Key Role of Corncob Based-Hydrochar (HC) in the Enhancement of Visible Light Photocatalytic Degradation of 2,4-Dichlorophenoxyacetic Acid Using a Derivative of ZnBi-Layered Double Hydroxides.

A superior heterojunction of HC-ZnBi-LDO was synthesized in two steps, namely hydrothermal carbonization, followed by co-precipitation. The 2% HC-ZnBi-LDO heterojunction photocatalysts could degrade over 90.8% of 30 mg/L 2,4-dichlorophenoxyacetic acid (2,4-D) using 1.0 g/L of the catalyst after 135 min of visible light exposure at pH 4. The activity of 2% HC-ZnO-LDO was remarkably stable. Approximately 86.4-90.8% of 30 mg/L 2,4-D was degraded, and more than 79-86.4% of TOC was mineralized by 2% HC-ZnBi-LDO at pH 4 after 135 min of visible light exposure during four consecutive cycles. The rapid separation and migration of charge carriers at the interfaces between HC and ZnBi-LDO were achieved within 2% HC-ZnBi-LDO. Moreover, the electron acceptor characteristic of HC in 2% HC-ZnBi-LDO caused the recombination of charge carriers to decrease significantly, thus generating more reactive radicals, such as hydroxyl radicals (OH●) and superoxide radicals (O2●-). These results demonstrate that the novel 2% HC-ZnBi-LDO is a superior photocatalyst for the remediation of hazardous organic pollutants.

Preparation of Ti/SnO2-Sb/La-ßPbO2 electrode and its application in the degradation of some pollutants including prednisolone and 8-Hydroxyquinoline.

In this work, a novel La-doped ßPbO2 (Ti/SnO2-Sb/La-ßPbO2) was prepared using electrodeposition method and applied to the degradation of prednisolone (PRD), 8-Hydroxyquinoline (8-HQ), and other typical organic pollutants. Compared with the conventional electrode Ti/SnO2-Sb/ßPbO2, La2O3 doping enhanced oxygen evolution potential (OEP), reactive surface area, stability and repeatability of the electrode. The 10 g L-1 of La2O3 doping exhibited the highest electrochemical oxidation capability of the electrode with [•OH]ss being determined at 5.6 × 10-13 M. The quenching experiments were conducted to confirm the main oxidizing species (here: •OH) in the electrochemical process. The study showed that the pollutants were removed in the electrochemical (EC) process with different degradation rates and indicated that the second-order rate constant of organic pollutants towards •OH (kOP,•OH) has a linear relationship with the degradation rate of organic pollutants (kOP) in the electrochemical process. Another new finding in this work is that a regression line of kOP,•OH and kOP can be used to estimate kOP,•OH of an organic chemical, which cannot be determined using the competition method. kPRD,•OH and k8-HQ,•OH were determined to be 7.4 × 109 M-1 s-1 and (4.6-5.5) × 109 M-1 s-1, respectively. Compared with conventional supporting electrolyte (like SO42-), H2PO4- and HPO42- improved kPRD and k8-HQ by 1.3-1.6-fold, while SO32- and HCO3- inhibited kPRD and k8-HQ significantly, down to 80%. Additionally, the degradation pathway of 8-HQ was proposed based on the detection of intermediates from GC-MS.

Studying the kinetic of midodrine degradations using TLC stability approach: Application to dosage form and human plasma.

A simple, rapid and selective thin layer chromatographic method has been developed for estimation of the antihypotension drug, midodrine hydrochloride, in pure form, tablet, spiked plasma and artificially degraded samples. Separation was carried out using silica gel 60-F254 as a stationary and mobile phase consisting of methanol: methylene chloride: ammonia in ratio of 8:2:0.2. The detection was carried out at wavelength of 290 nm. The retardation factor was found to be 0.7 and 0.49 for midodrine and its main degradation product desglymidodrine. The method showed linearity for midodrine over a concentration range of 50-1500 ng/spot with good correlation and determination coefficient. The method was applied successfully for analysis of commercial tablets and oral drops with good recovery and without interference of excipients. The method also was applied for studying the stability of the cited drug under different stress conditions including acidic, alkaline, hydrolytic, oxidative and photo- degradations. Furthermore, the kinetic of acidic and alkaline degradations was investigated and the rate constants were found to be 0.620 and 0.074 K h-1 while half life time (t1/2) values were 1.12 and 9.32 h, respectively.

Electrochemical degradation of indigo carmine, P-nitrosodimethylaniline and clothianidin on a fabricated Ti/SnO2-Sb/Co-ßPbO2 electrode: Roles of radicals, water matrices effects and performance.

In this study, the kinetic degradation of several typical organic pollutants was performed on a synthetic electrode (Ti/SnO2-Sb/Co-ßPbO2). The surface structure and the electrochemical properties of the prepared electrode were investigated, confirming the successful preparation of the electrode using an electrochemical deposition method. The outer layer (Co-ßPbO2) played an important role in reducing the resistance of the electrode and improving its degradation efficiency. The results showed that indigo carmine (IC), p-nitrosodimethylaniline (RNO), and clothianidin (CLO) were effectively degraded within 20 min of electrolysis. Their degradation in the electrochemical process followed the first-order kinetic model with the degradation rate constant of IC being higher than that of RNO and CLO. This was proved by the difference in the reactivity of the target pollutants toward oxidizing radicals (i.e., •OH, SO4•-, and Cl•). Their second-order rate constant towards radicals were in the range of 109 - 1010 M-1 s-1 with the highest value being that for IC: k·OH,IC = 15.1 × 109 M-1 s-1 and [Formula: see text]  = 7.4 × 109 M-1 s-1. The study calculated the contribution of some oxidizing species, including direct electron transfer (DET), •OH, SO4•-, and other reactive oxygen species (ROS). Solution pH, supporting electrolyte, and water matrix affected the degradation efficiency of pollutants and the contribution of the oxidizing species. Br- and I- ions enhanced the degradation rate of organic pollutants, while Fe2+, HCO3-, and humic acid (HA) reduced it. In addition, the toxicity, total organic carbon (TOC) removal, mineralization current efficiency (MCE), energy consumption, recyclability and stability of the prepared electrode were studied, suggesting that the prepared Ti/SnO2-Sb/Co-ßPbO2 is a good candidate for treating organic pollutants using the electrochemical oxidation process.

Effects of process parameters in microwave-assisted extraction on the anthocyanin-enriched extract from Rhodomyrtus tomentosa (Ait.) Hassk and its storage conditions on the kinetic degradation of anthocyanins in the extract.

Rhodomyrtus tomentosa (Ait.) Hassk (RTH) is a plant distributed mainly in Southeast Asia that has long been used as a food or a folk remedy for various ailments. Anthocyanins extracted from RTH have received the attention of researchers as well as manufacturers in exploiting the application of this plant for commercial purposes. Several extraction methods have been performed, however, concerns about new extraction methods, extraction conditions as well as stability of anthocyanins during storage are issues that need to be evaluated. In this study, the process of extracting anthocyanins by microwave method and the stability of anthocyanins in RTH extraction were investigated. For the extraction method, the influence of solvent concentration (30-70%), application ratio (10:1-1:1 mL/g), microwave power (100-500W), and time (1-9 min) have been evaluated. A first-order kinetic model was also used to evaluate the variation of anthocyanin content during storage at different conditions, including 5 °C (refrigerator), 30 °C (room temperature), and 45 °C (incubator). The study results showed that the anthocyanin content had the greatest value of 137.54 mg/L when extracted with 50% ethanol solvent with the material/solvent ratio of 1:3 (g/ml) microwave power is 200W for 5 min. The first-order decomposition kinetics model showed that the t1/2 values of the RTH extract were 69.64, 28.66, and 19.8, respectively, for the storage temperatures of 5 °C, 30 °C, and 45 °C, respectively. During storage, anthocyanin content tends to decrease more rapidly under high-temperature conditions. In addition, a close correlation between anthocyanin content and antioxidant capacity was recorded at a high significance level R2 > 0.98.

The enhanced degradation behavior of oxytetracycline by black soldier fly larvae with tetracycline resistance genes in the larval gut: Kinetic process and mechanism.

Black soldier fly larvae (larvae) can digest organic wastes and degrade contaminants such as oxytetracycline (OTC). However, compared to the kinetic processes and enhanced mechanisms used in the traditional microbial degradation of OTC, those employed by larvae are largely uncharacterized. To obtain further details, a combined analysis of larval development, larval nutritional values (crude protein, crude fat and the composition of fatty acids) and the expression of tetracycline resistance genes (TRGs) in the larval gut was performed for the degradation of OTC added to substrates and for oxytetracycline bacterial residue (OBR). When the larvae were exposed to the substrates, the degradation processes were enhanced significantly (P < 0.01), with a 4.74-7.86-fold decrease in the degradation half-life (day-1) and a 3.34-5.74-fold increase in the final degradation efficiencies. This result was attributed to the abundant TRGs (with a detection rate of 35.90%∼52.14%) in the larval gut. The TRGs presented the resistance mechanisms of cellular protection and efflux pumps, which ensured that the larvae could tolerate elevated OTC concentrations. Investigation of the TRGs indicated that enzymatic inactivation enhanced OTC degradation by larvae. These findings demonstrate that the larval degradation of antibiotic contaminants is an efficient method based on abundant TRGs in the larval gut, even though OTC degradation results in OBR. In addition, a more optimized system for higher reductions in antibiotic levels and the expansion of larval bioremediation to other fields is necessary.

Design of novel p-n heterojunction ZnBi2O4-ZnS photocatalysts with impressive photocatalytic and antibacterial activities under visible light.

Heterojunction structures have attracted considerable attention for enhancing electron migration across interfaces. In this report, ZnBi2O4-ZnS(12%) heterojunction photocatalysts was found to be capable of degrading over 94% of indigo carmine in a 15 mg/L solution within 90 min of visible light irradiation at a catalytic dose of 1.0 g/L and pH 4. Furthermore, more than 82% of the total organic carbon (TOC) was removed, confirming the almost complete mineralization of the indigo carmine by ZnBi2O4-ZnS(12%). Moreover, the photocatalyst exhibited high stability and retained its photocatalytic activity up to the 5th cycle of operation without photocorrosion. The dramatic enhancement in the visible-light photocatalytic performance of the ZnBi2O4-ZnS heterojunctions over pristine ZnBi2O4 and ZnS was due to the formation of a superior heterojunction between the n-type semiconductor, ZnS, and the p-type semiconductor, ZnBi2O4. This heterojunction facilitated the separation and transfer of the photoinduced electron at the interfaces of the two semiconductors. Furthermore, the ZnBi2O4-ZnS(12%) exhibited an inhibition zone of 15 mm against fecal Escherichia coli (ATCC 8739), with a minimum inhibitory concentration (MIC) of 150 µg/mL. These results demonstrated that the novel ZnBi2O4-ZnS p-n-type heterojunction is a promising visible-light active photo-catalyst for the degradation of organic pollutants and inhibition of fecal E. coli.

Kinetic degradation study for the first licensed anti-influenza polymerase inhibitor, baloxavir marboxil, using high-performance liquid chromatography-mass spectrometry.

The first licensed polymerase inhibitor, baloxavir marboxil was recently approved for the treatment of influenza A and B viruses. Furthermore, there is growing interest in testing the antiviral activity of baloxavir marboxil against Coronavirus. Despite its critical clinical value, there is no information on the degradation products, pathways, or kinetics of baloxavir marboxil under various stress conditions. In this study, a new high-performance liquid chromatography-ultraviolet detection method for accurately quantifying baloxavir marboxil in the presence of its degradation products was developed. A study of degradation kinetics revealed that acidic, thermal neutral, and photolytic degradation reactions have zero-order kinetics, whereas basic and oxidative degradation reactions have first-order kinetics. The structural characterization of baloxavir marboxil degradation products was performed by coupling the optimized high-performance liquid chromatography method to the triple-quadrupole tandem mass spectrometer. The proposed approach was validated according to the International Council for Harmonisation Q2 (R1) requirements for accuracy, precision, robustness, specificity, and linearity. The validated new method was successfully used to analyze baloxavir marboxil as raw material and its pharmaceutical dosage form, Xofluza.

Insight into the Redox Reaction Heterogeneity within Secondary Particles of Nickel-Rich Layered Cathode Materials.

Nickel-rich LiNixCoyMn1-x-yO2 (nickel-rich NCM, 0.6 ≤ x < 1) cathode materials suffer from multiscale reaction heterogeneity within the electrode during the electrochemical energy storage process. However, owing to the lack of appropriate diagnostic tools, the systematic understanding and observation on the redox reaction heterogeneity at the individual secondary-particle level is still limited. Raman spectroscopy can not only reflect the depth of the redox reaction through probing the vibrational information on the metal-oxygen coordination structure but also sensitively detect the local structure changes of different regions within the secondary particle with suitable spatial resolution. Therefore, Raman spectroscopy is applied here to conveniently conduct the high-resolution and in-depth analysis of the rate-dependent reaction heterogeneity within nickel-rich NCM secondary particles. It is found that, under high-rate conditions, the oxidation/reduction reaction mainly occurs in the surface region of the particles and the cause of this particle-scale reaction heterogeneity is the limitation of the slow solid-phase Li+ diffusion and the transient charging/discharging processes. In addition, this reaction heterogeneity would aggravate the structural instability of the material continuously during the charging/discharging cycles, thus resulting in a slowdown in the kinetics of Li+ de/intercalation and the apparent capacity decay. This work can not only provide fundamental insight into the rational modification of high-power nickel-rich NCM materials but also guide the setting of electrochemical operating conditions for high-power lithium-ion batteries (LIBs).

Encapsulation and Degradation Kinetics of Bioactive Compounds from Sweet Potato Peel During Storage.

RESEARCH BACKGROUND: The aim of this work is to evaluate utilization of sweet potato peel as a source of bioactive compounds. The effect of solvents (acetone and acetone/ethanol mixture) on the extraction efficiency of total carotenoids and phenolics from sweet potato tuber, flesh and peel, and antioxidant activity were investigated. Sweet potato peel extract stood out in terms of antioxidant activity and was chosen for encapsulation by spray and freeze-drying. EXPERIMENTAL APPROACH: Encapsulation is an effective method to improve phytochemical stability by entrapping the core material with a coating agent. In this study, spray and freeze-drying techniques were applied for improving the stability of bioactive compounds (carotenoids and phenolics) using whey protein as a coating material. The main advantages of the applied techniques over the other encapsulation techniques are simplicity, continuity, effectiveness, availability and applicability. RESULTS AND CONCLUSIONS: Physicochemical characteristics revealed that spray drying resulted in the formation of lower size particles, better flow properties and encapsulation efficiency of carotenoids. The retention of encapsulated and non-encapsulated bioactive compounds was monitored during storage in daylight and dark conditions. Storage conditions affected the carotenoid retention, whereas higher degradation rate of all samples was observable in daylight. Phenolic compounds exhibited higher retention in all investigated samples. Degradation kinetic parameters suggest the longer shelf life of spray dried encapsulated extract and potent method for stabilization of bioactive ingredients. NOVELTY AND SCIENTIFIC CONTRIBUTION: This study demonstrates that the spray drying technique and utilization of sweet potato peel have a big potential for the development of functional additives with improved nutritional, colour and bioactive properties.

Stability of camu-camu encapsulated with different prebiotic biopolymers.

BACKGROUND: A viable possibility for the best use of bioactive compounds present in camu-camu, fruit native to the Amazonian rainforest, is the preparation of microcapsules using different biopolymers by the spray-drying technique, which would increase the possibilities for innovation in the food industry, as well as facilitate the application in different food matrices. In this context, the chemical, physicochemical, and morphological properties and stability of camu-camu extract (peel and pulp) spray-dried using maltodextrin, inulin, and oligofructose as encapsulating agents were investigated, as well as lyophilized camu-camu extract (CEL). Different relative humidities (22%, 51%, and 75%) and temperatures (25 °C and 45 °C) were evaluated. RESULTS: The moisture, water activity, and solubility values varied from 18.4 to 107.9 g water per kilogram dry powder, 0.06 to 0.27, and 950.80 to 920.28 g microparticles per kilogram of water respectively. Retention of the bioactive compounds varied in the ranges 5.5-7.1 g per kilogram ascorbic acid fresh weight and 7.2-9.0 g per kilogram anthocyanins fresh weight. The increase in temperature and relative humidity during storage provided a significant decrease in the stability of the bioactive compounds for all treatments. However, the CEL presented higher water adsorption kinetics and degradation under all storage conditions, indicating the importance of the use of encapsulating agents. CONCLUSION: In general, the prebiotic biopolymers used as encapsulating agents in the microencapsulation of extracts of camu-camu by spray-drying presented satisfactory results, suggesting that this technique is an effective strategy to increase the stability of bioactive compounds contained in fruits and vegetables. © 2020 Society of Chemical Industry.

Kinetic investigation and lifetime prediction of Cs-NIPAM-MBA-based thermo-responsive hydrogels.

This study attempted to clarify the influence of a cross-linker, N,N-methylenebisacrylamide (MBA), and N-isopropylacrylamide (NIPAM) on the non-isothermal kinetic degradation, solid state and lifetime of hydrogels using the Flynn-Wall-Ozawa (F-W-O), Kissinger, and Coats-Redfern (C-Red) methods. The series of dual-responsive Cs-PNIPAM-MBA microgels were synthesized by soapless-emulsion free radical copolymerization in an aqueous medium at 70 °C. The thermal properties were investigated using thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) under nitrogen atmosphere. The apparent activation energy using the chosen Flynn-Wall-Ozawa and Kissinger methods showed that they fitted each other. Meanwhile, the type of solid state mechanism was determined using the Coats-Redfern method proposed for F1 (pure Cs) and F2 (Cs-PNIPAM-MBA hydrogel series) types, which comprise random nucleation with one nucleus reacting on individual particles, and random nucleation with two nuclei reacting on individual particles, respectively. On average, a higher Ea was attributed to the greater cross-linking density of the Cs hydrogel.

Changes of Major Antioxidant Compounds and Radical Scavenging Activity of Palm Oil and Rice Bran Oil during Deep-Frying.

Changes in antioxidant properties and degradation of bioactives in palm oil (PO) and rice bran oil (RBO) during deep-frying were investigated. The alpha (α)-tocopherol, gamma (γ)-tocotrienol and γ-oryzanol contents of the deep-fried oils were monitored using high performance liquid chromatography, and antioxidant activity was determined using 2-diphenyl-1-picryl hydrazyl (DPPH) radical scavenging activity. Results revealed that the antioxidant activity of PO decreased significantly (p < 0.05), while that of RBO was preserved after deep-frying of fries. As expected, the concentration of α-tocopherol in PO and γ-tocotrienol in both PO and RBO decreased significantly (p < 0.05) with increased frying. Results also showed that γ-tocotrienol was found to be more susceptible to degradation compared to that of α-tocopherol in both PO and RBO. Interestingly, no significant degradation of α-tocopherol was observed in RBO. It is suggested that the presence of γ-oryzanol and γ-tocotrienol in RBO may have a protective effect on α-tocopherol during deep-frying.