Degradation Kinetics Research Articles

Study on Thermal Oxygen Aging Characteristics and Degradation Kinetics of PMR350 Resin.

The thermal stability and aging kinetics of polyimides have garnered significant research attention. As a newly developed class of high thermal stability polyimide, the thermal aging characteristics and degradation kinetics of phenylene-capped polyimide prepolymer (PMR350) have not yet been reported. In this article, the thermo-oxidative stability of PMR350 was investigated systematically. The thermal degradation kinetics of PMR350 resin under different atmospheres were also analyzed using the Flynn-Wall-Ozawa method, the Kissinger-Akahira-Sunose method, and the Friedman method. Thermogravimetric analysis (TGA) results revealed that the 5% thermal decomposition temperature (Td5%) of PMR350 in a nitrogen atmosphere was 29 °C higher than that in air, and the maximum thermal degradation rate was 0.0025%/°C, which is only one-seventh of that observed in air. Isothermal oxidative aging results indicated that the weight loss rate of PMR350 and the time-dependence relationship follow a first-order exponential growth function. PMR350 resin thermal decomposition reaction under air atmosphere includes one stage, with a degradation activation energy of approximately 57 kJ/mol. The reaction model g(α) fits the F2 model, and the integral form is given by g(α) = 1/(1 - α). In contrast, the thermal decomposition reaction under a nitrogen atmosphere consists of two stages, with degradation activation energies of 240 kJ/mol and 200 kJ/mol, respectively. The reaction models g(α) correspond to the A2 and D3 models, with the integral forms represented as g(α) = [-ln(1 - α)]2 and g(α) = [1 - (1 - α)1/3]2 due to the oxygen accelerating thermal degradation from multiple perspectives. Moreover, PMR350 resin maintained high hardness and modulus even after thermal aging at 350 °C for 300 h. The results indicate that the resin exhibits excellent resistance to thermal and oxygen aging. This study represents the first systematic analysis of the thermal stability characteristics of PMR350 resin, offering essential theoretical insights and data support for understanding the mechanisms of thermal stability modification in PMR350 and its engineering applications.

In vitro degradation of 3D-printed polycaprolactone\\biomimetic hydroxyapatite scaffolds: Impact of the sterilization method

In the transition from the laboratory to the clinic, the sterilization of medical devices becomes a fundamental and mandatory step to ensure patient safety. This work evaluates the impact of three different sterilization methods - autoclave, ethylene oxide and gamma irradiation - on the physicochemical properties and degradation kinetics of 3D-printed polycaprolactone\\calcium deficient hydroxyapatite (PCL\\CDHA) scaffolds for bone regeneration. The in vitro degradation test was performed in phosphate buffer saline solution at 47 °C for 18 weeks by recording the evolution of pH, scaffold morphology, swelling degree, mass loss as well as polymer content, molecular weight and crystallinity. The results showed that under thermally accelerated degradation, the scaffolds underwent hydrolytic bulk degradation without altering the pH of the soaking medium nor compromising the morphology and integrity of the constructs. Although the structural integrity of the scaffolds was maintained, autoclaving severely deteriorated the properties of the polymer, resulting in a faster degradation pattern, confirming that it is not an appropriate sterilization method for PCL\\CDHA scaffolds. While ethylene oxide had no significant effect on degradation, gamma irradiation slightly accelerated hydrolysis by chain scission. However, due to the porous nature of the scaffolds, the use of ethylene oxide is inadvisable due to the risk of gas trapping in the pores. Therefore, gamma irradiation, a non-toxic, effective, predictable and reproducible sterilization method, is considered the most appropriate.

Production of pyrite-based catalysts supported on graphene oxide and zinc oxide to treat drug mixture via advanced oxidation processes.

Advanced oxidation processes (AOP) stood out as an efficient alternative for the treatment of organic contaminants. In this work, there were proposed syntheses of mixed catalysts of pyrite and graphene oxide and pyrite and zinc oxide to treat a mixture of the drugs atenolol and propranolol in aqueous solution through the photo-Fenton process with ultraviolet radiation. The efficiency of the methodologies used in the syntheses was confirmed through different characterization analyses. It was verified that the pyrite and zinc oxide catalyst led to the best contaminant degradation percentages with values equal to 88 and 84% for the groups monitored at the wavelengths (λ) of 217 and 281nm. The degradation kinetics presented a good fit to the kinetic model proposed by Chan and Chu (2003) with R2 equal to 0.99, indicating a pseudo-first-order degradation profile. Finally, toxicity tests were carried out with two types of seeds, watercress and cabbage, for the solution before and after treatment. The cabbage seeds showed a reduction in germination percentages for the samples after treatments, while no toxicity was observed for watercress ones. This highlights the importance of evaluating the implications caused by products in relation to different organisms representing the biota.

Optimizing junction interface integrity between 3D/2D defect pyrochlore Bi1.8Fe0.2WO6 and g-C3N4 nanostructures: A novel multifunctional nanocomposite for enhanced photocatalytic and photo-electrocatalytic water splitting and water remediation applications

In this work, a simplistic composite fabrication of defect pyrochlore Bi1.8Fe0.2WO6 (BFWO) and g-C3N4 (g-CN) was carried out to augment the photocatalytic degradation kinetics and Hydrogen (H2) evolution rate. The structural confirmation through XRD and FTIR confirmed the successful formation of pristine g-C3N4, BFWO NPs, and their composites. FESEM micrographs revealed multilayered sheet-like formation for C3N4 whereas irregular cuboid-shaped structure for BFWO NPs. In the composite formation, the sheets tended to appear wrapped around the BFWO NPs. The UV-DRS absorbance spectra exhibited a highlighted increase in the absorbance region towards the visible light region following a decrease in the band gap. The photoluminescence lifetime studies revealed an enhanced lifetime of excitons to 6.21 ns for 50:50 (g-C3N4: BFWO) composite formation, whereas pristine g-CN displayed an average lifetime of about 4.79 ns. The degradation efficacy in the removal of RhB and MB from water revealed up to 100% and 95.5% removal rates in under 90 mins and 180 mins respectively using the 50:50 composite formation. Similarly, the H2 evolution rate was significantly improved and exhibited up to 370 μmol/h/g. The photo-electrochemical studies revealed a sharp charge separation of excitons for 50:50 (g-C3N4: BFWO) with a maximum photocurrent density of -0.54 μA/cm2 @ 0 V which is 3.6 times and 13.5 times higher than bare g-CN and BFWO. 1.33 V vs. RHE for OER kinetics and -0.09 V vs RHE for HER kinetics were the minimal onset potential exhibited for equal ratios of BFWO and g-CN. Coupled with the heightened charge separation, reduced recombination rate, and optimal band edge positions, the photocatalytic efficiency in the degradation of RhB and MB and water-splitting reactions were improved.

The Impact of Temperature and the Duration of Freezing on a Hydrogel Used for a 3D-Bioprinted In Vitro Skin Model.

Skin bioprinting has the potential to revolutionize treatment approaches for injuries and surgical procedures, while also providing a valuable platform for assessing and screening cosmetic and pharmaceutical products. This technology offers key advantages, including flexibility and reproducibility, which enable the creation of complex, multilayered scaffolds that closely mimic the intricate microenvironment of native skin tissue. The development of an ideal hydrogel is critical for the successful bioprinting of these scaffolds with incorporated cells. In this study, we used a hydrogel formulation developed in our laboratory to fabricate a 3D-bioprinted skin model. The hydrogel composition was carefully selected based on its high compatibility with human skin cells, incorporating alginate, methyl cellulose, and nanofibrillated cellulose. One of the critical challenges in this process, particularly for its commercialization and large-scale production, is ensuring consistency with minimal batch-to-batch variations. To address this, we explored methods with which to preserve the physicochemical properties of the hydrogels, with a focus on freezing techniques. We validated the pre-frozen hydrogels' printability, rheology, and mechanical and surface properties. Our results revealed that extended freezing times significantly reduced the viscosity of the formulations due to ice crystal formation, leading to a redistribution of the polymer chains. This reduction in viscosity resulted in a more challenging extrusion and increased macro- and microporosity of the hydrogels, as confirmed by nanoCT imaging. The increased porosity led to greater water uptake, swelling, compromised scaffold integrity, and altered degradation kinetics. The insights gained from this study lay a solid foundation for advancing the development of an in vitro skin model with promising applications in preclinical and clinical research.

Assessing Lettuce Exposure to a Multi-Pharmaceutical Mixture in Soil: Insights from LC-ESI-TQ Analysis and the Impact of Biochar on Pharmaceutical Bioavailability.

Agricultural practices introduce pharmaceutical (PhAC) residues into the terrestrial environment, potentially endangering agricultural crops and human health. This study aimed to evaluate various aspects related to the presence of pharmaceuticals in the lettuce-soil system, including bioconcentration factors (BCFs), translocation factors (TFs), ecotoxicological effects, the influence of biochar on the PhAC bioavailability, persistence in soil, and associated environmental and health risks. Lettuce (Lactuca sativa L.) was exposed to a mixture of 25 PhACs in two scenarios: initially contaminated soil (ranging from 0 to 10,000 ng·g-1) and soil irrigated with contaminated water (ranging from 0 to 1000 μg·L-1) over a 28-day period. The findings revealed a diverse range of BCFs (0.068-3.7) and TFs (0.032-0.58), indicating the uptake and translocation potential of pharmaceuticals by lettuce. Significant ecotoxicological effects on L. sativa, including weight change and increased mortality, were observed (p < 0.05). Interestingly, biochar did not significantly affect PhAC uptake by L. sativa (p > 0.05), while it significantly influenced the soil degradation kinetics of 12 PhACs (p < 0.05). Additionally, the estimated daily intake of PhACs through the consumption of L. sativa suggested negligible health risks, although concerns arose regarding the potential health risks if other vegetable sources were similarly contaminated with trace residues. Furthermore, this study evaluated the environmental risk associated with the emergence of antimicrobial resistance (AMR) in soil, as medium to high. In conclusion, these findings highlight the multifaceted challenges posed by pharmaceutical contamination in agricultural environments and emphasize the importance of proactive measures to mitigate the associated risks to both environmental and human health.

Influence of polypropylene and high-density polyethylene on isothermal pyrolytic degradation of discarded bakelite: Kinetic analysis and batch pyrolysis studies

The recycling of thermosetting plastics such as discarded bakelite poses greater challenges than thermoplastic polymers like polypropylene (PP) and high-density polyethylene (HDPE), particularly through pyrolysis requiring specialized reactors. This study examines the isothermal thermal degradation kinetics and batch pyrolysis behaviors of bakelite, along with its blends with PP and HDPE, emphasizing the characterization of pyrolytic oils for designing optimized reactors. For the study on isothermal thermal degradation kinetics, isothermal thermogravimetric analysis was performed at specified temperatures (300, 350, 400, 450, and 500°C), chosen based on the predominant non-isothermal degradation behavior of bakelite. The batch pyrolysis of discarded bakelite and blended bakelite with PP/HDPE is carried out at 450°C. The chemical composition analysis of pyrolytic oils is performed using Fourier transform infrared (FTIR) spectroscopy, with comprehensive compound analysis conducted using Gas Chromatography-Mass Spectrometry (GCMS). Isothermal thermogravimetry at temperatures ranging from 300°C to 500°C reveals increased thermal degradation with rising pyrolytic temperatures, reaching maximum weight losses of 55 % for bakelite, 82.74 % for PP-bakelite blends, and 90.8 % for HDPE-bakelite blends at 500°C. The isothermal kinetics study reveals that bakelite degrades via D1-diffusion, polypropylene-blended bakelite via A2-Avrami-Erofeyev, and high-density polyethylene-blended bakelite via A3-Avrami-Erofeyev, with activation energies of 17.178, 7.193, and 3.550 kJ/mol, and Arrhenius constants of 0.095, 0.042, and 0.017 min.−1, respectively. The highest condensable yield of 58.76 % during PP-blended bakelite co-pyrolysis underscores its potential for resource recovery. FTIR and GC-MS confirm the presence of alkanes, cycloalkanes, alkenes, cycloalkenes, aromatic hydrocarbons, and oxygenated compounds in the pyrolytic oils, providing detailed insights into their chemical composition. These findings offer critical insights into the thermal degradation behavior and kinetics of bakelite and polypropylene/high-density polyethylene-blended bakelite, highlighting opportunities for efficient waste plastic utilization through pyrolysis for resource recovery and energy generation, and providing essential knowledge for designing isothermal pyrolysis reactors.

Synergistic Regulation of Polyselenide Dissolution and Na‐Ion Diffusion of Se‐Vacancy‐Rich Bismuth Selenide toward Ultrafast and Durable Sodium‐Ion Batteries

AbstractMetal selenides (MSes) have great potential as candidate anode materials in high‐specific‐energy sodium‐ion batteries (SIBs) but are plagued by rapid capacity degradation and slow kinetics. Here, it is reveal that the Bi2Se3 anode discharge process involves multiple‐types of sodium polyselenides (Na‐pSex) which suffer from terrible dissolution and shuttling properties. Based on these observations, a nanoflower‐like composite of dual carbon‐confined Bi2Se3−x crystallites is designed via facile defect chemistry. The robust dual N‐doped carbon layer suppresses the precipitation and aggregation of Bi2Se3, significantly alleviating the dissolution and shuttle effect of Na‐pSex. Theoretical calculations indicate that the pyridine/pyrrole nitrogen sites exhibit strong van der Waals resistance and chemisorption properties against Na2Se4 and Na2Se2. Furthermore, the abundant Se vacancies improve the inherent conductivity of Bi2Se3, reduce the diffusion barrier of Na+, and accelerate the reaction kinetics. Consequently, the resulting Bi2Se3−x@DNC electrode exhibits extraordinary durability (over 2000 cycles at 10.0 A g−1) and high‐rate capability (354.4 mAh g−1 at 75.0 A g−1), propelling the battery performance to new heights. Encouragingly, the assembled hybrid capacitor displays competitive rate performance and an ultra‐long lifespan exceeding 40 000 cycles, making the Bi2Se3−x@DNC electrode a promising candidate for SIBs.

A CuBTC/CuS Photocatalyst for Organic Dyes: Degradation Kinetics and Mechanistic Insights

AbstractOrganic dyes derived from industrial processes have harmful potential to aquatic systems and require novel oxidative treatment. Metal‐organic frameworks (MOF) couple high adsorption capacity and photocatalytic action, which can be improved through heterojunctions. In this work, CuBTC (MOF) photocatalyst was synthesized by an electrochemical methodology, and the in situ CuS templated formation by addition of Na2S solution, giving CuBTC/CuS composites. The synthesized CuBTC MOF and CuBTC/CuS composites were characterized by XRD, FTIR, TGA, and EDX. The adsorptive capacity and photocatalytic properties were evaluated by the photocatalytic performance against methylene blue (MB) aqueous solution, under dark and simulated solar irradiation. Under simulated solar irradiation, the CuBTC/CuS achieved 87 % dye photodegradation after 120 min, 1.7 times higher than CuBTC. The photocatalytic action mechanisms were investigated by free‐radical capture experiments. At the equilibrium, the photocatalytic process presented pseudo‐first‐order (PFO) and pseudo‐second‐order (PSO) non‐linear kinetic models, showing a higher correlation with the PFO model, with a rate constant of 94.3×10−3 min−1. The photocatalytic performance of the composite was also evaluated over five cycles, decreasing to 68 %. The proposed strategy showed promise for the developing of highly effective materials to combat water pollution.

Bubbles Counting Using Organic Pollutants Degradation as a Probe

Relying on the fact that both of chemical and physical impacts of sonication are in strong relation to the number of acoustic cavities, the present paper introduces an innovative technique for the estimation of the number of active bubbles using the degradation of nonvolatile pollutants in the bulk liquid as a probe. The internal (gas pages) and external (liquid) bubble sonochemistry were simulated to track the radicals generation and use for nonvolatile pollutants degradation (in the liquid phase). To this end, COPASI® chemical kinetics software has been used for optimizing the acoustic bubble number density by linking the instantaneous bubble gas reaction (described by a bubble dynamic model accounting for the radical dissolution mechanism) and the aqueous free radicals degradation kinetics [i.e. concentration vs. time] of several nonvolatile organics (phenol, 4-chlorophenol, dyes…). Based on this strategy, the number density of active bubbles was determined for different operating circumstances (i.e. acoustic intensity, frequency, liquid temperature and saturation gas type). The performance of our method was evaluated by comparing our findings to those available in the literature, where an excellent agreement was established. Our technique showed that the number density monotonously goes up with increasing ultrasound frequency from 200 to 1140kHz, regardless of the experimental conditions used in this investigation. The opposite behavior has been obtained with the increase of the liquid temperature and acoustic intensity. Additionally, it has been noticed that the variation in the number of cavities with respect to the nature of saturating gas is frequency-dependent. At a frequency of 200kHz, the number of bubbles is in the order: O2>Ar>air. However, over this frequency (>200kHz), the number of acoustic bubbles is in the order: O2>air>Ar. On the other hand, it has been shown that below a frequency of ~860kHz, the variation of void fraction (ε) is synchronized with change in number density (N); nevertheless, over this value (>860kHz), these two parameters (N, ε) are no longer closely connected. As a result, in this case (>860kHz), the evaluation of number density from the total volume fraction of bubbles could not be directly performed without more information regarding the bubbles population, (e.g. size distribution, bubble-bubble interactions, bubbles deformation…etc.). Finally, the current proposed technique is flexible and can determine the number density of active bubbles for a wide range of operating conditions and circumstances.

E3 ubiquitin ligase FBXO22 inhibits SARS-CoV-2 replication via promoting proteasome-dependent degradation of NSP5.

The ubiquitin-proteasome system is frequently employed to degrade viral proteins, thereby inhibiting viral replication and pathogenicity. Through an analysis of the degradation kinetics of all the SARS-CoV-2 proteins, our study revealed rapid degradation of several proteins, particularly NSP5. Additionally, we identified FBXO22, an E3 ubiquitin ligase, as the primary regulator of NSP5 ubiquitination. Moreover, we validated the interaction between FBXO22 and NSP5, demonstrating that FBXO22-mediated ubiquitination of NSP5 facilitated its recognition by the proteasome, leading to subsequent degradation. Specifically, FBXO22 catalyzed the formation of K48-linked polyubiquitin chains on NSP5 at lysine residues 5 and 90. Knockdown of FBXO22 resulted in decreased NSP5 ubiquitination levels, increased stability, and enhanced ability to evade the host innate immune response. Notably, the protein level of FBXO22 were negatively correlated with SARS-CoV-2 load, highlighting its importance in inhibiting viral replication. This study elucidates the molecular mechanism by which FBXO22 mediates the degradation of NSP5 and underscores its critical role in limiting viral replication. The identification of FBXO22 as a regulator of NSP5 stability provides new insights and potential avenues for targeting NSP5 in antiviral strategies.

Co-metabolic growth and microbial diversity: Keys for the depletion of the α, δ, β and γ-HCH isomers

The objective of this study was the isolation and enrichment of microbiomes capable of degrading the main hexachlorocyclohexane isomers quantified in environmental matrices, e.g.: the α, δ, β and γ-HCH isomers. Four microbiomes were isolated and enriched from an HCH-contaminated dumpsite in Italy, both in the presence of HCH isomers (1:1:1:1) as the sole carbon sources and under co-metabolic growth conditions in presence of glucose (0.1 % v/v). The microbiomes were assessed for their relevant metabolic capabilities. A quantitative metabarcoding approach was employed to analyze the compositional evolution of the four microbiomes during the enrichment phase and the phase of testing of the HCH isomers degradation kinetics. The use of a co-metabolic substrate during enrichment process was essential for selecting microbiomes with higher biodiversity. All microbiomes efficiently degraded the α, δ, and γ-HCH isomers. The highest efficiency in the β-HCH degradation capacity was positively correlated to the highest biodiversity of the microbiome, and the involvement of Chryseobacterium and Asinibacterium sps. have been proposed for a recorded increment in bacterial load during the HCH degradation process.

β-Cyclodextrin-Modified Cotton Fabric for Medical and Hospital Applications with Photodynamic Antibacterial Activity Using Methylene Blue

The use of cyclodextrins in textiles for the development of biofunctional fabrics represents an interesting alternative for the advancement of dental, medical, and hospital materials. Cyclodextrins can interact with the chemical groups present in cotton fibers, leading to the formation of a nanostructured surface with specific functional properties, including antibacterial activity. Although there are numerous antibacterial textile finishes, the use of methylene blue as a cyclodextrin host molecule for photodynamic applications in textile materials remains to be investigated. This is because methylene blue is a photosensitive dye capable of generating singlet oxygen (1O2) when illuminated, which inactivates the pathogenic microorganisms that may be present in wounds. The objective of this study was to develop a biofunctionalized and photoactivatable cotton fabric with antimicrobial properties for use in the cosmetic or medical industries. The materials obtained were characterized via scanning electron microscopy (SEM), Fourier transform infrared spectroscopy with attenuated total reflection (FTIR-ATR), the determination of cotton fabric functionalization dyeing variables, colorimetry, UV-VIS spectrophotometry, degradation of 9,10-anthracenediyl-bis(methylene)dimalonic acid (ABDA), photodegradation tests, and microbiological analysis. The results showed that the textile was functionalized with β-cyclodextrin, mainly evidenced by the appearance of the band at 1730 cm−1, indicating the formation of the ester group. Thus, when exposed to light, the non-functionalized material showed greater photobleaching, about 60%, compared to the material treated with cyclodextrin. This result was also reflected in the ABDA degradation kinetics, with the treated material showing 592.00% (first phase) and 966.20% (second phase) higher degradation than the untreated sample. Finally, the photodynamic activity was determined based on the antimicrobial properties of the textile, showing a reduction of more than 99% without exposure to light and 100% when exposed to light. It is believed that this study could open avenues for future research and the development of antimicrobial fabrics, as well as demonstrate the efficiency of the treatment with cyclodextrin in relation to photobleaching.

57 In vitro degradation kinetics of protein and starch from equine feedstuffs (corn, beet pulp, oat hulls, soybean meal, whey, timothy, and alfalfa hay)

57 In vitro degradation kinetics of protein and starch from equine feedstuffs (corn, beet pulp, oat hulls, soybean meal, whey, timothy, and alfalfa hay)

PSIII-18 Effects of dietary exogenous fibrolytic enzymes on ruminal degradation kinetics of beef steers offered a high- and low-quality feedlot growing diets

PSIII-18 Effects of dietary exogenous fibrolytic enzymes on ruminal degradation kinetics of beef steers offered a high- and low-quality feedlot growing diets

Determination of degradation for sulfo-SIAB, SM(PEG)2, and sulfo-GMBS by RPLC-UV analysis

Bi-functional N-Hydroxysuccinimide (NHS) linkers are widely used in the conjugation processes linking an immunogen with a carrier protein capable of boosting immunity. A potential vaccine candidate against HIV-1, called fusion peptide (FP), is covalently linked to the recombinant tetanus toxoid heavy-chain fragment C (rTTHC) via this type of linker. A reversed-phase liquid chromatography (RPLC-UV) method was used to monitor the linker’s degradation kinetics in various buffers, mimicking the steps in the conjugation process. The kinetics of the reactivities of the linkers are revealed in this study and can provide a good guidance to help effective conjugation process before these linkers are completely hydrolyze to the inactive degradants. Three cross-linkers degradation pathways were evaluated: Sulfosuccinimidyl (4-iodoacetyl) aminobenzoate (Sulfo-SIAB), PEGylated SMCC (SM(PEG)2), and N-γ-maleimidobutyryl-oxysulfosuccinimide ester (Sulfo-GMBS). We have reported kinetics for Sulfo-SIAB.

Heterogeneous degradation kinetics of typical pyrimidine pesticides toward OH radicals

Pirimiphos-methyl (PMM) and pirimicarb (PM) are two typical N,N-dialkyl substituted pyrimidine pesticides widely applied in agriculture. They are emitted into the atmosphere via spraying and post-application volatilization, but their heterogeneous degradation kinetics toward OH radicals has not been well characterized. Therefore, the degradation rates of particle-associated PMM and PM with OH radicals were studied under different conditions including particle type, relatively humidity (RH), and temperature. The experimental results indicated that the degradation rates of PMM and PM adsorbed on hydrophilic SiO2 particles were faster than those adsorbed on hydrophobic SiO2 particles, suggesting that heterogeneous kinetics was affected by surface properties of SiO2 particles. The degradation rates of PMM and PM adsorbed on these two kinds of SiO2 particles under experimental conditions ranged from (10.8 ± 0.7) × 10−12 and (6.1 ± 0.8) × 10−12 to (28.0 ± 1.7) × 10−12 and (13.5 ± 1.2) × 10−12 cm3 molecule−1 s−1, respectively. Additionally, these rate constants showed a negative relationship with increasing RH level (20−80%) while a positive relationship with elevating temperature (5−35 °C). Arrhenius expressions for their heterogeneous degradation and the corresponding activation energies were calculated. According to the obtained degradation rates, the atmospheric lifetimes of particle-associated PMM and PM toward OH radicals were in the ranges of 9.9–25.8 and 20.7−46.1 h, respectively, suggesting that OH-initiated heterogeneous degradation might be an important pathway during their atmospheric transformation processes. The experimental kinetic data obtained in this work are in favor of improving the understandings of atmospheric lifetimes of particle-associated PMM and PM, and also highlight that the environmental factors including particle type, RH, and temperature should be seriously taken into account for determining the atmospheric lifetimes of pesticides.

Effects of novel halogen-free flame-retardant binary additives on thermal stability, degradation kinetics and flame retardancy of cotton cellulose biomacromolecule

The principal component of cotton fibers is the cellulose biological macromolecule. However, its highly flammable nature has significantly constrained its utilization in fields where flame retardancy is essential. Herein, in this work, a highly effective binary composite flame retardant coating (APP/MEL-SWCNHs) with ammonium polyphosphate and modified single-walled carbon nanohorns (MEL-SWCNHs) was chemically attached to cotton fabric. With the add-on of 11.3 %, the treated cotton fabric (APP/MEL-SWCNHs)4 exhibited remarkable flame-retardant and self-extinguishing properties. Its LOI value increased to 23.7 ± 0.1 %, and the damage length was significantly reduced from 30.0 ± 0.1 % cm to 7.9 ± 0.1 % cm compared to the pristine cotton fabric. Despite partial carbonization, (APP/MEL-SWCNHs)4 preserved its original structure. Importantly, in the cone calorimeter test, both the pHRR and THR of (APP/MEL-SWCNHs)4 were drastically decreased by 71.8 % and 35.8 %, respectively. The APP/MEL-SWCNHs coating functioned as a flame retardant by inhibiting the emission of flammable volatiles, releasing non-flammable gases, and encouraging the formation of char layer during combustion. Significantly, thermal degradation kinetic analysis revealed that the third-order kinetic equation (O3) was found to have the strongest correlation with (APP/MEL-SWCNHs)4 in both air and N2 atmospheres. The higher activation energy (E) for (APP/MEL-SWCNHs)4 confirmed that incorporating MEL-SWCNHs improved the thermal stability of the char layer.

Effect of Fermented Soy Beverage on Equol Production by Fecal Microbiota.

Soy consumption is associated with health benefits, mainly linked to the ability of the intestinal microbiota to metabolize the glycosylated isoflavones into more bioactive compounds, such as equol. Because Bifidobacterium pseudocatenulatum INIA P815 is able to efficiently deglycosylate daidzin into daidzein, the aim of this work was to confirm the influence of soy beverages fermented by B. pseudocatenulatum INIA P815 for enhancing equol production by fecal microbiota. Firstly, fecal samples from 17 participants were characterized in vitro, and we observed that 35.3% of them were able to produce equol from daidzein. In addition, the kinetics of equol production and degradation by fecal microbiota were evaluated, determining that 30-85% of equol is degraded after 24 h of incubation. Finally, the influence of fermented soy beverage on improving the production of equol by selected equol-producing fecal samples and by the equol-producing strain Slackia isoflavoniconvertens was analyzed through a colonic model. Fermented soy beverage enhanced the equol production from S. isoflavoniconvertens as well as the fecal samples whose microbiota showed high rates of equol degradation. The results obtained confirm that the fermentation of soy beverages with selected bacterial strains improves the functional properties of these beverages in terms of isoflavone metabolism and equol production.

Investigation of thermal, optical properties, AC conductivity and broadband dielectric spectroscopy of poly(ethyl methacrylate)/poly(vinyl chloride) polymer blend

This work reports the structural, thermal, optical and electrical properties of PEMA, PVC and their polyblends. These properties are investigated by FTIR, TGA, UV/Vis and broadband dielectric spectroscopy. FTIR spectra showed that the characteristic bands of PEMA and PVC are affected by blending and displayed red and blue shifts confirming that an intermolecular interaction between PEMA and PVC is occurred. Thermal degradation kinetics of PEMA, PVC and its polyblend samples is investigated in details and the thermal properties of each decomposition stage are estimated. UV measurements analysis revealed that Urbach energy (EU) is increased while optical bandgap decreased upon increasing the PVC content. The indirect and direct band gap (Eig/Edg) values are decreased from (3.95/4.21) to (3.10/3.92) eV. Also, upon increasing the content of PVC, the lattice dielectric constant (εL) is increased from 2.71 to 7.83. Wemple-DiDomenico model is applied for investigating the refractive index dispersion and to calculate the oscillator and dispersion energies. It is observed that the linear/nonlinear parameters are increased nonlinearly with increasing the PVC content. χ(1), χ(3) and n2 values are found to increase from 0.104, 0.213 × 10−13 and 4.01 × 10−12 to 0.363, 31.26 × 10−13 and 5.33 × 10−12. These results make PEMA/PVC polyblend strong candidates for use in the development and design of advanced optoelectronic devices. AC conductivity (σac) and dielectric measurements are carried out at various temperatures in wide frequency range. Jonscher power law is applied and showed that the predominant conduction mechanism in our samples is overlapping large-polaron tunneling (OLPT). The dielectric constant and electrical impedance are found to be frequency and temperature dependent. The investigation of the electric modulus (M*) revealed that M′ is increased non-linearly with increasing the frequency, while M″ spectra displayed two different modes of relaxation. The interfacial polarization (IP) is observed in low frequency region, while, dipolar relaxation is detected in high frequency region.