Elucidating sulfate radical-induced oxidizing mechanisms of solid-phase pharmaceuticals: Comparison with liquid-phase reactions.

As a class of organic micropollutants of global concern, pharmaceuticals have prevalent distributions in the aqueous environment (e.g., groundwater and surface water) and solid matrices (e.g., soil, sediments, and dried sludge). Their contamination levels have been further aggravated by the annually increased production of expired drugs as emerging harmful wastes worldwide. Sulfate radicals (SO4•-)-based oxidation has attracted increasing attention for abating pharmaceuticals in the environment, whereas the transformation mechanisms of solid-phase pharmaceuticals remain unknown thus far. This investigation presented for the first time that SO4•-, individually produced by mechanical force-activated and heat-activated persulfate treatments, could effectively oxidize three model pharmaceuticals (i.e., methotrexate, sitagliptin, and salbutamol) in both solid and liquid phases. The high-resolution mass spectrometric analysis suggested their distinct transformation products formed by different phases of SO4•- oxidation. Accordingly, the SO4•--mediated mechanistic differences between the solid-phase and liquid-phase pharmaceuticals were proposed. It is noteworthy that the products from both systems were predicted with the remaining persistence, bioaccumulation, and multi-endpoint toxicity. Therefore, some post-treatment strategies need to be considered during practical applications of SO4•--based technologies in remediating different phases of micropollutants. This work has environmental implications for understanding the comparative transformation mechanisms of pharmaceuticals by SO4•- oxidation in remediating the contaminated solid and aqueous matrices.

Unveiling the treatment-driven secondary risks of pharmaceuticals: New lessons from calcium channel blocker transformation by multiple oxidants.

The worldwide detection of numerous pharmaceuticals and their transformation products (TPs) in different environmental matrices has gained considerable concern about their potential ecological hazards. Increasing evidence suggested that calcium channel blockers (CCBs) are ubiquitous pharmaceutical pollutants in natural waters. However, their TPs, reaction pathways, and secondary risks have been limitedly known during oxidative water treatment. This study systematically assessed the TP formation and transformation mechanisms of two typical CCBs (i.e., amlodipine, AML; verapamil, VER) oxidized by ferrate(VI), permanganate, and ozone, as well as the in silico prediction on the TPs' properties. The high-resolution mass spectrometer analysis suggested a total of 16 TPs of AML and 8 TPs of VER identified for these reaction systems. Transformation of AML mainly proceeded through hydroxylation of the aromatic ring, ether bond cleavage, NH2 substitution by a hydroxyl group, and H-abstraction, while VER was oxidized via hydroxylation/opening of the aromatic ring and cleavage of the CN bond. Notably, certain TPs of both CCBs were estimated with low biodegradation, multi-endpoint toxicity, and high persistence and bioaccumulation, suggesting their severe risks to aquatic ecosystems. This study has implications for understanding the environmental behaviors, fate, and secondary risks of the globally prevalent and concerned CCBs under oxidative water treatment scenarios.

Predicting the Risk of Type B Aortic Dissection Using Hemodynamic Parameters in Aortic Arches: A Comparative Study between Healthy and Repaired Aortas.

BACKGROUND AND OBJECTIVE: The development of acute aortic dissection (AD) remains unpredictable due to the intricate nature of the AD mechanism and the varied patient-specific aortic anatomy. The aim of this study was to simulate the hemodynamic parameters in the aortas before the onset of TBAD with healthy controls. METHODS: This study numerically assessed the effectiveness of hemodynamic indicators in predicting the risk of type B AD (TBAD) by investigating the differences in hemodynamic parameters between healthy and repaired aortas (aortas before TBAD development). Four wall shear stress (WSS)-based indicators and three helicity-based indicators were adopted and analyzed. RESULTS: The results showed that more pathological anatomical feathers can be observed in the repaired aortas. For WSS-based indicators, only averaged cross flow index (CFI) and oscillatory shear index OSI (CFI, 1.03 ± 0.07 vs. 0.83 ± 0.10 and OSI, 0.12 ± 0.03 vs. 0.04 ± 0.02) (all p<0.001) were significantly higher in the repaired aortas than those in the healthy aortas. On the other hand, average helicity in the repaired aortas also showed a significant difference compared with that in healthy aortas (h1, 3.88 ± 5.55 vs. -8.03 ± 14.16) (p<0.05). Furthermore, the skewed helical structure and flow disturbance was found in the repaired aortas. CONCLUSION: 1) There are marked differences in pathological anatomical features, such as aortic dilation, elongation and tortuosity between the healthy aortas and repaired aortas, and the corresponding hemodynamic indicators also have also been significantly changed. 2) Compared with anatomical characteristics, hemodynamic indicators may be more accurate for predicting the risk and location of TBAD, such as the OSI and CFI index were significantly enhanced in the region where the entry tears have occurred. 3) In clinical practice, anatomical features remain important factors for assessing the risk for development of TBAD; however, hemodynamic analyses with quantitative data and more visualizing characteristics have showed promising potential in this aspect.

Emerging periodate-based oxidation technologies for water decontamination: A state-of-the-art mechanistic review and future perspectives.

With the ever-increasing severity of the ongoing water crisis, it is of great significance to develop efficient, eco-friendly water treatment technologies. As an emerging oxidant in the advanced oxidation processes (AOPs), periodate (PI) has received worldwide attention owing to the advantages of superior stability, susceptible activation capability, and high efficiency for decontamination. This is the first review that conducts a comprehensive analysis of the mechanism, pollutant transformation pathway, toxicity evolution, barriers, and future directions of PI-based AOPs based on the scientific information and experimental data reported in recent years. The pollutant elimination in PI-based AOPs was mainly attributed to the in situ generate reactive oxygen species (e.g., •OH, O(3P), 1O2, and O2•-), reactive iodine species (e.g., IO3• and IO4•), and high-valent metal-oxo species with exceptionally high reactivity. These reactive species were derived from the PI activated by the external energy, metal activators, alkaline, freezing, hydroxylamine, H2O2, etc. It is noteworthy that direct electron transport could also dominate the decontamination in carbon-based catalyst/PI systems. Furthermore, PI was transformed to iodate (IO3-) stoichiometrically via an oxygen-atom transfer process in most PI-based AOPs systems. However, the production of I2, I-, and HOI was sometimes inevitable. Furthermore, the transformation pathway of typical micropollutants was clarified, and the in silico QSAR-based prediction results indicated that most transformation products retained biodegradation recalcitrance and multi-endpoint toxicity. The barriers faced by the PI-based AOPs were also clarified with potential solutions. Finally, future perspectives and research directions are highlighted based on the current state of PI-based AOPs. This review enhances our in-depth understanding of PI-based AOPs for pollutant elimination and identifies future research needs to focus on the reduction of toxic byproducts.

Removal of chloramphenicol antibiotics in natural and engineered water systems: Review of reaction mechanisms and product toxicity.

Chloramphenicol antibiotics are widely applied in human and veterinary medicine. They experience natural attenuation and/or chemical degradation during oxidative water treatment. However, the environmental risks posed by the transformation products of such organic contaminants remain largely unknown from the literature. As such, this review aims to summarize and analyze the elimination efficiency, reaction mechanisms, and resulting product risks of three typical chloramphenicol antibiotics (chloramphenicol, thiamphenicol, and florfenicol) from these transformation processes. The obtained results suggest that limited attenuation of these micropollutants is observed during hydrolysis, biodegradation, and photolysis. Comparatively, prominent abatement of these compounds is accomplished using advanced oxidation processes; however, efficient mineralization is still difficult given the formation of recalcitrant products. The in silico prediction on the multi-endpoint toxicity and biodegradability of different products is systematically performed. Most of the transformation products are estimated with acute and chronic aquatic toxicity, genotoxicity, and developmental toxicity. Furthermore, the overall reaction mechanisms of these contaminants induced by multiple oxidizing species are revealed. Overall, this review unveils the non-overlooked and serious secondary risks and biodegradability recalcitrance of the degradation products of chloramphenicol antibiotics using a combined experimental and theoretical method. Strategic improvements of current treatment technologies are strongly recommended for complete water decontamination.

[Role of astacene in mice skeletal muscle and muscle cell mRNA expression of energy metabolism-related genes].

In order to examine the role of astacene on mice body development and the expression of energy metabolism related genes in mice, we treated mice (Kunming white) and primary culture of mouse muscle cells with astacene of higher and lower concentration. Then the total mRNA was extracted from the muscle tissue and cells respectively, and the mRNA levels of UCP3 and LXRalpha were detected by RT-PCR in all the samples. Compared with the control group, the body weight of mice in high concentrations of astacene group grown slowly, and the expressions of UCP3 genes decreased significantly in muscle tissue of the 10th day and the 30th day as well as the cells of treated for 24 h (P<0.05). The expression of LXRalpha gene increased significantly in all samples (P<0.05) and reached its peak at 72 h (P<0.01). With the treatment of lower concentration of astacene, the expressions of UCP3 and LXRalpha gene mRNA in muscle tissue did not alter much, but in muscle cells treated for 24 h, the mRNA level of UCP3 gene decreased significantly (P<0.05), and LXRalpha gene increased significantly (P<0.05). The results suggest that astacene has a role in regulating the energy use in mice muscle.