Search Results (126)

Our Goal is to identify how colorectal cancer (CRC) arises in the single-layered cell epithelium (simple columnar epithelium) that lines the luminal surface of the large intestine. Background: We recently reported that the dynamic organization of cells in colonic epithelium is encoded by five biological rules and conjectured that colon tumorigenesis involves an autocatalytic tissue renewal reaction. Introduction Our objective was to define how altered crypt turnover explains tissue disorganization that leads to adenoma morphogenesis and CRC. Hypothesis: Changes in rate of tissue renewal-based cell polymerization leads to epithelial expansion and tissue disorganization during adenoma histogenesis. Methods: Accordingly, we created a computational model that considers the structure of colonic epithelium to be a polymer of cells and that tissue renewal is autocatalytic. Indeed, self-renewal of stem cells in colonic crypts continuously produces cells that act like monomers to form a polymer of cells (an interconnected, continuous cell sheet) in a polymerization-based process. Our model is a system of nonlinear differential equations that simulates changes in human crypt cell population dynamics. Results: We investigated how changes occur in the proportion of different cell types during adenoma development in FAP patients. The results show premalignant colonic crypts have a decreased rate of tissue renewal due to APC-mutation. Discussion: This slower rate of cell polymerization causes a rate-limiting step in the crypt renewal process that expands the proliferative cell population size. Conclusions: Our findings provide a mechanism that explains how a prolonged rate of crypt renewal leads to tissue disorganization with local epithelial expansion, infolding, and contortion during adenoma morphogenesis.: Full article

Motivation: We aim to study the boundary stability and persistence of positive odes in mathematical epidemiology models by importing structural tools from chemical reaction networks. This is largely a review work, which attempts to congregate the fields of mathematical epidemiology (ME), and chemical reaction networks (CRNs), based on several observations. We started by observing that epidemiologic strains, defined as disjoint blocks in either the Jacobian on the infected variables, or as blocks in the next generating matrix (NGM), coincide in most of the examples we studied, with either the set of critical minimal siphons or with the set of minimal autocatalytic sets (cores) in an underlying CRN. We leveraged this to provide a definition of the disease-free equilibrium (DFE) face/infected set as the union of either all minimal siphons, or of all cores (they always coincide in our examples). Next, we provide a proposed definition of ME models, as models which have a unique boundary fixed point on the DFE face, and for which the Jacobian of the infected subnetwork admits a regular splitting, which allows defining the famous next generating matrix. We then define the interaction graph on minimal siphons (IGMS), whose vertices are minimal siphons, and whose edges indicate the existence of reactions producing species in one siphon from species in another. When this graph is acyclic, we say the model exhibits an Acyclic Minimal Siphon Decomposition (AMSD). For AMSD models whose minimal siphons partition the infection species, we show that the NGM is block triangular after permutation, which implies the classical max structure of the reproduction number $R_0$ for multi-strain models. In conclusion, using irreversible reaction networks, minimal siphons and acyclic siphon decompositions, we provide a natural bridge from CRN to ME. We implement algorithms to compute IGMS and detect AMSD in our Epid-CRN Mathematica package (which already contain modules to identify minimal siphons, criticality, drainability, self-replicability, etc.). Finally, we illustrate on several multi-strain ME examples how the block structure induced by AMSD, and the ME reproduction functions, allow expressing boundary stability and persistence conditions by comparing growth numbers to 1, as customary in ME. Note that while not addressing the general Persistence Conjecture mentioned in the title, our work provides a systematic method for deriving boundary instability conditions for a significant class of structured models. Full article

We have investigated the structural, morphological, magnetic, and up-conversion luminescence properties of the Yb³⁺/Er³⁺-doped LiGdF₄ nanocrystals precipitated in the silica glassy matrix. Morphological analysis showed uniform distribution of LiGdF₄ nanocrystals (tens of nm in size), embedded in silica glass matrix. FTIR spectroscopy analysis showed trifluoracetates thermolysis with silica lattice formation and structural analysis by XRD is consistent with the LiGdF₄ crystallization process, most likely through an autocatalytic reaction. The stress and crystalline lattice distortion are assigned to the doping and glass matrix environment where the growth process occurs. The EPR spectra associated with the Gd³⁺ ions have shown a well-defined spectrum in the xerogel, associated with the trifluoroacetate ligand environment. In the LiGdF₄ nanocrystals, the broad and unresolved spectrum is due to an envelope of unresolved anisotropic fine structure and a high dipole–dipole interaction between the Gd³⁺/Yb³⁺/Er³⁺ paramagnetic ions. Under 980 nm laser light pumping, we observed the characteristic “blue”, “green” and “red” up-conversion luminescences of the Er³⁺ ions through Yb → Er energy transfer process, that imply three and two-photon process; near UV up-conversion luminescence of Gd³⁺ is observed at about 280–300 nm where Yb → Er and Er → Gd energy transfer is involved. The UC luminescence properties can be improved up to two times by additional Yttrium co-doping due to the induced crystal field distortion. Full article

The high-temperature thermal stability of dexamethasone (DEX) was systematically investigated under nitrogen and air atmospheres using non-isothermal thermogravimetry at heating rates of 0.1–20 °C·min⁻¹. The thermal decomposition was found to initiate below the melting temperature, proceeding via a three-step pathway that generated a complex mixture of volatile and condensed by-products (~10% solid residuum at 550 °C). Kinetic modeling was realized using the single-curve multivariate kinetic analysis (sc-MKA), and was based on the autocatalytic framework with temperature-dependent parameters, combined with consequent reaction mechanisms. An excellent agreement of the theoretical model with the experimental data enabled reliable predictive extrapolations to pharmaceutical processing conditions. Whereas the onset of degradation was observed at ~180–190 °C, significant decomposition rates (>1% mass loss during first 5 min) were only reached above 220 °C, well above the processing windows of most pharmaceutical polymers. Consequently, dexamethasone can be considered thermally stable for hot-melt extrusion and fused deposition modeling, except in high-temperature-processing applications involving polymers such as, e.g., polylactic acid, polyvinyl alcohol, or thermoplastic polyurethanes. Importantly, the study highlights that reliable kinetic predictions require measurements across a broad heating-rate range and in both oxidizing and inert atmospheres, with special emphasis on low heating rates (≤0.2 °C·min⁻¹), which proved critical for capturing early-stage degradation. These findings provide a rigorous kinetic framework for ensuring safe incorporation of DEX into advanced pharmaceutical and medical device formulations. Full article

Extant core metabolic cycles such as the TCA cycle and its related analog pathways utilize carboxylic acids as metabolites, with thioesters playing a key role. We examine if sugars from the potentially autocatalytic formose reaction can be converted to carboxylic acids in the absence of enzymes by calculating the thermodynamics and kinetics of such pathways. We zero in on a mechanism involving the addition of a thiol to an aldehyde, followed by intramolecular disproportionation to form a thioester that can be hydrolyzed into its carboxylic acid. This route is thermodynamically favorable but can have kinetic bottlenecks. We find that elimination of H₂O or H₂S is often the rate-determining step, and that alpha di-carbonyl reactants that do not require such a step are more feasible in the absence of catalysts. Full article

Currently, numerous conventional airport runways suffer from cracking distresses and cannot meet their structural and functional requirements. To address the urgent demand for rapid and durable maintenance of airport runways, this study investigates the material optimization and curing behavior of cold-mix epoxy asphalt (CEA) for non-disruptive overlays. Eight commercial CEAs were examined through tensile and overlay tests to evaluate their strength, toughness, and reflective cracking resistance. Two high-performing formulations (CEA 1 and CEA 8) were selected for further curing characterization using differential scanning calorimetry (DSC) tests, and the non-isothermal curing kinetics were analyzed with different contents of Component C. The results reveal that CEA 1 and CEA 8 were selected as promising formulations with superior toughness and reflective cracking resistance across a wide temperature range. DSC-based curing kinetic analysis shows that the curing reactions follow an autocatalytic mechanism, and activation energy decreases with conversion, confirming a self-accelerating process of CEA. The addition of Component C effectively modified the curing behavior, and CEA 8 with 30% Component C reduced curing time by 60%, enabling traffic reopening within half a day. The curing times were accurately predicted for each type of CEA using curing kinetic models based on autocatalytic and iso-conversional approaches. These findings will provide theoretical and practical guidance for high-performance airport runway overlays, supporting rapid repair, extended service life, and environmental sustainability. Full article

We study a computational model of a protocell, in which an autocatalytic reaction sustains itself inside a lipid vesicle. The autocatalytic reaction drives volume growth via osmosis. Membrane area grows due to addition of lipids from the environment. The membrane growth rate depends on the external lipid concentration and on the tension in the membrane. In the absence of division, a cell either reaches a state of homeostasis or grows to a point where the internal reaction collapses. If a cell becomes elongated, it can divide into two smaller spherical vesicles, conserving the total volume and area. We determine when it is energetically favorable for a large vesicle to divide. Division requires the buildup of a difference between the lipid areas on the outer and inner leaflets of the membrane. Division occurs most easily when the rate of flipping of lipids between leaflets is relatively slow. If the flipping is too fast, the parent cell grows large without dividing. There is a typical size at which division occurs, producing two daughter cells of unequal sizes. The smaller and larger daughters regrow to the same typical size before the next division. Protocells with an active metabolism reach a stable state where the internal autocatalytic reaction and the membrane growth are well balanced. Active protocells can grow and divide in conditions where an inactive vesicle without an internal reaction cannot. Full article

Micro Light Emitting Diode (Micro-LED) technology, characterized by exceptional brightness, low power consumption, fast response, and long lifespan, holds significant potential for next-generation displays, yet its commercialization hinges on resolving challenges in high-density interconnect fabrication, particularly micrometer-scale bump formation. Traditional fabrication approaches such as evaporation enable precise bump control but face scalability and cost limitations, while electroplating offers lower costs and higher throughput but suffers from substrate conductivity requirements and uneven current density distributions that compromise bump-height uniformity. Emerging alternatives include electroless plating, which achieves uniform metal deposition on non-conductive substrates through autocatalytic reactions albeit with slower deposition rates; ball mounting and dip soldering, which streamline processes via automated solder jetting or alloy immersion but struggle with bump miniaturization and low yield; and photosensitive conductive polymers that simplify fabrication via photolithography-patterned composites but lack validated long-term stability. Persistent challenges in achieving micrometer-scale uniformity, thermomechanical stability, and environmental compatibility underscore the need for integrated hybrid processes, eco-friendly manufacturing protocols, and novel material innovations to enable ultra-high-resolution and flexible Micro-LED implementations. This review systematically compares conventional and emerging methodologies, identifies critical technological bottlenecks, and proposes strategic guidelines for industrial-scale production of high-density Micro-LED displays. Full article

Non-isothermal differential scanning calorimetry (DSC) and Raman microscopy were used to study the crystallization behavior of the 20–50 μm amorphous nifedipine (NIF) powder. In particular, the study was focused on the diffusionless glass-crystal (GC) growth mode occurring below the glass transition temperature (T_g). The exothermic signal associated with the GC growth was indeed directly and reproducibly recorded at heating rates q⁺ ≤ 0.5 °C·min⁻¹. During the GC growth, the α_p polymorphic phase was exclusively formed, as confirmed via Raman microscopy. In addition to the freshly prepared NIF samples, the crystallization of the powders annealed for 7 h at 20 °C was also monitored—approx. 50–60% crystallinity was achieved. For the annealed NIF powders, the confocal Raman microscopy verified a proportional absence of the crystalline phase on the sample surface (indicating its dominant formation along the internal micro-cracks, which is characteristic of the GC growth). All DSC data were modeled in terms of the solid-state kinetic equation paired with the autocatalytic model; the kinetic complexity was described via reaction mechanism based on the overlap of 3–4 independent processes. The kinetic trends associated with decreasing q⁺ were identified, confirming the temperature-dependent kinetic behavior, and used to calculate a theoretical kinetic prediction conformable to the experimentally performed 7 h annealing at 20 °C. The theoretical model slightly underestimated the true extent of the GC growth, predicting the crystallinity to be 35–40% after 7 h (such accuracy is still extremely good in comparison with the standard kinetic approaches nowadays). Further research in the field of kinetic analysis should thus focus on the methodological ways of increasing the accuracy of considerably extrapolated kinetic predictions. Full article

This study explores the relation between catalyst research and chemical reaction engineering for developing ethanol to butadiene (ETB) technologies. An ETB process involves two distinct steps: ethanol dehydrogenation to acetaldehyde and butadiene synthesis. The catalyst functions can be tailored separately or imbedded in a single formulation, leading to two-stage and one-stage processes. The performance of selected ETB catalysts is confronted with predictions based on chemical equilibrium, considering the simultaneous formation of products, by-products and impurities. The analysis shows that, essentially, the performance of ETB catalysts is controlled by kinetic factors. A shortlist of relevant catalysts for industrial implementation is proposed. The analysis highlights two key issues for industrial reactor design: catalyst deactivation/regeneration and the use of inert gas as a major process cost. The first issue is addressed by developing a comprehensive fluidized bed reactor model operating in the bubbling regime, capable of handling complex reaction kinetics. Good performance close to plug flow is obtained with bubbles at a size of 4 to 8 cm and with intensive mass transfer. The simulation reveals an autocatalytic effect of acetaldehyde on the butadiene formation favored by a well-mixed dense phase. The second study investigates the optimization of the chemical reaction section in a reactor–separation–recycle system via economic potential. The costs associated with the catalytic reactor and the catalyst charge, including regeneration, along with the costs of recycling reactants and of an inert gas if used, are key factors in determining the optimal operation region. This approach, verified by simulation in Aspen Plus^TM, points out that better robustness and a limited use of an inert gas are necessary for developing industrial catalysts for the one-stage ETB process. Full article

The optimal harvest date (OHD) for the long-term storage of apple fruits is of the utmost importance, not only for maintaining high quality levels, but also because the ripening stage, regulated by the autocatalytic activity of the internal ethylene concentration, greatly affects the VOCs’ synthesis. During apple ripening, chemical compounds undergo changes that affect the fruit’s overall quality, particularly its aromatic profile. Three main classes of organic molecules—aldehydes, alcohols, and esters—play a key role in these modifications. This study investigated the potential of proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) for the rapid, non-destructive monitoring of VOC profiles in ‘Red Delicious’ and ‘Granny Smith’ apples over a 7-week shelf-life period across three harvest dates with different ripening stages. More than 300 mass peaks in the PTR-ToF-MS spectra of the apple headspace were detected. A total of 127 of them were considered to be relevant for further analysis. Furthermore, respiration rate and I_AD index were used for the non-destructive assessment of the ripening progress during the 7 weeks of shelf-life and for integrating the VOC results. Full article

Cellulose acetate (CA) motion picture films are subjected to degradation, especially due to the “vinegar syndrome”, a de-acetylation process catalyzed by high temperature, humidity, and acidity. Acetic acid is released as a by-product of this reaction and acts as a catalyst that triggers an autocatalytic process. The main aim of this study was to evaluate the use of metal oxide, hydroxide, and carbonate nanoparticles, as well as their composite inorganic–organic systems, for the adsorption of acetic acid and the inhibition of the deacetylation process. Various nanoparticles (Ca(OH)₂, ZnO and CaCO₃) were compared in terms of their ability to adsorb glacial acetic acid vapors through gravimetry analysis, Fourier Transform Infrared (FTIR) Spectroscopy, X-ray diffraction (XRD), and Thermogravimetric Analysis (TGA). The variation in the size and morphology of the nanoparticles was investigated via Scanning Electron Microscopy (SEM), too. Subsequently, the most promising nanoparticles (ZnO) were incorporated into composite organic–inorganic systems, made of Whatman paper (WP) and polyvinyl alcohol formaldehyde (PVF) xerogels, and their ability to adsorb acetic acid vapors was again evaluated. Finally, the performances of both the pure ZnO nanoparticles and the organic–inorganic composite systems as inhibitors of the “vinegar syndrome” were assessed on artificially degraded motion picture films using a specifically developed and validated multi-analytical protocol. Full article

Turing’s instability has been widely introduced to explain the formation of several biological and ecological patterns, such as the skin patterning of fish or animals, wings of butterflies, pigmentation, and labyrinth patterns of the cerebral cortex of mammals. Such a mechanism may occur in the ecosystem due to the differential diffusion dispersal that happen if one of the constituent species results in the activator or the prey, showing a tendency to undergo autocatalytic growth. The diffusion of the constituent species activator is a random mobility function called passive diffusion. If the other species in the system (the predator/inhibitor) disperses sufficiently faster than the activator, then the spatially uniform distribution of species becomes unstable, and the system will settle into a stationary state. This paper introduced Turing’s mechanism in our reaction–taxis–diffusion model to simulate the harmful algal bloom (HAB) pattern. A numerical approach, the Runge–Kutta method, was used to deal with this system of reaction–taxis–diffusion equations, and the findings were qualitatively compared to the aerial patterns obtained by a drone flying over Torment Lake in Nova Scotia (Canada) during the bloom season of September 2023. Full article

Phthalonitrile-based resins and benzoxazine play important roles in the field of advanced materials because of their excellent properties. In order to understand the effect of the backbone’s structure on the curing kinetics and properties of the multifunctional resin matrices, different kinds of phthalonitrile containing benzoxazine with various backbone structures were designed and prepared. The curing processes and curing behaviors were investigated by differential scanning calorimetry (DSC). With the assistance of the orthogonal test analysis method, the kinetic parameters, including activation energy E_α, were evaluated and calculated. Results indicated that an autocatalytic model for the curing reaction of various phthalonitrile−containing benzoxazine resins was confirmed. Nevertheless, the activation energies for reactions of benzoxazine and nitrile groups were significantly changed due to the steric hindrance derived from the backbone’s structures. The thermal stability of polymers cured at various temperatures was evaluated by TGA testing. Then, their mechanical properties were investigated and confirmed with SEM images of fracture surfaces. Also, the thermal expansion characteristics of the various polymers were investigated. Results demonstrated that this work proposed an improved matrix resin system with outstanding thermal stability and mechanical properties that broadened the foundation and ideas for subsequent research. Full article

Thermal decomposition (pyrolysis) of coal bottom ash (collected after lignite combustion in coal-fired power plant TEKO-B, Republic of Serbia) was investigated, using the simultaneous TG-DTG techniques in an inert atmosphere, at various heating rates. By using the XRD technique, it was found that the sample (CBA-TB) contains a large amount of anorthite, muscovite, and silica, as well as periclase and hematite, but in a smaller amount. Using a model-free kinetic approach, the complex nature of the process was successfully resolved. Thermodynamic analysis showed that the sample is characterized by dissociation reactions, which are endothermic with positive activation entropy changes, where spontaneity is achieved at high reaction temperatures. The model-based method showed the existence of a complex reaction scheme that includes two consecutive reaction steps and one single-step reaction, described by a variety of reaction models as nucleation/growth phase boundary-controlled, the second/n-th order chemical, and autocatalytic mechanisms. It was established that an anorthite I1 phase breakdown reaction into the incongruent melting product (CaO·Al₂O₃·2SiO₂) represents the rate-controlling step. Autocatalytic behavior is reflected through chromium-incorporated SiO₂ catalyst reaction, which leads to the formation of chromium(II) oxo-species. These catalytic centers are important in ethylene polymerization for converting light olefin gases into hydrocarbons. Adiabatic T_D24 prediction simulations of the process were also carried out. Based on safety analysis through validated kinetic parameters, it was concluded that the tested sample exhibits high thermal stability. Applied thermal treatment was successful in promoting positive changes in the physicochemical characteristics of starting material, enabling beneficial end-use of final products and reduction of potential environmental risks. Full article