A novel pseudo six-component synthesis of functionalized pyrazoles in ethanol by cascade reaction

Molecular Diversity - Novel-substituted pyrazoles were synthesized using an aminal-based approach. The key steps in the synthetic strategy involve the formation of 1,1-dihydrazino-2-nitroethylene...     

An efficient and new protocol for the Heck reaction using palladium nanoparticle‐engineered dibenzo‐18‐crown‐6‐ether/MCM‐41 nanocomposite in water

Palladium nanoparticle‐incorporated mesoporous organosilica (MCM‐41‐Crown.Pd) was synthesized via the grafting of dibenzo‐18‐crown‐6‐ether moieties on the MCM‐41 surface, followed by reaction of the nanocomposite with palladium acetate and then its reduction in ethanol. The cavity of the immobilized dibenzo‐18‐crown‐6 as host material can stabilize the palladium nanoparticles effectively and prevent their aggregation and separation from the surface. The structure of the nanocomposite was characterized using various techniques. The catalytic properties of the nanocomposite in the Heck coupling reaction, one of the most useful transformations in organic synthesis, between aryl halides and olefins in water were also explored. The main advantages of the method are low cost, high yields, easy work‐up and short reaction time. The nanocatalyst can be easily separated from a reaction mixture and was successfully examined for seven runs, with a slight loss of catalytic activity.     

Reverse atom transfer radical polymerization of methyl methacrylate in the presence of Azo-functionalized carbon nanotubes: a grafting from approach

After oxidation of carbon nanotubes (CNT), its carboxyl groups were subsequently converted to acyl chloride and hydroxyl functionalities. Subsequently, 4,4′-azobis (4-cyanopentanoic acid) (ACPA) was attached to the hydroxyl groups of nanotubes by an esterification reaction to yield azo initiator-anchored nanotubes (CNTAzo). Then, grafting from reverse atom transfer radical polymerization of methyl methacrylate in the presence of CNTAzo in different weight percents was carried out. Appearance of N_1s band in the spectrum of CNTAzo originates from the covalent attachment of ACPA on CNT. Successful functionalization of CNT with EG, ACPA, and PMMA was also proved by FTIR. SEC results show that molecular weight and PDI values of the attached chains are higher. XRD and Raman spectroscopy were used to study the structural characteristics of the CNTs. Graft density of modifier and PMMA in various CNTs was evaluated by TGA. Finally, morphology of the CNTs was studied by scanning and transmission electron microscopies.     

Sensitive voltammetric determination of diclofenac using room-temperature ionic liquid-modified carbon nanotubes paste electrode

An ionic liquid-modified carbon nanotubes paste electrode (IL/CNTPE) has been fabricated using hydrophilic ionic liquid (n-hexyl-3-methylimidazolium hexafluoro phosphate) as a binder. This electrode showed enhanced electrochemical response and strong analytical activity towards the direct electrochemical oxidation of diclofenac (DCF). The electron transfer coefficient, α, and charge transfer resistance (R _ct) of DCF at the modified electrode were calculated. Under optimal conditions at pH 7.0, the anodic peak currents increased linearly with the concentration of DCF in the range of 0.5–300 μmol L^?1 with a detection limit of 0.2 μmol L^?1 (3σ). The interferences of foreign substances were investigated. Differential pulse voltammetry was used to check the applicability of the proposed sensor to the determination of DCF in real samples with satisfactory results.     

Temperature-induced dispersive solid-phase extraction as a new approach for preconcentration of Sudan dyes in water and food samples prior to the determination by high-performance liquid chromatography

This study introduced a new microextraction method named temperature-induced dispersive solid-phase extraction. The performance of the method was demonstrated with the determination of Sudan dyes in food and natural water samples. In this method, a low quantity of sorbent was added to the aqueous solution and the mixture was shaken manually for about one minute. Then, the solution was heated in an ultrasonic water bath, and the sorbent was dissolved. Subsequently, the solution was cooled down with ice water, and consequently, the solubility of the sorbent was reduced in the sample solution and became cloudy. The phase separation was accelerated by centrifugation. The upper liquid phase was picked up using a syringe, and the remainder was solved in methanol and introduced into the HPLC for analysis. Various parameters affecting the extraction yield were evaluated. Analytical parameters, including limits of detection (0.011–0.016 μg/L) and quantification (0.038–0.055 μg/L), relative standard deviations (2.3%–3.1%), and preconcentration factor (40) proved the high efficiency of the developed method for the analysis of Sudan dyes. The proposed method was used to measure Sudan dyes in water and food samples and showed good extraction recoveries (95.0%–103.5%).     

On the PPh3 catalyzed reaction between dibenzoylacetylene and vicinal -OH and -SH acids. One-pot synthesis of 1,3-dioxolane derivative

The efficient conjugate addition of vicinal - OH and - SH acids such as ethylene glycol and 1,2-ethanedithiol to dibenzoylacetylene in the presence of PPh3 leads to different products depending on the reaction conditions. Ab initio calculations at HF/6-31G* level shows that the unsymmetrical envelope conformation of 2,2-disubstituted 1,3-dioxolane 1 is more stable than the half-chair and Cs symmetric envelope forms.     

Alcohol‐based deep eutectic solvent as a carrier of SiO2@Fe3O4 for the development of magnetic dispersive micro‐solid‐phase extraction method: Application for the preconcentration and determination of morin in apple and grape juices,diluted and acidic extract of dried onion and green tea infusion samples

In this study, a hydrophilic deep eutectic solvent was synthesized as a carrier and disperser of magnetic nanoparticles based on ferrofluid and used to develop the dispersive micro‐solid‐phase extraction method. Ethylene glycol/tetramethylammonium chloride deep eutectic solvent and SiO₂@Fe₃O₄ were used to provide the highly stable ferrofluid with strong sorbing properties without any additional stabilizer, which was employed to extract and determine morin in apple and grape juices, diluted and acidic extract of dried onion, and green tea infusion samples. The dispersibility of SiO₂@Fe₃O₄ and prevention of its aggregation in the sample solution were improved using the deep eutectic solvent‐based ferrofluid. Also, it facilitated the fast injection of sorbent into the sample solution that led to an increase of the contact surface between the sorbent and analyte, and reduction of the extraction time and consumption of the sorbent. The important experimental parameters influencing the extraction efficiency of morin were examined. Under the optimal conditions, a linear calibration curve was obtained in the range of 3–500 µg/L with a determination coefficient of 0.9994. The limits of detection and quantification were of 0.91 and 2.98 µg/L, respectively. While an extraction recovery of 97.7% with relative standard deviation of 3.8% (interday) was obtained via three replicated measurements on a 30 µg/L of morin standard solution, the enrichment factor was 39.1. Finally, this method was successfully used to extract and preconcentrate morin in various samples, followed with their determination by high‐performance liquid chromatography with ultraviolet detection.     

A Simple Method for Melatonin Determination in the Presence of High Levels of Tryptophan using an Unmodified Carbon Paste Electrode and Square Wave Anodic Stripping Voltammetry

Electrochemical determination of melatonin in the presence of tryptophan is a challenge because of the coincidence of voltammetric signals of these compounds when executing a voltammetric technique. The new method for selective determination of melatonin based on the square wave anodic stripping voltammetry determination of an electroactive product of melatonin was suggested here. This product is produced by previously applied positive pre-potential to a carbon paste electrode, immersed in the test solution. By this means, the electrochemical signal of melatonin was separated effectively from that of tryptophan, making it possible to determine melatonin in the presence of a high concentration of tryptophan. The effect of important parameters on electrode performance was studied and optimized. The optimum response was obtained at pH=2 and utilizing the pre-potential magnitude of +0.8 V, applied for 10 s. A linear relationship was found between peak current intensity and melatonin concentrations over the range of 5.00×10⁻⁷ to 8.00×10⁻⁵ mol L⁻¹. A detection limit of 8.30×10⁻⁸ mol L⁻¹ was calculated for the method (S/N=3). The selectivity of the method was considerably high, because of the independence of melatonin signal to the presence of higher amounts of some potentially interfering agents such as ascorbic acid, tryptophane glucose, etc. As an analytical application, the proposed sensor was used for the determination of melatonin in pharmaceutical and food samples.