The effect of ZnSO4 and Fe2(SO4)3 on the pyrolysis of cocoa shells: A tg-FTIR study.

Pyrolysis stands out as one potential route for valorizing abundant agro-industrial cocoa residues. However, the products of this reaction, particularly bio-oil, do not possess the required quality for direct use in many applications. Thus, this study explores the use of iron sulfate and zinc sulfate as potential catalysts in the pyrolysis of these residues. In this investigation, the biomass, previously ground and dried, was impregnated with varying percentages of ferric sulfate and zinc sulfate. The TG-FTIR technique was employed to ascertain the effect of these salts on the pyrolysis of cocoa shell. The results were fitted with the DAEM model with three pseudo-components. It was determined that both salts induced alterations in the DTG profiles of the thermal decomposition of cocoa shell. In the evolved gases, compounds such as CO2, H2O, CH4, CO, HCN, and oxygenated compounds like HCOOH and CH3COOH were detected. Ferric sulfate significantly influenced the activation energies governing the reactions of the three pseudo-components. Conversely, the presence of zinc sulfate did not alter the activation energies associated with the decomposition of cocoa shell pseudo-components. Both catalysts induced alterations in the infrared spectra of the evolved gases, which is primarily evident in the relative intensities of bands corresponding to the stretching vibrations of constituent groups within CO2, CO, water, and oxygenated compounds.

Mechanistic study of the differences in lactic acid bacteria resistance to freeze- or spray-drying and storage.

Lactobacillus delbrueckii subsp. bulgaricus and Lactiplantibacillus plantarum are two lactic acid bacteria (LAB) widely used in the food industry. The objective of this work was to assess the resistance of these bacteria to freeze- and spray-drying and study the mechanisms involved in their loss of activity. The culturability and acidifying activity were measured to determine the specific acidifying activity, while membrane integrity was studied by flow cytometry. The glass transitions temperature and the water activity of the dried bacterial suspensions were also determined. Fourier transform infrared (FTIR) micro-spectroscopy was used to study the biochemical composition of cells in an aqueous environment. All experiments were performed after freezing, drying and storage at 4, 23 and 37 °C. The results showed that Lb. bulgaricus CFL1 was sensitive to osmotic, mechanical, and thermal stresses, while Lpb. plantarum WCFS1 tolerated better the first two types of stress but was more sensitive to thermal stress. Moreover, FTIR results suggested that the sensitivity of Lb. bulgaricus CFL1 to freeze-drying could be attributed to membrane and cell wall degradation, whereas changes in nucleic acids and proteins would be responsible of heat inactivation of both strains associated with spray-drying. According to the activation energy values (47-85 kJ/mol), the functionality loss during storage is a chemically limited reaction. Still, the physical properties of the glassy matrix played a fundamental role in the rates of loss of activity and showed that a glass transition temperature 40 °C above the storage temperature is needed to reach good preservation during storage. KEY POINTS: • Specific FTIR bands are proposed as markers of osmotic, mechanic and thermal stress • Lb. bulgaricus CFL1 was sensitive to all three stresses, Lpb. plantarum WCFS1 to thermal stress only • Activation energy revealed chemically limited reactions ruled the activity loss in storage.

Study on the thermal behaviour of spontaneous combustion of open-pit minerals.

To study thermal behaviour during spontaneous combustion of an open-pit coal mine, mixed slag (coal, oil shale, and coal gangue) was taken as the research object. Laser thermal conductivity analyser and differential scanning calorimetry were used to test thermophysical parameters and heat release characteristics of the minerals. The parameters can be employed to calculate the apparent activation energy using the Arrhenius equation and evaluate the thermal behaviour of open-pit mixed slag. The results indicate that thermophysical parameters have stage characteristics. Thermal diffusivity and thermal conductivity of minerals, especially mixed slag, have a strong correlation with temperature. Heat flow of minerals exhibits five characteristic stages, and heat flow of the samples is consistent with the change in heating rate. During the heating process, thermal diffusivity and heat flow of the mixed slag are between those of a single mineral. Except for the mixed slag at 15 and 20 °C/min, the initial exothermic temperature of the other samples is mainly concentrated at 50-80 °C. Thermal energy release of the sample is mainly concentrated in the accelerated exothermic stage and rapid exothermic stage. Thermal energy release of mixed slag in rapid exothermic stage is always greater than that in accelerated exothermic stage, and the proportion of thermal energy release in these two stages exceeds 98 %. The apparent activation energy during the accelerated exothermic stage is lower, making it easier to release heat, and rapid exothermic stage is relatively high, which can readily lead to heat accumulation. Thermal analysis reveals that the thermal behaviour of mixed slag is significantly different from that of a single mineral. Its unique exothermic characteristics can provide a more accurate theoretical basis for the prevention and control of environmental pollution caused by slag spontaneous combustion.

Estimation of diffusion coefficients during carrots cooking in arsenious solution at different temperatures.

This study is based on an investigation of the transport phenomenon, specifically the quantification of arsenic diffusion in carrots within a temperature range of 89 °C-99 °C using a thin plate model. Studying the diffusion of arsenic in carrots is important due to its toxicity, as it can concentrate during cooking. The World Health Organization considers arsenic as one of the ten chemical substances of public health concern. In this study, biennial hybrid carrots of the Nantesa variety were cooked whole with their epidermis in an aqueous solution containing diarsenic trioxide with an As concentration of 5 mgL-1 at 89 °C, 94 °C, and 99 °C. The cooking times of the carrots at different temperatures were based on a specific degree of tenderness, with a value of ≤3 kg m-2. The evaluated data showed consistency with increasing temperature. The calculated effective diffusion coefficients at temperatures of 89 °C, 94 °C, and 99 °C were 5.84E-09 m2s-1, 1.08E-08 m2s-1, and 2.51E-08 m2s-1 for the flesh (DL), and 1.601E-11 m2s-1, 2.15E-11 m2s-1, and 4.39E-11 m2s-1 for the epidermis (DE), respectively. The activation energy for diffusion was determined to be 159.54 kJmol-1 for the and 110.68 kJmol-1 for the epidermis. Similar behaviours were observed in different radial positions of the carrot, where the arsenic content decreased from the periphery to the centre, consistent with studies on diffusion phenomena with other solutes in food. The novelty was the detailed quantification of arsenic diffusion in the Nantes-type hybrid carrot matrix. This study is limited to a specific concentration of 5 mgL-1 of arsenic solution. The findings of this study may have significant implications for public health and food safety.

Analysis of Diffusion Coefficients of Iron Monoboride and Diiron Boride Coating Formed on the Surface of AISI 420 Steel by Two Different Models: Experiments and Modelling.

In the present work, two mathematical diffusion models have been used to estimate the growth of the iron monoboride and diiron boride coating formed on AISI 420 steel. The boronizing of the steel was carried out with the solid diffusion packing method at a boronizing temperature of 1123 K-1273 K. Experimental results show the two-coating system consists of an outer monoboride and an inner diiron boride coating with a predominantly planar structure at the propagation front. The depth of the boride coating increases according to temperature and treatment time. A parabolic curve characterizes the propagation of the boride coatings. The two proposed mathematical models of mass transfer diffusion are founded on the solution corresponding to Fick's second fundamental law. The first is based on a linear boron concentration-penetration profile without time dependence, and the second model with time dependence (exact solution). For both models, the theoretical law of parabolic propagation and the average flux of boron atoms (Fick's first fundamental law) at the growth interfaces (monoboride/diiron boride and diiron boride/substrate) are considered to estimate the propagation of the boride coatings (monoboride and diiron boride). To validate the mathematical models, a programming code is written in the MATLAB program (adaptation 7.5) designed to simulate the growth of the boride coatings (monoboride and diiron boride). The following parameters are used as input data for this computer code: (the layer thicknesses of the FeB and Fe2B phases, the operating temperature, the boronizing time, initial formation time of the boride coating, the surface boron concentration limits, FeB/Fe2B and Fe2B/Fe growth interfaces, and the mass transfer diffusion coefficient of boron in the iron monoboride and diiron boride phases). The outputs of the computer code are the constants εFeB and εFe2B. The assessment of activation energies of AISI 420 steel for the two mathematical models of mass transfer is coincident (QFeB=221.9 kJ∙mol-1 and QFe2B=209.1 kJ∙mol-1). A numerical analysis was performed using a standard Taylor series for clarification of the proximity between the two models. SEM micrographs exhibited a strong propensity toward a flat-fronted composition at expansion interfaces of the iron monoboride and diiron boride coating, confirmed by XRD analysis. Tribological characterizations included the Vickers hardness test method, pin-on-disc, and Daimler-Benz Rockwell-C indentation adhesion tests. After thorough analysis, the energies were compared to the existing literature to validate our experiment. We found that our models and experimental results agreed. The diffusion models we utilized were crucial in gaining a deeper understanding of the boronizing behavior of AISI 420 steel, and they also allowed us to predict the thicknesses of the iron monoboride and diiron boride coating. These models provide helpful approaches for predicting the behavior of these steels.

Thermal and compositional characterization of chicken, beef, and pork cartilage to establish its lifetime.

The thermal behavior of commercial chicken, beef, and pork cartilage, were studied using thermal analysis techniques. We use thermogravimetry (TGA) to study their thermal stability between room temperature and 500 °C; differential scanning calorimetry (DSC) in a temperature range between - 50 °C and 300 °C to determine their phase changes associated with endothermic or exothermic processes, and mass spectrometry coupled to TGA to determine the release of elements as they are heated; the results are similar for the three samples. In the thermogravimetric analysis, three different phases were found corresponding to the stages of dehydration (21 °C < T < 100 °C), decomposition (100 °C < T < 300 °C, and degradation (300 °C < T < 500 °C). The DSC study shows two endothermic anomalies corresponding to melting of the aqueous content (-25 °C < T < 25 °C) and evaporation of the aqueous content (27 °C < T < 175 °C), with required enthalpies of 137.30 J/g and 1193 J/g, respectively. Mass spectrometry evidenced the release of molecules such as nitrogen, oxygen, carbon dioxide, and calcium. This study intends to give an approximation to the possible behavior of commercial cartilage that is stored for use in surgery, in no way is it intended to simulate the behavior within the human body, since the biological and physicochemical parameters inside the body are not studied. From the TGA results for different heating rates, we calculated the activation energies required in each of the phases, whose values are 3250,95 J/mol in the dehydration stage, 5130,63 J/mol for decomposition, and 22,677,52 J/mol for degradation. With the activation energies and following the Toops theory (TOOP, 1971) [13], we proceeded to calculate the lifetime in the completion of the three stages or what in thermogravimetric analysis, is known as useful life per stage, finding that a sample of cartilage stored under ambient conditions, after 62 days it loses its initial properties. Which provides an important parameter for the storage of possible synthetic biomaterials with properties similar to cartilage. It is clear that here the useful life or the change of the original properties due to temperature effects is studied, which under the Arrhenius theory is transferred to the kinetic study over time.

Thermodynamic Study of Leaching Conditions of Galena with Citrate Ions and Hydrogen Peroxide as Oxidizing Agent.

Galena is the most important mineral for lead production, as it is the main source of lead in the world. Currently, the concentrates of this mineral are mainly treated using pyrometallurgical methods, creating several environmental problems, such as the generation of toxic and greenhouse gases. In addition, these processes involve high energy consumption, which limits their applicability. Hydrometallurgical routes are proposed as alternative processes for obtaining some metals such as silver, copper, gold, etc. The drawback of these processes is that the minerals tend to be passive in aqueous media. To mitigate this issue, researchers have used extreme conditions of pressure and temperature (6 atm. and 155 °C) or the use of very corrosive conditions. In this sense, the use of complexing agents that dissolve the metals of interest has been proposed. Citrate ion is one of the most promising complexing agents for galena leaching, obtaining high percentages of dissolution in relatively short times. Unfortunately, there has not been enough investigation about the concentration optimization of the complexing in the pH range from 5 to 9. In this sense, thermodynamic diagrams, such as the Pourbaix diagrams, are very useful for this purpose. Therefore, in this work, the effects of pH and temperature on the leaching of galena in citrate ion solutions are studied thermodynamically and experimentally. The experimental work was carried out with pure galena samples with a particle size of +149 - 74 µm (-100 + 200 mesh). The results show that higher recoveries were obtained working at a pH of 8 and at temperatures of 30 and 40 °C. The thermodynamic and experimental data demonstrated that the existence of an optimal concentration of citrate ion, due the extraction of lead from galena, has a greater reaction rate at a relatively low initial concentration of 0.3 M. This is due the formation of the complex lead citrate 1 (Pb(cit)-).

Kinetics of moisture loss applied to the baking of snacks with pregelatinized cassava starch.

Moisture loss kinetics is a complex process defined as the liquid removal from a solid by thermal application. The purposes of the study were to obtain kinetic curves of moisture loss during the baking of cassava snacks and establish which processes govern the moisture loss, recognize which mathematical models describe the moisture loss curves more precisely, and determine activation energy (Ea) and effective diffusivity (Deff ). Experimental data were obtained through baking at four temperatures formulations for snacks with different dehydrated cassava puree (DCP) proportions. Page's and Chávez Méndez's models showed the best fits. We calculated Deff and Ea employing the analytical solution of Fick's Second Law for the geometry of plane plates. Deff values increase with DCP but did not show a trend. The range found was from 5.22E-06 to 2.93E-05 m2 /s. The results of Ea showed that the mixture of flours produced an increase in the energy necessary to initiate the effective diffusion (24.84 kJ/mol) compared to the samples without mixing (15.54 kJ/mol). Moisture loss curves show that the diffusion process governs a large part of the process. PRACTICAL APPLICATION: Given the need to increase research for the development of the cassava industry, which currently has low competitiveness compared to less expensive products such as corn, various efforts are being made to generate new products that can replace wheat flour, at least in part. However, it is necessary to research how this substitution affects the various steps of the production system, including baking. During baking, one of the most significant processes is moisture loss. In this sense, the kinetic modeling of the moisture loss process parameters is mainly helpful in the food industry. The mathematical models of moisture loss processes are used to design new or improved baking systems or even control the process.

Rheological and Functional Properties of Dark Chocolate with Partial Substitution of Peanuts and Sacha Inchi.

Chocolate is a widely consumed product, due to the contribution of fats and antioxidant compounds; the addition of other components makes it possible to increase the content of polyunsaturated fatty acids, although they can affect its rheological properties. The influence of the partial addition of peanut paste and Sacha Inchi on the rheological and functional properties of dark chocolate was evaluated. Cocoa beans, peanuts, and Sacha Inchi were refined in order to obtain the cocoa paste (PC), peanut paste (PM), and Sacha Inchi paste (PSI). Then, mixtures between 0 to 20% of PM and PSI were formulated, and the rheological properties were evaluated at 30, 40, and 50 °C; these were adjusted to mathematical models. Functional groups were identified by FTIR in ATR mode, and it was observed that the partial addition of PM and PSI did not show significant changes in the shear stress and apparent viscosity of the mixture, although they did show dependence on temperature. The Herschel−Bulkley model showed a better adjustment (R2 > 0.999), reporting behavior index values, n < 1.0, and indicating pseudo-plastic behavior for pastes and formulations. The yield limit τy and the consistency index kH increased significantly with the addition of PM and PSI, but they decreased with increasing temperature. The activation energy show values between 13.98 to 18.74 kJ/mol, and it increased significantly with the addition of PM and PSI. Infrared analysis evidenced the presence of polyunsaturated fatty acids, coming mainly from PSI and PM. The addition of PM and PSI does not influence the rheological properties and allows for an increase in the content of polyunsaturated fatty acids.

Storage Conditions and Adsorption Thermodynamic Properties for Purple Corn.

Adsorption isotherms provide insight into the thermodynamic properties governed by food storage conditions. Adsorption isotherms of purple corn of the Canteño variety were evaluated at 18, 25, and 30 °C, for the equilibrium relative humidity (ERH) range between 0.065 and 0.95. The equilibrium moisture (Xe) was determined by the continuous weight-change method. Seven mathematical models of isotherms were modeled, using the coefficient of determination R2, mean absolute error (MAE), and estimated standard error (ESE) as the convergence criterion. Thermodynamic parameters such as isosteric heat (qst), Gibbs Free Energy (ΔG), differential entropy (ΔS), activation energy (Ea), and compliance with the isokinetic law were evaluated. It was observed that the adsorption isotherms presented cross-linking around 75% ERH and 17% Xe, suggesting adequate storage conditions at these values. The GAB and Halsey models reported better fit (R2 > 97%, MAE < 10%, ESE < 0.014 and random residual dispersion). The reduction of Xe from 17 to 7%, increases qst, from 7.7022 to 0.0165 kJ/g, while ΔG decreases considerably with the increase in Xe, presenting non-spontaneous endergonic behavior, and linear relationship with ΔS, evidencing compliance with the isokinetic theory, governed by qst. Ea showed that more energy is required to remove water molecules from the upper layers bound to the monolayer, evaluated using CGAB. The models predicted the storage conditions, and the thermodynamic parameters show the structural stability of the purple corn grains of the Canteño variety during storage.

Rheology and Tack Properties of Biodegradable Isodimorphic Poly(butylene succinate)-Ran-Poly(ε-caprolactone) Random Copolyesters and Their Potential Use as Adhesives.

The sole effect of the microstructure of biodegradable isodimorphic poly(butylene succinate)-ran-poly(ε-caprolactone) random copolyesters on their rheological properties is investigated. To avoid the effect of molecular weight and temperature, two rheological procedures are considered: the activation energy of flow, Ea, and the phase angle versus complex modulus plots. An unexpected variation of both parameters with copolyester composition is observed, with respective maximum and minimum values for the 50/50 composition. This might be due to the peculiar chain configurations of the copolymers that vary as a function of comonomer distribution within the chains. The same chain configuration variations are responsible for the isodimorphic character of the copolymers in the crystalline state. Tack tests, performed to study the viability of the copolyesters as environmentally friendly hot melt adhesives (HMA), reveal a correlation with rheological results. Tackiness parameters, particularly the energy of adhesion obtained from stress-strain curves during debonding experiments, are enhanced as melt elasticity increases. Based on the carried-out analysis, the link microstructure-rheology-tackiness is established, allowing selecting the best performing HMA sample considering the polymer chemistry of the system.

Natural Aging of Ethylene-Propylene-Diene Rubber under Actual Operation Conditions of Electrical Submersible Pump Cables.

Ethylene-propylene-diene monomer (EPDM) rubbers used in electric submersible pump (ESP) cables were analyzed after being aged in actual operation conditions in oil wellbores. These rubbers constitute the insulation and jacket layers of the ESP cables. EPDM rubbers from four different cables operating during different time intervals (2 and 4.8 years) at different depths (from 760 to 2170 m) below sea level were studied. To verify the effects of the long exposure on the rubber performance, thermal analysis was performed to determine the thermal stability and activation energy of degradation. In addition, structural analysis, through vibrational spectroscopy and crosslinking fraction assessment, was carried out. The mechanical properties of the aged rubbers were inferred through the measurement of hardness, while the absorption of a service fluid was studied by gravimetry. The results showed only minor changes in the thermal, structural, mechanical and barrier properties of the EPDM-based ESP cable layers. It is suggested that the thermo-oxidation mechanism followed by chain scission does not have a role in the degradation of EPDM within the aged ESP cables, and no sign of variation of crosslink fractions has been encountered. Therefore, it was concluded that EPDM-based layers seem not to be weak links in the configuration of modern ESP systems.

Effect of pretreatment and temperature on the drying kinetics and physicochemical and techno-functional characteristics of pumpkin (Cucurbita maxima).

The study was carried out to assess fresh slices and thermally pretreated pumpkin (Cucurbita maxima) dried at temperatures of 55 °C, 60 °C, 65 °C, and 70 °C. The drying kinetics and quality attributes of the dried product were determined, and results indicated that the modified Page model was the best fit, with activation energies of 29.47 kJ mol-1 and 16.06 kJ mol-1 for drying fresh and thermally pretreated slices, respectively. A significant effect (p < 0.05) related to thermal pretreatment and temperature was evidenced on the physicochemical properties. The fresh pulp powders presented the following ranges of moisture and color (ΔE), 7.10%-8.31% w.b.; 21.23-25.23, respectively, and for the pretreated pulp powders, they were 8.94%-11.54% w.b., and from 19.00- 28.30, respectively. There were no significant effects on the techno-functional properties in the powders; cold water solubility was 5.36%-6.46%, water absorption capacity was 3.42-6.52 g/g, and oil absorption capacity was 1.00-1.30 g/g. The carbohydrate and fiber contents significantly decreased in the pretreated powder. An increase in antioxidant activity was found in fresh and thermally pretreated pulp powder at a temperature of 70 °C, presenting values between 2.23-2.98 µmol Trolox equivalent g-1d.b. evaluated by the DPPH method and between 40.48-45.92 µmol Trolox equivalent g-1d.b. by ABTS, and no significant differences (p > 0.05) were determined after pulp pretreatment. The total content of carotenoids presented retention percentages for fresh pulp powders of 52.09%, 41.92%, 30.55%, and 22.79%, while for pretreated pulp powders, they were 30.67%, 32.86%, 24.84%, and 14.71% when dried at temperatures of 55 °C, 60 °C, 65 °C, and 70 °C, respectively. The powders obtained from heat-pretreated pumpkin pulp showed significant differences (p < 0.05) in physicochemical characteristics and total carotenoids, but they were not found (p > 0.05) in the techno-functional properties and antioxidant activity evaluated by the DPPH and ABTS methods.

Description of Cumbeba (Tacinga inamoena) Waste Drying at Different Temperatures Using Diffusion Models.

One approach to improve sustainable agro-industrial fruit production is to add value to the waste generated in pulp extraction. The processing of cumbeba (Tacinga inamoena) fruits generates a significant amount of waste, which is discarded without further application but can be a source of bioactive compounds, among other nutrients. Among the simplest and most inexpensive forms of processing, convective drying appears as the first option for the commercial utilization of fruit derivatives, but it is essential to understand the properties of mass transfer for the appropriate choice of drying conditions. In this study, cumbeba waste was dried at four temperatures (50, 60, 70 and 80 °C). Three diffusion models were fitted to the experimental data of the different drying conditions. Two boundary conditions on the sample surface were considered: equilibrium condition and convective condition. The simulations were performed simultaneously with the estimation of effective mass diffusivity coefficients (Def) and convective mass transfer coefficients (h). The validation of the models was verified by the agreement between the theoretical prediction (simulation) and the experimental results. The results showed that, for the best model, the effective mass diffusivities were 2.9285 × 10-9, 4.1695 × 10-9, 8.1395 × 10-9 and 1.2754 × 10-8 m2/s, while the convective mass transfer coefficients were 6.4362 × 10-7, 8.7273 × 10-7, 8.9445 × 10-7 and 1.0912 × 10-6 m/s. The coefficients of determination were greater than 0.995 and the chi-squares were lower than 2.2826 × 10-2 for all simulations of the experiments.

Photooxidation of 2-(tert-Butyl)-3-Methyl-2,3,5,6,7,8-Hexahydroquinazolin-4(1H)-one, an Example of Singlet Oxygen ene Reaction.

Singlet oxygen ene reactions produce 2-(tert-butyl)-4a-hydroperoxy-3-methyl-2,4a, 5,6,7,8-hexahydroquinazolin-4(3H)-one quantitatively during diffusion crystallization of 2-(tert-butyl)-3-methyl-2,3,5,6,7,8-hexahydroquinazolin-4(1H)-one in n-hexane/CH2Cl2 solvent mixture. To confirm this photo-oxidation, a 1H-NMR study in CDCl3 was performed with exposure to ambient conditions (light and oxygen), with neither additional reactants nor catalysts. A theoretical study at the B3LyP/6311++G** level using the QST2 method of locating transition states suggests a two-step mechanism where the intermediate, which unexpectedly did not come from the peroxide intermediate, has a low activation energy.

Characterization of the trypsin-III from Monterey sardine (Sardinops caeruleus): Insights on the cold-adaptation from the A236N mutant.

Trypsins (E.C. 3.4.21.4) are digestive enzymes that catalyze the hydrolysis of peptide bonds containing arginine and lysine residues. Some trypsins from fish species are active at temperatures just above freezing, and for that are called cold-adapted enzymes, having many biotechnological applications. In this work, we characterized a recombinant trypsin-III from Monterey sardine (Sardinops caeruleus) and studied the role of a single residue on its cold-adapted features. The A236N mutant from sardine trypsin-III showed higher activation energy for the enzyme-catalyzed reaction, it was more active at higher temperatures, and exhibited a higher thermal stability than the wild-type enzyme, suggesting a key role of this residue. The thermodynamic activation parameters revealed an increase in the activation enthalpy for the A236N mutant, suggesting the existence of more intramolecular contacts during the activation step. Molecular models for both enzymes suggest that a hydrogen-bond involving N236 may contact the C-terminal α-helix to the vicinity of the active site, thus affecting the biochemical and thermodynamic properties of the enzyme.

Kinetics of thermal degradation and lifetime study of poly(vinylidene fluoride) (PVDF) subjected to bioethanol fuel accelerated aging.

PVDF was prepared by compression molding, and its phase content/structure was assessed by WAXD, DSC, and FTIR-ATR spectroscopy. Next, PVDF samples were aged in bioethanol fuel at 60 °C or annealed in the same temperature by 30 ─ 180 days. Then, the influence of aging/annealing on thermal stability, thermal degradation kinetics, and lifetime of the PVDF was investigated by thermogravimetric analysis (TGA/DTG), as well as the structure was again examined. The crystallinity of ~41% (from WAXD) or ~49% (from DSC) were identified for unaged PVDF, without significant changes after aging or annealing. This PVDF presented not only one phase, but a mixture of α-, ß- and γ-phases, α- and ß-phases with more highlighted vibrational bands. Thermal degradation kinetics was evaluated using the non-isothermal Ozawa-Flynn-Wall method. The activation energy (E a ) of thermal degradation was calculated for conversion levels of α = 5 ─ 50% at constant heating rates (5, 10, 20, and 40 °C min─1), α = 10% was fixed for lifetime estimation. The results indicated that temperature alone does not affect the material, but its combination with bioethanol reduced the onset temperature and E a of primary thermal degradation. Additionally, the material lifetime decreased until about five decades (T f = 25 °C and 90 days of exposition) due to the fluid effect after aging.

"Transitivity": A Code for Computing Kinetic and Related Parameters in Chemical Transformations and Transport Phenomena.

The Transitivity function, defined in terms of the reciprocal of the apparent activation energy, measures the propensity for a reaction to proceed and can provide a tool for implementing phenomenological kinetic models. Applications to systems which deviate from the Arrhenius law at low temperature encouraged the development of a user-friendly graphical interface for estimating the kinetic and thermodynamic parameters of physical and chemical processes. Here, we document the Transitivity code, written in Python, a free open-source code compatible with Windows, Linux and macOS platforms. Procedures are made available to evaluate the phenomenology of the temperature dependence of rate constants for processes from the Arrhenius and Transitivity plots. Reaction rate constants can be calculated by the traditional Transition-State Theory using a set of one-dimensional tunneling corrections (Bell (1935), Bell (1958), Skodje and Truhlar and, in particular, the deformed ( d -TST) approach). To account for the solvent effect on reaction rate constant, implementation is given of the Kramers and of Collins-Kimball formulations. An input file generator is provided to run various molecular dynamics approaches in CPMD code. Examples are worked out and made available for testing. The novelty of this code is its general scope and particular exploit of d -formulations to cope with non-Arrhenius behavior at low temperatures, a topic which is the focus of recent intense investigations. We expect that this code serves as a quick and practical tool for data documentation from electronic structure calculations: It presents a very intuitive graphical interface which we believe to provide an excellent working tool for researchers and as courseware to teach statistical thermodynamics, thermochemistry, kinetics, and related areas.

Caracterización y estabilidad de un extracto rico en antocianinas a partir de corteza de gulupa / Characterization and stability of an extract rich in anthocyanins from passion purple fruit peel / Caracterização e estabilidade de um extrato rico em antocianinas de cortez de fruta roxa da paixão

Resumen La gulupa es una fruta originaria de la región amazónica, cuyo epicarpio es un subproducto con alto potencial en antioxidantes como las antocianinas. Por lo anterior, los objetivos de este estudio fueron realizar una extracción por solvente, a partir del epicarpio, para obtener un extracto rico en antocianinas; caracterizar su capacidad antioxidante y realizar la cinética de degradación de antocianinas monoméricas durante el almacenamiento a tres temperaturas (-14 ± 2 °C, 5 ± 1 °C y 21 ± 0,7 °C). En consecuencia, se obtuvo un extracto con un contenido de antocianinas de 165 ±9 mg cianidina-3-O-glucosido/L. La capacidad antioxidante fue de 464 ± 19 y 366 ± 7 μmol Trolox/100 g de extracto, según los ensayos FRAP y DPPH respectivamente, y un contenido de vitamina C de 2,07 ± 0,04 mg ácido ascórbico/100 g de extracto. La cinética de degradación se definió por el orden uno con las siguientes constantes: 2, 1·10-3, 8, 6·10-3 y 2,7·10-2 días-1 para -14 ± 2 °C, 5 ± 1 °C y 21 ± 0,7 °C respectivamente, generando una energía de activación de 46, 0·103 J/mo'l. Por consiguiente, se concluyó que es posible obtener, a partir del epicarpio de gulupa, extractos ricos en compuestos de alto valor como las antocianinas, los cuales son afectados por la temperatura de almacenamiento, siendo este un factor para considerar durante su aplicación en matrices alimentarias.

Abstract Purple passion fruit is a fruit from the Amazon region whose epicarp is a by-product with high potential as a source of anthocyanins. The objective of this investigation was to do a solvent extraction from the epicarp to obtain an extract rich in anthocyanins, and then, to characterize its antioxidant capacity, and evaluate the anthocyanin kinetic degradation during storage at three temperatures (-14 ± 2 °C, 5 ± 1 °C and 21 ± 0,7 °C). In consequence, an extract was obtained with an anthocyanin content of 165 ± 9 mg cyanidin-3-O-glucoside/L, an antioxidant capacity of 464 ± 19 and 366 ± 7 μmol Trolox/100 g extract according to FRAP and DPPH assays respectively, and a vitamin C content of 2.07 ± 0.04 mg ascorbic acid/100 g extract. The degradation kinetics was defined by order one with the following degradation constants: 2,1·10-3, 8,6·10-3 and 2,7·10-2 days-1 for -14 ± 2 °C, 5 ± 1 °C and 21 ± 0,7 °C, respectively, which corresponds to an activation energy of 46.0·10-3 J/mol. Therefore, it is concluded that is possible to obtain, from purple passion fruit epicarp, high-value compounds extract rich, such as anthocyanin, that is affected by storage temperature, which is an important factor during its use in food matrices.

Resumo O maracujá roxo é uma fruta nativa da região amazónica cujo epicarpo é um subproduto com alto potencial em antioxidantes como as antocianinas. Por conseguinte, o objectivo deste estudo foi a extracção por solventes a partir de epicarpo para se obter um extracto rico em antocianinas, caracterizar a sua capacidade antioxidante e executar a cinética de degradação de antocianinas monoméricas durante o armazenamento a três temperaturas (-14 ± 2 °C, 5 ± 1 °C e 21 ± 0,7 °C). Portanto, obteve-se um extracto contendo antocianina 165 ± 9 mg de cianidina-3-glucósido ou/L, a capacidade antioxidante de 464 ± 19 e 366 ± 7 micromol Trolox/100 g de extrato de acordo com o ensaio de FRAP e DPPH, e vitamina C de 2,07 ± 0,04 mg de ácido ascórbico/100 g de extrato. A cinética de degradação foi definida por ordem um com as seguintes constantes: 2,1·10-3, 8,6·10-3 e 2,7·10-2 dias-1 para -14 ± 2 °C, 5 ± 1 °C e 21 ± 0,7 °C respectivamente, gerando uma energia de ativação de 46,0·103 J/mol. Portanto, conclui-se que é possível obter, a partir de gulupa epicarpo, extrai rico em compostos de alto valor, tais como as antocianinas, as quais são afectadas por temperatura de armazenamento, sendo este um factor para ter em conta a sua aplicação em matrizes alimentares.

Reliability of X7R Multilayer Ceramic Capacitors During High Accelerated Life Testing (HALT).

Multilayer ceramic capacitors (MLCC) are essential components for determining the reliability of electronic components in terms of time to failure. It is known that the reliability of MLCCs depends on their composition, processing, and operating conditions. In this present work, we analyzed the lifetime of three similar X7R type MLCCs based on BaTiO3 by conducting High Accelerated Life Tests (HALT) at temperatures up to 200 °C at 400 V and 600 V. The results were adjusted to an Arrhenius equation, which is a function of the activation energy (Ea) and a voltage stress exponent (n), in order to predict their time to failure. The values of Ea are in the range of 1⁻1.45 eV, which has been reported for the thermal failure and dielectric wear out of BaTiO3-based dielectric capacitors. The stress voltage exponent value was in the range of 4⁻5. Although the Ea can be associated with a failure mechanism, n only gives an indication of the effect of voltage in the tests. It was possible to associate those values with each type of tested MLCC so that their expected life could be estimated in the range of 400⁻600 V.