Final Degradation Products Research Articles

Activation of Persulfate by NiFe-Layered Double Hydroxides Toward Efficient Degradation of Doxycycline in Water

In recent years, the excessive use and improper disposal of antibiotics have led to their pervasive presence in the environment, resulting in significant antibiotic pollution. To address this pressing issue, the present study synthesized nickel–iron-layered double hydroxides (NiFe-LDHs) with varying molar ratios using a hydrothermal method, employing these LDHs as catalysts for the oxidative degradation of doxycycline, with peroxymonosulfate (PMS) serving as the oxidant. X-ray diffraction analysis confirmed that the synthesized NiFe-LDHs exhibited a hexagonal crystal structure characteristic of layered double hydroxides. Experimental results demonstrated that the catalytic efficiency of NiFe-LDHs increased with both the dosage of the catalyst and the concentration of PMS, achieving a high degradation efficiency for doxycycline at a catalyst concentration of 0.5 g/L. Furthermore, the catalytic performance was notably effective across a range of pH conditions, with the highest degradation efficiency being observed at a Ni–Fe molar ratio of 3:1. The activation of PMS by NiFe-LDHs for the catalytic degradation of pollutants primarily occurs through singlet oxygen (1O2), superoxide radicals (O2−·), and sulfate radicals (SO4−·). The study also proposed three potential degradation pathways for doxycycline, indicating that the final degradation products have lower environmental toxicity. This research offers novel approaches and methodologies for the treatment of antibiotic-contaminated wastewater.

The Stability of Manganese Oxides Under Laser Irradiation During Raman Analyses: I. Compact Versus Channel Structures

ABSTRACTManganese oxides/oxyhydroxides (MnOx) are based on Mnn+O6 and Mnn+O4 polyhedra arranged such as to form compact, channel or layered structures. In geology, they are precious archives of past redox conditions for palaeoclimatic reconstructions; in material sciences, they are used for a variety of applications, from pigments to environmental remediation and energy storage. Thus, the fast, remote and non‐destructive identification of MnOx is critical in several disciplines. Micro‐Raman spectroscopy is often used for this purpose, although a systematic characterization of their stability under the laser beam is still lacking. In this work, we present our results on the behaviour of the most common MnOx having compact and channel structures when a 532‐nm laser with intensity between ~23 μW/μm2 and ~36.8 mW/μm2 is used. The compact structures of manganosite (NaCl‐like) and hausmannite (spinel‐like) are stable up to ~36.8 mW/μm2. The stability of oxides with channel structures depends on channel size, charge of channel cations and valence state of Mn. Hausmannite is the final degradation product of all MnOx with channel structures, irrespective of the starting phase. Pyrolusite, manganite, hollandite and romanéchite are relatively stable under the laser beam, and the transition to the spinel structure occurs above 2.5 mW/μm2 while the degradation of cryptomelane and todorokite starts ~226 μW/μm2. The analysis of MnOx thus needs very accurate experimental conditions to avoid misleading and incorrect phase identifications. Based on our data, we propose an analytical protocol for a proper characterization of these minerals via Raman spectroscopy.

Efficient degradation of the polysaccharide extracted from Enteromorpha prolifera by using a novel polysaccharide lyase family 28 enzyme with high activity

The polysaccharides originated from Enteromorpha species exhibited versatile physiological activities and great potential in food and medicine industries. The oligosaccharides, which prepared from polysaccharide by enzymatic hydrolysis, retained the excellent activity as polysaccharide, and then revealed better solubility, bioavailability and effectiveness. However, there are few reports on Enteromorpha polysaccharide (EP)-degrading enzymes for efficient degradation of EP and high-valued utilization of Enteromorpha biomass. Herein, a novel EP-degrading enzyme, EPD1, was identified and heterologously expressed. It could efficiently hydrolyze the EP with high activity (985.755 U/mg) and exhibited optimal activity at 50 °C and a pH of 10.0. The Km value of EPD1 was 7.5512 mg·mL−1 and the Vmax value was 4.9109 μmol·min−1·mL−1. Furthermore, EPD1 demonstrated cold adaptation as evidenced by minimal activity loss following incubation at temperatures below 30 °C for 1 h. HPLC and ESI-MS analysis revealed that EPD1 could produce disaccharides, trisaccharides and tetrasaccharides as the final degradation products from EPs. In conclusion, a novel EP-degrading enzyme with high activity and excellent performance was identified and it can expand the database of EP-degrading enzymes and provide the possibility to make full use of EPs.

Deciphering the degradation of sulfonamides by UV/chlorination in aqueous solution: kinetics, reaction pathways, and toxicological evolution

UV/Cl is a cost-effective process and is often used in municipal water treatment plants as well as in industrial applications. UV/Cl method is found highly effective in degrading contaminants, including pathogens, The conventional methods for water treatment have been proven inefficient for the complete elimination of pollutants and generate harmful by-products in the environment. This study evaluated the efficacy of three different treatment methods, chlorination alone, UV photolysis, and UV/Cl, for the degradation of sulfonamides (SAs) in water. The results highlighted that UV/Cl treatment was an efficient method for enhancing the degradation of sulfisoxazole (SFX), sulfadimethoxine (SAT), and sulfaguanidine (SG), with substrates degrading in 5, 6.5, and 4 min. The study also investigated the reactive species generated in the UV/Cl system and found that ·OH was the species responsible for the elimination of SFX. Additionally, the study explored the intermediate products generated during the degradation of SFX under the UV/Cl system, identifying VI distinct degradation pathways. The presence of ·OH radicals significantly enhanced the degradation of SFX, while some chlorine species also contributed to the degradation. The study predicted the toxicity of degradation products from the UV/Cl system using the ECOSAR (Ecological Structure Activity Relationships) program and found that the final degradation products of SFX were non-toxic, but concerns were raised about acute toxicity.

Cobalt-Modified Biochar from Rape Straw as Persulfate Activator for Degradation of Antibiotic Metronidazole

A cobalt-loaded magnetic biochar (Co-MBC) catalyst was synthesized to enhance the removal of metronidazole (MNZ). Study explored the performance and mechanism of MNZ degradation by Co-MBC activated permonosulfate (PMS). Results showed that cobalt oxides were effectively deposited onto the biochar surface, new oxygen functional groups were added to the modified biochar, and the presence of the metallic element Co enhanced the efficiency of PMS activation in the composite. More than 90% of MNZ was removed after 60 min with a catalyst dosage of 0.2 g/L and a PS concentration of 1 mM. After four reuses, Co-MBC still showed excellent catalytic performance to degrade over 75% of MNZ. The reaction system performed well even in the presence of inorganic anions and organic macromolecules. However, the degradation rate was inhibited under alkaline conditions. The quenching experiment indicated that •SO4−, •OH, 1O2, and •O2− synergistically degraded MNZ, and that•SO4− played a dominant role. LC-MS was applied to assess intermediate degradation products, in which CO2, H2O, and NO3− were the final degradation products, and potential degradation pathways were suggested. In conclusion, Co-MBC was an efficient and stable catalytic material, and its ability to activate PMS was improved to effectively degrade antibiotics, a typical priority pollutant.

The complete degradation of 1,2-dichloroethane in Escherichia coli by metabolic engineering

1,2-Dichloroethane (1,2-DCA), a widely utilized chemical intermediate and organic solvent in industry, frequently enters the environment due to accidental leaks and mishandling during application processes. Thus, the in-situ remediation of contaminated sites has become increasingly urgent. However, traditional remediation methods are inefficient and costly, while bioremediation presents a green, efficient, and non-secondary polluting alternative. In this study, an engineered strain capable of completely degrading 1,2-DCA was constructed. We introduced six exogenous genes of the 1,2-DCA degradation pathway into E. coli and confirmed their normal transcription and efficient expression in this engineered strain through qRT-PCR and proteomics. The degradation experiments showed that the strain completely degraded 2 mM 1,2-DCA within 12 h. Furthermore, the results of isotope tracing verified that the final degradation product, malic acid, entered the tricarboxylic acid cycle (TCA) of E. coli and was ultimately fully metabolized. Also, morphological changes in the engineered strain and control strain exposed to 1,2-DCA were observed under SEM, and the results revealed that the engineered strain is more tolerant to 1,2-DCA than the control strain. In conclusion, this study paved a new way for humanity to deal with the increasingly complex environmental challenges.

Efficient toluene degradation using Bacillus subtilis biofilm-supported Mn–Ce/zeolite catalysts

This study investigated a new approach for synthesizing Bacillus subtilis biofilm-supported Mn–Ce/zeolite catalysts for the degradation of gaseous toluene. Four different metal oxide nano-catalysts (ZMn, ZMnCe-10%, ZMnCe-20%, and ZMnCe-30%) were synthesized with varying ratios of manganese (Mn) and cerium (Ce) on zeolite nanoparticles. TEM, SEM, XRD, BET, XPS, and EDX mapping were used to examine these four samples, as well as simple zeolite. Based on these analyses, the catalytic activity of the prepared samples ZMn, ZMnCe-10%, ZMnCe-20%, and ZMnCe-30% for the complete oxidation of toluene and toluene intermediate products were tested with Non-thermal plasma (NTP) technology in a dielectric barrier discharge (DBD) reactor. Among all, ZMnCe-20% showed the highest toluene degradation efficiency (89%) at low concentrations (200 ​ppm) and humidity (>50%). Later, highly efficient and hydrophobic nano-biocatalysts were prepared by combining B. subtilis biofilm wild-type (WT) and engineered B. subtilis biofilm EPS with ZMnCe-20% catalyst. EPS is the main component found in biofilm matrix and plays a key role in influencing properties such as biofilm stability, electron transfer, surface roughness and hydrophobicity. Compared to WT B. subtilis biofilm, EPS overexpressed B. subtilis biofilm showed stronger growth and development on ZMnCe-20% nanocatalyst. Moreover, the NTP system packed with ZMnCe-20%/biofilm (EPS+) nano-biocatalyst exhibited the highest toluene degradation activity (99%) with (83%) CO2 selectivity, (up to 50%) reduction in NOx concentration and complete ozone decomposition at (250 ​ppm) toluene concentrations and increased humidity (>90%). High-energy electrons generated in the NTP system break the C–H and C–C bond between the rings of the toluene molecule, forming several byproducts which are later reacted with active radical species such as O, OH, and O3 and further converted into final degradation products (CO2 and H2O). The results demonstrated successful biofilm development and growth on the ZMnCe-20% catalyst with advanced features such as superhydrophobicity, H2O resistance, improved surface roughness, and electron generation. In short, the study's approach combines bioengineering and material science to develop sustainable nano-biocatalysts for removing VOCs in industrial and environmental settings.

Elucidation of Degradation Behavior of Nitrazepam, a Benzodiazepine Drug, under Basic Conditions: Study on Degradability of Drugs in Stomach (IV).

This study investigates the stability of nitrazepam (NZP), a benzodiazepine drug, under basic conditions, since alkaline putrefactive amines and ammonia are produced once bodies are left to decompose for a long period postmortem after a murder involving NZP or an accidental overdose of NZP. The degradation of NZP in an aqueous alkaline solution was investigated by LC/photodiode array detector (PDA) where the NZP degradation product was isolated and purified by solid-phase extraction using Oasis® MCX, and its chemical structure was determined by LC/time-of-flight (TOF)-MS, NMR spectroscopy, and single-crystal X-ray crystallography. The results revealed that NZP was immediately degraded under basic conditions with 2-amino-5-nitrobenzophenone being an intermediate which further degraded to provide 2-hydroxy-5-nitrobenzophenone as the final degradation product. These results are expected to be useful in clinical chemistry and forensic science, such as the detection of drugs during postmortem examination and suspected addiction.

Environmentally Friendly Degradation and Detoxification of Rifampicin by a Bacterial Laccase and Hydrogen Peroxide.

Antibiotics are micropollutants accumulating in our rivers and wastewaters, potentially leading to bacterial antibiotic resistance, a worldwide problem to which there is no current solution. Here, we have developed an environmentally friendly two-step process to transform the antibiotic rifampicin (RIF) into non-antimicrobial compounds. The process involves an enzymatic oxidation step by the bacterial CotA-laccase and a hydrogen peroxide bleaching step. NMR identified rifampicin quinone as the main product of the enzymatic oxidation. Growth of Escherichia coli strains in the presence of final degradation products (FP) and minimum inhibitory concentration (MIC) measurements confirmed that FP are non-anti-microbial compounds, and bioassays suggest that FP is not toxic to eukaryotic organisms. Moreover, competitive fitness assays between susceptible and RIF-resistant bacteria show that susceptible bacteria is strongly favoured in the presence of FP. Our results show that we have developed a robust and environmentally friendly process to effectively remediate rifampicin from antibiotic contaminated environments.

Reductive Degradation of N-Nitrosodimethylamine via UV/Sulfite Advanced Reduction Process: Efficiency, Influencing Factors and Mechanism

N-nitrosodimethylamine (NDMA), as an emerging nitrogenous disinfection byproduct, is strictly controlled by multiple countries due to its high toxicity in drinking water. Advanced reduction processes (ARPs) are a new type of water treatment technology that can generate highly reactive reducing radicals and make environmental contaminants degrade rapidly and innocuously. In this study, a systematic investigation on the kinetics of the NDMA degradation via the chosen UV/sulfite ARP and the impacts of some key parameters of reaction system was conducted. The results indicated that the UV/sulfite ARP was an efficient and energy saving method for the reductive degradation of NDMA. A total of 94.40% of NDMA was removed using the UV/sulfite ARP, while only 45.48% of NDMA was removed via direct UV photolysis under the same reaction conditions. The degradation of NDMA via the UV/sulfite ARP followed pseudo-first-order kinetics. Increasing both the UV light intensity and sulfite dosage led to a proportional increase in the NDMA removal efficiency. The alkaline condition favored the degradation of NDMA, with the removal efficiency increasing from 21.57% to 66.79% within the initial 5 min of the reaction when the pH increased from 3 to 11. The presence of dissolved oxygen substantially decreased the removal efficiency of NDMA due to the formation of oxidizing superoxide radicals, which competed with NDMA by capturing the reducing active radicals during the reaction. An analysis of the degradation products indicated that several refractory intermediates such as dimethylamine, methylamine and nitrite were completely decomposed via the UV/sulfite ARP, and the final degradation products were formate, ammonia and nitrogen.

Dynamic Surface Antifouling Materials

Comprehensive SummaryThe colonization of marine microorganisms, animals and plants on underwater surface forms marine biofouling. It has profound effects on marine industries. To solve the problem, we proposed a strategy of Dynamic Surface Antifouling (DSAF), i.e., continuously changing surfaces can effectively inhibit biofouling organisms landing and adhering, and developed degradable polymer based marine antifouling material. The degradation of polymer chain enables the surface dynamic or self‐renewing even on static conditions. The final degradation products of these polymers are low molecular weight molecules, and do not produce marine microplastics. Meanwhile, the degradable polymers act as carriers and controlled release systems for antifoulants, further improving the antifouling efficiency. This article reviews the development of dynamic surface antifouling materials.What is the most favorite and original chemistry developed in your research group?Synthesis of marine anti‐biofouling polymers.How do you get into this specific field? Could you please share some experiences with our readers?I happened to read a paper about marine biofouling on the internet three months later after I joined University of Science and Technology of China (USTC). Its adverse effects on marine industry and marine activities shocked me very much! No doubt, it makes great significance for our country and society to solve the problem. It is a challenge, but I like challenge, and I decided to get into this field. Realizing that the key is to develop new polymer resin, I was confident that I was able to solve the problem with my polymer chemistry and physics background. Actually, it is not easy. I have spent about 20 years in this project since then.What is the most important personality for scientific research?Curiosity, interest, concentration and persistence. How do you keep balance between research and family?I make a plan and organization for everything so I can keep a balance between family and work.Who influences you mostly in your life?Prof. Ming Jiang and Prof. Chi Wu, who are my PhD and post‐doctor supervisors, respectively. They taught me how to do research and how to choose a significant subject.What is your favorite journal(s)?Macromolecules, Journal of the American Chemical Society, Physical Review Letters.Could you please give us some advices on improving Chinese Journal of Chemistry?The journal may publish more papers about applications of chemistry and history of chemistry.

New insights into the degradation mechanism and risk assessment of HFPO-DA by advanced oxidation processes based on activated persulfate in aqueous solutions

Hexafluoropropylene oxide dimer acid (HFPO-DA) is widely used as a substitute for perfluorooctanoic acid (PFOA). HFPO-DA exhibits high water solubility and low adsorption potential, conferring significant fluidity in aquatic environments. Given that the toxicity of HFPO-DA is similar to PFOA, it is necessary to control its content in aquatic environments. Electrochemical and thermally-activated persulfates have been successfully used to degrade HFPO-DA, but UV-activated persulfates cannot degrade the compound. Given that research on degradation mechanisms is still incomplete and lacks kinetic research, the mechanism and kinetic calculations of oxidative degradation were studied in detail using DFT calculations. And the toxicity of HFPO-DA degradation intermediates and products was evaluated to reveal the feasibility of using advanced oxidation process (AOP) technology based on persulfate to degrade HFPO-DA in wastewater. The results showed that the committed step of HFPO-DA degradation was initiated by the electron transfer reaction of SO4•- radicals. This reaction is not spontaneous at room temperature and requires sufficient electrical or thermal energy to be absorbed from the external environment. The perfluoroalcohol produced during this reaction can subsequently undergo four possible reactions: H atom abstraction from alcohol groups by an OH radical; H atom abstraction by SO4•-; direct HF removal; and HF removal with water as the catalyst. The final degradation products of HFPO-DA mainly include CO2, CF3CF2COOH, CF3COOH, FCOOH and HF, which has been identified through previous experimental analysis. Ecotoxicity assessment indicates that degradation does not produce highly toxic intermediates, and that the final products are non-toxic, supporting the feasibility of persulfate-based AOP technologies.

Versatile Product Detection via Coupled Assays for Ultrahigh-Throughput Screening of Carbohydrate-Active Enzymes in Microfluidic Droplets.

Enzyme discovery and directed evolution are the two major contemporary approaches for the improvement of industrial processes by biocatalysis in various fields. Customization of catalysts for improvement of single enzyme reactions or de novo reaction development is often complex and tedious. The success of screening campaigns relies on the fraction of sequence space that can be sampled, whether for evolving a particular enzyme or screening metagenomes. Ultrahigh-throughput screening (uHTS) based on in vitro compartmentalization in water-in-oil emulsion of picoliter droplets generated in microfluidic systems allows screening rates >1 kHz (or >107 per day). Screening for carbohydrate-active enzymes (CAZymes) catalyzing biotechnologically valuable reactions in this format presents an additional challenge because the released carbohydrates are difficult to monitor in high throughput. Activated substrates with large optically active hydrophobic leaving groups provide a generic optical readout, but the molecular recognition properties of sugars will be altered by the incorporation of such fluoro- or chromophores and their typically higher reactivity, as leaving groups with lowered pKa values compared to native substrates make the observation of promiscuous reactions more likely. To overcome these issues, we designed microdroplet assays in which optically inactive carbohydrate products are made visible by specific cascades: the primary reaction of an unlabeled substrate leads to an optical signal downstream. Successfully implementing such assays at the picoliter droplet scale allowed us to detect glucose, xylose, glucuronic acid, and arabinose as final products of complex oligosaccharide degradation by glycoside hydrolases by absorbance measurements. Enabling the use of uHTS for screening CAZyme reactions that have been thus far elusive will chart a route toward faster and easier development of specific and efficient biocatalysts for biovalorization, directing enzyme discovery by challenging catalysts for reaction with natural rather than model substrates.

Hydrogenated silicene nanosheet functionalized scaffold enables immuno-bone remodeling.

An ideal implant needs to have the ability to coordinate the foreign body response and tissue regeneration. Here, Hydrogenated-silicon nanosheets (H-Si NSs) with favorable biodegradability are integrated and functionalized into a β-tricalcium phosphate scaffold (H-Si TCP) for bone defect healing. H-Si TCP can greatly improve bone regeneration through osteoimmunomodulation-guided biodegradation in vivo. The spatiotemporal regulation of degradation products replenishes sufficient nutrients step by step for the entire process of bone repair. Extracellular and intracellular reactive oxygen species (ROS) are first downregulated by reaction with H-Si NSs, followed by marked M2 polarization, remodeling the micro-environment timely for immune-bone regeneration. The release of primary reaction products awakened bone marrow mesenchymal stem cells (BMSCs), which are converted into osteoblasts anchored on scaffolds. Subsequently, biomineralization is promoted by the final degradation products. The intrinsic ROS-responsive, immunoregulatory, and osteo-promotive capability of 2D H-Si NSs makes such composite H-Si TCP scaffold a highly potential alternative for the treatment of critical bone defect.

Yeast-derived biochar to load CoFe2O4: Degradation of tetracycline hydrochloride by heterogeneous activation of peroxymonosulfate

The development of high-efficiency catalysts is essential for activating peroxymonosulfate (PMS) to degrade organic pollutants. In this study, yeast-derived biochar (YBC) supported cobalt ferrite composite catalyst (CoFe2O4/YBC) was successfully synthesized, which can heterogeneous activate PMS to degrade tetracycline hydrochloride (TCH). The results showed that CoFe2O4/YBC could activate PMS effectively and stably owing to the synergistic effect of YBC and CoFe2O4. The degradation rate of TCH was nearly 95% under the optimal conditions, and it was still more than 90% after four cycles. Furthermore, according to quenching tests and electron paramagnetic resonance (EPR) detection, it was confirmed that ·OH, SO4·-, O2·-, and 1O2 were involved in TCH degradation, and 1O2 played a key role. After identifying the intermediates produced by TCH's degradation, two potential TCH degradation pathways were suggested. Further ECOSAR (2.0) software analysis revealed that the ecotoxicity of the final degradation products of TCH was small. This study demonstrates that the as-prepared CoFe2O4/YBC is an efficient and environmentally friendly PMS activation catalyst with great potential for application in the remediation of polluted aquatic environments.

A unique and well-designed 2D graphitic carbon nitride with sponge-like architecture for enhanced visible-light photocatalytic activity

A unique and well-designed 2D graphitic carbon nitride (g-CN) with sponge-like architecture has been successfully synthesized by engineering supramolecular self-assembly and well-organized SiO2 nanoparticles. The resulting material showed great optical and textural characteristics with plenty of open and uniform pores, which are very helpful whether for multiple light scattering or mass transfer. The formation of boosted delocalized π-conjugated electrons at the molecular level and condensed heptazine building blocks result in enhanced carrier density and charge transfer dynamics. Optical emission spectroscopy and time‐resolved fluorescence lifetime (TRPL) strongly confirmed the enhancement of light harvesting and prolonged charge carrier lifetime. The optimized sample exhibited a degradation performance of 95% of bisphenol A (BPA, 10 mg L–1) after 60 min under visible–light irradiation at pH = 5. All the scavenging experiments, probing experiments as well as electron paramagnetic resonance (EPR) confirm that •O2– is the dominant reactive species that fragments bisphenol A. Interestingly, density functional theory (DFT) calculations unveil that the BPA interaction with a modified g-CN containing porous structure is energetically more favorable than non-porous pure g-CN. Moreover, the toxicity assessment showed that the final degradation products were placed in the non-harmful category based on acute and chronic toxicity. This study presents a promising strategy to modify the g-CN properties and provides an efficient technique for boosting its visible–light photocatalytic activity.

Elucidation of Degradation Behavior of Hydroxy Group-Containing Benzodiazepines in Artificial Gastric Juice: Study on Degradability of Drugs in Stomach (III).

The degradation behavior of three benzodiazepines (BZPs)-lormetazepam (LMZ), lorazepam, and oxazepam-with hydroxy groups on the diazepine ring in artificial gastric juice and the effect of storage pH conditions on drug degradability were monitored using an LC/photodiode array detector (PDA) to estimate their pharmacokinetics in the stomach. Although the three BZPs degraded in artificial gastric juice, none could be restored, despite increasing the storage pH, implying that the degradation reaction was irreversible. As for LMZ, we discussed the physicochemical parameters, such as the activation energy and activation entropy involved in the degradation reaction as well as the reaction kinetics; one of the degradation products was isolated and purified for structural analysis. In the LMZ degradation experiment, peaks corresponding to degradation products, (A) and (B), were detected through the LC/PDA measurements. Regarding the degradation behavior, we hypothesized that LMZ was degraded into (B) via (A), where (A) was an intermediate and (B) was the final product. Although the isolation of degradation product (A) was challenging, degradation product (B) could be isolated and was confirmed to be "methanone, [5-chloro-2-(methylamino)phenyl](2-chlorophenyl)-" based on structure determination using various instrumental analyses. The compound exhibited axis asymmetry as determined using single-crystal X-ray structure analysis. Because the formation of degradation product (B) was irreversible, it would be prudent to target the final degradation product (B) and LMZ for identification when detecting LMZ in human stomach contents, such as during forensic dissection.

Exploring the mechanisms of humic acid mediated degradation of polystyrene microplastics under ultraviolet light conditions

Microplastics (MPs) are emerging pollutants that interact extensively with dissolved organic matter (DOM) and this influences the environmental behavior of MPs in aqueous ecosystems. However, the effect of DOM on the photodegradation of MPs in aqueous systems is still unclear. The photodegradation characteristics of polystyrene microplastics (PS-MPs) in an aqueous system in the presence of humic acid (HA, a signature compound of DOM) under ultraviolet light conditions were investigated in this study through Fourier transform infrared spectroscopy coupled with two-dimensional correlation analysis, electron paramagnetic resonance, and gas chromatography-mass spectrometry (GC/MS). HA was found to promote higher levels of reactive oxygen species (0.631 mM of ▪OH), which accelerated the photodegradation of PS-MPs, with a higher degree of weight loss (4.3%), higher level of oxygen-containing functional groups, and lower average particle size (89.5 μm). Likewise, GC/MS analysis showed that HA contributed to a higher content of oxygen-containing compounds (42.62%) in the photodegradation of PS-MPs. Moreover, the intermediates and final degradation products of PS-MPs with HA were significantly different in the absence of HA during 40 days of irradiation. These results provide an insight into the co-existing compounds on the degradation and migration processes of MP and also support further research toward the remediation of MPs pollution in aqueous ecosystems.

Evaluating the in vivo stability of water-soluble PEG-PLA copolymers using FRET imaging

Biodegradable and biocompatible polymer materials with tunable physical properties present a great interest for controlled drug delivery applications. A good example is BEPO®, a clinical-stage in situ-forming depot technology based on the utilization of a blend of poly(ethylene glycol)-b-poly(D,L-lactic acid) (PEG-PLA) diblock and triblock amphiphilic copolymers dissolved in an organic solvent. Once injected, this technology will form a bioresorbable solid polymer depot that will allow the release of a drug from weeks to months. The safety of the final degradation products from this technology, i.e., PEG and lactic acid, is well-documented. However, little information exists about the fate of intermediate degradants, specifically of water-soluble PEG-PLA chains where the molecular weights of the PLA block are short. Herein, we designed a Förster Resonance Energy Transfer (FRET) system for short copolymers, suitable for longitudinal in vivo imaging in the subcutaneous space, allowing to follow the stability of these products. Our results confirm that these species, that might be leaked from BEPO® depots during degradation, are rapidly hydrolyzed in the subcutaneous space of mice, forming approved products by Health Authorities, i.e., PEG and PLA homopolymers and/or lactic acid.

Photo-oxidation degradation of metronidazole in hematite/sulfite system: Mechanism, kinetic, degradation pathway

In this study, the decomposition of metronidazole (MTZ) in the hematite (α-Fe2O3)/sulfite system and in the presence of ultraviolet light was investigated. Based on transmission electron microscopy (TEM) and field scanning electron microscopy (SEM) analysis, hematite nanoparticles were included an average diameter of 80 nm. The results showed the process performance under the acidic and natural conditions was very high, as the destructive performances of MTZ (after 5 min of reaction), at pHs of 3 and 7.5 were 80 % and 92 %, respectively. The efficiency of each of the UV/sulfite (US) and UV/hematite (UH) systems in the degradation of metronidazole was 30 % and 27 %, respectively, which indicated the very low efficiency of these systems when each was used alone. Enhanced performance was observed when both hematite/sulfite agents were simultaneously exposed to UV, so that more than 92 % of metronidazole was degraded under the selected conditions (sulfite/hematite/MTZ molar ratio of 1:3: MTZ concentration and pH of 7.5 after 5 min of reaction). The rate of MTZ destruction in one min (robs (mg L−1 min)) indicated the supremacy of UHS process over UH and US processes. It was found the anions in the water matrix affect the efficiency of the system. Tests to investigate the active radical species in the reaction medium proved the importance of the role of the two hydroxyl and sulfate radicals in MTZ decomposition. A comparison of the total cost, energy consumed, and robs between the different systems, revealed UHS system can be considered as an economically acceptable and efficient process in the destructive of MTZ. Based on analysis done, the final products of MTZ degradation using UHS process were characterized to be Acetaldehyde, 1H-imidazole, Hydroxy acetonitrile, Aminoacetonitrile, Glycine, Isoamyl benzyl ether, Alanine and Acetic acids.