Two rapid, simple, sensitive and selective derivative spectrofluorimetric methods (first and second derivative synchronous spectrofluorimetric (FDSFS and SDSFS) procedures) have been developed for the analysis of florfenicol in the presence of its various degradation products. FDSFS was applied to assay the drug in the presence of its alkaline, oxidative and photolytic degradation products while SDSFS was used to quantify it in the presence of its acidic degradation product. These methods permitted quantification of florfenicol at corresponding λ Em of 288, 287, 279 and 284 nm without interferences from any of its degradation products. Full validation procedures were applied to the suggested method according to International Conference of Harmonization guidelines. Moreover, different degradation kinetic parameters were calculated such as half-life (t 1/2), degradation rate constant (K) and activation energy (E a). Using the analytical eco-scale, green analytical procedure index and analytical greenness metric approach AGREE as greenness assessment tools, the proposed method was found to be environmentally friendly.

The encapsulation of β-carotene was investigated using pullulan and whey protein isolate (WPI) as a composite matrix at a weight ratio of 20:80, employing both spray-drying and freeze-drying techniques. The influence of processing parameters such as the concentration of wall material, flow rate, and inlet temperature for SP encapsulants, as well as wall-material concentration for FZ encapsulants, was examined in terms of encapsulation efficiency (EE). The morphology, structural characterization, moisture sorption isotherms, and thermal properties of the resulting encapsulants at optimum conditions were determined. Their stability was investigated under various levels of water activity, temperature conditions, and exposure to UV-Vis irradiation. β-carotene was efficiently encapsulated within SP and FZ structures, resulting in EE of approximately 85% and 70%, respectively. The degradation kinetics of β-carotene in both structures followed a first-order reaction model, with the highest rate constants (0.0128 day-1 for SP and 0.165 day-1 for FZ) occurring at an intermediate water-activity level (aw = 0.53) across all storage temperatures. The photostability tests showed that SP encapsulants extended β-carotene\'s half-life to 336.02 h, compared with 102.44 h for FZ encapsulants, under UV-Vis irradiation. These findings highlight the potential of SP encapsulants for applications in functional foods, pharmaceuticals, and carotenoid supplements.

This study investigated degradation behaviors of a nonsteroidal anti-inflammatory drug Nabumetone (NMT) and its major metabolite 6-methoxy-2-naphthylacetic acid (MNA) in the coupling process of ultraviolet and monochloramine (UV/NH2Cl). The second-order rate constants of the contaminants reacting with reactive radicals (HO•, Cl•, Cl2•⁻, and CO3•⁻) were determined by laser flash photolysis experiments. HO• and Cl• contributed predominantly with 52.3% and 21.7% for NMT degradation and 60.8% and 22.3% for MNA degradation. The presence of chlorides retarded the degradation of NMT, while promoted the destruction of MNA, which was ascribed to the photosensitization effects of MNA under UV irradiation. Density functional theory (DFT) calculations revealed that radical adduct formation (RAF) was dominant pathway for both HO• and Cl• reacting with the contaminants, and hydrogen atom transfer (HAT) preferred to occur on side chains of NMT and MNA. NMT reacted with NO2• through single electron transfer (SET) with the second-order rate constant calculated to be 5.35 × 107 (mol/L)-1 sec-1, and the contribution of NO2• was predicted to be 13.0% of the total rate constant of NMT in pure water, which indicated that NO2• played a non-negligible role in the degradation of NMT. The acute toxicity and developmental toxicity of NMT were enhanced after UV/NH2Cl treatment, while those of MNA were alleviated. The transformation products of both NMT and MNA exhibited higher mutagenicity than their parent compounds. This study provides a deep understanding of the mechanism of radical degradation of NMT and MNA in the treatment of UV/NH2Cl.

This study investigates the enzymatic degradation processes of different classes of polyhydroxyalkanoates (PHAs), a group of biopolymers naturally synthesized by various microorganisms. Medium chain length PHAs (mcl-PHAs) are distinguished biopolymers due to their biodegradability and diverse material properties. Using quartz crystal microbalance measurements as a valuable tool for accurate real-time monitoring of the enzymatic degradation process, the research provides detailed kinetic data, describing the interaction between enzymes and substrates during the enzymatic degradation process. Thin films of poly-3-hydroxybutyrate (PHB) and polyhydroxyoctanoate copolymer (PHO), containing molar fractions of about 84% 3-hydroxyoctanoate and 16% 3-hydroxyhexanoate, were exposed to scl-depolymerases from Pseudomonas lemoignei LMG 2207 and recombinant mcl-depolymerase produced in Escherichia coli DH5α harboring the plasmid pMAD8, respectively. Analyses based on a heterogeneous kinetic model for the polymer degradation indicated a six-fold stronger adsorption equilibrium constant of mcl-depolymerase to PHO. Conversely, the degradation rate constant was approximately twice as high for scl-depolymerases acting on PHB. Finally, the study highlights the differences in enzyme-substrate interactions and degradation mechanisms between the investigated scl- and mcl-PHAs.

A green micellar stability-indicating high-performance liquid chromatography method was developed for rupatadine fumarate determination in existence with its main impurity desloratadine. Separation was attained using Hypersil ODS column (150 × 4.6 mm, 5 μm), the micellar mobile phase consisted of 0.13 M sodium dodecyl sulfate, 0.1 M disodium hydrogen phosphate adjusted by phosphoric acid to pH 2.8 and 10% n-butanol. The column was maintained at 45◦ C and detection was carried out at 267 nm. A linear response was achieved over the range of 2-160 μg/ml for rupatadine and 0.4-8 μg/ml for desloratadine. The method was applied for rupatadine determination in alergoliber tablets and alergoliber syrup without the interference of methyl paraben and propyl paraben present as main excipients. Rupatadine fumarate revealed pronounced susceptibility to oxidation; further study of oxidative degradation kinetics was carried out. Rupatadine was found to follow pseudo-first-order kinetics when exposed to 10% H2 O2 at 60 and 80°C and the activation energy was found to be 15.69 Kcal/mol. At a lower temperature (40°C), degradation kinetics regression was best fitted as a polynomial quadratic relationship, thus rupatadine oxidation at a lower temperature tends to adopt a second-order kinetics rate. Oxidative degradation product structure was revealed using infrared and found to be rupatadine N-oxide at all temperature values.

Neonicotinoid insecticides (NEOs) are commonly used to prevent unwanted insects in urban fields. Degradation processes have been one of the important environmental behaviors of NEOs in an aquatic environment. In this research, hydrolysis, biodegradation, and photolysis processes of four typical NEOs (i.e., thiacloprid (THA), clothianidin (CLO), acetamiprid (ACE), and imidacloprid (IMI)) were examined through the adoption of response surface methodology-central composite design (RSM-CCD) for an urban tidal stream in South China. The influences of multiple environmental parameters and concentration levels on the three degradation processes of these NEOs were then evaluated. The results indicated that the three degradation processes of the typical NEOs followed a pseudo-first-order reaction kinetics model. The primary degradation process of the NEOs were hydrolysis and photolysis processes in the urban stream. The hydrolysis degradation rate of THA was the highest (1.97 × 10-5 s-1), and that of CLO was the lowest (1.28 × 10-5 s-1). The temperature of water samples was the main environmental factor influencing the degradation processes of these NEOs in the urban tidal stream. Salinity and humic acids could inhibit the degradation processes of the NEOs. Under the influence of extreme climate events, the biodegradation processes of these typical NEOs could be suppressed, and other degradation processes could be further accelerated. In addition, extreme climate events could pose severe challenges to the migration and degradation process simulation of NEOs.

The degradation and transformation of iodinated alkanes are crucial in the iodine chemical cycle in the marine boundary layer. In this study, MP2 and CCSD(T) methods were adopted to study the atmospheric transformation mechanism and degradation kinetic properties of CH3 I and CH3 CH2 I mediated by ⋅OH radical. The results show that there are three reaction mechanisms including H-abstraction, I-substitution and I-abstraction. The H-abstraction channel producing ⋅CH2 I and CH3 C ⋅ HI radicals are the main degradation pathways of CH3 I and CH3 CH2 I, respectively. By means of the variational transition state theory and small curvature tunnel correction method, the rate constants and branching ratios of each reaction are calculated in the temperature range of 200-600 K. The results show that the tunneling effect contributes more to the reaction at low temperatures. Theoretical reaction rate constants of CH3 I and CH3 CH2 I with ⋅OH are calculated to be 1.42×10-13 and 4.44×10-13  cm3  molecule-1  s-1 at T=298 K, respectively, which are in good agreement with the experimental values. The atmospheric lifetimes of CH3 I and CH3 CH2 I are evaluated to be 81.51 and 26.07 day, respectively. The subsequent evolution mechanism of ⋅CH2 I and CH3 C ⋅ HI in the presence of O2 , NO and HO2 indicates that HCHO, CH3 CHO, and I-atom are the main transformation end-products. This study provides a theoretical basis for insight into the diurnal conversion and environmental implications of iodinated alkanes.

First derivative synchronous fluorescence spectroscopy (FDSFS) was applied to detect and quantify either ciprofloxacin (CIP) or levofloxacin (LEV) simultaneously with their photodegradation products, where the photolytic pathway for each analyte was found to be pH dependent. Under the guidance of early published articles, the structure of the produced photolytic products could be concluded, and further related to their resultant fluorescence spectra. The proposed method was subjected to full validation procedure which enables its application in investigating the photodegradation kinetics for both drugs. The obtained kinetic parameters were in accordance with previous reports and could be linked to predict the antibacterial activity of the resultant photodegradation products. These facts prove the suitability of the suggested FDSFS to serve as a stability-indicating assay method and to trace the photofate of CIP and LEV in the ecosystem as potential contaminants. Furthermore, the greenness of the suggested analytical methodology was evaluated via \'Green Analytical Procedure Index\' (GAPI), which classifies it as an eco-friendly assay. Eventually, no extraction, treatment or preparation steps were needed during all analysis steps, which renders the proposed assay an appealing tool in environmental analysis.

BACKGROUND: The present study focused on the effect of isothermal treatment (5-90 °C) and pH (2.0-6.0) of aqueous olive leaf phenolic extract solutions on the kinetics of degradation of single and total phenolic compounds and radical scavenging activity, with the objective of predicting and optimizing the thermal treatments in foods enriched with olive leaf extracts.
RESULTS: The major compound, oleuropein, showed higher degradation at low pH 2.0 and temperature-dependent reaction rates, which fitted well a first-order kinetic model, with an estimated activation energy of 98.03 ± 0.08 kJ mol-1 . Oleuropein hydrolysis resulted in a zero-order increase in hydroxytyrosol concentration at same pH (Ea  = 71.59 ± 1.5 kJ mol-1 ), whereas a 100-fold slower degradation rate was observed at higher pH. Verbascoside was only degraded at pH 6.0, also following first-order kinetics. These changes in oleuropein and hydroxytyrosol concentrations led to significant changes in fluorescence maximum intensities centered around 315 and 360 nm and in the 425-500 nm spectral zone for samples at pH 6.0, which could be associated with verbacoside degradation. Conversely, analysis of total phenolic content and 2,2\'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) radical scavenging activity showed little changes, indicating a rather constant overall reducing capacity of the resulting pool of compounds after thermal treatments.
CONCLUSIONS: The present study can contribute to the knowledge related to oleuropein and phenolic fraction degradation as a result of matrix (pH) and processing. The kinetic parameters obtained could be applied for predicting and optimizing the thermal treatments in foods and drinks enriched with olive leaf extracts. © 2022 Society of Chemical Industry.

The wastewater generated from textile industries is highly colored and contains dyes including azo dyes, which are toxic to human and water-living organisms. The treatment of these azo dyes using conventional treatment techniques is challenging due to their recalcitrant properties. In the current study, the effect of additional Fe2+ on electrocoagulation (EC) using Fe electrodes has been studied for the removal of methyl orange (MO) azo dye. pH between 4-5 was found to be optimum for EC and treatment efficiency decreased with increasing dye concentrations. With the addition of Fe2+ salt, dye removal for a certain concentration was increased with the increase of current density and Fe2+ up to a certain limit and after that, the removal efficiency decreased. The COD, color and dye removals were 88.5%, 93.1% and 100%, respectively, for EC of 200 mg.L-1 dye solution using only 0.20 mmol.L-1 Fe2+ for 0.40 mA cm-2 current density, whereas for EC, the respective removal efficiencies were 76.7%, 63.4% and 82.4% for 32 min. The respective operating cost for EC was $768 kg-1 removed dye ($0.342 m-3), whereas, for EC with additional Fe2+ salt, it was $350 kg-1 removed dye ($0.189 m-3). The kinetic results revealed that the first-order kinetic model was fitted best for EC, whereas the second-order kinetic model was best fitted for Fe2+ added EC. For real textile wastewater, 57.6% COD removal was obtained for 0.15 mmol.L-1 Fe2+ added EC compared to 27.8% COD removal for EC for 32 min. Based on the study we can conclude that Fe2+ assisted EC can be used for effective treatment of textile wastewater containing toxic compounds like azo dyes.