ZnO-decorated green-synthesized multi-doped carbon dots from Chlorella pyrenoidosa for sustainable photocatalytic carbamazepine degradation.

The promising green synthesis of carbon dots (CDs) from microalga Chlorella pyrenoidosa was achieved using simple hydrothermal and microwave-assisted methods. Doping of nanomaterials by nonmetals (N, S, and P) was confirmed by X-ray photoelectron spectroscopy (XPS), while the existence of metals in the CDs was confirmed by inductively coupled plasma optical emission spectroscopy (ICP-OES) and transmission electron microscopy (TEM), and Mg, Ca, K, and Na were found as the dominant doped metals. The novel nanomaterials with excellent photoluminescence (PL) properties were used for the modification of ZnO obtained by a simple hydrothermal process. In this regard, a series of ZnO decorated with multi-doped carbon dots (xCDs) was prepared and their photocatalytic properties were evaluated. The ZnO-xCD photocatalysts were characterized by various advanced techniques including X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), XPS, Brunauer-Emmett-Teller (BET), PL, ultraviolet-visible (UV-vis) spectroscopy and electrochemical impedance spectroscopy (EIS) analysis. The photocatalytic behaviour of the obtained materials was investigated in the degradation of carbamazepine (CBZ). The influence of the synthesis method of xCDs and their content on the activity of the photocatalyst was examined. The photocatalyst ZnO modified with 3% xCDs obtained by the microwave-assisted method revealed the highest effectiveness for CBZ degradation and allowed for a first-order degradation rate of 2.85 times in comparison with non-modified ZnO. The improvement of the photocatalytic process was achieved by support with peroxymonosulphate resulting in up to 3.18 times a first order kinetic rate constant compared with that of simple photocatalysis in the presence of ZnO-xCDs. Taken together, our synthesized multi-doped CDs and their nanohybrids with ZnO, can be considered as promising candidates for photocatalytic applications.

Potential of Silver Nanoparticles in Overcoming the Intrinsic Resistance of Pseudomonas aeruginosa to Secondary Metabolites from Carnivorous Plants.

Carnivorous plants are exemplary natural sources of secondary metabolites with biological activity. However, the therapeutic antimicrobial potential of these compounds is limited due to intrinsic resistance of selected bacterial pathogens, among which Pseudomonas aeruginosa represents an extreme example. The objective of the study was to overcome the intrinsic resistance of P. aeruginosa by combining silver nanoparticles (AgNPs) with secondary metabolites from selected carnivorous plant species. We employed the broth microdilution method, the checkerboard titration technique and comprehensive phytochemical analyses to define interactions between nanoparticles and active compounds from carnivorous plants. It has been confirmed that P. aeruginosa is resistant to a broad range of secondary metabolites from carnivorous plants, i.e., naphthoquinones, flavonoids, phenolic acids (MBC = 512 µg mL-1) and only weakly sensitive to their mixtures, i.e., extracts and extracts' fractions. However, it was shown that the antimicrobial activity of extracts and fractions with a significant level of naphthoquinone (plumbagin) was significantly enhanced by AgNPs. Our studies clearly demonstrated a crucial role of naphthoquinones in AgNPs and extract interaction, as well as depicted the potential of AgNPs to restore the bactericidal activity of naphthoquinones towards P. aeruginosa. Our findings indicate the significant potential of nanoparticles to modulate the activity of selected secondary metabolites and revisit their antimicrobial potential towards human pathogenic bacteria.

Critical study of crop-derived biochars for soil amendment and pharmaceutical ecotoxicity reduction.

In this study, biochars (BCs) produced from crops (straw and seeds) were tested for the applicability as additive to soils. The effect on pH, water capacity and cation exchange capacity of soil were tested. The ability for the sorption of pharmaceuticals (beta-blockers, anti-inflammatory drugs, sulfonamides, 17α-ethinylestradiol, carbamazepine, caffeine) using the batch sorption test was performed, and the effect of water pH was investigated. In addition, the metals removed from the biochar was analyzed as a potential toxicity factor. The mechanism of adsorption (Langmuir, Freundlich) was tested for sulfadimetoxine. The effect of the rye-derived biochar on water cress germination and the reduction of the sulfonamides toxicity to this plant was tested. The advantages of crop-derived biochar application to different soils (sand soil, clay soil and reference soil) was presented. It was found that tested BCs effectively increase the water capacity of soils, especially sand type soil, but in the same time it had increase the pH of pure-buffering soils. The driving force of pharmaceutical sorption was its ionization form - the highest sorption occurs for cations, medium for neutral forms, while the lowest sorption for anions. The opposite situation have been noted for desorption from biochar. The washing of biochars increases sorption for the neutral and anionic species, but not for the cations. The application of biochars into the soils can from one site protect the plants from toxic impact of sulfonamides, but from the other hamper the root prolongation by the pH increase.

Insights into Mechanisms of Electrochemical Drug Degradation in Their Mixtures in the Split-Flow Reactor.

The recirculating split-flow batch reactor with a cell divided into anolyte and catholyte compartments for oxidation mixture of cytostatic drugs (CD) was tested. In this study, kinetics and mechanisms of electrochemical oxidization of two mixtures: 5-FU/CP and IF/CP were investigated. The order of the CD degradation rate in single drug solutions and in mixtures was found to be 5-FU < CP < IF. In the 5-FU/CP mixture, kapp of 5-FU increased, while kapp of CP decreased comparing to the single drug solutions. No effect on the degradation rate was found in the CP/IF mixture. The presence of a second drug in the 5-FU/CP mixture significantly altered mineralization and nitrogen removal efficiency, while these processes were inhibited in IF/CP. The experiments in the different electrolytes showed that •OH and sulphate active species can participate in the drug's degradation. The kapp of the drugs was accelerated by the presence of Cl- ions in the solution. Chlorine active species played the main role in the production of gaseous nitrogen products and increased the mineralisation. Good results were obtained for the degradation and mineralisation processes in mixtures of drugs in municipal wastewater-treated effluent, which is beneficial from the technological and practical point of view.

Optimization of a procedure for the simultaneous extraction of polycyclic aromatic hydrocarbons and metal ions by functionalized and non-functionalized carbon nanotubes as effective sorbents.

In this publication, a new dispersive solid-phase extraction (dSPE) method combined with gas chromatography-mass spectrometry and atomic absorption spectrometry was developed for the simultaneous determination of 9 PAHs and chromium, cadmium, and lead ions in water samples. For this purpose, non-modified multi-walled carbon nanotubes (MWCNTs) and modified -MWCNTs (OH-MWCNTs and COOH-MWCNTs) were used as sorbents. Parameters affecting the extraction, such as the amount of sorbent, the pH of the sample, the composition and volume of eluents and the extraction time were optimized. Sequential elution was applied using 6mL of dichloromethane for the elution of PAHs and 5mL of 3M HNO3 for cadmium, lead, and chromium. The optimal values of other parameters were as follows: 50mg of sorbent per 250mL of water sample, pH in a range from 6 to 7 and 30min of contact time between the sorbent and analytes. The results demonstrated the high extraction capability of modified MWCNTs with recoveries between 80 and 101% for cadmium, chromium, and lead ions and between 83 and 92% for PAHs. Finally, the optimized method was validated, and the matrix effects were determined.

Metallothioneins 1 and 2, but not 3, are regulated by nutritional status in rat white adipose tissue.

BACKGROUND: Cumulating evidence underlines the role of adipose tissue metallothionein (MT) in the development of obesity and type 2 diabetes. Fasting/refeeding was shown to affect MT gene expression in the rodent liver. The influence of nutritional status on MT gene expression in white adipose tissue (WAT) is inconclusive. The aim of this study was to verify if fasting and fasting/refeeding may influence expression of MT genes in WAT of rats. RESULTS: Fasting resulted in a significant increase in MT1 and MT2 gene expressions in retroperitoneal, epididymal, and inguinal WAT of rats, and this effect was reversed by refeeding. Altered expressions of MT1 and MT2 genes in all main fat depots were reflected by changes in serum MT1 and MT2 levels. MT1 and MT2 messenger RNA (mRNA) levels in WAT correlated inversely with serum insulin concentration. Changes in MT1 and MT2 mRNA levels were apparently not related to total zinc concentrations and MTF1 and Zn transporter mRNA levels in WAT. Fasting or fasting/refeeding exerted no effect on the expression of MT3 gene in WAT. Addition of insulin to isolated adipocytes resulted in a significant decrease in MT1 and MT2 gene expressions. In contrast, forskolin or dibutyryl-cAMP (dB-cAMP) enhanced the expressions of MT1 and MT2 genes in isolated adipocytes. Insulin partially reversed the effect of dB-cAMP on MT1 and MT2 gene expressions. CONCLUSIONS: This study showed that the expressions of MT1 and MT2 genes in WAT are regulated by nutritional status, and the regulation may be independent of total zinc concentration.