in water is attributed to the smaller size of scandium ions (Sc3+), enhancing its catalytic efficiency. Sc(OTf)3 has a longstanding history in organic synthesis, facilitating a wide range of reactions including aldol, Michael, allylation, Friedel‐Crafts acylations, Diels‐Alder, Mannich, cycloadditions (including cyclopropanation), and cascade reactions. The increasing utilization of Sc(OTf)3 over the past decade underscores the necessity for updated insights. This review provides a concise overview of the versatility of Sc(OTf)3 as a catalyst, focusing on developments from 2017 to 2024.
In Situ Alloying Enabled by Active Liquid Metal Filler for Self‐Healing Composite Polymer Electrolytes
Authors: Wu Kai , Ju Zhengyu , Zhang Bowen , Marschilok Amy C. , Takeuchi Esther S. , Takeuchi Kenneth J. , Yu Guihua
Published: August 2024

Solid inorganics, known for kinetically inhibiting polymer crystallization and enhancing ionic conductivity, have attracted significant attention in solid polymer electrolytes. However, current composite polymer electrolytes (CPEs) are still facing challenges in Li metal batteries, falling short of inhibiting severe dendritic growth and resulting in very limited cycling life. This study introduces Ga62.5In21.5Sn16 (Galinstan) liquid metal (LM) as an active liquid alternative to conventional passive solid fillers, aiming at realizing self‐healing protection against dendrite problems. Compared to solid inorganics, for example silica, LM droplets could more significantly reduce polymer crystallinity and enhance Li‐ion conductivity due to their liquid nature, especially at temperatures below the polymer melting point. More importantly, LMs are unraveled as dynamic chemical traps, which are capable of blocking and consuming lithium dendrites upon contact via in situ alloying during battery operation and further inhibiting dendritic growth due to the lower deposition energy barrier of the formed Li‐LM alloy. As a proof of concept, by strategically designing an asymmetric CPE with the active LM filling, a solid‐state Li/LiFePO4 battery achieves promising full‐cell functionality with notable rate performance and stable cycle life. This active filler‐mediated self‐healing approach could bring new insights into the battery design in versatile solid‐state systems.
Revealing the Dynamic Evolution of Electrolyte Configuration on the Cathode‐Electrolyte Interface by Visualizing (De) Solvation Processes
Authors: Luo Haiyan , Ji Xiangyu , Zhang Baodan , Chen Ming , Wu Xiaohong , Zhu Yuanlong , Yu Xiaoyu , Wang Junhao , Zhang Haitang , Hong Yuhao , Zou Yeguo , Feng Guang , Qiao Yu , Zhou Haoshen , Sun Shi‐Gang
Published: August 2024

Electrolyte engineering is crucial for improving cathode electrolyte interphase (CEI) to enhance the performance of lithium‐ion batteries, especially at high charging cut‐off voltages. However, typical electrolyte modification strategies always focus on the solvation structure in the bulk region, but consistently neglect the dynamic evolution of electrolyte solvation configuration at the cathode‐electrolyte interface, which directly influences the CEI construction. Herein, we reveal an anti‐synergy effect between Li+‐solvation and interfacial electric field by visualizing the dynamic evolution of electrolyte solvation configuration at the cathode‐electrolyte interface, which determines the concentration of interfacial solvated‐Li+. The Li+ solvation in the charging process facilitates the construction of a concentrated (Li+‐solvent/anion‐rich) interface and anion‐derived CEI, while the repulsive force derived from interfacial electric field induces the formation of a diluted (solvent‐rich) interface and solvent‐derived CEI. Modifying the electrochemical protocols and electrolyte formulation, we regulate the “inflection voltage” arising from the anti‐synergy effect and prolong the lifetime of the concentrated interface, which further improves the functionality of CEI architecture.
Dual‐Metal Sites Drive Tandem Electrocatalytic CO2 to C2+ Products
Authors: Xie Guixian , Guo Weiwei , Fang Zijian , Duan Zongxia , Lang Xianzhen , Liu Doudou , Mei Guoliang , Zhai Yanling , Sun Xiaofu , Lu Xiaoquan
Published: August 2024

The electrochemical conversion of CO2 into valuable chemicals is a promising route for renowable energy storage and the mitigation of greenhouse gas emission, and production of multicarbon (C2+) products is highly desired. Here, we report a 1.4 %Pd−Cu@CuPz2 comprising of dispersive CuOx and PdO dual nanoclusters embedded in the MOF CuPz2 (Pz=Pyrazole), which achieves a high C2+ Faradaic efficiency (FEC2+) of 81.9 % and C2+ alcohol FE of 47.5 % with remarkable stability when using 0.1 M KCl aqueous solution as electrolyte in a typical H‐cell. Particularly, the FE of alcohol is obviously improved on 1.4 %Pd−Cu@CuPz2 compared to Cu@CuPz2. Theoretical calculations have revealed that the enhanced interfacial electron transfer facilitates the adsorption of *CO intermediate and *CO−*CO dimerization on the Cu−Pd dual sites bridged by Cu nodes of CuPz2. Additionally, the oxophilicity of Pd can stabilize the key intermediate *CH2CHO and promote subsequent proton‐coupled electron transfer more efficiently, confirming that the formation pathway is skew towards *C2H5OH. Consequently, the Cu−Pd dual sites play a synergistic tandem role in cooperatively improving the selectivity of alcohol and accelerating reductive conversion of CO2 to C2+.
Unraveling C‐Selective Ring‐Opening of Phosphiranes with Carboxylic Acids and Other Nucleophiles: A Mechanistically‐Driven Approach
Authors: Ghosh Avisek , Van Nguyen Thi Hong , Bellanger Corentin , Chelli Saloua , Ahmad Mohammad , Saffon‐Merceron Nathalie , Taillier Catherine , Dalla Vincent , Mayer Robert J. , Dixon Isabelle M. , Lakhdar Sami
Published: August 2024

Phosphiranes are weak Lewis bases reacting with only a limited number of electrophiles to produce the corresponding phosphiranium ions. These salts are recognized for their propensity to undergo reactions with oxygen pronucleophiles at the phosphorus site, leading to the formation of phosphine oxide adducts. Building on a thorough mechanistic understanding, we have developed an unprecedented approach that enables the selective reaction of carboxylic acids, and other nucleophiles, at the carbon site of phosphiranes. This method involves the photochemical generation of highly reactive carbenes, which react with 1‐mesitylphosphirane to yield ylides. The latter undergoes a stepwise reaction with carboxylic acids, resulting in the production of the desired phosphines. In addition to DFT calculations, we have successfully isolated and fully characterized the key intermediates involved in the reaction.
Preserving Molecular Tuning for Enhanced Electrocatalytic CO2‐to‐Ethanol Conversion
Authors: Fu Weiwei , Li Yuke , Chen Jiayi , Chen Jingyi , Xi Shibo , Zhang Jia , Wang Lei
Published: August 2024

Modifying catalyst surface with small molecular‐additives presents a promising avenue for enhancing electrocatalytic performance. However, challenges arise in preserving the molecular‐additives and maximizing their tuning effect, particularly at high current densities. Herein, we develop an effective strategy to preserve the molecular‐additives on electrode surface by applying a thin protective layer. Taking 4‐dimethylaminopyridine (DMAP) as an example of a molecular‐additive, the hydrophobic protection layer on top of the DMAP‐functionalized Cu‐catalyst effectively prevents its leaching during CO2 electroreduction (CO2R). Consequently, the confined DMAP molecules substantially promote the CO2‐to‐multicarbon conversion at low overpotentials. For instance, at a potential as low as −0.47 V vs. reversible hydrogen electrode, the DMAP‐functionalized Cu exhibits over 80 % selectivity towards multi‐carbon products, while the pristine Cu shows only ~35 % selectivity for multi‐carbon products. Notably, ethanol appears as the primary product on DMAP‐functionalized Cu, with selectivity approaching 50 % at a high current density of 400 mA cm−2. Detailed kinetic analysis, in situ spectroscopies, and theoretical calculations indicate that DMAP‐induced electron accumulations on surface Cu‐sites decrease the reaction energy for C−C coupling. Additionally, the interactions between DMAP and oxygenated intermediates facilitate the ethanol formation pathway in CO2R. Overall, this study showcases an effective strategy to guide future endeavors involving molecular tuning effects.
Preparation of Magnetic Fe‐Decorated Carbon Nanosheets From Waste Facemasks for Quantitative Detection of Flavonoids
Authors: Lian Jiajia , Chai Silin , Han Ying , Yang Dan , Liu Pei , Liu Qingyun
Published: August 2024

Many studies relating to the preparation of magnetic composites from various raw materials have been reported. However, for the first time, the magnetic Fe‐decorated carbon nanosheets (FeCNs) were prepared using waste facemasks with iron‐containing nose strip as both carbon source and iron source. The uniform decoration of Fe3O4 nanoparticles not only endows carbon matrix with magnetic separation property but also enriches the lamellar structure to furnish more catalytically active sites. The as‐prepared FeCNs nanozymes behave optimal peroxidase‐like activity under pH of 4 and temperature of 50°C, excellent reusability, and substrate affinity. Based on FeCNs, a convenient colorimetric strategy was successfully constructed for flavonoid detection in simulated and real samples. Experimental and theoretical results show that hydroxyl radicals (•OH) and superoxide radical (•O2−) are the major active species in the reactions that are catalyzed by FeCNs in the presence of H2O2. And the generation of these radicals can be attributed to the electron transfer between Fe2+/Fe3+ pairs and H2O2 molecules. This work provides a new way for preparing magnetic carbon‐based nanozymes and realizes the resource utilization of waste facemasks.
Assessment of the synergy of hydrophobicity and thermal conductivity in epoxy/graphite oxide composite coatings
Authors: Gholamnejad Zeinab , Abdeali Golnoosh , Bahramian Ahmad Reza
Published: August 2024

In various industrial applications, especially within the internal pipes of heat exchanger devices, there is a crucial need for surface coatings that offer both superhydrophobic properties and high thermal conductivity. Achieving the balance between these two characteristics is essential for optimizing heat transfer performance along metal pipe walls and mitigating the formation of water droplets on the surface. This research focuses on the development of polymer composite coatings to address these dual requirements, providing protection against humid environments, resistance to dew formation, and simultaneous enhancement of thermal conductivity. The key challenge lies in selecting a coating type that provides low surface energy and polarity, thereby achieving the desired hydrophobic properties while also maintaining adequate thermal conductivity. This study formulates polymer composite coatings utilizing laser‐modified epoxy resin and strategically integrates graphite oxide particles. These graphite particles undergo modification through oxidation to enhance compatibility with epoxy. In conjunction with graphite oxide modification, the resulting laser‐modified coatings exhibit super‐hydrophobic characteristics with an enhanced water contact angle of 162° and a low contact angle hysteresis (<5°). Furthermore, the epoxy/graphite oxide composite coatings demonstrate improved thermal conductivity, marking a significant 261% increase compared to pure epoxy, elevating it from .234 to .846 W/mK.
Biobased rubber toughened poly(lactic acid) blend for sustainable packaging films: The role of optical purity of poly(lactic acid)
Authors: Rosli Noor Afizah , Chen Ruey Shan , Dufresne Alain , Ahmad Ishak , Ahmad Sahrim , Shahdan Dalila , Shamene Bathumalai
Published: August 2024

This study investigates the novel effect of poly(lactic acid) (PLA) optical purity on PLA/liquid natural rubber (LNR) blend films fabricated by solution casting. An investigation was conducted to examine how different levels of PLA optical purity affect the mechanical, structural, morphological, thermal, and barrier properties of PLA/LNR films. Infrared spectroscopy analysis revealed that the D‐isomer content of PLA significantly affected the chemical interactions between the LNR and PLA. The favorable chemical interaction between the LNR and PLA with a high D‐isomer content also increased the elongation at break by 300%. Morphological investigations proved that the chemical interaction also improved the dispersion and reduced the size of the LNR droplets formed in the PLA matrix. Notably, while low D‐isomer PLA blends showed decreased crystallinity (Xc) upon LNR addition, high D‐isomer PLA blends exhibited increased Xc by 460%, leading to a 42% increase in oxygen transmission rate. Additionally, hydrolytic degradation of high D‐isomer PLA increased by 259% with increasing LNR content. Overall, optical purity of PLA plays an important role in determining the properties of PLA blends.
The influence of the molecular structure of binary block‐type styrene‐butadiene rubber on dynamic mechanical properties under normal and high‐pressure conditions
Authors: Wang Wenheng , Zhang Chunqing , Liao Mingyi
Published: August 2024

Through anionic two‐stage polymerization, block‐type styrene‐butadiene rubber (SSBR) with systematically regulable low‐temperature loss peaks is successfully prepared. The influence of 1,2‐Bd unit in the soft segment of block‐type SSBR on mechanical properties, dynamic mechanical properties, and microscopic morphology is studied, while pressure factors are introduced into dynamic mechanical studies. The block‐type SSBR with a soft segment containing 21.9 wt% of 1,2‐Bd exhibits the highest tensile strength, elongation at break, and tear strength. Under atmospheric pressure, the soft segment 1,2‐Bd unit influences the dynamic mechanical properties by altering the chain segment's motion loss capability. As the mass fraction of 1,2‐Bd increases from 21.9 to 58.6 wt%, tanδmaxincreases, the glass transition temperature of the soft segment increases from −59.0 to −18.9°C. Additionally, influenced by thermodynamic compatibility, the microscopic morphology transitions from strong separation to weak separation. Pressure affects dynamic mechanical properties by altering the free volume of the chain segments. Pressure reduces tanδmax, increasesTg, and raises the averageTgof the soft segment by 11°C. TheKvalue of the linear equation representing the relationship between the soft segmentTgand the mass fraction of 1,2‐Bd is unaffected by pressure.
Thermal kinetic, mechanical and wear properties of glass fiber reinforced polyamide 6 thermoplastic composites
Authors: Vikram Kamlendra , Pramanik Sumit , Bhaumik Shubrajit
Published: August 2024

Polyamide 6 (PA6) thermoplastic‐based composites are often used in automobile, aerospace, marine, and biomedical applications. Here, PA6 and its composites with varied chopped glass fiber (GF) concentrations of 5, 10, and 20 mass% were fabricated by injection molding. The specimens were characterized by structural, thermal kinetic, mechanical, as well as tribological analyses. Tribological performance was evaluated in dry pin‐on‐disc test apparatus with three different levels of time, speed, and load factors. The PA6/GF composites showed high decomposition activation energy compared to pure PA6. Thermal activation, Ea increased to 46.16% with increasing of GF content up to 10 mass% in the composites compared to PA6. PA6/5GF exhibited best mechanical properties (e.g., strength = 44.46 MPa and Hardness = 45.2). Addition of GF in PA6 significantly improved tribological properties, coefficient of friction (COF) and specific wear rate (WR) besides thermal stability and mechanical properties of the composites. Especially, COF and WR of PA6/5GF composite decreased by 17%–65% and 68%–92%, respectively, compared to PA6. ANOVA statistical results determined the significant contribution of the tribological factors to the performance metrics of the composites for COF and WR. Therefore, the PA6/5GF composite would highly be useful for tie‐rod gears and bearings as a crucial structural component in automotive bodywork.
Fabrication of POE/POE‐g‐PHEMA/EuFT light conversion films for photovoltaic modules
Authors: Xu Mengnan , Zhang Zhiyuan , Tao Jiajun , Nai Yan , Su Chenglong , Jiang Shan
Published: August 2024

In this paper, the rare earth europium complex Eu(FTFA)3TPPO2 (EuFT) was synthesized by using europium as the central ion, 4‐trifluoro‐1‐(2‐furanyl)‐1,3‐butanedione (FTFA) as the first ligand, and triphenylphosphine oxide (TPPO) as the second ligand. The structure was characterized by Fourier transform infrared spectroscopy (FTIR), and the photoluminescence process was investigated by UV and fluorescence spectra. The luminescent film was prepared by adding EuFT and the compatibilizer POE‐g‐PHEMA into the POE matrix, which can convert the UV light to the red light, and improve the photovoltaic conversion efficiency while reducing the effect of UV aging on the cell. Experimental results show that the complex can absorb UV light (200–400 nm) and emit red light (612 nm), the luminescent film also maintains good luminescence performance. The peel strength of POE/POE‐g‐PHEMA/EuFT film achieves 23.9 N cm−1，while that of POE film is 12.8 N cm−1. The silicon cell prepared by POE/POE‐g‐PHEMA/EuFT film also showed higher EQE in UV region, and its current density–voltage (J–V) curve revealed that Jsc increased from 33.05 to 34.25 mA/cm2, the conversion efficiency increased from 12.99% to 13.39%, and the relative efficiency increased by 3.08%. The rare earth europium complex effectively improved the photoelectric conversion efficiency of solar cells.
Nc‐RNA‐mediated low expression of AZIN1 correlated with unfavorable prognosis in kidney renal clear cell carcinoma
Authors: Zeng Xinyi , Du Shen , Geng Lou , Ma Jiexian
Published: August 2024

Objective

Kidney renal clear cell carcinoma (KIRC, ccRCC) is the most common type of renal cancer with high recurrence and mortality. It has long been recognized that Antizyme inhibitor 1 (AZIN1) serves as a pro‐oncogenic molecule in multiple cancers. However, the clinicopathological features of AZIN1 in KIRC remain unexplored.

Materials and Methods

The Cancer Genome Atlas (TCGA, TIMER, and GEPIA) were employed for pan‐cancer expression and survival analysis of AZIN1, indicating the unique anti‐tumor role of AZIN1 in KIRC. The expression and clinical characteristics of AZIN1 in KIRC were further proven via Human Protein Atlas and TCGA. single‐sample GSEA was employed to investigate the immune infiltration of AZIN1. Then the downstream pathways were illustrated via the LinkedOmics, Metascape, and Cytoscape databases. The possible upper regulating noncoding RNAs (ncRNAs) were analyzed from five programs‐TargetScan, StarBase, miRanda, PITA, and miRmap.

Results

AZIN1 is downregulated in KIRC patients. Lower levels of AZIN1 were linked with unfavorable outcomes in KIRC patients. The AZIN1 expression was positively related to immune cell infiltration in KIRC. We also elucidated a possible upstream regulatory ncRNA of AZIN1 in KIRC namely STK4‐AS1/AC068338.2‐miR‐106b‐5p‐AZIN1 axis as well as the downstream signaling pathways.

Conclusion

This study illustrated the unique anti‐tumor role of AZIN1 in KIRC and provided potential value for guiding immunotherapy and targeted therapy.
Orthogonal Control of Nucleic Acid Function via Chemical Caging‐Decaging Strategies
Authors: Wang Xiangnan , Wen Siyu , Wu Zhenkun , Jiang Jian‐Hui
Published: August 2024

The ability to precisely control the function of nucleic acids plays an important role in biosensing and biomedicine. In recent years, novel strategies employing biological, physical, and chemical triggers have been developed to modulate the function of nucleic acids spatiotemporally. These approaches commonly involve the incorporation of stimuli‐responsive groups onto nucleic acids to block their functions until triggers‐induced decaging restore activity. These inventive strategies deepen our comprehension of nucleic acid molecules’ dynamic behavior and provide new techniques for precise disease diagnosis and treatment. Focusing on the spatiotemporal regulation of nucleic acid molecules through the chemical caging‐decaging strategy, we here present an overview of the innovative triggered control mechanisms and accentuate their implications across the fields of chemical biology, biomedicine, and biosensing.
Dioxygen Controlled Chemodivergent Cross‐Coupling of Primary and Secondary Alcohols Using Noninnocent Azo Aromatic Complexes of Cobalt(II) as Catalysts
Authors: Kamal  , Samanta Subhas
Published: August 2024

Herein, employing pincer like cobalt (II) complexes containing redox noninnocent azo‐benzimidazole ligand a switchable and chemodivergent catalytic cross‐coupling of primary and secondary alcohols is reported. The reactions are environmentally benign and atom efficient. It liberates water and hydrogen gas as the only byproducts. While the reaction in inert condition gives
alkylated ketones, in presence of air as well as lower temperature and base loading selectively results in
unsaturated ketones. Both the catalytic protocols have very good functional group tolerance. Thus, a wide range of substrates have been found to be effective for the synthesis of
alkylated ketones as well as
unsaturated ketones via dehydrogenative cross‐coupling reaction of alcohols. Several control experiments and kinetic studies were performed to elucidate the reaction pathways.
Electrocatalytic Synthesis of Organonitrogen Compounds via C−N Coupling from NOx and Carbon Source
Authors: Zhou Yiyang , Ding Chunmei , Li Can
Published: August 2024

Nitrogen oxide (NOx) is an attractive nitrogen source. Electrocatalytic NOx reduction coupled with the conversion of carbon source molecules offers a potential route for sustainable synthesis of valuable nitrogenous organics. This review discusses recent progress on the synthesis of electrocatalytic organonitrogen compounds (such as oximes, amino acids, amines, amides and urea) via C−N coupling from NOx and carbon source. The electrocatalytic performance, catalyst structure and especially reaction mechanism are discussed. Current challenges, catalyst design principles, the understanding on reaction mechanisms, as well as possible strategies for improving reaction selectivity and activity are proposed, which will guide future researches in the electrocatalytic conversion of NOx and carbon source.
Enhanced Oxygen Reduction Reaction Via Oxygen Vacancy‐Rich Silica‐Supported Ag/Pd Nanoshells
Authors: dos Santos Pereira Fellipe , Anchieta e Silva Felipe , Azevedo Silva Augusto César , de Jesus Gomes Varela Júnior Jaldyr , Mateus Pinatti Ivo , Rojas Alex , Mantilla Angeles , Alcântara Ana C. S. , Baraldi Dourado Andre Henrique , Tofanello Aryane , Atsushi Tanaka Auro , Silva Rodrigues Thenner , Suller Garcia Marco Aurélio
Published: August 2024

Herein, we demonstrated the fine‐tuning of catalysts’ active phase by employing AgPd nanoshells with distinct Ag/Pd ratios synthesized via a galvanic replacement method for the oxygen reduction reaction (ORR). However, more interestingly, the subsequent immobilization of such Ag/Pd ratios onto silica further influenced the support characteristics, creating an increasing concentration of oxygen vacancies in this typically inert support — a surprising and unparalleled outcome attested by electrochemical impedance spectroscopy, electron paramagnetic resonance, and theoretical calculation. Such a phenomenon promoted obtaining an optimized electro/photocatalyst with exceptional activity, facilitating not just the ORR but also the photochemical water‐splitting reaction. Curiously, adjusting the Ag/Pd ratio also affected the ORR mechanism, which was switched from a 2‐electron to a 4‐electron after optimization. Finally, Ag38Pd62/SiO2, the catalyst with the best proportion, exhibited a remarkable hydrogen production rate of 1039.8 μmol/gcatalyst during 300 minutes of water splitting, surpassing the performance of the conventional Degussa TiO2 P25 catalyst.
Co‐W (Hydr)oxide with Ultralow Ru Promotes Water Dissociation Coupled H+ Abstraction in Alkaline HER
Authors: M Rama Prakash , G Nasrin Banu , Neppolian Bernaurdshaw , Sengeni Anantharaj
Published: August 2024

The hydrogen evolution reaction in alkaline water electrolysis is facilitated through the electrodeposition of trimetallic catalyst on nickel foam using the chronoamperometry technique. Specifically, the trimetallic catalyst CoWRu@NF is deposited onto a nickel foam substrate. The catalytic performance of this trimetallic catalytic electrode for the Hydrogen Evolution Reaction (HER) is then assessed in a 1.0 M potassium hydroxide (KOH) solution. This specially designed trimetallic catalytic electrode system efficiently provides the more active sites through the Co component. Subsequently, it facilitates the reduction of protons (H+) to generate hydrogen gas using the Ru component. Tungsten acts as a co‐catalyst in the system for water dissociation promotor by removing hydroxide formed after water dissociation and preventing the deactivation of Ruthenium by certain reaction intermediates. The CoWRu@NF trimetallic catalyst demonstrates excellent activity, showcasing a low overpotential (−8 mV) to achieve a current density of (−10 mA/cm2. Additionally, it exhibits low Tafel slope values (101.2 mV dec−1), credited to the presence of cobalt and tungsten alongside Ruthenium in the catalytic system. This configuration is specifically designed to enhance the kinetics of the hydrogen‐evolving reaction.
Controlled Photooxidation via Singlet Oxygen Generation by Triplet Harvesting in a Heavy Atom Free Pure Organic Dithienylethene‐Naphthalene Diimide
Authors: Bag Sayan Kumar , Mondal Bijan , Karmakar Manisha , Das Subhadeep , Patra Abhijit , Thakur Arunabha
Published: August 2024

Noninvasive control over the reversible generation of singlet oxygen (1O2) has found the enormous practical implications in the field of biomedical science. However, metal‐free pure organic emitters, connected with a photoswitch, capable of generating “on‐demand” 1O2 via triplet harvesting remain exceedingly rare; therefore, the utilization of these organic materials for the reversible control of singlet oxygen production remains at its infancy. Herein, an ambient triplet mediated emission in quinoline‐dithienylethene (DTE)‐core‐substituted naphthalene diimide (cNDI) derivative is unveiled via delayed fluorescence. The quinoline‐DTE‐cNDI triad displayed enhanced photoswitching efficiency via double FRET mechanism. It was found to have direct utilization in controlled photosensitized organic transformations via efficient generation of singlet oxygen (yield ΦΔ~0.55 in DCM and 0.73 in methanol). The designed molecule exhibits a long‐lived emission (τ∼1.1 μs) and very small singlet‐triplet splitting (ΔEST) of 0.13 eV empowering it to display delayed fluorescence. Comprehensive steady state and time‐resolved emission spectroscopy (TRES) analyses along with DFT calculations offer detailed understandings into the excited‐state manifolds of organic compound and energy transfer (ET) pathways involved in 1O2 generation.
Metal Cocatalyst Engineering in Metal‐Semiconductor Hybrid Photocatalysts Achieves a Fivefold Enhancement of Hydrogen Evolution
Authors: Park Bumjin , Park Won‐Woo , Choi Ji Yong , Bang Kodong , Kim Sungjoo , Choi Ye‐Jin , Sul Soohwan , Kwon Oh‐Hoon , Song Hyunjoon
Published: August 2024

This study explores the optimal morphology of photochemical hydrogen evolution catalysts in a one‐dimensional system. Systematic engineering of metal tips on precisely defined CdSe@CdS dot‐in‐rods is conducted to exert control over morphology, composition, and both factors. The outcome yields an optimized configuration, a Au−Pt core‐shell structure with a rough Pt surface (Au@r‐Pt), which exhibits a remarkable fivefold increase in quantum efficiency, reaching 86 % at 455 nm and superior hydrogen evolution rates under visible and AM1.5 G irradiation conditions with prolonged stability. Kinetic investigations using photoelectrochemical and time‐resolved measurements demonstrate a greater extent and extended lifetime of the charge‐separated state on the tips as well as rapid water reduction kinetics on high‐energy surfaces. This approach sheds light on the critical role of cocatalysts in hybrid photocatalytic systems for achieving high performance.
Steric Engineering of Rotaxane Catalysts: Benefits and Limits of Using the Mechanical Bond in Catalyst Design
Authors: Struth F. Robin , Jansen Dennis , Pairault Noël , Schumacher Marcel , Uteschil Florian , Linders Jürgen , Mayer Christian , Gröschel André H. , Goldup Stephen M. , Niemeyer Jochen
Published: August 2024

The mechanical bond is emerging as a novel design element in catalyst development. Here, we report a series of 1,1’‐binaphthyl‐2,2’‐diol (BINOL) based catalysts in which the number of interlocked macrocycles is varied. Unsurprisingly, the macrocycles have a profound steric influence on the catalytic performance of these molecules. However, in the enantioselective transformations examined, the macrocycles are detrimental to catalyst stereoselectivity whereas in lactide polymerization, they increase the molecular weight of the polymeric product.
Developing Allosteric Inhibitors of SARS‐CoV‐2 RNA‐Dependent RNA Polymerase
Authors: Chayka Artem , Danda Matěj , Dostálková Alžběta , Spiwok Vojtěch , Klimešová Anna , Kapisheva Marina , Zgarbová Michala , Weber Jan , Ruml Tomáš , Rumlová Michaela , Janeba Zlatko
Published: August 2024

The use of Fpocket and virtual screening techniques enabled us to identify potential allosteric druggable pockets within the SARS‐CoV‐2 RNA‐dependent RNA polymerase (RdRp). Of the compounds screened, compound 1 was identified as a promising inhibitor, lowering a SARS‐CoV‐2 RdRp activity to 57 % in an enzymatic assay at 10 μM concentration. The structure of compound 1 was subsequently optimized in order to preserve or enhance inhibitory activity. This involved the substitution of problematic ester and aromatic nitro groups with more inert functionalities. The N,N’‐diphenylurea scaffold with two NH groups was identified as essential for the compound's activity but also exhibited high toxicity in Calu‐3 cells. To address this issue, a scaffold hopping approach was employed to replace the urea core with potentially less toxic urea isosteres. This approach yielded several structural analogues with notable activity, specifically 2,2’‐bisimidazol (in compound 55 with residual activity RA=42 %) and (1H‐imidazol‐2‐yl)urea (in compounds 59 and 60, with RA=50 and 28 %, respectively). Despite these advances, toxicity remained a major concern. These compounds represent a promising starting point for further structure‐activity relationship studies of allosteric inhibitors of SARS‐CoV‐2 RdRp, with the goal of reducing their cytotoxicity and improving aqueous solubility.
Nanoradiopharmaceuticals: An Attractive Concept in Oncotherapy
Authors: Hou Ruitong , Liu Ning , Li Feize
Published: August 2024

Radiopharmaceuticals are of significant importance in the fields of tumor imaging and therapy. In recent decades, the increasing role of nanotechnology has led to the attractive concept of nanoradiopharmaceuticals. Consequently, it is imperative to provide a concise summary of the necessary guidelines to facilitate the translation of nanoradiopharmaceuticals. In this work, we have presented the contents of radiolabeling strategies and some applications of nanoradiopharmaceuticals. Such a framework can assist researchers in identifying more pertinent insights or making more informed decisions in the study of nanoradiopharmaceuticals.
One‐Year Follow‐Up: Schema Therapy for Patients With Borderline Personality Disorder and Comorbid Alcohol Use Disorder
Authors: Boog Michiel , Visser Mette C. , Clarijs Loes , Franken Ingmar H. A. , Arntz Arnoud
Published: August 2024

This article describes the 1‐year follow‐up of a study into the effectiveness of Schema Therapy (ST) for borderline personality disorder (BPD) and comorbid alcohol use disorder (AUD). In the original study, 20 of these patients participated in a multiple baseline case series design study. The results of the original study were promising (a significant decrease of BPD and AUD symptoms). The present study is aimed at examining the longer term benefits of ST for BPD and comorbid AUD. One year after the cessation of the investigational therapy, 17 of the original participants agreed to participate in this follow‐up study. T‐ or Wilcoxon signed rank tests were performed to compare 1‐year follow‐up to start of therapy (baseline). The results suggest that the main therapeutic improvements were generally preserved at 1‐year follow‐up. These findings add to the idea that integrated ST for BPD and comorbid AUD might be effective, also in the long term. A randomized clinical trial is indicated to substantiate this idea.
Cellulose Acetates in Hydrothermal Carbonization: A Green Pathway to Valorize Residual Bioplastics
Authors: Ischia Giulia , Marchelli Filippo , Bazzanella Nicola , Ceccato Riccardo , Calvi Marco , Guella Graziano , Gioia Claudio , Fiori Luca
Published: August 2024

Bioplastics possess the potential to foster a sustainable circular plastic economy, but their end‐of‐life is still challenging. To sustainably overcome this problem, this work proposes the hydrothermal carbonization (HTC) of residual bioplastics as an alternative green path. The focus is on cellulose acetate – a bioplastic used for eyewear, cigarette filters and other applications – showing the proof of concept and the chemistry behind the conversion, including a reaction kinetics model. HTC of pure and commercial cellulose acetates was assessed under various operating conditions (180–250 °C and 0–6 h), with analyses on the solid and liquid products. Results show the peculiar behavior of these substrates under HTC. At 190–210 °C, the materials almost completely dissolve into the liquid phase, forming 5–hydroxymethylfurfural and organic acids. Above 220 °C, intermediates repolymerize into carbon‐rich microspheres (secondary char), achieving solid yields up to 23 %, while itaconic and citric acid form. A comparison with pure substrates and additives demonstrates that the amounts of acetyl groups and derivatives of the plasticizers are crucial in catalyzing HTC reactions, creating a unique environment capable of leading to a total rearrangement of cellulose acetates. HTC can thus represent a cornerstone in establishing a biorefinery for residual cellulose acetate.
Punctuated aggradation and flow criticality in deep water channel systems
Authors: Kneller Ben , Valdez Buso Victoria
Published: August 2024

Submarine channels are conduits for the transfer of material to deep water by sediment gravity flows. Some channels clearly show meandering patterns in planform that have attracted comparisons with fluvial systems. Many submarine channels, however, are aggradational. Transitions from meandering (at grade) channels to aggradational channels have been described in the subsurface, from seismic data. A field example is presented here in which these meandering and aggradational states may alternate several times during the overall development of a fourth‐order sequence before the system is temporarily or permanently abandoned. This implies a change in flow state from one where successive flows behave similarly over extended periods, to one in which the flow parameters are progressively changing. The cause of these cyclic changes is unclear. The generation of sedimentary architectures so strikingly comparable to those of meandering fluvial systems provides strong evidence in favour of stably stratified, essentially two‐layer flows, in which the lower high‐density part is channel‐confined, with a normal (i.e. fluvial‐like) secondary circulation, and the upper, low‐density part extends onto the overbank regions adjacent to the channel, with minimal mixing and entrainment. Such flows are described as subcritical, in line with published experimental and numerical work, allowing that the critical Froude number in such settings may not be unity. The switch to an aggradational state may be linked to changes in flow criticality, but the ultimate driver for these alternations in flow properties remains unknown.