Search Results (7,193)

Divinylisoprene rubber, a copolymer of butadiene and isoprene, is used as raw material for rubber technical products, combining isoprene rubber’s elasticity and butadiene rubber’s wear resistance. These properties depend quantitatively on the copolymer composition, which depends on the kinetics of its synthesis. This work aims to theoretically describe how the monomer mixture composition in the butadiene–isoprene copolymerization affects the activity of the TiCl₄–Al(i-C₄H₉)₃ catalytic system (expressed by active sites concentration) via kinetic modeling. This enables development of a reliable kinetic model for divinylisoprene rubber synthesis, predicting reaction rate, molecular weight, and composition, applicable to reactor design and process intensification. Active sites concentrations were calculated from experimental copolymerization rates and known chain propagation constants for various monomer compositions. Kinetic equations for active sites formation were based on mass-action law and Langmuir monomolecular adsorption theory. An analytical equation relating active sites concentration to monomer composition was derived, analyzed, and optimized with experimental data. The results show that monomer composition’s influence on active sites concentration is well described by a two-step kinetic model (physical adsorption followed by Ti–C bond formation), accounting for competitive adsorption: isoprene adsorbs more readily, while butadiene forms more stable active sites. Full article

Redwood (Sequoia sempervirens (Lamb. ex D. Don) Endl.) is a fast-growing, long-lived conifer native to a narrow coastal zone along the western seaboard of the United States. Redwood can accumulate very high amounts of carbon in plantation settings and continuous cover forestry (CCF) represents a highly profitable option, particularly for small-scale forest growers in the North Island of New Zealand. We evaluated the profitability of conceptual CCF regimes using two case study forests: Blue Mountain (109 ha, Taranaki Region, New Zealand) and Spring Creek (467 ha, Manawatu-Whanganui Region, New Zealand). We ran a strategic harvest scheduling model for both properties and used its results to guide a tactical-spatially explicit model harvesting small 0.7 ha units over a period that spanned 35 to 95 years after planting. The internal rates of return (IRRs) were 9.16 and 10.40% for Blue Mountain and Spring Creek, respectively, exceeding those considered robust for other forest species in New Zealand. The study showed that small owners could benefit from carbon revenue during the first 35 years after planting and then switch to a steady annual income from timber, maintaining a relatively constant carbon stock under a continuous cover forestry regime. Implementing adjacency constraints with a minimum green-up period of five years proved feasible. Although small coupes posed operational problems, which were linked to roading and harvesting, these issues were not insurmountable and could be managed with appropriate operational planning. Full article

Background: A precise drug delivery system enables the optimization of treatments with minimal side effects if it can deliver medication only when activated by a specific light source. This study presents a controlled drug delivery system based on poly(lactic-co-glycolic acid) (PLGA) microparticles (MPs) designed for the sustained release of vancomycin hydrochloride. Methods: The MPs were co-loaded with indocyanine green (ICG), a near-infrared (NIR) responsive agent, and fabricated via the double emulsion method.They were characterized for stability, surface modification, biocompatibility, and antibacterial efficacy. Results: Dynamic light scattering and zeta potential analyses confirmed significant increases in particle size and surface charge reversal following chitosan coating. Scanning electron microscopy revealed uniform morphology in uncoated MPs (1–10 $\mathsf{\mu }$m) and irregular surfaces post-coating. Stability tests demonstrated drug retention for up to 180 days. Among formulations, PVI1 exhibited the highest yield (76.67 ± 1.3%) and encapsulation efficiency (56.2 ± 1.95%). NIR irradiation (808 nm) enhanced drug release kinetics, with formulation PVI4 achieving over 48.9% release, resulting in improved antibacterial activity. Chitosan-coated MPs (e.g., PVI4-C) effectively suppressed drug release without NIR light for up to 8 h, with cumulative release reaching only 10.89%. Without NIR light, bacterial colonies exceeded 1000 CFU; NIR-triggered release reduced them below 120 CFU. Drug release data fitted best with the zero-order and Korsmeyer–Peppas models, suggesting a combination of diffusion-controlled and constant-rate release behavior. Conclusions: These results demonstrate the promise of chitosan-coated NIR-responsive PLGA MPs for precise, on-demand antibiotic delivery and improved antibacterial performance. Full article

Carbon monoxide (CO) is a major toxic gas emitted from vehicle exhaust, industrial processes, and incomplete fuel combustion, posing serious environmental and health risks. Catalytic oxidation of CO into less harmful CO₂ is an effective strategy to reduce these emissions. In this study, we investigated the catalytic performance of platinum (Pt) single atoms doped on C₃N monolayers with various vacancy defects, including single carbon (C_V) and nitrogen (N_V) vacancies, using density functional theory (DFT) calculations. Our results demonstrate that Pt@N_V-C₃N exhibited the most favorable catalytic properties, with the highest O₂ adsorption energy (−3.07 eV). This performance significantly outperforms Pt atoms doped at other vacancies. It can be attributed to the strong binding between Pt and nitrogen vacancies, which contributes to its excellent resistance to Pt aggregation. CO oxidation on Pt@N_V-C₃N proceeds via the Eley–Rideal (ER2) mechanism with a low activation barrier of 0.41 eV for the rate-determining step, indicating high catalytic efficiency at low temperatures. These findings suggest that Pt@N_V-C₃N is a promising candidate for CO oxidation, contributing to developing cost-effective and environmentally sustainable catalysts. The strong binding of Pt atoms to the nitrogen vacancies prevents aggregation, ensuring the stability and durability of the catalyst. The kinetic modeling further revealed that the ER2 mechanism offers the highest reaction rate constants over a wide temperature range (273–700 K). The low activation energy barrier also facilitates CO oxidation at lower temperatures, addressing critical challenges in automotive and industrial pollution control. This study provides valuable theoretical insights for designing advanced single-atom catalysts for environmental remediation applications. Full article

Dry Turkish oak (Quercus cerris) sawdust, untreated and treated with three activators, (H₃PO₄, NaOH and H₂O₂) was pyrolyzed under limited-oxygen conditions to obtain biochar samples. The electrochemical properties of these samples were tested and compared to the properties of several commercial carbon blacks. The electrochemical characterization was performed via cyclic voltammetry, analyzing the response toward two commonly used redox probes, [Fe(CN)₆]^3−/−4− and [Ru(NH₃)₆]^2+/3+. The influence of the scan rate on this response was investigated, and the resulting data were used to obtain the values of the heterogenous charge transfer constant, k₀. Higher k₀ values were observed for carbon blacks than for investigated biochar samples. The detection of 4-nitrophenol and heavy metal ions was used to assess the applicability of biochars for electroanalytical purposes. The response of untreated biochar was comparable with the response of Vulcan carbon black, which showed the best response of all analyzed carbon blacks. Full article

This study presents a simulation-based damage modeling and fatigue risk assessment of a reusable ceramic matrix composite thruster designed for short-duration, green bipropellant propulsion systems. The thruster is constructed from a fiber-reinforced ultra-high temperature ceramic matrix composite composed of zirconium diboride, silicon carbide, and carbon fibers. Time-resolved thermal and structural simulations are conducted on a validated thruster geometry to characterize the severity of early-stage thermal shock, stress buildup, and potential degradation pathways. Unlike traditional fatigue studies that rely on empirical fatigue constants or Paris-law-based crack-growth models, this work introduces a simulation-derived stress-margin envelope methodology that incorporates ±20% variability in temperature-dependent material strength, offering a physically grounded yet conservative risk estimate. From this, a normalized risk index is derived to evaluate the likelihood of damage initiation in critical regions over the 0–10 s firing window. The results indicate that the convergent throat region experiences a peak thermal gradient rate of approximately 380 K/s, with the normalized thermal shock index exceeding 43. Stress margins in this region collapse by 2.3 s, while margin loss in the flange curvature appears near 8 s. These findings are mapped into green, yellow, and red risk bands to classify operational safety zones. All the results assume no active cooling, representing conservative operating limits. If regenerative or ablative cooling is implemented, these margins would improve significantly. The framework established here enables a transparent, reproducible methodology for evaluating lifetime safety in ceramic propulsion nozzles and serves as a foundational tool for fatigue-resilient component design in green space engines. Full article

Diagnosing digital flexor tendon sheath (DFTS) pathologies, particularly manica flexoria (MF) tears, can be challenging with standard imaging modalities. Standing low-field MRI tenography (MRIt) may improve the detection rate of MF tears. This study aimed to compare ultrasonography, contrast radiography, pre-contrast MRI, and MRIt to detect naturally occurring MF lesions in horses undergoing tenoscopy. Ten horses with a positive DFTS block, which underwent contrast radiography, ultrasonography, MRI, MRIt, and tenoscopy were included. Two radiologists evaluated the images and recorded whether an MF lesion was present and determined the lesion side. Sensitivity and specificity were calculated for each modality using tenoscopy as a reference. MRIt and contrast radiography detected MF lesions with the same frequency, both showing 71% sensitivity and 100% specificity. Pre-contrast MRI and ultrasonography detected MF lesions with a lower sensitivity (57%); however, the MRI (100%) demonstrated a higher specificity than ultrasonography (33%). Adding contrast in MRI changed the sensitivity from (4/7 lesions) 57% to (5/7 lesions) 71%, with a constant high specificity (100%). MRIt diagnoses MF tears with a similar sensitivity to contrast radiography, with the same specificity, but with the added benefit of lesion laterality detection. The combined advantages of the anatomical detail of the T1 sequence and the post-contrast hyperintense appearance of the fluid may help diagnose MF tears and identify intact MFs. However, this needs to be substantiated in a larger number of cases. Full article

This paper presents a method for optimizing the inertia constants and damping coefficients of interconnected virtual synchronous generators (VSGs) using a genetic algorithm. The goal of optimization is to find a balance between minimizing the rate of change of frequency (RoCoF) and enhancing controllability. Five controllability-based metrics are tested: the minimum eigenvalue, the sum of the two smallest eigenvalues, the maximum eigenvalue, the trace, and the determinant of the controllability Gramian matrix. The approach includes the oscillatory modes’ damping ratio constraints to ensure the small-signal stability of the entire system. The results of optimization on the IEEE 9-bus system with three VSGs show that the proposed method improves controllability, reduces RoCoF, and maintains the desired oscillation damping. The proposed approach was tested through time-domain simulations. Full article

Detection of small vessels is of great significance for maritime safety assurance, abnormal vessel tracking, illegal fishing supervision, and combating smuggling. However, the radar reflection intensity of small vessels is low, making them difficult to detected with the radar’s constant false-alarm rate (CFAR) algorithm. To enhance the detection capability for small vessels, we propose an improved CFAR scheme. Specifically, we first compared traditional CFAR processing results of radar data with automatic identification system (AIS) data to identify some special targets. These special targets, which possessed AIS information, but remained undetected by radar, enabled an iTransformer model to generate more reasonable CFAR threshold adjustments. iTransformer adaptively lowered the threshold of the areas around these targets until they were detected by radar. This process made it easier to discover the small boats in the surrounding area. Experimental results showed that our method reduces the missed detection rate of small vessels by 73.4% and the false-alarm rate by 60.7% in simulated scenarios, significantly enhancing the CFAR detection capability. Overall, our study provides a new solution for ensuring maritime navigation safety and strengthening illegal supervision, while also offering new technical references for the field of radar detection. Full article

The reliability of passive samplers in measuring volatile organic compounds (VOCs) in indoor air depends on whether the uptake rate is constant given the environmental conditions and sampler exposure duration. The first phase of this study evaluated the performance of charcoal-based, solvent-extracted passive samplers (e.g., Radiello^® 130 passive samplers with white diffusive bodies) over exposure periods ranging from 1 week to 1 year in a test house with known vapor intrusion (VI). Chloroform %Bias values exceeded the ±30% acceptance criterion after 4 weeks exposure. Benzene, hexane, and trichloroethylene (TCE) concentrations were within the acceptance criterion for up to three months. Toluene and tetrachloroethylene (PCE), the two least volatile compounds, demonstrated uniform uptake rates over one year. In the second phase of this study, testing of the longer exposure times of 6 months and 1 year were evaluated with three additional passive samplers: Waterloo Membrane Sampler^TM (WMS^TM), SKC 575 with secondary diffusive cover, and Radiello^® 130 passive samplers with yellow diffusive bodies. The SKC 575 and Radiello^® 130 passive samplers produced acceptable results (%Bias ≤ 30%) over the 6-month exposure period, while the WMS^TM sampler results favored petroleum hydrocarbon more than chlorinated solvent uptake. After the 1-year exposure period, the passive sampler performances were acceptable under specific conditions of this study. The results suggest that all three samplers can produce acceptable results over exposure time periods beyond 30 days and up to a year for some compounds. Full article

This study analyzes the thermal degradation of PVA and PVA/glycerol films in air under varying heating rates. Thermogravimetric analysis (TGA) of pure PVA in both air and inert atmospheres confirmed that oxidative conditions significantly influence degradation, particularly at lower heating rates. For PVA/glycerol films in air, deconvolution of the differential thermogravimetry (DTG) curves during the main degradation stage revealed distinct peaks attributable to the degradation of glycerol, PVA/glycerol complexes, and PVA itself. Isoconversional methods showed that, for pure PVA in air, the apparent activation energy (Ea) increased with conversion, suggesting the simultaneous occurrence of multiple degradation mechanisms, including oxidative reactions, whose contribution changes over the course of the degradation process. In contrast, under an inert atmosphere, Ea remained nearly constant, consistent with degradation proceeding through a single dominant mechanism, or through multiple steps with similar kinetic parameters. For glycerol-plasticized films in air, Ea exhibited reduced dependence on conversion compared with that of pure PVA in air, with values similar to those of pure PVA under inert conditions. These results indicate that glycerol influences the oxidative degradation pathways in PVA films. These findings are relevant to high-temperature processing of PVA-based materials and to the design of thermal treatments—such as sterilization or pyrolysis—where control over degradation mechanisms is essential. Full article

Background/Objectives: Rotator cuff calcific tendinopathy (RCCT) is one of the most common causes of non-traumatic shoulder pain. To date, there is still no consensus regarding the most effective method for its treatment. Ultrasound-guided percutaneous aspiration is suggested during the reabsorption phase of calcific metaplasia. We aimed to evaluate the effectiveness of ultrasound-guided lavage for RCCT from a clinical and radiological perspective. Methods: We involved patients affected by RCCT of the supraspinatus tendon. The approach used for the calcification lavage was the one-needle technique, consisting in inserting a 16–18 G needle on a 20 mL syringe with 0.9% saline solution, in the calcific metaplasia, under ultrasound guidance, using an in-plane approach; the repetitive action of pressing and releasing the plunger was repeated until the contents of the syringe became milky, at which point the syringe was replaced with a new one, always containing saline solution. The physiotherapy treatment began 7 days after the procedure. We assessed the Numeric Rating Scale, the Gartner classification, the Disability of the Arm, Shoulder and Hand scale, the Constant–Murley shoulder score, and the passive range of motion of flexion and abduction. Results: We included 23 subjects. The analysis of the data at baseline and t1 showed a statistically significant improvement in all the functional variables (p < 0.05). This result was mainly evident for pain, with a p-value of 0.001. Conclusions: The findings of the present prospective case series study showed an improvement in the clinical and radiological outcomes after ultrasound-guided percutaneous aspiration for rotator cuff calcific tendinopathy. Full article

In Gram-negative bacteria, lipopolysaccharides (LPSs, also known as endotoxin) can induce extensive immune responses that will enable victims to produce severe septic shock syndrome. Because of the high mortality of sepsis in the face of standard treatment, advance detoxification schemes are urgently needed in clinics. Herein, we described a supramolecular detoxification approach via direct host–guest complexation by a giant macrocycle. Cationic pentaphen[3]arene (CPP3) bearing multiple quaternary ammonium groups was screened as a candidate antidote. CPP3 exhibited robust binding affinity toward LPS with an association constant of (4.79 ± 0.29) × 10⁸ M⁻¹. Co-dosing with an equivalent amount of CPP3 has been demonstrated to decrease LPS-induced cytotoxicity on a cellular level through inhibiting ROS generation and proinflammatory cytokine expression. In vivo experiments have further proved that post-treatment by CPP3 could significantly improve the survival rate of LPS-poisoned mice from 0 to 100% over a period of 3 days, and inflammatory abnormalities and tissue damage were also alleviated. Full article

Accurate peak detection in the frequency domain is fundamental to reliable range estimation in Frequency-Modulated Continuous-Wave (FMCW) radar systems, particularly in challenging conditions characterized by a low signal-to-noise ratio (SNR) and phase noise impairments. This paper presents a comprehensive comparative analysis of five peak detection algorithms: FFT thresholding, Cell-Averaging Constant False Alarm Rate (CA-CFAR), a simplified Matrix Pencil Method (MPM), SVD-based detection, and a novel Learned Thresholded Subspace Projection (LTSP) approach. The proposed LTSP method leverages singular value decomposition (SVD) to extract the dominant signal subspace, followed by signal reconstruction and spectral peak analysis, enabling robust detection in noisy and spectrally distorted environments. Each technique was analytically modeled and extensively evaluated through Monte Carlo simulations across a wide range of SNRs and oscillator phase noise levels, from $-100$ dBc/Hz to $-70$ dBc/Hz. Additionally, real-world validation was performed using a custom-built harmonic FMCW radar prototype operating in the 2.4–2.5 GHz transmission band and 4.8–5.0 GHz harmonic reception band. Results show that CA-CFAR offers the highest resilience to phase noise, while the proposed LTSP method delivers competitive detection performance with improved robustness over conventional FFT and MPM techniques. Furthermore, the hardware feasibility of each algorithm is assessed for implementation on a Xilinx FPGA platform, highlighting practical trade-offs between detection performance, computational complexity, and resource utilization. These findings provide valuable guidance for the design of real-time, embedded FMCW radar systems operating under adverse conditions. Full article

Rowing is a cyclic sport that consists of repetitive biomechanical actions, with performance being influenced by the balance between propulsive and resistive forces. The current study aimed to assess the relationships between intracycle velocity variation (IVV) and key biomechanical and performance variables in male and female single scullers. Twenty-three experienced rowers (10 females) completed a 2000 m rowing competition, during which boat position and velocity were measured using a 15 Hz GPS, while cycle rate was derived from the integrated triaxial accelerometer sampling at 100 Hz. From these data, it was possible to calculate distance per cycle, IVV, the coefficient of velocity variation (CVV), and technical index values. Males presented higher mean, maximum and minimum velocity, distance per cycle, CVV, and technical index values than females (15.40 ± 0.81 vs. 13.36 ± 0.88 km/h, d = 0.84; 21.39 ± 1.68 vs. 18.77 ± 1.52 km/h, d = 1.61; 11.15 ± 1.81 vs. 9.03 ± 0.85 km/h, d = 1.45; 7.68 ± 0.32 vs. 6.89 ± 0.97 m, d = 0.69; 14.13 ± 2.02 vs. 11.64 ± 1.93%, d = 2.06; and 34.25 ± 4.82 vs. 26.30 ± 4.23 (m²/s·cycle), d = 4.56, respectively). An association between mean velocity and intracycle IVV, CVV, and cycle rate (r = 0.68, 0.74 and 0.65, respectively) was observed in males but not in female single scullers (which may be attributed to anthropometric specificities). In female single scullers, mean velocity was related with distance per cycle and was associated with technical index in both males and females (r = 0.76 and 0.66, respectively). Despite these differences, male and female single scullers adopted similar pacing strategies and CVV remained constant throughout the 2000 m race (indicating that this variable might not be affected by fatigue). Differences were also observed in the velocity–time profile, with men reaching peak velocity first and having a faster propulsive phase. Data provided new information on how IVV and CVV relate to commonly used biomechanical variables in rowing. Technical index (r = 0.87): distance per cycle was associated with technical index in both males and females (r = 0.76 and 0.66, respectively). Future studies should include other boat classes and other performance variables such as the power output and arc length. Full article