An alginate-based eutectogel impregnated with polyvinylpyrrolidone/benzoic acid deep eutectic solvent and magnetic carboxylated multiwalled carbon nanotubes: Evaluated as sorbent in green microextraction of pesticides.

This article presents the synthesis and application of a novel magnetic eutectogel constituting a polymeric deep eutectic solvent (PDES), carboxylated multiwall carbon nanotube (MWCNT-COOH), and super-dispersible/super-paramagnetic polyvinylpyrrolidone coated-Fe3O4 nanocrystals incorporated in alginate gel. Different methods were used for the characterization of novel polymeric based DES gel including FT-NMR, ATR-FTIR, and SEM were used. The novel DES eutectogel was used for the extraction of pesticides from honey. The modified eutectogel with PDES, MWCNT, and PDES-MWCNT showed 1.8-, 1.4-, and 2.5-fold enhancement in the sorption efficiency under green magnetic micro-solid-phase extraction (MSPE) method before GC-MS analysis. Important factors including the acidity of the samples, adsorption and desorption conditions, and the ionic strength of the preparation solution were investigated. The matrix effect, specificity, the quantification limits (0.023-1.023 µg kg-1), linear dynamic range (0.023-500 µg kg-1 with R2 of 0.9845-0.9986), relative standard deviations (<8.4%), were evaluated. In addition, the method was used to analyze 12 pesticides in four samples of honey. In the spiked concentration range of 0.1 to 10 µg kg-, the obtained recoveries were between 73.2 and 110.8% (RSD% = 8.1%, n = 3).

Synthesis of a magnetic micro-eutectogel based on a deep eutectic solvent gel immobilized in calcium alginate: Application for green analysis of melamine in milk and dairy products.

A new three-component magnetic eutectogel composed of a crosslinked copolymeric deep eutectic solvent (DES) and polyvinylpyrrolidone-coated Fe3O4 nano-powder impregnated in calcium alginate gel was synthesized and applied as a sorbent material in a green alternative micro solid-phase extraction of melamine in milk and dairy products. The analyses were performed using the HPLC-UV technique. The copolymeric DES was prepared through thermally-induced free-radical polymerization of [2-hydroxyethyl methacrylate]:[thymol] DES (1:1 mol ratio) as functional monomer, azobisisobutyronitrile (as initiator), and ethylene glycol dimethacrylate (as crosslinker). The sorbent was characterized using ATR-FTIR, 1H & 13C FT-NMR, SEM, VSM, and BET techniques. The stability of the eutectogel in water and its effect on the pH of the aqueous solution was studied. A one-at-a-time approach was applied to optimize the impact of significant factors influencing sample preparation efficiency (sorbent mass, desorption conditions, adsorption time, pH, and ionic strength). The method validation was performed by evaluating matrix-matched calibration linearity (2-300 µg kg-1, r2 = 0.9902), precision, system suitability, specificity, enrichment factor, and matrix effect. The obtained limit of quantification (0.38 µg kg-1) was lower than the established maximum level for melamine by Food and Drug Administration (FDA) (0.25 mg kg-1), Food and Agriculture Organization (FAO) (0.5 & 2.5 mg kg-1), and The European Union (EU) (2.5 mg kg-1) in milk and dairy products. The optimized procedure was applied for the analysis of melamine in bovine milk, yogurt, cream, cheese, and ice cream. The obtained normalized recoveries of 77.4-105.3% (RSD% <7.0%) were acceptable regarding the practical default range set by the European Commission (70-120%, RSD≤20%). The sustainability and green aspects of the procedure were evaluated by the Analytical Greenness Metric Approach (0.6/1.0) and the Analytical Eco-Scale tool (73/100). This paper presents the first-time synthesis and application of this micro-eutectogel for the analysis of melamine in milk and milk-based dairy products.

Green vortex-assisted emulsification microextraction using a ternary deep eutectic solvent for extraction of tetracyclines in infant formulas.

A novel green alternative vortex-assisted emulsification liquid-liquid microextraction based on a new hydrophobic deep eutectic solvent (DES) was developed to extract tetracyclines in infant formulas. Five new ternary DESs were synthesized and tested in this regard. Among them [thymol]:[ethylene glycol]:[benzyl alcohol] (2:2:1) DES demonstrated the highest extraction efficiency. The analyzes were performed by HPLC. The DES was characterized by attenuated total reflectance-FTIR, nuclear magnetic resonance spectroscopy, and octanol-water partition coefficient. The effect of type, mole ratio, and volume of DES, dispersing agent, pH, and ionic strength was studied. The limits of quantification and linear range were 3-9.32 and 3-500 µg kg-1, respectively. The method was applied to detect tetracyclines in infant formulas, and the recoveries were obtained as 68.9-102.0 % with relative standard deviations < 9 %. The procedure greenness was assessed using the Analytical Eco-Scale. This paper represents the first application of a novel ternary DES to analyze tetracyclines in infant formulas.

Protective effects of bioactive phytochemicals from Mentha piperita with multiple health potentials.

Mentha piperita essential oil was bactericidal in order of E. coli> S. aureus > Pseudomonas aeruginosa > S. faecalis > Klebsiella pneumoniae. The oil with total phenolics of 89.43 ± 0.58 µg GAE/mg had 63.82 ± 0.05% DPPH inhibition activity with an IC (50) = 3.9 µg/ml. Lipid peroxidation inhibition was comparable to BHT and BHA. A 127% hike was noted in serum ferric-reducing antioxidant power. There was 38.3% decrease in WBCs count, while platelet count showed increased levels of 214.12%. Significant decrease in uric acid level and cholesterol/HDL and LDL/HDL ratios were recorded. The volatile oil displayed high cytotoxic action toward the human tumor cell line. The results of this study deserve attention with regard to antioxidative and possible anti-neoplastic chemotherapy that form a basis for future research. The essential oil of mint may be exploited as a natural source of bioactive phytopchemicals bearing antimicrobial and antioxidant potentials that could be supplemented for both nutritional purposes and preservation of foods.

Antimicrobial property, antioxidant capacity, and cytotoxicity of essential oil from cumin produced in Iran.

Cumin (Cuminum cyminum) is one of the commonly used spices in food preparations. It is also used in traditional medicine as a stimulant, a carminative, and an astringent. In this study, we characterized the antimicrobial, antioxidant, and cytotoxic activities of cumin. E. coli, S. aureus, and S. faecalis were sensitive to various oil dilutions. The total phenol content of the essential oil was estimated to be 33.43 microg GAE/mg of the oil. The oil showed higher antioxidant activity compared with that of BHT and BHA. The cumin essential oil exhibited a dose-dependent scavenging of DPPH radicals and 5.4 microg of the oil was sufficient to scavenge 50% of DPPH radicals/mL. At a concentration of 0.1 microL/mL, oil destructed Hela cells by 79%. The antioxidant activity of cumin essential oil might contribute to its cytotoxic activity. Acute and subchronic toxicity was studied in a 30-d oral toxicity study by administration to Wistar rats of the essential oil. A 17.38% decrease in WBCs count, and 25.77%, 14.24%, and 108.81% increase in hemoglobin concentration, hematocrit, and platelet count, respectively, were noted. LDL/HDL ratio was reduced to half, which adds to the nutritional effects of cumin. Thus, cumin with a high phenolic content and good antioxidant activity can be supplemented for both nutritional purposes and preservation of foods.

Phytotherapeutic prevention of dental biofilm formation.

The antimicrobial and biofilm formation preventive properties of Mentha piperita and Rosmarinus officinalis essential oils and chlorhexidine were assessed against Streptococcus mutans and Streptococcus pyogenes. 26 and 20 compounds were identified by GC and GC-MS analysis in hydrodistilled oils from M. piperita and R. officinalis, respectively. The minimal bactericidal concentrations (MBC) of the M. piperita and R. officinalis oils and chlorhexidine were (6000, 2000, 8000 ppm) and (1000, 4000, 1000 ppm) for S. mutans and S. pyogenes, respectively. The decimal reduction time (D) of S. mutans exposed to the oils at their MBC levels was 2.8 min while chlorhexidine showed a longer time. The D values of S. pyogenes on exposure to the MBC levels of M. piperita and R. officinalis oils and of chlorhexidine were 2.14, 4.28 and 2.8 min, indicating a higher efficacy of M. piperita oil. Biofilm formation was performed by growing S. mutans culture with and without essential oils in LB medium in polystyrene tubes. In vitro biofilm inhibitory properties were in the order M. piperita > R. officinalis > chlorhexidine. In vivo experiments on the antibiofilm properties revealed that all concentrations of the oils were significantly (p < 0.001) more effective than chlorhexidine. In conclusion, essential oils may be considered as safe agents in the development of novel antibiofilm agents.

Phytotherapeutic inhibition of supragingival dental plaque.

Antimicrobial activities and biofilm-formation preventive properties of Mentha piperita and Cuminum cyminum essential oils and chlorhexidine were assessed against Streptococcus mutans and Streptococcus pyogenes. Gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) analysis led to the identification of 26 and 32 compounds in the essential oils of M. piperita and C. cyminum, respectively. Minimal bactericidal concentrations (MBC) of the oils and chlorhexidine and microbial decimal reduction time (D value) were determined. Antibacterial and in vivo biofilm preventive efficacies of all the concentrations of M. piperita oil were significantly (p<0.001) higher. The biofilm inhibitory properties in planktonic cultures were in M. piperita > chlorhexidine > C. cyminum order. In vivo experiments conducted on male and female volunteers who brushed with essential oil blended toothpastes indicated that lower concentrations of the oils, in particular the M. piperita oil, were significantly higher (p<0.001) and effective during the course of the study as compared to chlorhexidine. In conclusion, there may be a potential role for essential oils in the development of novel anticaries treatments.

Biochemical activities of Iranian Mentha piperita L. and Myrtus communis L. essential oils.

GC-MS analysis of essential oils of Iranian Mentha piperita and Myrtus communis extracted by hydrodistillation lead to identification of 26 and 32 compounds, respectively. The oils had good to excellent antimicrobial activities against Escherichia coli, Staphylococcus aureus and Candida albicans with the oil of M. piperita being more active. The findings suggest feasibility of application of M. piperita oil in treatment of the infections caused by C. albicans and E. coli. D-values on exposure to M. piperita and Myrtus communis oils were (2.14 and 2.8min), (1.4 and 12.8min) and (4.3 and 8.6min) for E. coli, S. aureus and C. albicans , respectively. The oils were screened for their possible antioxidant activities by two complementary test systems, namely DPPH free radical scavenging and beta-carotene/linoleic acid systems. M. piperirta oil exerted greater antioxidant activity than that of M. communis. Phytochemical and phytobiological characteristics of these oils may lead to extraction and production of active compounds in single or combined forms with useful applications.

Novel sulfate ion-selective polymeric membrane electrode based on a derivative of pyrilium perchlorate.

A sulfate ion-selective PVC membrane sensor based on 4-(4-bromophenyl)-2,6-diphenylpyrilium perchlorate (BDPP) as a novel sensing material is successfully developed. The electrode shows a good selectivity for sulfate ion with respect to common organic and inorganic anions. The sensor exhibits a good linear response with slope of -28.9+/-0.5 mV per decade over the concentration range of 1.0x10(-6)-1.0x10(-2) M, and a detection limit of 8.0x10(-7) M of SO(4)(2-) ions. The electrode response is independent of pH in the range of 4.0-9.0. The proposed sensor was applied as an indicator electrode in potentiometric titration of sulfate and barium ions, and to the determination of zinc in zinc sulfate tablets.