Search Results (13,308)

This study presents the synthesis and physicochemical characterization of coordination compounds formed between chrysin, a natural flavonoid, and transition metal ions: Mn(II), Co(II), and Zn(II). The complexes were obtained under mildly basic conditions and analyzed using elemental analysis, thermogravimetric analysis (TGA), silver-assisted laser desorption/ionization mass spectrometry (SALDI-MS), FT-IR spectroscopy, and ¹H NMR. The spectroscopic data confirm that chrysin coordinates as a bidentate ligand through the 5-hydroxyl and 4-carbonyl groups, with structural differences depending on the metal ion involved. The mass spectrometry results revealed distinct stoichiometries: 1:2 metal-to-ligand ratios for Mn(II) and Co(II), and 1:1 for Zn(II), with additional hydroxide coordination. Biological assays demonstrated that Co(II) and Mn(II) complexes exhibit enhanced antibacterial and anti-biofilm activity compared to free chrysin, particularly against drug-resistant Staphylococcus epidermidis, whereas the Zn(II) complex showed negligible biological activity. Full article

Rock bolts are crucial components in the subterranean support systems in underground mines that provide adequate structural reinforcement to the rock mass to prevent unforeseen hazards like rockfalls. This makes frequent assessments of such bolts critical for maintaining rock mass stability and minimising risks in underground mining operations. Where manual surveying of rock bolts is challenging due to the low-light conditions in the underground mines and the time-intensive nature of the process, automated detection of rock bolts serves as a plausible solution. To that end, this study focuses on the automatic identification of rock bolts within medium- to large-scale 3D point clouds obtained from underground mines using mobile laser scanners. Existing techniques for automated rock bolt identification primarily rely on feature engineering and traditional machine learning approaches. However, such techniques lack robustness as these point clouds present several challenges due to data noise, varying environments, and complex surrounding structures. Moreover, the target rock bolts are extremely small objects within large-scale point clouds and are often partially obscured due to the application of reinforcement shotcrete. Addressing these challenges, this paper proposes an approach termed DeepBolt, which employs a novel two-stage deep learning architecture specifically designed for handling severe class imbalance for the automatic and efficient identification of rock bolts in complex 3D point clouds. The proposed method surpasses state-of-the-art semantic segmentation models by up to 42.5% in Intersection over Union (IoU) for rock bolt points. Additionally, it outperforms existing rock bolt identification techniques, achieving a 96.41% precision and 96.96% recall in classifying rock bolts, demonstrating its robustness and effectiveness in complex underground environments. Full article

This work presents a semi-classical, quantum-corrected model of gravitational collapse for a charged, spherically symmetric dust cloud, extending the classical Oppenheimer–Snyder (OS) framework through loop quantum gravity effects. Our goal is to study phenomenological quantum modifications to geometry, without necessarily embedding them within full loop quantum gravity (LQG). Building upon the quantum Oppenheimer–Snyder (qOS) model, which replaces the classical singularity with a nonsingular bounce via a modified Friedmann equation, we introduce electric and magnetic charges concentrated on a massive thin shell at the boundary of the dust ball. The resulting exterior spacetime generalizes the Schwarzschild solution to a charged, regular black hole geometry akin to a quantum-corrected Reissner–Nordström metric. The Israel junction conditions are applied to match the interior APS (Ashtekar–Pawlowski–Singh) cosmological solution to the charged exterior, yielding constraints on the shell’s mass, pressure, and energy. Stability conditions are derived, including a minimum radius preventing full collapse and ensuring positivity of energy density. This study also examines the geodesic structure around the black hole, focusing on null circular orbits and effective potentials, with implications for the observational signatures of such quantum-corrected compact objects. Full article

In recent years, the majority of countries have focused on the development of earth-penetrating weapons and the construction of deep underground fortifications. It is therefore necessary to assess the damage to underground structures under the attacks of earth-penetrating weapons. In this paper, fluid–solid coupling and restarting methods are used to simulate the damage processes of a granite chamber subjected to the combined action of penetration and explosion with the commercial software of LS-DYNA R11. The applicability of the penetration model and the blasting model is verified by the previous penetration and blasting tests. The verified models are used to simulate the complete process of the underground granite chamber attacked by the earth-penetrating weapons. Based on peak particle velocity (PPV) damage criteria, the numerical results show that the hypervelocity impact of the earth penetrating weapons only causes local damage to the granite rock mass, and more serious damage is caused by the subsequent explosion. During the subsequent explosion, part of the detonation products and energy can escape along the penetration trajectory with the blast loading, resulting in the attenuation of blast stress waves. Subsequently, the relationship between the overlay thickness and the vibration attenuation in granite is also studied, which provides a fast method to determine the threshold damage level for an underground chamber to collapse under the attacks of earth-penetrating weapons. Full article

This study investigated the nuanced influence of urban morphology on the thermal performance of nine mass housing blocks (21–26, 28–30) in New Belgrade’s Central Zone. These blocks, showcasing diverse structures, provided a robust basis for evaluating the design parameters. ENVI-met simulations were used to assess two scenarios: an “asphalt-only” environment, isolating the urban structure’s impact, and a “real-world” scenario, including green infrastructure (GI). Overall, the findings emphasize that while GI offers mitigation, the inherent urban built structure fundamentally determines thermal outcomes. An urban block’s thermal performance, it turns out, is a complex interplay between morphological factors and local climate. Crucially, simple metrics like Green Area Percentage (GAP) and Building Coverage Ratio (BCR) proved unreliable predictors of thermal performance. This highlights the critical need for urban planning regulations to evolve beyond basic surface indicators and embrace sophisticated, context-sensitive design principles for effective heat mitigation. Optimal performance arises from morphologies that actively manage heat accumulation and facilitate its dissipation, a characteristic exemplified by Block 22’s integrated design. However, even the best-performing Block 22 remains warmer compared to denser central areas, suggesting that urban densification can be a strategy for heat mitigation. Given New Belgrade’s blocks are protected heritage, targeted GI reinforcements remain the only viable approach for improving the outdoor thermal comfort. Full article

The southern conifer Agathis australis (D.Don) Lindl. is a large and long-lived species endemic to Aotearoa New Zealand. It is threatened due to past logging activities, pathogen attack and potentially climate change, with increasing severity and frequency of drought and heatwaves across its distribution. Like many large tree species, little is known about the carbon dynamics of this ecologically and culturally significant species. We explored seasonal variations in non-structural carbohydrates (NSCs) and growth in trees ranging from 20 to 175 cm diameter at breast height (DBH). NSCs were seasonally stable with no measurable pattern across seasons. However, we found growth rates standardised to basal area and sapwood area (growth efficiency) declined with tree age and stem NSC concentrations (including total NSCs, sugars and starch) all increased as trees aged. Total NSC concentrations were 0.3%–0.6% dry mass for small trees and 0.8%–1.8% dry mass for larger trees, with strong relationships between DBH and total NSC, sugar and starch in stems but not roots. Cumulative growth efficiency across the two-year study period declined as tree size increased. Furthermore, there was an inverse relationship between growth efficiency across the two-year study period and NSC concentrations of stems. This relationship was driven by differences in carbon dynamics in trees of different sizes, with trees progressing to a more conservative carbon strategy as they aged. Simultaneously declining growth efficiency and increasing NSC concentrations as trees age could be evidence for active NSC accumulation to buffer against carbon starvation in larger trees. Our study provides new insights into changing carbon dynamics as trees age and may be evidence for active carbon accumulation in older trees. This may provide the key for understanding the role of carbon processes in tree longevity. Full article

As the core equipment for efficient wastewater treatment, the internal structure of microporous aeration bioreactors directly determines the mass transfer efficiency and treatment performance. Based on Computational Fluid Dynamics (CFD) technology, this study explores the optimization mechanism of a Spherical Grid-Structured on the internal flow field of the reactor through a 3D numerical simulation system, aiming to improve the aeration efficiency and resource utilization. This study used a combination of experimental and numerical simulations to compare and analyze different configurations of the Spherical Grid-Structure. The simulation results show that the optimal equilibrium of the flow field inside the reactor is achieved when the diameter of the grid sphere is 2980 mm: the average flow velocity is increased by 22%, the uniformity of the pressure distribution is improved by 25%, and the peak turbulent kinetic energy is increased by 30%. Based on the Kalman vortex street theory, the periodic vortex induced by the grid structure refines the bubble size to 50–80 microns, improves the oxygen transfer efficiency by 20%, increases the spatial distribution uniformity of bubbles by 35%, and significantly reduces the dead zone volume from 28% to 16.8%, which is a decrease of 40%. This study reveals the quantitative relationship between the structural parameters of the grid and the flow field characteristics through a pure numerical simulation, which provides a theoretical basis and quantifiable optimization scheme for the structural design of the microporous aeration bioreactor, which is of great significance in promoting the development of low-energy and high-efficiency wastewater treatment technology. Full article

One of the promising research areas involving carborane derivatives is boron neutron capture therapy (BNCT). Due to the high boron atom content in carborane molecules, these compounds are considered potential candidates for BNCT-based cancer treatment. Despite ongoing studies on various biologically active carboranyl-containing compounds, the search continues for substances that meet the stringent requirements of effective BNCT agents. In this study, the synthesis of carboranyl-containing derivatives of β-arylaliphatic acids is described, along with the investigation of their reactivity with primary and secondary amines, as well as with metals and their hydroxides. The molecular structures of the synthesized compounds were confirmed using Fourier-transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, and mass spectrometry (LC-MS). Cytotoxicity of the water-soluble compound potassium 3-(2-isopropyl-1,2-dicarba-closo-dodecaboran-1-yl)-3-phenylpropanoate was evaluated using several cell lines, including HdFn and MCF-7. Full article

A rotating imperfect ring resonator of the gyroscope is modeled by a rotating thin ring with evenly distributed point masses. The free response of the rotating ring structure at constant speed is investigated, including the steady elastic deformation and wave response. The dynamic equations are formulated by using Hamilton’s principle in the ground-fixed coordinates. The coordinate transformation is applied to facilitate the solution of the steady deformation, and the displacements and tangential tension for the deformation are calculated by the perturbation method. Employing Galerkin’s method, the governing equation of the free vibration is casted in matrix differential operator form after the separation of the real and imaginary parts with the inextensional assumption. The natural frequencies are calculated through the eigenvalue analysis, and the numerical results are obtained. The effects of the point masses on the natural frequencies of the forward and backward traveling wave curves of different orders are discussed, especially on the measurement accuracy of gyroscopes for different cases. In the ground-fixed coordinates, the frequency splitting results in a crosspoint of the natural frequencies of the forward and backward traveling waves. The finite element method is applied to demonstrate the validity and accuracy of the model. Full article

As an efficient clean energy technology, water electrolysis for hydrogen production has its efficiency limited by the sluggish oxygen evolution reaction (OER) kinetics, which drives the demand for the development of high-performance anode OER catalysts. This work constructs bimetallic (Al, Mn) co-doped nanoporous spinel CoFe₂O₄ (np-CFO) with a tunable structure and composition as an OER catalyst through a simple two-step dealloying strategy. The as-formed np-CFO (Al and Mn) features a hierarchical flaky configuration; that is, there are a large number of fine nanosheets attached to the surface of a regular micron-sized flake, which not only increases the number of active sites but also enhances mass transport efficiency. Consequently, the optimized catalyst exhibits a low OER overpotential of only 320 mV at a current density of 10 mA cm⁻², a minimal Tafel slope of 45.09 mV dec⁻¹, and exceptional durability. Even under industrial conditions (6 M KOH, 60 °C), it only needs 1.83 V to achieve a current density of 500 mA cm⁻² and can maintain good stability for approximately 100 h at this high current density. Theoretical simulations indicate that Al and Mn co-doping could indeed optimize the electronic structure of CFO and thus decrease the energy barrier of OER to 1.35 eV. This work offers a practical approach towards synthesizing efficient and stable OER catalysts. Full article

The strategic construction of heterojunctions through a simple and efficient strategy is one of the most effective means to boost the photocatalytic activity of semiconductor materials. Herein, a thiazole-linked covalent organic framework (TZ-COF) with large surface area, well-ordered pore structure, and high stability was developed. To further boost photocatalytic activity, the TZ-COF was synthesized in situ on the surface of Cu₂O through a simple multicomponent reaction, yielding an encapsulated composite material (Cu₂O@TZ-COF-18). In this composite, the outermost COF endows the material with abundant redox active sites and mass transfer channels, while the innermost Cu₂O exhibits unique photoelectric properties. Notably, the synthesized Cu₂O@TZ-COF-18 was proven to have the heterojunction structure, which can efficiently restrain the recombination of photogenerated electron–hole pairs, thereby enhancing the photocatalytic performance. The photocatalytic degradation of tetracycline demonstrated that 3-Cu₂O@TZ-COF-18 had the highest photocatalytic efficiency, with the removal rate of 96.3% within 70 min under visible light, which is better than that of pristine TZ-COF-18, Cu₂O, the physical mixture of Cu₂O and TZ-COF-18, and numerous reported COF-based composite materials. 3-Cu₂O@TZ-COF-18 retained its original crystallinity and removal efficiency after five cycles in photodegradation reaction, displaying high stability and excellent cycle performance. Full article

Biocatalysis is one of the oldest fields that has been used in industrial applications, with one of the earliest purposeful examples being the mass production of acetic acid from an immobilized Acinetobacter strain in the year 1815. Efficiency, specificity, reduced reaction times, lower overall costs, and environmental friendliness are some advantages biocatalysis has over conventional chemical synthesis, which has made biocatalysis increasingly used in industry. We highlight three necessary fields that are fundamental to advancing industrial biocatalysis, including biocatalyst engineering, solvent engineering, and mechanistic engineering. However, the fundamental mechanism of enzyme function is often overlooked or given less attention, which can limit the engineering process. In this review, we describe how mechanistic enzymology benefits industrial biocatalysis by elucidating key fundamental principles, including the k_cat and k_cat/K_m parameters. Mechanistic enzymology presents a unique field that provides in-depth insights into the molecular mechanisms of enzyme activity and includes areas such as reaction kinetics, catalytic mechanisms, structural analysis, substrate specificity, and protein dynamics. In line with the objective of protein engineering to optimize enzyme activity, we summarize a range of strategies reported in the literature aimed at improving the product release rate, the chemical step of catalysis, and the overall catalytic efficiency of enzymes. Further into this review, we delineate kinetic solvent viscosity effects (KSVEs) as a very efficient, cost-effective, and easy-to-perform method to probe different aspects of enzyme reaction mechanisms, including diffusion-dependent kinetic steps and rate-limiting steps. KSVEs are cost-effective because simple kinetic enzyme assays, such as the Michaelis–Menten kinetic approach, can be combined with them without the need for specialized and costly equipment. Other techniques in protein engineering and genetic engineering are also covered in this review. Additionally, we provide information on solvent systems in enzymatic reactions, details on immobilized biocatalysts, and common misconceptions that misguide enzyme design and optimization processes. Full article

Functional foods like flax (Linum usitatissimum L.) are rich sources of specialized metabolites that contribute to their nutritional and health-promoting properties. Understanding the biosynthesis of these compounds is essential for improving their quality and potential applications. However, dissecting complex metabolic networks in plants remains challenging due to the dynamic nature and interconnectedness of biosynthetic pathways. In this study, we present a synergistic approach combining stable isotopic labeling (SIL), Candidate Substrate–Product Pair (CSPP) networks, and a time-course study with high temporal resolution to reveal the biosynthetic fluxes shaping phenylpropanoid metabolism in young flax seedlings. By feeding the seedlings with ¹³C₃-p-coumaric acid and isolating isotopically labeled metabolization products prior to the construction of CSPP networks, the biochemical validity of the connections in the network was supported by SIL, independent of spectral similarity or abundance correlation. This method, in combination with multistage mass spectrometry (MSⁿ), allowed confident structural proposals of lignans, neolignans, and hydroxycinnamic acid conjugates, including the presence of newly identified chicoric acid and related tartaric acid esters in flax. High-resolution time-course analyses revealed successive waves of metabolite formation, providing insights into distinct biosynthetic fluxes toward lignans and early lignification intermediates. No evidence was found here for the involvement of chlorogenic or caftaric acid intermediates in chicoric acid biosynthesis in flax, as has been described in other species. Instead, our findings suggest that in flax seedlings, chicoric acid is synthesized through successive hydroxylation steps of p-coumaroyl tartaric acid esters. This work demonstrates the power of combining SIL and CSPP strategies to uncover novel metabolic routes and highlights the nutritional potential of flax sprouts rich in chicoric acid. Full article

The rabies virus (RABV) phosphoprotein (P protein) has multiple functions, including acting as the essential non-catalytic cofactor of the viral polymerase (L protein) for genome replication and transcription; the principal viral antagonist of the interferon (IFN)-mediated innate immune response; and the chaperone for the viral nucleoprotein (N protein). Although P protein is known to undergo phosphorylation by cellular kinases, the location and functions of the phosphorylation sites remains poorly defined. Here, we report the identification by mass-spectrometry (MS) of residues of P protein that are modified by phosphorylation in mammalian cells, including several novel sites. Analysis of P protein with phospho-mimetic and phospho-inhibitory mutations of three novel residues/clusters that were commonly identified by MS (Ser48, Ser183/187, Ser217/219/220) indicate that phosphorylation at each of these sites does not have a major influence on nuclear trafficking or antagonistic functions toward IFN signalling pathways. However, phosphorylation of Ser48 in the N-terminus of P protein impaired function in transcription/replication and in the formation of replication structures that contain complexes of P and N proteins, suggestive of altered interactions of these proteins. The crystal structure of P protein containing the S48E phospho-mimetic mutation indicates that Ser48 phosphorylation facilitates the binding of residues 41–52 of P protein into the RNA-binding groove of non-RNA-bound N protein (N⁰), primarily through the formation of a salt bridge with Arg434 of N protein. These data indicate that Ser48 modification regulates the cycling of P-N⁰ chaperone complexes that deliver N protein to RNA to enable transcription/replication, such that enhanced interaction due to S48E phospho-mimetic mutation reduces N protein delivery to the RNA, inhibiting subsequent transcription/replication processes. These data are, to our knowledge, the first to implicate phosphorylation of RABV P protein in conserved replication functions of the P gene. Full article

Background: Previous research has demonstrated that 20 kHz probe or 37 kHz bath sonication of poloxamers comprising polypropylene glycol (PPG) and polyethylene glycol (PEG) blocks can generate degradation byproducts that are toxic to mammalian cells and organisms. Herein, an investigation of a PEGylated phospholipid micelle was undertaken to identify low-molecular-weight sonolytic degradation byproducts that could be cytotoxic. The concern here lies with the fact that sonication is a frequently employed step in drug delivery manufacturing processes, during which PEGylated phospholipids can be subjected to shear forces and other extreme oxidative and thermal conditions. Methods: Control and 20 kHz-sonicated micelles of DSPE-mPEG2000 were analyzed using dynamic light scattering (DLS) and zeta potential analyses to study colloidal properties, matrix-assisted laser desorption/ionization–time of flight (MALDI-TOF) mass spectroscopy (MS) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy to study the structural integrity of DSPE-mPEG2000, and ¹H-NMR spectroscopy and high-performance liquid chromatography (HPLC) with ultraviolet (UV) detection to quantitate the formation of low-molecular-weight degradation byproducts. Results: MALDI-TOF-MS analyses of 20 kHz-sonicated DSPE-mPEG2000 revealed the loss of ethylene glycol moieties in accordance with depolymerization of the PEG chain; ¹H-NMR spectroscopy showed the presence of formate, a known oxidative/thermal degradation product of PEG; and HPLC-UV showed that the generation of formate was dependent on 20 kHz probe sonication time between 5 and 60 min. Conclusions: It was found that 20 kHz sonication can degrade the PEG chain of DSPE-mPEG2000, altering the micelle’s PEG corona and generating formate, a known ocular toxicant. Full article