bluuebunny/crossref_metadata_2025 huggingface dataset:
Effect of Deformation Mode on Grain Characteristics and Strength–Toughness of Al-Zn-Mg-Cu Alloy
Authors: Shi Guohui , Yu Mingyang , Zhu Kai , Ren Weicai , Wen Kai , Li Xiwu
Published: September 2024

The Al-Zn-Mg-Cu alloy plate is a structural material widely used in aerospace, and its rolling process plays a crucial role in determining its performance. This study investigated the effects of different pass combinations of forward and spread rolling on the grain characteristics, strength, and fracture toughness of Al-Zn-Mg-Cu aluminum alloy plates under industrial conditions. The results show that initially using a small pass reduction followed by a larger one can improve the grain width and thickness on the Long Transverse–Short Transverse surface. Additionally, increasing the spread rolling pass enhances the grain width-to-thickness ratio on the TS surface. Performance tests indicate that grain characteristics have minimal influence on room-temperature tensile properties. However, a higher grain width-to-thickness ratio significantly improves the alloy’s fracture toughness.
Elastic Modulus Measurement at High Temperatures for Miniature Ceramic Samples Using Laser Micro-Machining and Thermal Mechanical Analyzer
Authors: Zhang Zhao , Xiao Hai , Bordia Rajendra K. , Peng Fei
Published: September 2024

In this paper, we demonstrate a method of measuring the flexural elastic modulus of ceramics at an intermediate (~millimeter) scale at high temperatures. We used a picosecond laser to precisely cut microbeams from the location of interest in a bulk ceramic. They had a cross-section of approximately 100 μm × 300 μm and a length of ~1 cm. They were then tested in a thermal mechanical analyzer at room temperature, 500 °C, 800 °C, and 1100 °C using the four-point flexural testing method. We compared the elastic moduli of high-purity Al2O3 and AlN measured by our method with the reported values in the literature and found that the difference was less than 5% for both materials. This paper provides a new and accurate method of characterizing the high-temperature elastic modulus of miniature samples extracted from representative/selected areas of bulk materials.
Experimental Study on the Microstructure and Tribological Properties of Laser-Clad Ni60-WC Composite Coatings
Authors: Cao Yupeng , Yan Kai , Shi Weidong , Zhou Rui , Li Bin , Qin Jiaxin
Published: September 2024

To address the wear issues faced by the leg components of offshore platforms in harsh marine conditions, a Ni60-WC composite coating was fabricated on the surface of E690 high-strength steel using laser cladding. The microstructure, elemental distribution, microhardness, and tribological properties of the composite coating were characterized and tested using XRD (X-ray diffraction), SEM (scanning electron microscopy), EDS (energy-dispersive spectrometry), a microhardness tester, and a multifunctional tribometer. The study focused on the microstructure and tribological properties of the Ni60-WC composite coating. The results show that the composite coating primarily consists of γ-(Fe, Ni), WC, W2C, M23C6, and M6C phases, with cellular and dendritic structures at the top. WC and W2C, along with M23C6 and M6C, are precipitated from the W and C elements. The average hardness of the composite coating reached 569.5 HV, representing a 103% increase over the substrate hardness. The prepared composite coating exhibited a 32.6% increase in corrosion potential compared to the substrate. Additionally, the corrosion current density was reduced by 62.0%, indicating a significant enhancement in the corrosion resistance of the composite coating. The friction coefficient of the composite coating was reduced by 17.4% compared to the substrate, and wear volume was reduced by 79%, significantly enhancing the tribological performance of the coating due to reduced abrasive wear and fatigue wear.
A Lab-Scale Evaluation of Parameters Influencing the Mechanical Activation of Kaolin Using the Design of Experiments
Authors: Mañosa Jofre , Alvarez-Coscojuela Adrian , Maldonado-Alameda Alex , Chimenos Josep Maria
Published: September 2024

This research investigates the mechanical activation of kaolin as a supplementary cementitious material at the laboratory scale, aiming to optimize milling parameters using the response surface methodology. The study evaluated the effects of rotation speed and milling time on the amorphous phase content, the reduction in crystalline kaolinite, and impurity incorporation into the activated clay through the Rietveld method. The results demonstrated that adjusting milling parameters effectively enhanced clay activation, which is crucial for its use in low-carbon cements. High rotation speeds (300/350 rpm) and prolonged grinding times (90/120 min) in a planetary ball mill increased the pozzolanic activity by boosting the formation of amorphous phases from kaolinite and illite and reducing the particle size. However, the results evidenced that intermediate milling parameters are sufficient for reaching substantial degrees of amorphization and pozzolanic activity, avoiding the need for intensive grinding. Exceedingly aggressive milling introduced impurities like ZrO2 from the milling equipment wear, underscoring the need for a balanced approach to optimizing reactivity while minimizing impurities, energy consumption, and equipment wear. Achieving this balance is essential for efficient mechanical activation, ensuring the prepared clay’s suitability as supplementary cementitious materials without excessive costs or compromised equipment integrity.
Effect of Laser Parameters on Fracture Properties of Laser-Repaired Cracks with Micro/NanoMaterial Addition: Multiscale Analysis
Authors: Li Yinyin , Jiang Wei , Li Meiqiu
Published: September 2024

In laser crack repair processes, laser parameters have significant influence on repair quality. Improper combination of laser process parameters may result in defects—such as porosity, ablation, and coarse grain size—in remelted zones. A trans-scale computational model is established by combining crystal plasticity finite elements and variable-node finite elements. The influence of microstructure characteristics such as grain size and porosity of the repair layer on the cumulative plastic slip (CPS) on the dominant slip system at the meso-scale and the J-integral at the macro-scale is studied to explore the effect of laser process parameters on repair quality. The results show that when the laser power is 1800 W and the heating time is 0.5 s, the grain size and porosity of the repaired specimen are the smallest. The J-integral of the repaired specimen is more than 8% smaller than that of the unrepaired specimen and about 3% smaller than that of the repaired specimen, with a laser power of 2000 W and a heating time of 1 s. Pores increase the CPS of the crystal around the pores, especially when a pore have sharp corners. Selecting appropriate laser process parameters can not only refine grain size but also reduce the volume fraction of pores and thus reduce the J-integral and eventually improve repair quality of repaired specimens. The study investigates the relationship of process parameter–microstructure–repair quality in the laser repair process and provides a method for studying the mechanical behavior of materials at macro and micro scales.
The Influence of Elastic Support of Component Glass Panes on Deflection and Stress in Insulating Glass Units—Analytical Model
Authors: Respondek Zbigniew
Published: September 2024

Insulating glass units (IGUs) are the most common filling for external building envelopes. These elements have many advantages related to the thermal protection of buildings. However, some climatic loads are generated or modified due to the sealed gas cavity between the glass panes. The gas enclosed in the cavities changes its parameters under external load, which affects the operational deflection and stress in an IGU. In most computational models describing this phenomenon, the component panes are assumed to be simply supported on the edge spacer, which is considered a sufficient approximation. This article, which continues previous work, assumes that the component glass panes can be supported elastically at the edges. The parameter describing this connection is rotational stiffness. Based on the theory of linear–elastic plates, coefficients were determined to calculate the change in cavity volume, deflection, and stress in glass panes. Then, the results of calculations of the influence of rotational stiffness and static values in exemplary IGUs of various structures, loaded with changes in atmospheric pressure and wind, are presented. It was found that a feedback loop occurs here. The deflection and stress in elastically supported single panes are lower than in the case of those simply supported. However, the lower susceptibility to deflection of the component panes weakens the gas interaction in the cavity, and the resultant load on these panes increases. The influence of rotational stiffness on the resulting static values may therefore vary. In the analyzed examples, this influence was primarily negative for symmetrical loads and clearly positive for wind loads.
Investigation of the Effect of Oxide Additives on the Band Gap and Photocatalytic Efficiency of TiO2 as a Fixed Film
Authors: Ghiloufi Mabrouka , Schnabel Tobias , Mehling Simon , Kouass Salah
Published: September 2024

The effects of various additives (Y2O3, Ga2O3, and WO3) on photocatalytic degradation efficiency under UV light-emitting diodes (LEDs) and the optical properties of TiO2 Degussa P25 were investigated using ketoprofen and diclofenac, two non-steroidal anti-inflammatory drugs commonly detected in German rivers. Experimental results demonstrated that thin films containing these additives exhibited similar photocatalytic degradation efficiencies as pure TiO2, achieving a 30% degradation of ketoprofen over 150 min. In contrast, the Y2O3/TiO2 thin film showed significantly improved performance, achieving a 46% degradation of ketoprofen in 180 min. Notably, the Y2O3/TiO2 system was three times more effective in degrading diclofenac compared to pure TiO2. Additionally, the Y2O3/TiO2 photocatalyst retained its activity over three successive cycles with only a slight decrease in efficiency. The photocatalytic degradation of both organic pollutants followed first-order kinetics with all photocatalysts. The investigation included SEM imaging to assess the surface homogeneity of the thin films and UV-vis solid-state spectroscopy to evaluate the impact of the additives on the energy band gap of TiO2.
Experimental Determination and Simulation Validation: Johnson–Cook Model Parameters and Grinding Simulation of 06Cr18Ni11Ti Stainless Steel Welds
Authors: Zhang Shengfang , Leng Zhiyi , Duan Qiang , Gu Hongtao , Lu Mingjie , Wang Ziguang , Liu Yu
Published: September 2024

Hydrogen permeation resistance in the welded region of 06Cr18Ni11Ti steel is relatively weak due to surface defects, which need high integrity surface machining. The parameters of the welding material for 06Cr18Ni11Ti steel are currently unavailable, which causes some inconvenience for simulation studies. To fill the lack of 06Cr18Ni11Ti steel weld material parameters in the relevant literature at the present stage, the quasi-static tensile test at different strain rates and notch specimen tensile tests were conducted in this paper and determined the Johnson–Cook (J-C) constitutive model parameters and Johnson–Cook failure model parameters. Subsequently, a multi-grain grinding simulation model was built based on W-M fractal dimension theory by using the determined material parameters. The influence of processing parameters on grinding heat was analyzed. Grinding experiments were conducted to analyze the influence of processing parameters on grinding heat and grinding force. By comparing the simulation and experimental results, it is revealed that the average error is 9.37%, indicating relatively small discrepancy. It is demonstrated that the grinding simulation model built in this paper could efficiently simulate the grinding process, and the determined weld material parameters of 06Cr18Ni11Ti steel have been verified to possess high accuracy and reliability.
Creating the Slider Tester Repair Recommendation System to Enhance the Repair Step by Using Machine Learning
Authors: Udomsup Rattaphong , Nuchkum Suphatchakan , Srisertpol Jiraphon , Donjaroennon Natthapon , Leeton Uthen
Published: September 2024

This project aims to develop a recommendation system to mitigate looping issues in HDD slider testing using the Amber testing machine (Machine A). Components simulating the HDD often fail and require repair before re-testing. However, post-repair, there is a 34% probability that the component (referred to as Product A) will experience looping, characterized by repeated failures with error code A. This recurring issue significantly hampers testing efficiency by reducing the number of successful slider tests. To address this challenge, we propose a dual-approach recommendation system that provides technicians with actionable insights to minimize the occurrence of looping. For previously analyzed components, a collaborative filtering technique utilizing implicit ratings is employed to generate recommendations. For new components, for which prior data are unavailable, a cosine similarity approach is applied to suggest optimal actions. An automatic training system is implemented to retrain the model as new data become available, ensuring that the recommendation system remains robust and effective over time. The proposed system is expected to offer precise guidance to technicians, thereby improving the overall efficiency of the testing process by reducing the frequency of looping issues. This work represents a significant advancement in enhancing operational reliability and productivity in HDD slider testing.
Detection of Broken Bars in Induction Motors Operating with Closed-Loop Speed Control
Authors: Muzio Francesca , Mantione Lorenzo , Garcia-Calva Tomas , Frosini Lucia , Morinigo-Sotelo Daniel
Published: September 2024

Rotor bar breakage in induction motors is often detected by analysing the signatures in the stator current. However, due to the alteration of the current spectrum, traditional methods may fail when inverter-fed motors operate with closed-loop control using a cascade structure to regulate the speed. In this paper, the potential of zero-sequence voltage analysis to detect this fault is investigated, and a new index to quantify the severity of the fault based on this signal is proposed. Signals from motors operating under different control strategies and signals from motors powered from the mains are considered to verify the robustness of the proposed fault severity index. As a result, in all the analysed conditions the value of the proposed index for the healthy motor is found to be approximately 0.010, while for the faulty machine it is between 0.110 and 0.252.
Integrated Intelligent Control of Redundant Degrees-of-Freedom Manipulators via the Fusion of Deep Reinforcement Learning and Forward Kinematics Models
Authors: Chen Yushuo , Su Shijie , Ni Kai , Li Cunjun
Published: September 2024

Redundant degree-of-freedom (DOF) manipulators offer increased flexibility and are better suited for obstacle avoidance, yet precise control of these systems remains a significant challenge. This paper addresses the issues of slow training convergence and suboptimal stability that plague current deep reinforcement learning (DRL)-based control strategies for redundant DOF manipulators. We propose a novel DRL-based intelligent control strategy, FK-DRL, which integrates the manipulator’s forward kinematics (FK) model into the control framework. Initially, we conceptualize the control task as a Markov decision process (MDP) and construct the FK model for the manipulator. Subsequently, we expound on the integration principles and training procedures for amalgamating the FK model with existing DRL algorithms. Our experimental analysis, applied to 7-DOF and 4-DOF manipulators in simulated and real-world environments, evaluates the FK-DRL strategy’s performance. The results indicate that compared to classical DRL algorithms, the FK-DDPG, FK-TD3, and FK-SAC algorithms improved the success rates of intelligent control tasks for the 7-DOF manipulator by 21%, 87%, and 64%, respectively, and the training convergence speeds increased by 21%, 18%, and 68%, respectively. These outcomes validate the proposed algorithm’s effectiveness and advantages in redundant manipulator control using DRL and FK models.
Optimal Trajectory Planning for Wheeled Robots (OTPWR): A Globally and Dynamically Optimal Trajectory Planning Method for Wheeled Mobile Robots
Authors: Luo Dingji , Huang Xuchao , Huang Yucan , Miao Mingda , Gao Xueshan
Published: September 2024

In recent years, with the widespread application of indoor inspection robots, efficient motion planning has become crucial. Addressing the issue of discontinuous and suboptimal robot trajectories resulting from the independent nature of global and local planning, we propose a novel optimal path-planning method for wheeled mobile robots. This method leverages differential flatness to reduce dimensionality and decouple the problem, achieving globally optimal, collision-free paths in a two-dimensional flat output space through diagonal search and polynomial trajectory optimization. Comparative experiments in a simulated environment demonstrate that the proposed improved path search algorithm reduces search time by 46.6% and decreases the number of visited nodes by 43.1% compared to the original algorithm. This method not only ensures the optimal path and efficient planning but also ensures that the robot’s motion trajectory satisfies the dynamic constraints, verifying the effectiveness of the proposed optimal path planning algorithm for wheeled mobile robots.
Non-Linear Plasma Wave Dynamics: Investigating Chaos in Dynamical Systems
Authors: Ghandour Raymond , Karar Abdullah S. , Al Barakeh Zaher , Barakat Julien Moussa H. , Ur Rehman Zia
Published: September 2024

This work addresses the significant issue of plasma waves interacting with non-linear dynamical systems in both perturbed and unperturbed states, as modeled by the generalized Whitham–Broer–Kaup–Boussinesq–Kupershmidt (WBK-BK) Equations. We investigate analytical solutions and the subsequent emergence of chaos within these systems. Initially, we apply advanced mathematical techniques, including the transform method and the G′G2 method. These methods allow us to derive new precise solutions and enhance our understanding of the non-linear processes dominating plasma wave dynamics. Through a systematic analysis, we identify the conditions under which the system transitions from orderly patterns to chaotic behavior. This investigation provides valuable insights into the fundamental mechanisms of non-linear wave propagation in plasmas. Our results highlight the dynamic interplay between non-linearity and variation, leading to chaos, which may be useful in predicting and potentially controlling similar phenomena in practical applications.
Stochastic Phase Model with Reflective Boundary and Induced Beating: An Approach for Cardiac Muscle Cells
Authors: Zhou Guanyu , Hayashi Tatsuya , Tokihiro Tetsuji
Published: September 2024

We examine stochastic phase models for the community effect of cardiac muscle cells. Our model extends the stochastic integrate-and-fire model by incorporating irreversibility after beating, induced beating, and refractoriness. We focus on investigating the expectation and variance in the synchronized beating interval. Specifically, for a single isolated cell, we obtain the closed-form expectation and variance in the beating interval, discovering that the coefficient of variation has an upper limit of 2/3. For two coupled cells, we derive the partial differential equations for the expected synchronized beating intervals and the distribution density of phases. Furthermore, we consider the conventional Kuramoto model for both two- and N-cell models. We establish a new analysis using stochastic calculus to obtain the coefficient of variation in the synchronized beating interval, thereby improving upon existing literature.
Development of a New Swine Model Resembling Human Empty Nose Syndrome
Authors: Park Dan Bi , Jang David W. , Kim Do Hyun , Kim Sung Won
Published: September 2024

Background and Objectives: Empty nose syndrome (ENS) is a debilitating condition that often results from traumatic or iatrogenic causes, such as nasal surgery. There are various conservative and surgical treatments for ENS, but their effectiveness remains uncertain. Therefore, the development of animal models that accurately mimic human ENS is essential for advancing effective treatment strategies. Materials and Methods: To investigate ENS development, turbinoplasty was performed in the nasal cavity of swine, entailing partial removal of the ventral turbinate using turbinectomy scissors followed by electrocauterization. After 56 days, samples were obtained for histological and morphological analyses. Results: A significant reduction in the volume of the ventral turbinate in the ENS model led to an expansion of the nasal cavity. Histological analysis revealed mucosal epithelial changes similar to those observed in ENS patients, including squamous cell metaplasia, goblet cell metaplasia, submucosal fibrosis, and glandular atrophy. Biomarkers related to these histopathological features were identified, and signals potentially contributing to squamous cell metaplasia were elucidated. Conclusions: The swine ENS model is anticipated to be instrumental in unraveling the pathogenesis of ENS and may also be useful for evaluating the effectiveness of various treatments for ENS.
Unravelling the Roles of Bacterial Nanomachines Bistability in Pathogens’ Life Cycle
Authors: Gory Romain , Personnic Nicolas , Blaha Didier
Published: September 2024

Bacterial nanomachines represent remarkable feats of evolutionary engineering, showcasing intricate molecular mechanisms that enable bacteria to perform a diverse array of functions essential to persist, thrive, and evolve within ecological and pathological niches. Injectosomes and bacterial flagella represent two categories of bacterial nanomachines that have been particularly well studied both at the molecular and functional levels. Among the diverse functionalities of these nanomachines, bistability emerges as a fascinating phenomenon, underscoring their dynamic and complex regulation as well as their contribution to shaping the bacterial community behavior during the infection process. In this review, we examine two closely related bacterial nanomachines, the type 3 secretion system, and the flagellum, to explore how the bistability of molecular-scale devices shapes the bacterial eco-pathological life cycle.
Hybrid Hydroxyapatite–Metal Complex Materials Derived from Amino Acids and Nucleobases
Authors: Jiménez-Pérez Alondra , Martínez-Alonso Marta , García-Tojal Javier
Published: September 2024

Calcium phosphates (CaPs) and their substituted derivatives encompass a large number of compounds with a vast presence in nature that have aroused a great interest for decades. In particular, hydroxyapatite (HAp, Ca10(OH)2(PO4)6) is the most abundant CaP mineral and is significant in the biological world, at least in part due to being a major compound in bones and teeth. HAp exhibits excellent properties, such as safety, stability, hardness, biocompatibility, and osteoconductivity, among others. Even some of its drawbacks, such as its fragility, can be redirected thanks to another essential feature: its great versatility. This is based on the compound’s tendency to undergo substitutions of its constituent ions and to incorporate or anchor new molecules on its surface and pores. Thus, its affinity for biomolecules makes it an optimal compound for multiple applications, mainly, but not only, in biological and biomedical fields. The present review provides a chemical and structural context to explain the affinity of HAp for biomolecules such as proteins and nucleic acids to generate hybrid materials. A size-dependent criterium of increasing complexity is applied, ranging from amino acids/nucleobases to the corresponding macromolecules. The incorporation of metal ions or metal complexes into these functionalized compounds is also discussed.
Strategies for Mitigating Phosphoric Acid Leaching in High-Temperature Proton Exchange Membrane Fuel Cells
Authors: Xu Zhongming , Chen Nanjie , Huang Sheng , Wang Shuanjin , Han Dongmei , Xiao Min , Meng Yuezhong
Published: September 2024

High-temperature proton exchange membrane fuel cells (HT-PEMFCs) have become one of the important development directions of PEMFCs because of their outstanding features, including fast reaction kinetics, high tolerance against impurities in fuel, and easy heat and water management. The proton exchange membrane (PEM), as the core component of HT-PEMFCs, plays the most critical role in the performance of fuel cells. Phosphoric acid (PA)-doped membranes have showed satisfied proton conductivity at high-temperature and anhydrous conditions, and significant advancements have been achieved in the design and development of HT-PEMFCs based on PA-doped membranes. However, the persistent issue of HT-PEMFCs caused by PA leaching remains a challenge that cannot be ignored. This paper provides a concise overview of the proton conduction mechanism in HT-PEMs and the underlying causes of PA leaching in HT-PEMFCs and highlights the strategies aimed at mitigating PA leaching, such as designing crosslinked structures, incorporation of hygroscopic nanoparticles, improving the alkalinity of polymers, covalently linking acidic groups, preparation of multilayer membranes, constructing microporous structures, and formation of micro-phase separation. This review will offer a guidance for further research and development of HT-PEMFCs with high performance and longevity.
Engineering Thermoresponsive Poly(N-isopropylacrylamide)-Based Films with Enhanced Stability and Reusability for Efficient Bone Marrow Mesenchymal Stem Cell Culture and Harvesting
Authors: Yang Lei , Sun Luqiao , Sun Yuanyuan , Qiu Guangwei , Fan Xiaoguang , Sun Qing , Lu Guang
Published: September 2024

Poly(N-isopropylacrylamide) (PNIPAM) offers a promising platform for non-invasive and gentle cell detachment. However, conventional PNIPAM-based substrates often suffer from limitations including limited stability and reduced reusability, which hinder their widespread adoption in biomedical applications. In this study, PNIPAM copolymer films were formed on the surfaces of glass slides or silicon wafers using a two-step film-forming method involving coating and grafting. Subsequently, a comprehensive analysis of the films’ surface wettability, topography, and thickness was conducted using a variety of techniques, including contact angle analysis, atomic force microscopy (AFM), and ellipsometric measurements. Bone marrow mesenchymal stem cells (BMMSCs) were then seeded onto PNIPAM copolymer films prepared from different copolymer solution concentrations, ranging from 0.2 to 10 mg·mL−1, to select the optimal culture substrate that allowed for good cell growth at 37 °C and effective cell detachment through temperature reduction. Furthermore, the stability and reusability of the optimal copolymer films were assessed. Finally, AFM and X-ray photoelectron spectroscopy (XPS) were employed to examine the surface morphology and elemental composition of the copolymer films after two rounds of BMMSC adhesion and detachment. The findings revealed that the surface properties and overall characteristics of PNIPAM copolymer films varied significantly with the solution concentration. Based on the selection criteria, the copolymer films derived from 1 mg·mL−1 solution were identified as the optimal culture substrates for BMMSCs. After two rounds of cellular adhesion and detachment, some proteins remained on the film surfaces, acting as a foundation for subsequent cellular re-adhesion and growth, thereby implicitly corroborating the practicability and reusability of the copolymer films. This study not only introduces a stable and efficient platform for stem cell culture and harvesting but also represents a significant advance in the fabrication of smart materials tailored for biomedical applications.
Laser Desorption of Explosives from the Surface of Different Real-World Materials Studied Using C2Cl6-Dopant-Assisted Ion Mobility Spectrometry
Authors: Maťaš Emanuel , Petrík Matej , Sabo Martin , Matejčík Štefan
Published: September 2024

A highly efficient and sensitive ion mobility spectrometry (IMS) system with laser desorption sampling was applied for rapid explosive detection using different surface materials. This portable IMS detector, powered by a battery, offers mobility and is suitable for use in the field or combat zones. The laser desorption (LD) sampling of common explosives (Trinitrotoluene—TNT; Dinitrotoluenes—DNTs; Hexogene—RDX; pentaerythritol tetranitrate—PETN; plastic explosives—Compound 4 (C-4) and Semtex) on a wide range of common surface materials, such as metal, ceramic, plastic, glass, drywall, paper, wood, and textiles, was studied. Successful detection was achieved on nearly all surfaces except flammable materials (paper, wood, and textiles). The limit of detection (LOD) was determined for each explosive and specific surface, demonstrating an impressive LOD of 7 ng/mm2 for TNT. RDX, C-4, PETN, and Semtex achieved LOD values of 15 ng/mm2, while DNTs showed an LOD of approximately 50 ng/mm2.
Synthesis and Anticancer Activity Assessment of Zelkovamycin Analogues
Authors: Xie Xinrong , Huang Hongshun , Jaiswal Yogini S. , Su Shaoyang , Yang Linxia , Fan Yu , Guan Yifu , Williams Leonard L. , Bian Hedong
Published: September 2024

The zelkovamycin family is a class of cyclic octapeptides with potent antibacterial and antiviral activity. Due to their unique chemical structures and excellent bioactivity, zelkovamycins have consistently attracted the interest of synthetic chemists. However, only the total synthesis of zelkovamycin and zelkovamycin G has been reported until now. The current work presents, for the first time, the synthesis of zelkovamycin analogues, along with their anticancer activity assessment. Firstly, the corresponding chain peptide based on the amino acid sequence of zelkovamycin H was synthesized using the Fmoc solid-phase peptide strategy. This was followed by cyclization under high dilution conditions to obtain compound 21, and its structure was elucidated by NMR analysis. The results confirm that compound 21 is not the natural product of zelkovamycin H. We deduced that during the synthesis of peptide 12, the D-Abu residue epimerized to the L-Abu form, leading to the formation of peptide 20, which blocked our efforts during the synthesis of zelkovamycin H. Two more analogues, 22 and 23, were synthesized by changing the structure of amino acid residues using the same strategy. The anticancer activity of analogues 21–23 against Huh-7 cells was evaluated in vitro; however, their IC50 values were >50 μM.
Mechanisms of Atomic Oxygen Erosion in Fluorinated Polyimides Investigated by Molecular Dynamics Simulations
Authors: Zhou Shengrui , Zhang Li , Zou Liang , Ayubi Bilal Iqbal , Wang Yiwei
Published: September 2024

Traditional polyimides have highly conjugated structures, causing significant coloration under visible light. Fluorinated colorless polyimides, known for their light weight and excellent optical properties, are considered ideal for future aerospace optical lenses. However, their lifespan in low Earth orbit is severely limited by high-density atomic oxygen (AO) erosion, and the degradation behavior of fluorinated polyimides under AO exposure is not well understood. This study uses reactive molecular dynamics simulations to model two fluorinated polyimides, PMDA-TFMB and 6FDA-TFMB, with different fluorine contents, to explore their degradation mechanisms under varying AO concentrations. The results indicate that 6FDA-TFMB has slightly better resistance to erosion than PMDA-TFMB, mainly due to the enhanced chemical stability from its -CF3 groups. As AO concentration increases, widespread degradation of the polyimides occurs, with AO-induced cleavage and temperature-driven pyrolysis happening simultaneously, producing CO and OH as the main degradation products. This study uncovers the molecular-level degradation mechanisms of fluorinated polyimides, offering new insights for the design of AO erosion protection systems.
Synthesis of Novel Planar-Chiral Charge-Compensated nido-Carborane-Based Amino Acid
Authors: Gruzdev Dmitry A. , Telegina Angelina A. , Ezhikova Marina A. , Kodess Mikhail I. , Levit Galina L. , Krasnov Victor P.
Published: September 2024

Amino acids with unusual types of chirality and their derivatives have recently attracted attention as precursors in the synthesis of chiral catalysts and peptide analogues with unique properties. In this study, we have synthesized a new nido-carborane-based planar-chiral amino acid, in the molecule of which the amino group is directly bonded to the B(3) atom, and the carboxyl group is attached to the B(9) atom through the CH2S+(Me) fragment. 3-Amino-9-dimethylsulfonio-nido-carborane, prepared in three steps from 3-amino-closo-carborane in a high yield, was a key intermediate in the synthesis of the target planar-chiral amino acid. The carboxymethyl group at the sulfur atom was introduced by the demethylation reaction of the dimethylsulfonio derivative, followed by S-alkylation. The structure of new 3,9-disubstituted nido-carboranes was studied for the first time using NMR spectroscopy. The resonances of all boron atoms in the 11B NMR spectrum of 3-amino-9-dimethylsulfonio-nido-carborane were assigned based on the 2D NMR correlation experiments. The nido-carborane-based planar-chiral amino acid and related compounds are of interest as a basis for peptide-like compounds and chiral ligands.
Biosorption Ability of Pharmaceutically Active Compounds by Anabaena sp. and Chroococcidiopsis thermalis
Authors: Pogrzeba Jerzy , Poliwoda Anna
Published: September 2024

Drug overuse harms the biosphere, leading to disturbances in ecosystems’ functioning. Consequently, more and more actions are being taken to minimise the harmful impact of xenopharmaceuticals on the environment. One of the innovative solutions is using biosorbents—natural materials such as cells or biopolymers—to remove environmental pollutants; however, this focuses mainly on the removal of metal ions and colourants. Therefore, this study investigated the biosorption ability of selected pharmaceuticals—paracetamol, diclofenac, and ibuprofen—by the biomass of the cyanobacteria Anabaena sp. and Chroococcidiopsis thermalis, using the LC-MS/MS technique. The viability of the cyanobacteria was assessed by determining photosynthetic pigments in cells using a UV–VIS spectrophotometer. The results indicate that both tested species can be effective biosorbents for paracetamol and diclofenac. At the same time, the tested compounds did not have a toxic effect on the tested cyanobacterial species and, in some cases, stimulated their cell growth. Furthermore, the Anabaena sp. can effectively biotransform DCF into its dimer.
Chemical Derivatization and Paper Spray Ionization Mass Spectrometry for Fast Screening of Retinoic Acid in Cosmetics
Authors: Bao Yuzhang , Guo Ningzi , Hu Xiaowen , Di Bin , Liu Yang , Sun Huimin
Published: September 2024

As a prescription drug, retinoic acid is listed as a banned cosmetic additive in the EU and China regulations. Currently, spectrophotometric methods, including thin-layer chromatography (TLC), high-performance liquid chromatography (HPLC), and HPLC–MS/MS, are commonly used for the determination of retinoic acid. As these conventional methods require complex pretreatment and are time-consuming, chemical derivatization combined with paper spray ionization mass spectrometry was developed for the fast detection of retinoic acid in cosmetics. N,N-dimethylpiperazine iodide (DMPI) was utilized as a derivatization reagent. Carboxylic acid in retinoic acid was derivatized to carry a positive charge and was subjected to mass spectrometry analysis. Results showed that compared with non-derivatized compounds, the detection limit was increased by about 50 times. The linearity in the range of 0.005–1 μg·mL−1 was good. The limit of detection (LOD) was 0.0013 μg·mL−1, and the limit of quantification (LOQ) was 0.0043 μg·mL−1. The recoveries of spiked samples were in the range of 95–105%, and the RSDs were below 5%. Derivatization and paper spray ionization MS render a quick, sensitive, and accurate method for the detection of retinoic acid in a complex matrix.
Unveiling the Dynamic Evolution of Catalytic Sites in N-Doped Leaf-like Carbon Frames Embedded with Co Particles for Rechargeable Zn–Air Batteries
Authors: Lian Yuebin , Xu Weilong , Du Xiaojiao , Zhang Yannan , Bian Weibai , Liu Yuan , Xiao Jin , Xiong Likun , Bai Jirong
Published: September 2024

The advancement of cost-effective, high-performance catalysts for both electrochemical oxygen reduction reactions (ORRs) and oxygen evolution reactions (OERs) is crucial for the widespread implementation of metal–air batteries. In this research, we fabricated leaf-like N-doped carbon frames embedded with Co nanoparticles by pyrolyzing a ZIF-L/carbon nanofiber (ZIF-L/CNF) composite. Consequently, the optimized ZIF-L/CNF-700 catalyst exhibit exceptional catalytic activities in both ORRs and OERs, comparable to the benchmark 20 wt% Pt/C and RuO2. Addressing the issue of diminished cycle performance in the Zn–air battery cycle process, further detailed investigations into the post-electrolytic composition reveal that both the carbon framework and Co nanoparticles undergo partial oxidation during both OERs and ORRs. Owing to the varying local pH on the catalyst surface due to the consumption and generation of OH− by OERs and ORRs, after OERs, the product is reduced-size Co particles, while after ORRs, the product is outer-layer Co(OH)2-enveloping Co particles.
A Dy(III) Coordination Polymer Material as a Dual-Functional Fluorescent Sensor for the Selective Detection of Inorganic Pollutants
Authors: Wang Ying , An Baigang , Li Si , Chen Lijiang , Tao Lin , Fang Timing , Guan Lei
Published: September 2024

A Dy(III) coordination polymer (CP), [Dy(spasds)(H2O)2]n (1) (Na2Hspasds = 5-(4-sulfophenylazo)salicylic disodium salt), has been synthesized using a hydrothermal method and characterized. 1 features a 2D layered structure, where the spasda3− anions act as pentadentate ligands, adopting carboxylate, sulfonate and phenolate groups to bridge with four Dy centers in η3-μ1: μ2, η2-μ1: μ1, and monodentate coordination modes, respectively. It possesses a unique (4,4)-connected net with a Schläfli symbol of {44·62}{4}2. The luminescence study revealed that 1 exhibited a broad fluorescent emission band at 392 nm. Moreover, the visual blue color has been confirmed by the CIE plot. 1 can serve as a dual-functional luminescent sensor toward Fe3+ and MnO4− through the luminescence quenching effect, with limits of detection (LODs) of 9.30 × 10−7 and 1.19 × 10−6 M, respectively. The LODs are relatively low in comparison with those of the reported CP-based sensors for Fe3+ and MnO4−. In addition, 1 also has high selectivity and remarkable anti-interference ability, as well as good recyclability for at least five cycles. Furthermore, the potential application of the sensor for the detection of Fe3+ and MnO4− was studied through simulated wastewater samples with different concentrations. The possible sensing mechanisms were investigated using Ultraviolet-Visible (UV-Vis) absorption spectroscopy and density functional theory (DFT) calculations. The results revealed that the luminescence turn-off effects toward Fe3+ and MnO4− were caused by competitive absorption and photoinduced electron transfer (PET), and competitive absorption and inner filter effect (IFE), respectively.
A Study of Differential Topology on the Magnetically Induced Isotropically Averaged Lorentz Force Density of a Few Simple Molecules
Authors: Orza Michele , Summa Francesco F. , Zanasi Riccardo , Monaco Guglielmo
Published: September 2024

Quantum chemical topology addresses the study of the chemical structure by applying the tools of differential topology to scalar and vector fields obtained by quantum mechanics. Here, the magnetically induced isotropically averaged Lorentz force density was computed and topologically analyzed for 11 small molecules. Critical points (attractors, repellers, and saddles) were determined and trajectories connecting the attractors computed. It is shown that kinds and numbers of the critical points are to some extent transferable in similar molecules. CC bonds of different orders are endowed with critical points of different kinds close to their center. The sum of topological indices of the isolated critical points is influenced by the presence of repellers on the outer part of the molecules.
Structural Optimization of Isoquinoline Derivatives from Lycobetaine and Their Inhibitory Activity against Neuroendocrine Prostate Cancer Cells
Authors: Zhang Zhuo , Shen Qianqian , Ji Yiyi , Ma Yanjie , Hou Haiyang , Yang Huajie , Zhu Yinjie , Chen Yi , Hu Youhong
Published: September 2024

Neuroendocrine prostate cancer (NEPC) is a highly aggressive cancer that is resistant to hormone therapy and characterized by poor prognosis, as well as limited therapeutic options. Since the natural product lycobetaine was reported to exhibit good antitumor activities against various types of cancers, we initially simplified the scaffold of lycobetaine to obtain the active compound 1, an isoquinoline derivative with an aryl moiety substitution at the 4-position, which showed apparent antiproliferative activities against NPEC cell line LASCPC-01 in vitro. Subsequently, we carried out structural optimization and systematic structure–activity relationship (SAR) studies on compound 1, leading to the discovery of compound 46, which demonstrated potent inhibitory activities against the LASCPC-01 cell line with an IC50 value of 0.47 μM. Moreover, compound 46 displayed remarkable selectivity over prostate cancer cell line PC-3 with a selectivity index greater than 190-fold. Further cell-based mechanism studies revealed that compound 46 and lycobetaine can effectively induce G1 cell cycle arrest and apoptosis dose dependently. However, lycobetaine inhibited the expression of neuroendocrine markers, while compound 46 slightly upregulated these proteins. This suggested that compound 46 might exert its antitumor activities through a different mechanism than lycobetaine, warranting further study.
Development of a Simple and Validated LC–MS/MS Method for Quantitative Determination of Ketotifen in Beagle Dog Plasma and Its Application to Bioequivalence Study of Ketotifen Syrup Dosage Form
Authors: Song Eunseo , Shim Wang-Seob , Choi Doowon , Song Yuna , Jo Hyeong Geun , Lee Soobok , Jung Suk Han , Choi Yeo Jin , Lee Kyung-Tae
Published: September 2024

A highly accurate, precise, and simple liquid chromatography-tandem mass spectrometry (LC–MS/MS) method for ketotifen (KTF) estimation from Beagle dog plasma was developed and validated, with ketotifen-d3 (KTF-d3) as the internal standard (IS). KTF and IS were detected on an API 4000 mass spectrometer in multiple reaction monitoring (MRM) mode in electrospray ionization (ESI) positive ionization mode. The transitions were monitored at m/z 310.2 → 96.0 for KTF and m/z 313.2 → 99.1 for IS. KTF and IS were extracted from plasma using liquid-liquid extraction with methyl tertiary-butyl ether and then analyzed for 3 min with extracted samples (7 µL) into the LC–MS/MS system. Analytes were separated on a Luna® Hilic column (50 × 2.0 mm i.d., 3 μm) using the Nexera X2 HPLC. The mobile phase A consisted of 10 mmol/L ammonium formate (pH 3.0), while mobile phase B consisted of 0.05% formic acid in acetonitrile. The ratio of mobile phase was 5:95 (v/v) at a flow rate of 0.2 mL/min. The method has been thoroughly validated in accordance with the bioanalytical method validation guidelines established by the Ministry of Food and Drug Safety in Korea and the U.S. Food and Drug Administration, addressing selectivity, lower limit of quantification, linearity, carryover, precision, accuracy, recovery, matrix effect, and stability. The developed LC–MS/MS method was effectively utilized for the bioequivalence assessment of ketotifen in Beagle dog plasma following the oral administration of ketotifen syrup.
Recent Progress on Low-Temperature Selective Catalytic Reduction of NOx with Ammonia
Authors: Park Eun Duck
Published: September 2024

Selective catalytic reduction of nitrogen oxides (NOx) with ammonia (NH3-SCR) has been implemented in response to the regulation of NOx emissions from stationary and mobile sources above 300 °C. However, the development of NH3-SCR catalysts active at low temperatures below 200 °C is still needed to improve the energy efficiency and to cope with various fuels. In this review article, recent reports on low-temperature NH3-SCR catalysts are systematically summarized. The redox property as well as the surface acidity are two main factors that affect the catalytic activity. The strong redox property is beneficial for the low-temperature NH3-SCR activity but is responsible for N2O formation. The multiple electron transfer system is more plausible for controlling redox properties. H2O and SOx, which are often found with NOx in flue gas, have a detrimental effect on NH3-SCR activity, especially at low temperatures. The competitive adsorption of H2O can be minimized by enhancing the hydrophobic property of the catalyst. Various strategies to improve the resistance to SOx poisoning are also discussed.
On the Simulation of Photoreactions Using Restricted Open-Shell Kohn–Sham Theory
Authors: Büchel Ralf , Álvarez Luis , Grage Jan , Maniscalco Dominykas , Frank Irmgard
Published: September 2024

It is a well-established standard to describe ground-state chemical reactions at an ab initio level of multi-electron theory. Fast reactions can be directly simulated. The most widely used approach is density functional theory for the electronic structure in combination with molecular dynamics for the nuclear motion. This approach is known as ab initio molecular dynamics. In contrast, the simulation of excited-state reactions at this level of theory is significantly more difficult. It turns out that the self-consistent solution of the Kohn–Sham equations is not easily reached in excited-state simulations. The first program that solved this problem was the Car–Parrinello molecular dynamics code, using restricted open-shell Kohn–Sham theory. Meanwhile, there are alternatives, most prominently the Q-Chem code, which widens the range of applications. The present study investigates the suitability of both codes for the molecular dynamics simulation of excited-state motion and presents applications to photoreactions.
Formulating Sustainable Emulsions: Mandelic Acid and Essential Oils as Natural Preservatives
Authors: Pavlačková Jana , Egner Pavlína , Mokrejš Pavel , Janalíková Magda
Published: September 2024

Emulsion products with natural antimicrobials are becoming increasingly popular for topical application. Mandelic Acid is interesting in cosmetics due to its potent exfoliating properties, which have driven advancements in skincare technologies. Essential oils have various properties, of which the most useful in cosmetics are those that do not cause irritation, smell pleasant, and have other beneficial properties such as antimicrobial effects. Emulsions with Mandelic Acid and essential oils from Satureja montana, Lemongrass, and Litsea cubeba were formulated and microbiologically tested for their preservative effectiveness. The effect of the treatments on skin condition was monitored by non-invasive diagnostic methods, such as hydration, transepidermal water loss, and pH value. Sensory analysis revealed that the matrix containing Mandelic Acid alone or combined with Litsea Cubeba Oil was the best-performing formulation, consistent with the compliant results of antimicrobial efficacy. The topical form of this cosmetic product has demonstrated excellent preservative activity and desirable biophysical efficacy on the skin.