An Efficient and Facile Synthesis of Quinoxaline Derivatives Catalyzed by KHSO4 at Room Temperature

Summary. A facile synthesis of quinoxaline derivatives catalyzed by KHSO₄ in very high yields at room temperature is reported.     

An ultrasensitive fluorescence sensor for determination of trace levels of copper in blood samples

A novel SBA-15-based fluorescent sensor, SBA-PI: mesoporous SBA-15 structure modified with iminostilbene groups, was designed, synthesized, and characterized by Fourier transform-infrared spectroscopy (FT-IR), ultraviolet–visible spectroscopy, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), thermogravimetric analysis (TGA), low-angle X-ray diffraction techniques (low-angle XRD), and N₂ adsorption–desorption techniques. The SBA-PI as a sensor with a selective behavior for detection of Cu²⁺ comprises iminostilbene carbonyl as the fluorophore group. The SBA-PI sensor displays an excellent fluorescence response in aqueous solutions and the fluorescence intensity quenches remarkably upon addition of Cu²⁺. Other common interfering ions even at high concentration ratio showed either no or very small changes in the fluorescence intensity of SBA-PI in the absence of Cu²⁺. A limit of detection of 8.7 × 10⁻⁹ M for Cu²⁺ indicated that this fluorescence sensor has a high sensitivity and selectivity toward the target copper (II) ion. The fabricated Cu²⁺ sensor was successfully applied for the determination of the Cu²⁺ in human blood samples without any significant interference. With the selective analysis of Cu²⁺ ions down to 0.9 nM in blood, the sensor is a promising and a novel detection candidate for Cu²⁺ and can be applied in the clinical laboratory. A reversibility and accuracy in the fluorescence behavior of the sensor was found in the presence of I^¯ that was described as a masking agent for Cu²⁺.

Graphical abstract

     

Headspace solvent microextraction of trihalomethane compounds into a single drop

Headspace solvent microextraction (HSME) into a single drop is developed for the determination of six trihalomethanes, CH2Cl2, CHCl3, C4H9Cl, CCl4, C2HCl3, and C2Cl4, in aqueous solution. A drop of benzyl alcohol containing bromoform, as an internal standard, is used for extraction. The analytes are extracted by suspending a 3-microL drop directly from the needle of a microsyringe. The needle passes through the septum of a vessel, and the needle tip appears above the surface of the solution. After the prescribed extraction time, the drop is drawn back into the syringe. The syringe is then removed, and its content is injected directly into a gas chromatography column for analysis. The main parameters affecting the HSME process, such as stirring speed, microdrop volume, sample solution temperature, microsyringe needle temperature, sample volume, solution pH, extracting solvent, and ionic strength of the solution, are studied. Also, the linear range and precision of the method are examined.     

SnCl4 and SbCl5 promoted aromatization of enamines

Aromatic amines have been synthesized efficiently from enamines using SnCl₄ and SbCl₅ in CH₂Cl₂ at room temperature.     

Adsorptive Behavior of Methylene Blue onto Sawdust of Sour Lemon,Date Palm,and Eucalyptus as Agricultural Wastes

In the present study, to remove methylene blue (MB) from aqueous solution, some agricultural residues and cheap bioadsorbents such as sawdust of palm trees, eucalyptus, and sour lemon were used. To do this, significant parameters like contact time, temperature, pH, initial concentration, and adsorbent dosage were checked. The results affirmed that the best conditions for MB adsorption from aqueous solution were obtained such as the temperature of 25?°C, pH of 8, adsorbent dosage of 2g/L, contact time of 120?minutes, and dye concentration of 5?mg/l which under these conditions the adsorption efficiencies determined were 95.8, 93.4, and 92.8% using sawdust of palm tree, eucalyptus, and sour lemon, respectively. Also, the equilibrium behavior of adsorbents showed that the Freundlich model could better predict the adsorption behavior of the process due to having a larger correlation coefficient (R²). The maximum biosorption capacities by Langmuir isotherm model were also obtained 54, 53.5, and 52.4?mg/g for sawdust of palm trees, eucalyptus, and lemon, respectively, which were significant amounts. In addition, kinetic behavior of adsorption showed that pseudo-second-order model can describe the kinetics of the adsorption process better than the pseudo-first-order model. Moreover, kinetic, equilibrium, and thermodynamic behaviors of adsorption affirmed that the biosorption process was desirable, physisorption, spontaneous, and exothermic.     

Potentiometric determination of ultratrace amounts of fluoride enriched by zirconia in a flow system

A satisfactory method was described for separation and preconcentration of ultratrace amounts of fluoride ions enriched by zirconia (ZrO₂) as an inorganic ion exchanger. Fluoride ions can be adsorbed rapidly and selectively on zirconia from an acidic solution (pH 4.8) then reversibly desorbed by increasing pH up to 13. A flow system consisting of a column packed with zirconia impregnated on cellulose fibers and an ion-selective electrode was used for the determination of fluoride. The RSD was found to be 1.6% and the detection limit defined by S/N = 3 was 3 × 10⁻⁹ mol L⁻¹. The interference effects of various ions, such as nitrate, sulfate, halides, alkaline, and alkaline earth ions, which may be found in the environmental water, were studied, and it was found that they were tolerated even at high concentrations. The method was applied to determine fluoride in drinking water, which contains ultratrace amounts of fluoride. The concentration of fluoride was found to be 42 μg L⁻¹, which is confirmed by spiking 2 μmol fluoride to the drinking water with a recovery of 99%. Published in Russian in Zhurnal Analiticheskoi Khimii, 2006, Vol. 61, No. 2, pp. 179–183. The text was submitted by the authors in English.     

Synthesis and Spectroscopic Study of Some New Phosphoramidates,Crystal Structures of N‐Benzoyl‐N′,N″‐bis(azetidinyl)phosphoric Triamide and N‐Benzoyl‐N′,N″‐bis(hexamethylenyl)phosphoric Triamide

Some new N‐carbonyl, phosphoramidates with formula C₆H₅C(O)N(H)P(O)R₂ (R = NC₃H₆ ( 1 ), NC₆H₁₂ ( 2 ), NHCH₂CH=CH₂ ( 3 ), N(C₃H₇)₂ ( 4 )) and CCl₃C(O)N(H)P(O)R′₂ (R′ = NC₃H₆ ( 5 ), NHCH₂CH=CH₂ ( 6 )) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR and IR spectroscopy and elemental analysis. The structures were determined for compounds 1 and 2 . Compound 1 exists as two crystallographically independent molecules in crystal lattice. Both compounds 1 and 2 produced dimeric aggregates via intermolecular ‐P=O…H‐N‐ hydrogen bonds, which in compound 2 is a centrosymmetric dimer. In compounds with four‐membered ring amine groups, ³J(P,C)>²J(P,C), in agreement with our previous studies about five‐membered ring amine groups. Also, ³J(P,C) values in compounds 1 and 5 are greater than in compounds with five‐, six‐ and seven‐membered ring amine groups.     

Selective Acetylation of Alcohols and Amines with Ethyl Acetate in the Presence of H<Subscript>6</Subscript>[PMo<Subscript>9</Subscript>V<Subscript>3</Subscript>O<Subscript>40</Subscript>] as the Catalyst

Summary. Acetylation of various alcohols and benzyl amine was tested in the presence of H₆[PMo₉V₃O₄₀], a mixed addenda heteropolyacid, in ethyl acetate under reflux condition. Phenols and anilines are not affected under the reaction conditions. Selective transestrification of alcohols can be achieved in the presence of phenol and aniline derivatives using this method.     

Solid Phase Extraction and Flame Atomic Absorption Spectrometric Determination of Trace Amounts of Zinc and Cobalt Ions in Water Samples

A simple and rapid method for the preconcentration of Co²⁺ and Zn²⁺ as their 2-guanidino-benzimidazole chelates is proposed using an octadecyl silica cartridge. The retained analytes were recovered with a mixture of 5mL of 0.01M HNO₃ and 5mL of methanol. The metal ions in the effluent were determined by flame atomic absorption spectrometry. The effect of different parameters, such as sample matrix, amount of ligand, type of eluent for elution of ions from cartridge, flow rates of sample solution and eluent, breakthrough volume, and limit of detection, were evaluated. The effects of various cationic and anionic interferences on the percent recovery of Co²⁺ and Zn²⁺ were also studied. Quantitative extraction efficiencies were obtained by elution of the cartridge with a minimal amount of solvent. Hence, with a typical preconcentration factor of 50, the limits of detections of the proposed method are 0.26 and 1.62ngmL^–1 for Zn²⁺ and Co²⁺, respectively. The method was applied to the determination of zinc and cobalt ions in different water samples.     

Vieta–Fibonacci wavelets: Application in solving fractional pantograph equations

In this paper, the Vieta–Fibonacci wavelets as a new family of orthonormal wavelets are generated. An operational matrix concerning fractional integration of these wavelets is extracted. A numerical scheme is established based on these wavelets and their fractional integral matrix together with the collocation technique to solve fractional pantograph equations. The presented method reduces solving the problem under study into solving a system of algebraic equations. Several examples are provided to show the accuracy of the method.