A molecularly imprinted poly 2-aminophenol-gold nanoparticle-reduced graphene oxide composite for electrochemical determination of flutamide in environmental and biological samples.

A selective and sensitive electrochemical sensor based on reduced graphene oxide, gold nanoparticles, and molecularly imprinted poly 2-aminophenol was developed for electrochemical determination of flutamide in environmental and biological samples. The composite fabrication was electrochemically carried out and the composite was characterized by Fourier transform infrared, proton and carbon nuclear magnetic resonance, field emission scanning electron microscopy, and energy-dispersive X-ray spectrometry. The spectroscopic results showed that polymerization of molecularly imprinted poly 2-aminophenol took place through a ladder structure system. After optimization of effective parameters on the response of the sensor, the obtained linear range, relative standard deviation (for a concentration of 50 µg L-1 with five replicates) and limit of quantification for flutamide determination were determined to be 2-375 µg L-1, 1.54% and 0.8 µg L-1, respectively. The results showed that the application of poly 2-aminophenol in the structure of the proposed sensor using a molecular imprinting approach made the sensor highly selective toward flutamide, distinguishing it from similar nitro-containing compounds. The prepared sensor was successfully utilized to analyze environmental water and urine samples. The obtained results showed that the proposed method is in agreement with the HPLC method and can be used as a reliable alternative method for the analysis of flutamide.

A metal-catex composite electrode for determination of paraquat in various samples by Ad-differential pulse cathodic stripping voltammetry.

In this work, a novel kind of metal-catex composite electrode for determination of paraquat (PQ) by adsorptive differential pulse voltammetry is introduced. The metal-catex composite electrode was fabricated by cathodic electropolymerization of p-nitrophenol and p-nitrobenzoic acid in the presence of tin (II) chloride as a scaffold for composite structure on prepared glassy carbon electrode. Electropolymerization was carried out in sodium acetate medium. The surface of the fabricated electrode was characterized with field emission scanning electron microscope and energy-dispersive X-ray spectrometry. The obtained results show that there are Sn nanoparticles in the structure of the catex-composite. Chemical structure of metal-catex composite electrode was investigated using FTIR (ATR), 13C NMR, H NMR and a suitable mechanism for electropolymerization has been proposed. This metal-catex composite electrode was applied for determinations of PQ using sodium acetate buffer solutions at pH = 6.5 as an electrolyte solution. All parameters influencing the performance of the fabricated electrode were studied and optimized. The proposed electrode exhibits good linearity versus PQ concentration in the range of 3.8 × 10-8 to 7.7 × 10-7 mol L-1 and shows a manifold increase in sensitivity (more than 30 times) as compared to the glassy carbon electrode. The LOQ of this electrode was 7.78 × 10-9 mol L-1, which is comparable with that of other electrochemical methods. The mean, standard deviation and relative standard deviation for seven repetitive determinations of paraquat (7.78 × 10-8 mol L-1) were measured to be 7.75 × 10-8 mol L-1, ±0.29 × 10-8 mol L-1, and 3.75% respectively. This electrode was applied for the determination of paraquat in natural water, natural juice, potatoes and onions. The introduced electrode shows good stability with repeated use and over long periods (about 20 days). There is a good agreement between the results for water analysis by this method and the standard method.

A new composite based on graphene oxide-poly 3-aminophenol for solid-phase microextraction of four triazole fungicides in water and fruit juices prior to high-performance liquid chromatography analysis.

An environmentally friendly method which is based on preparation and use of a new composite consisting of poly 3-aminophenol and graphene oxide for solid-phase microextraction of triazole fungicides from natural water and juices is introduced. The composite was synthesized by in-situ polymerization of 3-aminophenol and graphene oxide in weak alkaline media. By using the obtained results from the characterization, a suitable mechanism for polymerization and a proper structure for the polymer were proposed. Under optimal conditions, there are linear relationships between concentration of triazoles and their HPLC peak areas in the range of 0.5-100 µg L-1. The recovery percentages, pre-concentration factors and LOQ for all triazoles were 95.2-98.0%, about 200 and 0.2-0.4 µg L-1, respectively. The offered method was applied for extraction and determination of triazoles from natural water, some juices and it represents a promising alternative method for analysis of triazoles.

Synthesis of graphene oxide-based poly(p-aminophenol) composite and its application in solid phase extraction of trace amount of Ni(II) from aquatic samples.

The results of investigations about the polymerization of p-aminophenol in neutral-weak alkaline medium (pH = 7-8) in our lab showed that the produced polymer which was insoluble in water and soluble in methanol has high tendency to form selectively a blue complex with Ni(II). Investigations into the chemical structure of polymer showed that polymer has a special structure, similar to polyamine in which the aromatic rings are connected through O-bridges. Based on these data, it was decided to polymerize p-aminophenol in situ on graphene oxide (GO) and use as a new sorbent for selective separation and preconcentration of trace amount of Ni(II) from water samples. By this, the rate of sorption of Ni(II) will also be increased considerably with respect to GO alone. Resulting composite (GO-Pp-AP) was characterized by FT-IR, XRD, FE-SEM, and EDS. The obtained data confirmed the uniform growth of the polymer on the GO and the absence of granular particles. The composite shows high tendency and high rate of sorption of Ni(II) and consequently was utilized for solid phase extraction (SPE) of Ni(II) ions before its determination by flame atomic absorption (FAAS). The effects of important parameters on the recovery of Ni(II) were investigated. The presence of foreign ions has no meaningful effect on the recovery percentage of Ni(II). Under the optimum conditions, limit of detection and relative standard deviation were found to be 0.70 µg L-1 and 1.8% (for n = 6; at 20 µg L-1 of Ni(II)), respectively. Testing the standard reference material and analyzing the spiked real samples exhibit that the procedure can be successfully employed for determination of Ni(II) in natural water and wastewater samples. Graphical abstract ᅟ.

Efficacy of Nanoencapsulated Thymus eriocalyx and Thymus kotschyanus Essential Oils by a Mesoporous Material MCM-41 Against Tetranychus urticae (Acari: Tetranychidae).

Inspite of well-established potentiality of plant essential oils as biopesticides, their environmentally low persistence is considered as a hindering obstacle for its commercialization. In the present study, chemical composition and toxicity of essential oils isolated from leaves of Thymus eriocalyx and Thymus kotschyanus were evaluated against two-spotted spider mite, Tetranychus urticae. The chemicals present in the crude oil were found to be thymol (28.83%), oleic acid (11.51%), palmitic acid (8.60%), borneol (5.72%), ρ-cymene (3.60%), and 1,8-cineole (3.57%) in the essential oil of T. eriocalyx, and camphene (35.59%), linalyl acetate (20.47%), linalool (14.75%), α-terpineol (13.87%), and geranyl acetate (3.07%) in the essential oil of T. kotschyanus. The essential oils had strong fumigant toxicity on the adult females of Te. urticae and their fumigation persistence was prolonged until 6 and 5 d, respectively, for T. eriocalyx and T. kotschyanus. Loading of essential oils in MCM-41 increased their stability and persistence was extended up to 20 and 18 d for T. eriocalyx and T. kotschyanus. Further, mite mortality increased from 80 to 203 mites by T. eriocalyx and from 58 to 186 mites by T. kotschyanus nanoencapsulated essential oils. Based on these results, nanoencapsulation of T. eriocalyx and T. kotschyanus essential oils in MCM-41 may be a useful method for their application in the management of Te. urticae.

Engineering of a disulfide loop instead of a Zn binding loop restores the anti-proliferative, anti-angiogenic and anti-tumor activities of the N-terminal fragment of endostatin: Mechanistic and therapeutic insights.

Although considerable effort has been devoted to understanding the molecular mechanism of endostatin's anti-cancer activity, the role of its Zn bound N-terminal loop has not been completely clarified. To investigate whether Zn binding or the N-terminal loop is involved in the anti-cancer properties of endostatin, we compared the structure and biological activity of a native Zn binding endostatin peptide (ES-Zn) with three variants: a Zn free variant (ES), a variant containing both a Zn binding site and a disulfide bond (ES-SSZn), and a variant including a disulfide loop but incapable of Zn binding (ES-SS). Spectroscopic studies indicated that ES-Zn and ES-SS consist of random coil and ß structures, whereas ES-SSZn and ES fold into random coils. Theoretical analysis proposed that ES-Zn and ES-SS have a similar binding site to αVß3 integrin. The anti-proliferative activity of endostatin was retained by all peptides except ES, and the in vitro anti-angiogenic property was preserved in ES-Zn and ES-SS. Remarkably, breast tumor growth and CD31 activity were inhibited more effectively by ES-SS than by ES-Zn. Therefore, a correlation exists between the N-terminal loop and anti-cancer properties of endostatin fragment and a disulfide loop may be more promising than a Zn binding loop for inhibiting tumor growth.

Determination of Se(IV) in natural waters by adsorptive stripping voltammetry of 5-nitropiazselenol.

The high tendency of 5-nitropiazselenol for self-accumulation on thin mercury film electrode was used innovatively for determination of Se(IV) in natural waters. 5-Nitropiazselenol was formed by reaction between Se(IV) and 4-nitro-1,2-phenylenediamine in acidic solution and self-accumulation process was carried out directly from reaction media. The adsorbed 5-nitropiazselenol was stripped in HCl solution by DP cathodic potential scan. All parameters influencing the measurement were optimized and evaluated. Detection limit of this method is 0.06 ng mL(-1). Interferences of various cations and anions were studied. The adsorption tendency of some other piazselenols made by some aromatic ortho-diamines was also investigated. The problems arising from applying potential during accumulation process in natural waters analysis were discussed. This method was applied for determination of Se(IV) in natural waters collected from some internationally registrated lagoons south of Caspian Sea. The obtained results were compared with the results of ICP-AES and DPCSV after electrochemical preconcentration.

Determination of selenium in natural waters by adsorptive differential pulse cathodic stripping voltammetry.

In this work bovine albumin was used innovatively as a medium for adsorptive accumulation of Se-I(2) on thin mercury film electrode. Se-I(2) was formed by reaction between Se(IV) and iodide in HCl media. The adsorbed Se-I(2) was stripped in 0.05 M HCl by differential pulse cathodic potential scan. The proposed method was successfully applied to analysis of Se(IV) and Se(VI) in natural waters sampled from some lagoons south of Caspian Sea. The optimum reaction conditions and other analytical parameters and influence of cations and anions were studied. The detection limit was 0.37 ng mL(-1). The obtained results were compared with the results of DPCSV after electrochemical preconcentration, HG-AAS and ICP-AES.