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1.
Polymers (Basel) ; 16(18)2024 Sep 10.
Article in English | MEDLINE | ID: mdl-39339015

ABSTRACT

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.

2.
Polymers (Basel) ; 16(18)2024 Sep 13.
Article in English | MEDLINE | ID: mdl-39339052

ABSTRACT

A series of partially bio-based and biodegradable poly(propylene terephthalate-co-adipate) (PPTA) random copolymers with different components were prepared by the melt polycondensation of petro-based adipic acid and terephthalic acid with bio-based 1,3-propanediol. The microstructure, crystallization behavior, thermal properties, and enzymatic degradation properties were further investigated. The thermal decomposition kinetics was deeply analyzed using Friedman's method, with the thermal degradation activation energy ranging from 297.8 to 302.1 kJ/mol. The crystallinity and wettability of the copolymers decreased with the increase in the content of the third unit, but they were lower than those of the homopolymer. The thermal degradation activation energy E, carbon residue, and reaction level n all showed a decreasing trend. Meanwhile, the initial thermal decomposition temperature (Td) was higher than 350 °C, which can meet the requirements for processing and use. The PPTA copolymer material still showed excellent thermal stability. Adding PA units could regulate the crystallinity, wettability, and degradation rate of PPTA copolymers. The composition of PPTA copolymers in different degradation cycles was characterized by 1H NMR analysis. Further, the copolymers' surface morphology during the process of enzymatic degradation also was observed by scanning electron microscopy (SEM). The copolymers' enzymatic degradation accorded with the surface degradation mechanism. The copolymers showed significant degradation behavior within 30 days, and the rate increased with increasing PA content when the PA content exceeded 45.36%.

3.
Pharmaceutics ; 16(9)2024 Aug 24.
Article in English | MEDLINE | ID: mdl-39339155

ABSTRACT

This article highlights the applicability of matrixing designs in stability studies for parenteral medications. The traditional approach involves extensive testing over the product's shelf-life. However, matrixing designs offer an alternative approach where only a fraction of samples is tested at each time point. The study conducted in this article focused on three parenteral medications and examined stability data under long-term condition. Degradation products were identified as critical parameter, and kinetics of degradation varied among the selected products. A systematic methodology was adopted to evaluate the data using different matrixing designs. The regression models obtained were assessed using statistical parameters S and R2. Also, each of the 28 matrixing designs were compared to the full design with statistical parameter RMSE and the shelf-life. The results confirmed that each of the evaluated matrixing designs can be applied, whether degradation product shows a linear or non-linear increase, and demonstrated that a reduction of two time points per batch is the most appropriate. In conclusion, this research contributes to the understanding of utilizing reduced matrixing designs in stability studies for parenteral medications and can be an effective strategy to reduce costs and time of stability testing while maintaining the necessary level of precision and reliability.

4.
Anal Bioanal Chem ; 416(24): 5387-5400, 2024 Oct.
Article in English | MEDLINE | ID: mdl-39145860

ABSTRACT

Berries are a rich source of natural antioxidant compounds, which are essential to profile, as they add to their nutritional value. However, the complexity of the matrix and the structural diversity of these compounds pose challenges in extraction and chromatographic separation. By relying on multivariate curve resolution alternating least squares (MCR-ALS) ability to extract components from complex spectral mixtures, our study evaluates the contributions of various extraction techniques to interference, extractability, and quantifying different groups of overlapping compounds using liquid chromatography diode array detection (LC-DAD) data. Additionally, the combination of these methods extends its applicability to evaluate polyphenol degradation in stored berry smoothies, where evolving factor analysis (EFA) is also used to elucidate degradation products. Results indicate that among the extraction techniques, ultrasonication-assisted extraction employing 1% formic acid in methanol demonstrated superior extractability and selectivity for the different phenolic compound groups, compared with both pressurized liquid extraction and centrifugation of the fresh berry smoothie. Employing MCR-ALS on the LC-DAD data enabled reliable estimation of total amounts of compound classes with high spectral overlaps. Degradation studies revealed significant temperature-dependent effects on anthocyanins, with at least 50% degradation after 7 months of storage at room temperature, while refrigeration and freezing maintained fair stability for at least 12 months. The EFA model estimated phenolic derivatives as the main possible degradation products. These findings enhance the reliability of quantifying polyphenolic compounds and understanding their stability during the storage of berry products.


Subject(s)
Fruit , Fruit/chemistry , Multivariate Analysis , Chromatography, Liquid/methods , Polyphenols/analysis , Least-Squares Analysis , Plant Extracts/chemistry , Anthocyanins/analysis , Anthocyanins/chemistry , Phenols/analysis , Phenols/chemistry , Chromatography, High Pressure Liquid/methods , Antioxidants/analysis , Antioxidants/chemistry
5.
Bioresour Technol ; 412: 131303, 2024 Nov.
Article in English | MEDLINE | ID: mdl-39214183

ABSTRACT

Methylpyridines are a class of highly toxic pyridine derivatives. In this study, a novel degrading bacterium was isolated for 3-methylpyridine (3-MP) degradation (Gordonia rubripertincta ZJJ, GenBank accession NO. OP430847.1; CCTCC M 2022975). The maximum specific degradation rate, half-saturation constant and inhibition constant were fitted to be 0.48 h-1, 88.3 mg L-1 and 924.0 mg L-1, respectively. During 3-MP biodegradation, the lost total organic carbon was transformed into CO2 (67.4 %) and biomass (32.6 %), and ammonia nitrogen was almost the sole inorganic species with a conversion rate of 36.3 %. Three metabolic pathways were possibly involved in 3-MP degradation: I) methyl oxidation followed by ring hydroxylation and hydrogenation; II) rupture of C=C and C-N bonds after ring reduction; III) initial ring hydroxylation. The study not only provides a novel strain for the high-efficient degradation of 3-MP, but also contributes to an in-depth understanding of 3-MP biotransformation.


Subject(s)
Biodegradation, Environmental , Pyridines , Pyridines/metabolism , Gordonia Bacterium/metabolism , Phylogeny , Biomass
6.
Environ Technol ; : 1-16, 2024 Aug 19.
Article in English | MEDLINE | ID: mdl-39157964

ABSTRACT

Water pollution caused by an abusive discharge of dye-containing wastewater leads to serious ecological risks. Conventional wastewater treatment methods have shortcomings of incomplete degradation, long-time treatment and secondary pollution. For the first time, a rotational hydrodynamic cavitation reactor (RHCR) equipped with a conical rotor has been designed to enhance the ozonation process for effective degradation of pollutants. The effects of rotational speed, discharge voltage, gas flow rate, liquid flow rate and initial pH on methylene blue (MB) degradation were deeply investigated. The optimised conditions were initial pH = 9, rotational speed = 1800 rpm, discharge voltage = 9.3 kV, gas flow rate = 60 mL/min and liquid flow rate = 80 mL/min. With the integration of ozonation and cavitation in RHCR, the MB degradation efficiency reached 95.2%, which was 15.6% higher than that of the individual ozonation method. The degradation process was proven to track the first-order kinetic model, with the reaction rate and synergy index were 0.232 min-1 and 1.78, respectively. Through the quenching experiments, it can be confirmed that the contribution proportion of hydroxyl radical during degradation was increased by 8.7% due to the enhancement of cavitation. A required energy consumption of 74.7 kWh/order/m3 and a total expense of 8.7 $/m3 were calculated. The energy consumption of the RHCR was approximately 80% lower than that of the recently reported degradation system combining ozonation and cavitation, with total expense reduced by 52%. The findings of this work provide a new water treatment method and offered theoretical references for the design of RHCR.

7.
Int J Biol Macromol ; : 134442, 2024 Aug 05.
Article in English | MEDLINE | ID: mdl-39209590

ABSTRACT

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.

8.
Environ Pollut ; 358: 124486, 2024 Oct 01.
Article in English | MEDLINE | ID: mdl-38972563

ABSTRACT

Chlorinated volatile organic compounds (Cl-VOCs) have dramatically biotoxicity and environmental persistence due to the presence of chlorine atoms, seriously jeopardizing ecological security and human health. Dichloromethane (DCM) as a model pollutant, is widely applied in solvents, extractants and cleaning agents in the pharmaceutical, chemical and food industries. In this study, highly biocompatible and conductive carbon cloth-titanium nitride-polyaniline (CC-TiN-PANI) bioelectrodes were obtained for DCM degradation in microbial electrolysis cell (MEC). The good adhesion of TiN and PANI on the electrode surface was demonstrated. The degradation kinetics were fitted by the Haldane model, compared to the CC bioelectrode (0.8 h-1), the proportion of maximum degradation rates to half-saturation concentration (Vmax/Km) of CC-TiN (1.4 h-1) and CC-TiN-PANI (2.2 h-1) bioelectrodes were enhanced by 1.8 and 2.8 times, respectively. Microbial community structure analysis illuminated that the dominant genera on the biofilm were Alicycliphilus and Hyphomicrobium, and the abundance was enhanced significantly with the modification of TiN and PANI. The dechlorination of DCM to formaldehyde could be catalyzed by DCM dehalogenase (DcmA) or by haloalkane dehalogenase (DhlA). And further oxidized to formate: 1) direct catalyzed by formaldehyde dehydrogenase (FdhA); 2) conjugated with glutathione by S-(hydroxymethyl)-glutathione synthase (Gfa), S-(hydroxymethyl)-glutathione dehydrogenase (FrmA) and S-formyl-glutathione hydrolase (FrmB); 3) conjugation with tetrahydrofolate (H4F) and/or tetrahydromethanopterin.


Subject(s)
Aniline Compounds , Electrodes , Methylene Chloride , Titanium , Aniline Compounds/metabolism , Aniline Compounds/chemistry , Methylene Chloride/chemistry , Methylene Chloride/metabolism , Titanium/chemistry , Carbon/metabolism , Microbiota , Biofilms
9.
Environ Pollut ; 358: 124533, 2024 Oct 01.
Article in English | MEDLINE | ID: mdl-38996994

ABSTRACT

Electrocatalytic coupled biofilter (EBF) technology organically integrates the characteristics of electrochemistry and microbial redox, providing ideas for effectively improving biological treatment performance. In this study, an EBF system was developed for enhanced degradation of cyclohexanone in contaminated water. Experimental results show that the system can effectively remove cyclohexanone in contaminated water. Under the optimal parameters, the removal rates of cyclohexanone, TP, NH4+-N and TN were 97.61 ± 1.31%, 76.31 ± 1.67%, 94.14 ± 2.13% and 95.87 ± 1.01% respectively. Degradation kinetics studies found that electrolysis, adsorption, and biodegradation pathways play a major role in the degradation of cyclohexanone. Microbial community analysis indicates that voltage can affect the structure of the microbial community, with the dominant genera shifting from Acidovorax (0 V) to Brevundimonas (0.7 V). Additionally, Acidovorax, Cupriavidus, Ralstonia, and Hydrogenophaga have high abundance in the biofilm and can effectively metabolize cyclohexanone and its intermediates, facilitating the removal of cyclohexanone. In summary, this research can guide the development and construction of highly stable EBF systems and is expected to be used for advanced treatment of industrial wastewater containing cyclohexanone.


Subject(s)
Biodegradation, Environmental , Cyclohexanones , Filtration , Waste Disposal, Fluid , Wastewater , Water Pollutants, Chemical , Cyclohexanones/chemistry , Cyclohexanones/metabolism , Wastewater/chemistry , Waste Disposal, Fluid/methods , Filtration/methods , Water Pollutants, Chemical/metabolism
10.
J Control Release ; 373: 667-687, 2024 Sep.
Article in English | MEDLINE | ID: mdl-39079659

ABSTRACT

In spite of available treatment options, glaucoma continues to be a leading cause of irreversible blindness in the world. Current glaucoma medications have multiple limitations including: lack of sustained action; requirement for multiple dosing per day, ocular irritation and limited options for drugs with different mechanisms of action. Previously, we demonstrated that pregabalin, a drug with high affinity and selectivity for CACNA2D1, lowered IOP in a dose-dependent manner. The current study was designed to evaluate pregabalin microemulsion eye drops and to estimate its efficacy in humans using in silico methods. Molecular docking studies of pregabalin against CACNA2D1 of mouse, rabbit, and human were performed. Pregabalin microemulsion eye drops were characterized using multiple in vivo studies and its stability was evaluated over one year at different storage conditions. Molecular docking analyses and QSPR of pregabalin confirmed its suitability as a new IOP-lowering medication that functions using a new mechanism of action by binding to CACNA2D1 in all species evaluated. Because of its prolonged corneal residence time and corneal penetration enhancement, a single topical application of pregabalin ME can provide an extended IOP reduction of more than day in different animal models. Repeated daily dosing for 2 months confirms the lack of any tachyphylactic effect, which is a common drawback among marketed IOP-lowering medications. In addition, pregabalin microemulsion demonstrated good physical stability for one year, and chemical stability for 3-6 months if stored below 25 °C. Collectively, these outcomes greatly support the use of pregabalin eye drops as once daily IOP-lowering therapy for glaucoma management.


Subject(s)
Emulsions , Intraocular Pressure , Molecular Docking Simulation , Ophthalmic Solutions , Pregabalin , Animals , Rabbits , Pregabalin/administration & dosage , Intraocular Pressure/drug effects , Humans , Ophthalmic Solutions/administration & dosage , Mice , Male , Drug Stability , Glaucoma/drug therapy , Cornea/metabolism , Cornea/drug effects , Antihypertensive Agents/administration & dosage , Antihypertensive Agents/chemistry , Antihypertensive Agents/pharmacokinetics , Female , Administration, Ophthalmic
11.
R Soc Open Sci ; 11(7): 231642, 2024 Jul.
Article in English | MEDLINE | ID: mdl-39076368

ABSTRACT

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.

12.
Environ Technol ; : 1-18, 2024 Jun 05.
Article in English | MEDLINE | ID: mdl-38837716

ABSTRACT

Diesel degradation and bacterial growth were investigated in soil, marine water, and freshwater ecosystems using Acinetobacter baumannii IITG19, Providencia vermicola IITG20, and their mixed culture. Both bacteria were found to be effective in all three ecosystems, with the best degradation occurring in freshwater. Acinetobacter baumannii IITG19 showed higher degradation (59%, 62%, and 76%) than Providencia vermicola IITG20 (31%, 57%, and 67%) in soil, marine water, and freshwater, respectively. Alkanes showed higher degradation than naphthenes and aromatics for both strains. The mixed culture showed higher diesel degradation efficiency than individual strains in all ecosystems. The overall degradation was similar in soil and marine water (66%), while freshwater showed the highest degradation of 81%. In the presence of the mixed culture, the degradation of alkanes was more than 90%. Bacterial growth was highest in freshwater and lowest in soil for both bacteria and the mixed culture. Metabolite analysis confirmed alcoholic degradation for alkanes and cyclo-alcoholic degradation for naphthenes. The degradation rate for mixed culture was higher than that of both the individual strains. The mixed culture had highest degradation rate constant in freshwater at 0.11 day-1 followed by that in marine ecosystem at 0.078 day-1. The rate constant was lowest for soil ecosystem at 0.066 day-1. Thus the mixed culture showed effectiveness in all three ecosystems, with its highest effectiveness observed in the freshwater ecosystem.

13.
Environ Monit Assess ; 196(7): 674, 2024 Jun 28.
Article in English | MEDLINE | ID: mdl-38942963

ABSTRACT

Solar Fenton is an important and extensively used advanced oxidation process (AOP) to degrade pharmaceutical pollutants. The objective of this study was to evaluate the performance of simultaneous degradation of the mixed pollutants (amoxicillin, acetaminophen, and ciprofloxacin) for an aqueous solution using the solar Fenton process. Operating parameters such as pH, iron doses, H2O2 doses, pollutant concentrations, and time were studied. From the experimental results, the ideal conditions were obtained for the removal of mixed pollutants such as pH 3, Fe2+ 0.04 mM, H2O2 4 mM, the concentration of the mixed pollutants 5 mg/L, solar radiation 400 W/m2, and time 10 min, respectively. The pseudo-first-order kinetics were utilized to investigate the degradation efficacy of the mixed pollutants. The result of the study indicates that the degradation efficiency was > 99% for the mixed pollutants. A maximum of 63% mineralization was observed, and hydroxyl radical scavenger effects were studied. The best optimal conditions were applied to assess the spiked wastewater (municipal wastewater (MWW) and hospital wastewater (HWW)). The highest elimination rates for AMX, ACET, and CIP were observed as 65%, 89%, and 85% for MWW and 76%, 92%, and 80% for HWW, respectively. The degraded by-products were detected by LC-ESI-MS in the water matrix (aqueous solution and spiked wastewater), and ECOSAR analysis was performed for the transformed products. The study concluded that the solar Fenton technique is promising and effective for the removal of mixed pollutants from the water matrix.


Subject(s)
Hydrogen Peroxide , Iron , Sunlight , Waste Disposal, Fluid , Water Pollutants, Chemical , Water Pollutants, Chemical/analysis , Water Pollutants, Chemical/chemistry , Hydrogen Peroxide/chemistry , Kinetics , Iron/chemistry , Waste Disposal, Fluid/methods , Wastewater/chemistry , Oxidation-Reduction , Ciprofloxacin/chemistry , Ciprofloxacin/analysis , Acetaminophen/chemistry , Acetaminophen/analysis , Amoxicillin/chemistry , Amoxicillin/analysis
14.
Foods ; 13(12)2024 Jun 19.
Article in English | MEDLINE | ID: mdl-38928875

ABSTRACT

The encapsulation of ß-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. ß-carotene was efficiently encapsulated within SP and FZ structures, resulting in EE of approximately 85% and 70%, respectively. The degradation kinetics of ß-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 ß-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.

15.
Heliyon ; 10(10): e31135, 2024 May 30.
Article in English | MEDLINE | ID: mdl-38774320

ABSTRACT

This study was conducted to observe the storage conditions, such as solvent and temperature, of lycopene content and degradation kinetics from red amaranth (Amaranthus gangeticus). Jelly was prepared using the extracted lycopene, the physicochemical properties and lycopene content. The extract with the maximum amount of lycopene was obtained by extraction with hexane, acetone and ethanol (2:1:1),50 ± 9 mg/kg. Higher lycopene degradation was observed at refrigerated temperature as compared to ambient temperature in hexane acetone (6:4) solvent throughout the storage periods. In this period, the initial lycopene concentration was measured to be 17 ± 8 mg/kg, whereas at the end of the storage time, it was found to be 3.0 ± 0.8 mg/kg. Hence, the results indicate that the hexane, acetone, and ethanol (in a ratio of 2:1:1) solvent method is viable for extracting and purifying lycopene from red amaranth at refrigerated temperature. This lycopene can serve as both a natural colorant and a value-added product. However, it is worth noting that lycopene can also be extracted and purified using recrystallization, column chromatography, and thin-layer chromatography (TLC) methods. The Winter melon jelly using lycopene from red amaranth contained moisture 29.6 %, ash 0.67 %, acidity 0.35 %, reducing sugar 26.8 %, non-reducing sugar 35.4 %, total soluble solid 66°brix and lycopene content 26.04 mg/kg. Proper utilization of lycopene extracted from red amaranth during the preparation of bakery, confectionary, baby food etc., may help and encourage the development of small-scale industries in the country.

16.
Environ Pollut ; 349: 123919, 2024 May 15.
Article in English | MEDLINE | ID: mdl-38582188

ABSTRACT

Microplastic (MP) contamination is in the spotlight today, yet knowledge of their interaction with other organic contaminants in the soil environment is limited. Concerns extend to endocrine disrupting chemicals (EDCs), known for their potential to interfere with the hormonal systems of organisms and for their persistence and widespread presence in the environment. In this study, the most frequently occurring EDCs were monitored both in alluvial soil and in soil contaminated with different MPs commonly found in soil media, polyethylene, polyamide, and polystyrene. Bisphenol A and parabens were the most rapidly dissipating compounds, followed by triclosan and triclocarban, with the latter showing poor degradation. Per- and polyfluoroalkyl substances (PFAS) showed high persistence as concentrations remained nearly constant throughout the experiment. Although they fitted well with first-order dissipation kinetics, most showed biphasic behavior. The co-occurrence of MPs in the soil influenced the kinetic behavior in most cases although the differences were not very marked. MPs could impact sorption-desorption processes, affecting contaminant mobility and bioavailability to organisms in soil. These findings strengthen evidence for the influence of MPs on the behavior of soil contaminants such as EDCs, not only as vectors or sources of contaminants but by affecting dissipation kinetics.


Subject(s)
Benzhydryl Compounds , Endocrine Disruptors , Environmental Monitoring , Microplastics , Soil Pollutants , Soil , Soil Pollutants/analysis , Endocrine Disruptors/analysis , Microplastics/analysis , Soil/chemistry , Benzhydryl Compounds/analysis , Triclosan/analysis , Phenols/analysis , Parabens/analysis , Carbanilides/analysis
17.
Ecotoxicol Environ Saf ; 277: 116378, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38663191

ABSTRACT

Pesticide residues and microplastics (MPs) in agricultural soils are two major concerns for soil health and food safety. The degradation of chlorpyrifos (CPF), an organophosphorus pesticide, releases phosphates. This process may be affected by the presence of MPs in the soil. The combination of CPF and MPs presence in the soil may thus produce interaction effects that alter the soil phosphorus (P) balance. This study explores the degradation pathways of CPF (6 mg kg-1, 12 mg kg-1 of CPF addition) in soils with different levels of polylactic acid MPs (PLA-MPs) (0.0 %, 0.1 %, 0.5 %, 1.0 % w/w), and analyzes soil P fractions and phosphatase enzyme activities to investigate soil P bioavailability under different treatments. Results show that the degradation of CPF fits to a first-order decay model, with half-lives (DT50) ranging from 11.0 to 14.8 d depending on PLA-MPs treatment. The concentration of its metabolite 3, 5, 6-trichloropyridine 2-phenol (TCP) reached a peak of 0.93-1.67 mg kg-1 within 7-14 days. Similarly, the degradation of CPF led to a significant transient increase in P bioavailability within 3-7 days (p < 0.05), with a peak range of 22.55-26.01 mg kg-1 for Olsen-P content and a peak range of 4.63-6.76 % for the proportions of available P fractions (H2O-P+NaHCO3-P+NaOH-P), before returning to prior levels (Olsen-P: 11.28-19.52 mg kg-1; available soil P fractions: 4.15-5.61 %). CPF degradation (6 mg kg-1) was significantly inhibited in soil with 1.0 % PLA-MPs addition. The effects of MPs and CPF on soil P fractions occur at different time frames, implying that their modes of action and interactions with soil microbes differ.


Subject(s)
Chlorpyrifos , Microplastics , Phosphorus , Soil Pollutants , Soil , Soil Pollutants/analysis , Soil Pollutants/metabolism , Phosphorus/analysis , Soil/chemistry , Biological Availability , Biodegradation, Environmental , Polyesters/chemistry , Polyesters/metabolism , Insecticides/analysis
18.
Chemosphere ; 356: 141780, 2024 May.
Article in English | MEDLINE | ID: mdl-38604516

ABSTRACT

The degradation of three anti-cancer drugs (ADs), Capecitabine (CAP), Bicalutamide (BIC) and Irinotecan (IRI), in ultrapure water by ozonation and UV-irradiation was tested in a bench-scale reactor and AD concentrations were measured through ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). A low-pressure mercury UV (LP-UV) lamp was used and degradation by UV (λ = 254 nm) followed pseudo-first order kinetics. Incident radiation in the reactor was measured via chemical actinometry using uridine. The quantum yields (φ) for the degradation of CAP, BIC and IRI were 0.012, 0.0020 and 0.0045 mol Einstein-1, respectively. Ozone experiments with CAP and IRI were conducted by adding ozone stock solution to the reactor either with or without addition of tert-butanol (t-BuOH) as radical quencher. Using this experimental arrangement, no degradation of BIC was observed, so a semi-batch setup was employed for the ozone degradation experiments of BIC. Without t-BuOH, apparent second order reaction rate constants for the reaction of the ADs with molecular ozone were determined to be 3.5 ± 0.8 ∙ 103 L mol-1 s-1 (CAP), 7.9 ± 2.1 ∙ 10-1 L mol-1 s-1 (BIC) and 1.0 ± 0.3 ∙ 103 L mol-1 s-1 (IRI). When OH-radicals (∙OH) were quenched, rate constants were virtually the same for CAP and IRI. For BIC, a significantly lower constant of 1.0 ± 0.5 ∙ 10-1 L mol-1 s-1 was determined. Of the tested substances, BIC was the most recalcitrant, with the slowest degradation during both ozonation and UV-irradiation. The extent of mineralization was also determined for both processes. UV irradiation was able to fully degrade up to 80% of DOC, ozonation up to 30%. Toxicity tests with Daphnia magna (D. magna) did not find toxicity for fully degraded solutions of the three ADs at environmentally relevant concentrations.


Subject(s)
Anilides , Antineoplastic Agents , Capecitabine , Irinotecan , Nitriles , Ozone , Tosyl Compounds , Ultraviolet Rays , Water Pollutants, Chemical , Ozone/chemistry , Nitriles/chemistry , Water Pollutants, Chemical/chemistry , Irinotecan/chemistry , Anilides/chemistry , Capecitabine/chemistry , Tosyl Compounds/chemistry , Antineoplastic Agents/chemistry , Kinetics , Tandem Mass Spectrometry , Chromatography, High Pressure Liquid
19.
Bio Protoc ; 14(8): e4975, 2024 Apr 20.
Article in English | MEDLINE | ID: mdl-38686344

ABSTRACT

The field of oligonucleotide therapeutics is rapidly advancing, particularly for combating orphan diseases and cancer. However, the intrinsic instability of oligonucleotides, especially RNA, poses a substantial challenge in the face of the harsh conditions encountered intracellularly and in circulation. Therefore, evaluating the stability of oligos in serum is of great significance when developing oligonucleotide therapeutics. This protocol outlines a dependable and reproducible method for preparing oligonucleotide duplexes, coupled with confirmation by gel electrophoresis. Subsequently, the protocol defines a mechanism to assess the stability of the oligo duplexes in serum. This protocol seeks to establish a standardized reference for researchers, enabling them to compare the impact of various modifications on oligo stability and assess the degradation kinetics effectively. Key features • Adaptable for use with small interfering RNA (siRNA), microRNA (miRNA), antisense oligonucleotides (ASOs), and other unmodified and modified oligonucleotides. • Does not necessitate any Biological Safety Level clearance and offers a rapid, cost-effective, and entirely in vitro procedure. • Allows researchers to evaluate multiple modification patterns that, when coupled with targeting activity, allow for selecting the best modification pattern prior to in vivo analysis.

20.
Bioresour Technol ; 401: 130732, 2024 Jun.
Article in English | MEDLINE | ID: mdl-38677386

ABSTRACT

Acetaminophen (APAP) is a frequently used, over-the-counter analgesic and antipyretic medication. Considering increase in global consumption, its ubiquity in environment with potential toxic impacts has become a cause of great concern. Hence, bioremediation of this emerging contaminant is of paramount significance. The present study incorporates a microcosm centric omics approach to gain in-depth insights into APAP degradation by Paracoccus sp. APAP_BH8. It can metabolize APAP (300 mg kg-1) within 16 days in soil microcosms. Genome analysis revealed potential genes capable of mediating degradation includes M20 aminoacylase family protein, guanidine deaminase, 4-hydroxybenzoate 3-monooxygenase, and 4-hydroxyphenylpyruvate dioxygenase. Whole proteome analysis showed differential expression of enzymes and bioinformatics provided evidence for stable binding of intermediates at the active site of considered enzymes. Metabolites identified were 4-aminophenol, hydroquinone, and 3-hydroxy-cis, cis-muconate. Therefore, Paracoccus sp. APAP_BH8 with versatile enzymatic and genetic attributes can be a promising candidate for formulating improved in situ APAP bioremediation strategies.


Subject(s)
Acetaminophen , Biodegradation, Environmental , Genomics , Proteomics , Acetaminophen/metabolism , Proteomics/methods , Genomics/methods , Paracoccus/metabolism , Paracoccus/genetics , Metabolomics , Proteome/metabolism
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