FT-ICR-MS combined with fluorescent spectroscopy reveals the driving mechanism of the spatial variation in molecular composition of DOM in 22 plateau lakes.

Dissolved organic matter (DOM) is the largest carbon pool and directly affects the biogeochemistry in lakes. In the current study, fourier transform ion cyclotron mass spectrometry (FT-ICR-MS) combined with fluorescent spectroscopy was used to assess the molecular composition and driving mechanism of DOM in 22 plateau lakes in Mongolia Plateau Lakes Region (MLR), Qinghai Plateau Lakes Region (QLR) and Tibet Plateau Lakes Region (TLR) of China. The limnic dissolved organic carbon (DOC) content ranged from 3.93 to 280.8 mg L-1 and the values in MLR and TLR were significantly higher than that in QLR. The content of lignin was the highest in each lake and showed a gradually decreasing trend from MLR to TLR. Random forest model and structural equation model implied that altitude played an important role in lignin degradation while the contents of total nitrogen (TN) and chlorophyll a (Chl-a) have a great influence on the increase of DOM Shannon index. Our results also suggested that the inspissation of DOC and the promoted endogenous DOM production caused by the inspissation of nutrient resulted in a positive relationship between limnic DOC content and limnic factors such as salinity, alkalinity and nutrient concentration. From MLR to QLR and TLR, the molecular weight and the number of double bonds gradually decreased but the humification index (HIX) also decreased. In addition, from the MLR to the TLR, the proportion of lignin gradually decreased, while the proportion of lipid gradually increased. Both above results suggested that photodegradation was dominated in lakes of TLR, while microbial degradation was dominated in lakes of MLR.

Composition of dissolved organic matter (DOM) in wastewater treatment plants influent affects the efficiency of carbon and nitrogen removal.

Wastewater treatment plants (WWTPs) play a critical role in receiving, removing, and discharging dissolved organic matter (DOM) in aquatic systems. To date, understanding the composition and fate of DOM in different WWTPs with various environmental and socioeconomic conditions is limited. This study analyzed DOM components in the influent and effluent samples from 49 WWTPs in China using EEM-PARAFAC and ESI-FT-ICR-MS methods. The influencing factors of DOM components in the influent were also analyzed. Geographic location and GDP showed significant (p < 0.05) correlations with DOM components in the influent. The removal efficiency of DOM in WWTPs was closely related to the DOM compositions, where carbohydrates, lipids, and protein-like components (removal efficiencies > 75 %) were more readily decomposed than the humic-like components, lignin, and tannin. The relative fraction of humic-like compound C3 in the influent was correlated negatively with total nitrogen (TN) and chemical oxygen demand (COD) removal in WWTPs (p < 0.05). Besides, the relative fraction of DOM containing the element sulfur also showed significant negative correlations with the humification of DOM (p < 0.05). The results from EEM-PARAFAC and ESI-FT-ICR-MS methods showed no obvious correlation for the DOM characterizations except for humic-like fluorescent fraction C3 and lignin, while significant positive correlations (p < 0.05) between the aromatic index (AI_mod) from the ESI-FT-ICR-MS analysis and the humification index (HIX) from spectrofluorimetry. This supports the use of these spectral indexes as simple surrogates to represent part chemical compositions in further research.

Molecular characteristics of microalgal extracellular polymeric substances were different among phyla and correlated with the extracellular persistent free radicals.

Extracellular polymeric substance (EPS) plays essential roles in microalgal adaptation to the external environment and aggregate formation. The molecular characteristics of EPS and extracellular persistent free radicals (PFRs) of 15 microalgal species belonging to three phyla were analyzed using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), three-dimensional fluorescence excitation-emission matrices combined with parallel factor analysis (EEM-PARAFAC), and Electron Paramagnetic Resonance Spectrometer (EPR). Lignin accounted for the highest proportion of EPS for Cyanophyta and the proportion of lipids was higher for Bacillariophyta. The presence of PFRs was detected on the cell surfaces of all microalgae species (excluding Cyclotella sp.). The intensity of carbon-centered PFRs was positively correlated with the proportions of humic-like component and lignin, but was negatively correlated with the proportion of lipids in microalgal EPS. Following EPS extraction, carbon- and oxygen-centered free radicals were still detectable on the surface of microalgae. Given the high intensity of PFRs produced by Cyanophyta, the level of PFRs in eutrophic lakes and reservoirs predominated by Cyanophyta may be considerably high. Other organisms in the water column, such as bacteria and zooplankton are bound to be stressed by elevated level of PFRs. The ecological functions and environmental risks of PFRs carried by microalgae still need to be explored in follow-up research.

Spatial distribution and risk assessment of certain antibiotics in 51 urban wastewater treatment plants in the transition zone between North and South China.

The release of antibiotics from WWTPs into the environment has raised increasing concern worldwide. The monitoring of antibiotics in WWTPs throughout a region is crucial for emerging pollutant management. A large-scale survey of the occurrence, distribution, and ecological risk of seven antibiotics in 51 WWTPs was conducted in Shaanxi Province, China. Norfloxacin and ofloxacin had the highest detection concentrations of 474.2 and 656.18 ng L-1, respectively. Antibiotic residues in effluents were decreased by 5.88-94.16 % after different treatment processes. In particular, A2O or mixed processes performed well in removing target antibiotic compounds simultaneously. The ecological risk posed by antibiotic compounds detected in effluents was calculated using the risk quotient (RQ). Norfloxacin, ofloxacin, tetracycline, and roxithromycin posed different levels of potential ecotoxicological risk (RQ = 0.02-7.59). Based on the sum of the RQ values of individual antibiotic compounds, each investigated WWTP showed potential ecological risk. WWTPs with high risk levels were mainly found in the central region, while those in the southern region exhibited low risk levels, and those in the northern region showed risk levels between medium and high. This comprehensive investigation provides promising results to support the safe use and control of antibiotics in the study area.

Evaluation of antityrosinase activity and mechanism, antioxidation, and UV filter properties of theaflavin.

Tyrosinase is a key metalloenzyme for the biosynthesis of melanin that plays a critical role in the prevention of skin damage caused by ultraviolet (UV) radiation. However, the overproduction of melanin may cause a variety of skin diseases. Due to the toxicity and inefficiency of existing tyrosinase inhibitors, it is urgent to identify safe and potent alternatives from natural sources. Theaflavin, a single-component extracted from black tea, has been found to possess a variety of pharmacological activities. Herein, the inhibition kinetics of theaflavin on tyrosinase and inhibitory mechanism were determined using spectroscopy, molecular docking, and zebrafish model. The results showed that theaflavin inhibited the diphenolase activity of tyrosinase in a reversible mixed type manner with IC50 of 229.75 µmol/L and hindered the synthesis of melanin in zebrafish. This may be due to the formation of eight hydrogen bonds and hydrophobic effects between theaflavin and tyrosinase according to the results of molecular docking. To study the possible effects on the prevention of free radical-mediated skin cancer and photoaging caused by UV radiation, the antioxidation and UV filter properties of theaflavin were further verified. This study demonstrates that theaflavin is a potential multifunctional compound that can be used in cosmetic and medicinal products.

Fabrication and Evaluation of Glabridin Tip-loaded Dissolving Microneedles.

BACKGROUND: The clinical application of glabridin in treating skin diseases has been constrained by the limitations of its poor chemical stability and low skin permeability. OBJECTIVE: Here, we describe Tip-loading Dissolving Microneedles (TDMNs) encapsulating drugs only in the tips of needles for glabridin delivery with improved stability and skin permeability. METHODS: The TDMNs fabricated by solvent casting technique had sufficient mechanical strength to penetrate through the excised rat's skin without fracture. Drug delivery efficiency and drug residual in the skin of TDMNs were 63.16% and 49.28%, respectively. Glabridin encapsulated in the tips of TDMNs was effectively delivered into the abdominal skin of rat, and the in vivo delivery efficiency was inversely proportional to the drug doses. RESULTS: Transepidermal Water Loss (TEWL) significantly increased to 34.80 g/m2·h after the application of TDMNs and returned to normal levels (11.31 g/m2·h) after 8 h, indicating that the TDMNs were well tolerated. The stability of glabridin at room temperature was appreciably improved when loaded in TDMNs. CONCLUSION: These results suggest that intradermal delivery of glabridin by TDMNs is a safe and efficient alternative to currently available routes of administration.

Structure-activity relationships of antityrosinase and antioxidant activities of cinnamic acid and its derivatives.

The related structure-activity relationships of cinnamic acid and its derivates have not been studied in details yet. Herein, antityrosinase and antioxidant activities of 18 compounds were evaluated. The results demonstrated that the substituents on the phenyl ring of cinnamic acid led to the enhancement of the inhibition on monophenolase and the weakening of the inhibition on diphenolase. Among these tested compounds, 9 was first discovered as a tyrosinase inhibitor in a reversible competitive manner with IC50 value of 68.6 ± 4.2 µm. Docking results demonstrated 9 located into the catalytic center of tyrosinase. Antioxidant assay indicated that only 1 hydroxyl group on the phenyl ring was not enough to possess the radical scavenging activity, and the number of hydroxyl groups may be more important. This study will be helpful in the development of new cinnamic acid derivates as tyrosinase inhibitors and antioxidants with higher efficacy.

A comparison study of applying natural iron minerals and zero-valent metals as Fenton-like catalysts for the removal of imidacloprid.

Natural iron minerals and zero-valent metals have been widely tested as catalysts for the Fenton-like process, but the systematical comparison study about their catalytic performance was rarely conducted, and the risk of the secondary pollution of toxic heavy metals was still not uncertain. In this paper, a comparison study of applying pyrite, ilmenite, vanadium titano-magnetite (VTM), zero-valent iron (ZVI), and zero-valent copper (ZVC) as Fenton-like catalysts for the removal of imidacloprid was performed. The results showed that ZVI exhibited the highest activity among the recyclable solid catalysts with a removal rate of 96.8% at initial pH 3 using 10.78 mmol/L H2O2, due to iron corrosive dissolution. Vanadium titano-magnetite (VTM) exhibited the best activity at first use among tested minerals but with low reusability. Pyrite with stable morphology showed a medium but sustainable ability to degrade imidacloprid, achieving a removal rate of 10.5% in the fifth use. The reaction much favored the acidic condition of initial pH around 2 or 3. Meanwhile, there was a significant positive correlation between removal efficiency and dissolved Fe or Cu concentration. Pyrite was considered to be a promising catalyst in Fenton-like reaction. It was suggested that the system proceeded predominantly through a homogeneous route via dissolved Fe or Cu ions. Except ZVC and VTM, other tested catalysts showed the low possibility of causing secondary pollution of toxic metals in the application of Fenton-like process.

Fabrication and characterization of dissolving microneedles for transdermal drug delivery of allopurinol.

Allopurinol (AP) is the first line drug in treating hyperuricemia and gout in clinical by oral drug delivery, which is associated with severe adverse effects and the hepatic first-pass effect. Herein, we first proposed AP encapsulated dissolving microneedles (DMNs) for transdermal drug delivery to realize the sustained drug release and avoid the hepatic first-pass effect, which will help to reduce the adverse effects and improve the bioavailability of AP. DMNs were fabricated by a suspension solution casting method with precisely controlled dose. They had sufficient mechanical strength to penetrate through the skin and resulted in the formation of hundreds of micropores in skin. The results of in vitro and ex vivo release experiments demonstrated that the release profile of DMNs was independent with the dose of AP, and they indeed had much higher drug delivery efficiency (DDE) than the equal amount of AP in solutions. In vivo DDE reached to 38.9% within 1 h, and the drug residual can be served as a drug reservoir for sustained drug release. The result of pharmacodynamic study further confirmed that the sustained release and the anti-hyperuricemia effect of DMNs encapsulating AP were achieved. Moreover, transepidermal water loss significantly increased to 49.50 ± 3.82 g/m2·h after the application of DMNs and returned to normal levels (12.25 ± 0.21 g/m2·h) after 8 h, indicating that the DMNs were well tolerated. These results suggest that transdermal drug delivery of AP by using DMNs is an efficient and safe alternative to currently available routes of administration.