Search Results (2,501)

The increasing integration of large language models (LLMs) into software engineering workflows under the term vibe-coding necessitates systematic empirical evaluation of their code generation capabilities, especially in the context of complex backend development and architectural decision-making. This study compares popular foundational models Google Gemini 3 Pro and DeepSeek-V3.1 for developing a Java/Spring Boot backend application using a structured prompt-chaining protocol following a typical vibe-coding process. The generated solutions were evaluated using several quantitative and qualitative criteria, including the number of corrective prompts, the extent of required manual code interventions, functional correctness, architectural robustness, maintainability-related design choices, latency, and test quality. The results show substantial differences between the two models. DeepSeek required twice as many corrective natural language prompts as Gemini, but both models required a similar number of manual interventions in the generated code, with 23 for DeepSeek and 20 for Gemini. The most pronounced difference was in architectural reasoning. Gemini autonomously introduced the Data Transfer Object design pattern, resulting in a decoupled architecture, although at a cost of a minor performance issue. In contrast, DeepSeek was better in development of boilerplate code but exposed raw JPA entities through the application interface leading to tight coupling and other issues. Gemini’s solution satisfied 90.25% of evaluated requirements compared to 68.08% for DeepSeek. Additionally, generated tests showed a higher success rate and broader code coverage, achieving 95.7% successful test execution and 55.9% code coverage for Gemini, compared to 74.1% and 45.6% for DeepSeek, respectively. The results indicate that within the paradigm of vibe-coding, even the best available foundational LLMs may still require expert human supervision, especially when the generated code is expected to satisfy specific requirements in production-oriented backend systems. Full article

Metabolic and cardiometabolic diseases are closely associated with mitochondrial dysfunction and redox imbalance. Ubiquinol–cytochrome c reductase core protein 2 (UQCRC2), a non-catalytic structural core subunit of mitochondrial respiratory chain Complex III, is increasingly recognized as a regulator of Complex III integrity, electron transfer, oxidative phosphorylation, and mitochondrial redox homeostasis. Under metabolic stress, reduced expression or functional impairment of UQCRC2 may promote electron leakage, mitochondrial reactive oxygen species (mtROS) generation, lipid peroxidation, impaired antioxidant defense, and disrupted glucose–lipid metabolism. These alterations may contribute to insulin resistance (IR), metabolic dysfunction-associated steatotic liver disease (MASLD), obesity, and cardiovascular disease (CVD). This review summarizes current evidence linking UQCRC2 dysfunction to mitochondrial bioenergetic failure, oxidative stress, inflammatory signaling, and cardiometabolic injury. We further discuss redox-regulatory pathways, including Nrf2, AMPK–SIRT1–PGC-1α, glutathione metabolism, and mitophagy, as well as pharmacological agents and natural compounds that may modulate UQCRC2-related mitochondrial responses. Collectively, these findings highlight UQCRC2 as a redox-sensitive mitochondrial node linking Complex III dysfunction to cardiometabolic injury and targeted redox-based interventions. Full article

The transfer-matrix method is employed to investigate a spin-1/2 Ising chain under open and periodic boundary conditions. It is demonstrated that finite-size Ising chains with antiferromagnetic coupling may exhibit significantly distinct magnetic behavior under open and periodic boundary conditions. While the open Ising chains display intriguing magnetic features regardless of the system size, mainly due to a specific contribution of boundary spins, the magnetic behavior of closed Ising chains depends basically on the number of spins. The closed Ising chains with an odd number of spins are subject to a geometric spin frustration leading to an additional plateau in the magnetization curve, which is naturally absent in the closed Ising chains with an even number of spins. Despite different microscopic origins, the magnetization curves of open and closed Ising chains with an odd number of spins exhibit an identical intermediate plateau, with only small quantitative differences appearing at moderate temperatures, which means that a geometric spin frustration of odd-membered rings is somewhat similar to the effect of open boundaries. The magnetization curves of the open Ising chains with an even number of spins differ drastically from those of the closed Ising chains due to the presence of an additional intermediate magnetization plateau. Furthermore, the initial susceptibility, inverse initial susceptibility, and susceptibility–temperature product are examined in detail as functions of temperature. These magnetic response functions demonstrate that the Curie constant and Weiss temperature represent fundamental characteristics of the magnetic system that are independent of the choice of boundary conditions. Full article

Grain moisture content is a key variable for safe storage, drying control, and quality management. Microwave sensing is attractive because water strongly modulates the complex relative permittivity (ε* = ε′ – jε″) of granular agricultural products, thereby shaping broadband scattering-parameter spectra. This study presents a meter-referenced feasibility evaluation of an interpretable S-parameter–permittivity–moisture chain using a vector network analyzer over 2–18 GHz. Wheat, maize, and mung bean were prepared at six moisture levels, and the moisture values were referenced to two commercial grain moisture meters (MC_ref) to represent rapid on-site benchmarking rather than absolute gravimetric moisture determination. Therefore, the reported errors should be interpreted as commercial-meter-referenced calibration indicators rather than absolute gravimetric moisture prediction accuracy. Two free-space configurations were compared on the same platform: a two-horn transmission setup under controlled packing and a metal-backed double-pass reflection setup intended to represent single-sided access under loose bulk packing. After SOLT calibration and empty-holder background normalization, ε′ and ε″ were retrieved via complex-domain nonlinear least-squares fitting of physics-based slab models to measured S21 spectra. The results show that moisture-dependent dielectric responses were grain- and configuration-dependent. In particular, ε″ generally provided a more robust moisture-sensitive feature in the free-space transmission configuration, whereas the optimal single-parameter predictor in the metal-backed configuration differed among grains. A mid-band frequency window of approximately 8–16 GHz provided more stable inversion by avoiding low-frequency coupling artefacts and high-frequency signal-to-noise degradation. The metal-backed configuration preserved moisture trends but yielded lower effective ε′ values, likely due to increased air fraction under loose packing. These results indicate that packing state, grain type, and frequency-window selection are critical factors for transferring microwave moisture calibration from laboratory measurements to practical grain-handling scenarios. Full article

Exhaust emission assessment of heavy-duty diesel engines is commonly based on complementary steady-state and transient procedures, represented by the World Harmonized Steady-State Cycle (WHSC) and the World Harmonized Transient Cycle (WHTC). However, under transient operation, tailpipe NO_x and CO₂ signals cannot be directly assigned to instantaneous engine operating states because the measured response is affected by transport delay, analyser dynamics, and signal dispersion within the measurement chain. This paper proposes a machine-learning-assisted dynamic synchronization framework for aligning engine operating signals with tailpipe emissions under transient conditions. The method uses actual engine torque as the primary dynamic reference and determines local effective alignment between emission readings and the engine operating states that generated them. The synchronized data are then evaluated using an XGBoost-based modelling approach to assess whether emission characteristics obtained from WHSC steady-state operation can be transferred to WHTC transient operation. The results show that the proposed synchronization improves the physical consistency of transient emission data and provides a more reliable basis for comparing stationary and dynamic test outcomes. The transferability analysis indicates good predictive consistency for CO₂, whereas NO_x shows only partial transferability, reflecting stronger transient sensitivity and more complex formation dynamics. The proposed framework supports intelligent emission-data preprocessing, data-driven interpretation of heavy-duty engine tests, and assessment of the representativeness of steady-state tests under transient operating conditions. Full article

Photobiomodulation (PBM) is a non-invasive therapeutic strategy that uses red and near-infrared (NIR) light in the 590–950 nm range to modulate the cellular and molecular pathways involved in retinal homeostasis. At the molecular level, PBM acts primarily through photon absorption by cytochrome c oxidase (CcO, complex IV of the mitochondrial electron transport chain), whose four metal centres—two copper (CuA and CuB) and two heme groups (heme a and heme a₃)—absorb light across approximately 600–1000 nm. Photon capture promotes photodissociation of inhibitory nitric oxide (NO) from the binuclear CuB–heme a₃ centre, accelerates electron transfer, restores the proton-motive force and increases ATP synthesis. These primary events trigger a coordinated molecular programme that includes (i) transient mitochondrial reactive oxygen species (ROS) bursts that activate the Nrf2/Keap1/ARE axis and upregulate phase II antioxidant enzymes (HO-1, NQO1, GCLC, SOD2, catalase, GPx); (ii) calcium- and cAMP-dependent secondary signalling that converges on PI3K/Akt, MAPK/ERK, AMPK and mTOR pathways; (iii) suppression of NF-κB-driven cytokine production (TNF-α, IL-1β, IL-6) and of NLRP3 inflammasome activation; (iv) downregulation of the HIF-1α/VEGF axis, particularly at 590 nm; (v) anti-apoptotic remodelling of the Bcl-2/Bax ratio with reduced cytochrome c release and caspase-3/9 activation; and (vi) PGC-1α/TFAM/NRF1-driven mitochondrial biogenesis, alongside restoration of fission/fusion homeostasis (Drp1, Mfn1/2, Opa1) and PINK1/Parkin-mediated mitophagy. Wavelength specificity has a defined molecular basis: 590 nm modulates VEGF signalling and RPE pump activity, 660 nm interacts with the CuB centre and enhances O₂ binding at CcO, and 850 nm is absorbed by CuA and supports electron entry into complex IV. A second molecular axis is the bidirectional crosstalk between PBM and the circadian system: mitochondrial respiration, ATP turnover and CcO activity oscillate over the 24 h cycle under the control of the BMAL1/CLOCK and PER/CRY core machinery, the NAD⁺/SIRT1–SIRT3 axis and REV-ERBα. Preliminary preclinical and human observations suggest that NIR-induced bioenergetic and functional gains may be coupled to this rhythm, with greater benefit reported when light is delivered in the morning window (≈08:00–11:00); this time dependence should be regarded as an emerging hypothesis rather than an established clinical principle. The clinical evidence is unevenly developed across indications. It is most robust for non-exudative age-related macular degeneration, where multiwavelength PBM (590/660/850 nm; Valeda Light Delivery System) has shown disease-modifying potential in randomized controlled trials (LIGHTSITE I–III and the LIGHTSITE IIIB extension), with sustained BCVA gains and reduced incidence of geographic atrophy over 24 months and beyond. Evidence for retinitis pigmentosa, central serous chorioretinopathy and, with red-light monotherapy, childhood myopia is at present limited to small or short-term studies and remains preliminary. This narrative review synthesizes the molecular machinery engaged by PBM, integrates clinical findings across retinal diseases and discusses how chronotherapeutic delivery of light, aligned with the molecular clock, may further optimize therapeutic efficacy. Full article

The intensification and continuous evolution of dairy sheep and goat farming have played an essential role in the development and implementation of milking equipment. The increasing demand for time-efficient milking procedures, reduced labour costs, sustained milk production, and optimal mammary health have driven the widespread adoption and optimisation of machine milking technologies. The objectives of this article are (i) the review of milking systems and relevant technological developments in milking equipment and (ii) the evaluation and description of their impact on udder health, as applied on dairy small ruminant farms. Milking systems used on farms depend on the available space and number of animals on the farms. Appropriate settings in milking systems are important for ensuring good milk quality; among them, vacuum level, pulsation rate and ratio are important characteristics that must be monitored regularly. Further, use of appropriate teatcups specific to the animal species to be milked is significant. An important aspect of proper maintenance of the milking system is the cleaning procedure after completion of milking. Points for consideration are quality and temperature of the water used for cleaning, use of detergents and disinfectants, and maintenance schedule and teatcup replacement. Some technological features that are part of milking systems include automatic vacuum shut off, electronic milk recording, electronic identification of animals, automatic flushing of milking clusters and automatic pre-stimulators. Farms will benefit from applying precision technologies, which will use data from tools related to animal genetic background, animal behavioural indicators, environmental conditions and disease-related functions for more holistic and cost-effective farm management. In this context, integration of sensor-based technologies in milking systems will be able to provide real-time information regarding quality of milk produced at individual and farm levels. Moreover, the introduction of automatic system flushing in-between animals during the milking procedure can contribute to breaking chains of potential bacterial transfer and reducing animal infections during milking. Overall, although machine milking has certainly contributed to improved efficiency, milk quality and labour conditions, flaws in system function may adversely affect mammary health. Full article

In this work, we investigated the incorporation of a fluorescent side group, fluorescein octyl ester (FOE), in benzodithiophene-based donor–acceptor terpolymers as a strategy to modulate excited-state behavior. Three FOE-containing terpolymers (P2-iIa-c), obtained at different polymerization times, were systematically evaluated against an analogous material without the fluorescent pendant unit (P1-iI). Thermal analysis revealed good thermal stability and an increase in glass transition temperature upon FOE incorporation, suggesting restricted segmental mobility and increased conformational constraints within the conjugated backbone. Optical characterization showed distinct absorption spectra with reaction time and shorter fluorescence lifetimes for the FOE-containing materials, consistent with the presence of additional excited-state deactivation pathways and intramolecular energy transfer processes within the terpolymer backbone. An approximate estimation of energy transfer efficiencies (≈60–65%) suggested that such processes may be operative within the system. Cyclic voltammetry measurements showed only minor variations in HOMO and LUMO energy levels between P1-iI and P2-iIa-c series, indicating that the conjugated backbone predominantly determined the frontier orbital energies despite side chain modification. Furthermore, photocurrent measurements from the bilayer device configuration exhibited a systematic increase in photocurrent for the FOE-containing material, supporting the role of excitonic modulation, rather than significant changes in interfacial energetic alignment. These results suggest that fluorescent side chain incorporation provides an effective strategy for regulating exciton dynamics while maintaining the electronic structure of the donor–acceptor terpolymer. Full article

Hepatocellular carcinoma is challenging to detect at an early stage, and its severity increases over time. Recently, the incidence of hepatocellular carcinoma has increased, partly due to lifestyle-related factors such as excessive alcohol intake, sedentary behavior, and diets high in fat, which contribute to the growing prevalence of fatty liver and hepatitis. Various therapeutic strategies are being explored for hepatocellular carcinoma, among which therapies targeting deubiquitinating enzymes (DUBs) have attracted growing attention. Ubiquitination acts as a crucial modulator in the regulation of intracellular signaling across many diseases. E3 ligase recognizes the target protein and transfers ubiquitin, received from the E2 enzyme, to the lysine residues of the substrate, thereby conferring specificity to the ubiquitination process. Once a ubiquitin chain is attached to a target protein by an E3 ligase, the protein is directed to the ubiquitin–proteasome system (UPS) for degradation. In this process, the 26S proteasome complex recognizes the ubiquitin chain and degrades the target protein, thereby serving as a major mechanism for maintaining protein homeostasis. Through this pathway, cells regulate signal transduction, eliminate abnormal proteins, and perform various essential functions. On the other hand, deubiquitinating enzymes (DUBs) recognize the ubiquitin chains on target proteins and remove them by hydrolyzing the isopeptide bonds of ubiquitin, thereby enabling the target proteins to evade degradation by the proteasome system. Furthermore, deubiquitinating enzymes independently remove ubiquitin from proteins and can serve as central regulators in signaling pathways related to hepatocellular carcinoma. Full article

To understand glycan–protein interactions at biological interfaces, designing surfaces modified with structurally controlled glycans is highly important. In particular, naturally occurring glycosaminoglycans (GAGs) possess periodic sugar arrangements that play important roles in protein recognition, highlighting the need for the development of periodic glycopolymer model systems that can serve as GAG mimics for quantitative interaction analysis. In this study, sequence-controlled periodic glycopolymers were synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization and immobilized onto gold surfaces to construct glycan-modified interfaces. The synthesized material was a terminally functionalized periodic glycopolymer with the most basic structure, consisting of alternating maltose-containing vinyl ether (MalVE) units and ethyl maleimide (EtMI) units, with a trithiocarbonate group at the ω-terminal. This trithiocarbonate group was converted to a thiol group for immobilization through Au–S bond formation. Structural characterization by ¹H NMR spectroscopy, size exclusion chromatography (SEC), MALDI-TOF mass spectrometry, and UV–vis spectroscopy confirmed the structure as designed. Quartz crystal microbalance (QCM) measurements verified the stable immobilization of thiol-terminated periodic glycopolymers on the gold surface, and allowed for estimation of graft density and quantitative analysis of glycan-protein interactions at the modified interface. The periodic glycopolymer-modified surfaces exhibited selective binding behavior toward concanavalin A (ConA) compared to bovine serum albumin (BSA), with apparent binding constants on the order of 10⁶–10⁷ L mol⁻¹. This enhanced binding behavior indicated that specific and multivalent interactions with proteins also occurred at periodic pendant maltose residues along the main chain. These results demonstrate that the gold surface modified with end-functional periodic glycopolymers synthesized by RAFT polymerization provides a versatile platform for quantitative analysis of glycan-protein interactions and suggests potential applications for periodic glycopolymers as functional materials. Full article

Background: Atrial fibrillation (AF) is the most common sustained cardiac arrhythmia and is strongly associated with atrial structural remodeling driven by activated cardiac fibroblasts. Autophagy has been implicated in AF-related atrial remodeling; however, the non-coding RNA mechanisms that govern autophagic activation in atrial fibroblasts under rapid electrical stress remain poorly understood. Methods: Human cardiac fibroblasts from adult atria (HCF-aa) were subjected to rapid electrical stimulation (RES) at 0.5 V/cm and 10 Hz. Expression levels of exosomal metastasis-associated lung adenocarcinoma transcript 1 (MALAT1), cytoplasmic miR-204-5p, and microtubule-associated protein light chain 3B (LC3B) were measured using quantitative real-time PCR and Western blot analyses. Luciferase reporter assays were performed to confirm direct molecular interactions. The functional roles of MALAT1 siRNA, miR-204-5p mimics/antagomirs, rapamycin, and 3-methyladenine (3-MA) on LC3B expression and autophagic activation were assessed by Western blot and immunofluorescence confocal microscopy for LC3B puncta formation. Results: RES significantly induced exosomal MALAT1 expression in a voltage- and time-dependent manner, peaking at 2 h post-stimulation, while cytoplasmic MALAT1 levels remained unchanged. Cytoplasmic miR-204-5p exhibited an initial transient rise followed by a significant decline at 2 h, inversely correlating with peak MALAT1 levels. LC3B mRNA and protein expression subsequently increased, peaking at 6 and 16 h, respectively. Luciferase reporter assays confirmed that miR-204-5p directly binds both the MALAT1 transcript and the 3′-UTR of LC3B mRNA. MALAT1 knockdown augmented miR-204-5p levels and suppressed LC3B expression, while miR-204-5p overexpression attenuated RES-induced LC3B upregulation and LC3B puncta accumulation. Conversely, miR-204-5p inhibition further enhanced autophagic activation, as evidenced by increased LC3B puncta density. Conclusions: In HCF-aa subjected to RES, MALAT1 functions intracellularly as a competing endogenous RNA to putatively sequester miR-204-5p, thereby de-repressing LC3B expression and promoting autophagic activation. Concurrent exosomal secretion of MALAT1 may additionally serve as a paracrine signal to neighboring cells, though this requires future conditioned-media transfer experiments to confirm. Full article

Salmonella remains one of the most critical zoonotic pathogens in the poultry sector, linked to animal disease, foodborne illness, and the global crisis of antimicrobial resistance (AMR). Poultry acts as a major reservoir, enabling Salmonella transmission from hatchery to retail products through horizontal, vertical, and environmental routes. Despite the use of biosecurity, vaccination, antibiotics, and chemical decontamination, effective and sustainable control across the poultry value chain remains difficult, particularly in the face of rising multidrug-resistant strains and growing consumer concerns over chemical residues. Bacteriophages (phages), viruses that selectively infect and lyse bacteria, have emerged as a promising biological alternative for Salmonella control. Although many studies have reported the effectiveness of phages against bacterial species, including Salmonella, in the poultry industry, reports on their full potential to combat antimicrobial-resistant Salmonella across the entire poultry value chain remain limited. Therefore, this review synthesizes current evidence on the application of phages throughout the poultry value chain, including on-farm interventions, processing plant decontamination, and food packaging and storage. Findings from the reviewed articles indicate over a 90% reduction in Salmonella spp. in poultry farms and post-harvest meat, along with lower mortality in phage-treated groups compared to untreated groups; however, these outcomes depend on several factors (e.g., phage strains, concentrations, application methods, and environmental conditions). Laboratory, pilot, and field studies consistently demonstrate that phage preparations, especially when formulated as cocktails or combined with complementary interventions, can achieve substantial reductions in Salmonella, including antibiotic-resistant serovars, in live birds, eggs, poultry environments, and meat products. Unlike antibiotics and chemical sanitizers, phages act with high specificity, preserving beneficial microbiota and maintaining the sensory and nutritional quality of poultry products. Their safety has been supported by toxicological and genomic assessments, and several phage-based products have obtained regulatory approval, including Generally Recognized as Safe (GRAS) status for food applications in the United States. By integrating efficacy, safety, regulatory, and practical deployment data, this review highlights bacteriophages as a scientifically validated and One Health–aligned tool capable of reducing Salmonella transmission from farm to fork across the poultry value chain, thereby laying the foundation for their future adoption in the poultry industry. Phage-based interventions offer a sustainable pathway to enhance food safety, limit antimicrobial resistance (AMR) dissemination, and strengthen consumer confidence in poultry products. However, the major limitation is the emergence of phage-resistant bacterial strains, as well as the potential involvement of some phages in the transfer of resistance and virulence genes, which could raise public concern. Nevertheless, the use of phage cocktails and whole-genome sequencing, involving tools such as ResFinder and virulence finder, can facilitate the selection of safe phages for application. Full article

The transition to a circular economy requires the safe management of sewage sludge through nutrient and energy recovery. However, pharmaceuticals and personal care products (PPCPs) present a significant challenge. These compounds tend to accumulate in sludge via sorption, shifting the environmental burden from the aqueous phase to the sludge. This manuscript provides a comprehensive review of the scientific literature on technical alternatives for valorizing sewage sludge and removing emerging contaminants. The study evaluates the limitations of conventional biological methods, such as anaerobic digestion and composting, which exhibit variable efficacy and are often insufficient to degrade some commonly used pharmaceuticals. On the contrary, thermal treatments (pyrolysis, gasification, and hydrothermal processes) are considered robust alternatives capable of achieving the high removal of chemical compounds. Furthermore, the article emphasizes the innovative potential of utilizing carbon-based byproducts (biochar and hydrochar) as adsorbents, catalysts, or soil amendment to enhance the removal of PPCPs within the treatment infrastructure itself. The integration of advanced thermal technologies is essential to mitigate the risks of contaminant transfer to the food chain and ensure a safe and sustainable nutrient cycle. Full article

Despite advances in reactor-based process intensification, the influence of hydrodynamic conditions on PFAS removal remains poorly understood. In particular, rotating bed reactors (RBRs), which are designed to enhance mass transfer, have not been systematically evaluated for PFAS removal or compared with conventional batch and fixed-bed column systems. This lack of comparative understanding limits the ability to assess their practical relevance for PFAS remediation. In this study, PFAS removal was investigated under intensified hydrodynamic conditions using an RBR and compared with batch and small-scale column systems with special focus on short-chain PFAS compounds. The RBR significantly enhanced adsorption kinetics, with pseudo-first-order rate constants increasing by 3 to 16-fold across PFAS, particularly for short-chain PFAS. For instance, PFBA exhibited near-complete removal within 12 h in the RBR, whereas only ~50% removal was achieved in batch conditions. However, faster kinetics did not translate into superior long-term breakthrough performance compared to the column treatment system. After 50 treatment cycles using ion exchange resin, PFBA reached approximately 40% C/C₀ in the RBR, while the column system maintained C/C₀ below 5%; similar trends were observed for PFPeA (15% vs. ~0.5%) and PFHxA (6.2% vs. ~0.2%). These findings reveal a fundamental trade-off between kinetic intensification and long-term treatment performance. The results highlight distinct design roles, with RBR systems enabling rapid and intensified treatment (e.g., staged or parallel configurations), while conventional column systems perform better for continuous operation and compliance control in PFAS remediation. Full article

The pyrolysis of polypropylene (PP) microplastics offers a potential route to convert plastic waste into fuel-range hydrocarbon mixtures and chemical feedstocks. However, the elementary radical pathways underlying the formation of medium-chain hydrocarbon fragments remain insufficiently resolved. In this study, a representative isotactic PP oligomer model (C₄₅H₉₂) was evaluated using a comparative density functional theory (DFT) framework. The main mechanistic analysis was based on M06-2X, ωB97X-D, and M11 calculations combined with the def2-TZVP basis set, whereas LANL2DZ was retained only as a lower-cost comparative level during reaction-pathway exploration. Thermochemical profiles were evaluated over a temperature range of 298–923 K. Three selected pathways involving mid-chain homolytic cleavage, intramolecular hydrogen transfer (backbiting), radical rearrangement, and β-scission were examined. Within the selected reaction set, Route 1 exhibited a comparatively more favorable thermochemical profile than Routes 2 and 3 and provided a mechanistically plausible sequence toward medium-chain hydrocarbon fragments. The −TΔS contribution strongly influenced the calculated Gibbs free-energy profiles because fragmentation increases the number of molecular species under the ideal-gas thermochemical approximation. Accordingly, the ΔG values were interpreted comparatively and were not treated as direct evidence of spontaneous fragmentation under condensed-phase pyrolysis conditions or as quantitative predictions of experimental product selectivity. Differences among the evaluated functionals further indicate that the relative description of radical intermediates and transition-state regions is method-dependent. These results provide a molecular-level framework for future studies integrating quantum-chemical calculations, microkinetic modeling, and experimental product characterization. Full article