Multicomponent reactions for the synthesis of new cyclopentadienephosphonate derivatives in water

A series of polysubstituted cyclopentadienephosphonate derivatives were synthesized via one-pot multicomponent reactions of primary amines and phosphites with activated acetylenic compounds in water as the solvent at room temperature.

Particularly valuable features of this method include high yields of products, broad substrate scope, short reaction time and a straightforward procedure.     

Monitoring the effects of homogeneity methanol/water/monomer on the mode of polymerization of styrene: dispersion polymerization versus emulsion polymerization

The polymerization of styrene (St) was carried out with varying amounts of methanol in aqueous medium. As methanol content decreased (to 50 %), the phase of polymerization mixture (methanol/water/monomer) changed to a heterogeneous state; the homogeneous state was obtained in samples that contain 75 and 100 % methanol. In order to verify the mechanism of polymerization in heterogeneous and homogeneous mixtures, the nucleus formation rate during polymerization, the stability equilibrium of the media and seeded particles, and the size of particles and their growth in polymerization were experimentally being monitored. With the homogeneous mixture in 75 wt% methanol, dumbbell, triangle, and peanut-like particles have been formed. On the other hand, the characteristics of the polymerization products were different from those typically obtained in the emulsion polymerization and in the sample with 100 wt% methanol dispersion polymerization. In the sample with 100 % methanol and in one with 50 % methanol, monodispersed spherical particles are formed in the final conversion. Thus, homogeneity in the aqueous methanol mixture can be a critical factor in determining the polymerization modes between dispersion and emulsion polymerization.     

Effect of Phosphate on Glucosamine Production by Ethanolic Fungus Mucor indicus

In this study, the effect of phosphorous compound concentration on the production of glucosamine by Mucor indicus was investigated. Changes in the yield of ethanol, the major metabolite of the fungus, were also followed besides. The alkali insoluble material of the biomass of the fungus mainly contained phosphates and polymers of glucosamine and N-acetyl glucosamine, i.e., chitin and chitosan. Yields of glucosamine (78–113 g/kg dry fungal biomass) and ethanol (200–370 g/kg glucose) were significantly affected by the phosphorous concentration. The results showed that lower concentrations of phosphorous favored the production of glucosamine while higher ethanol as well as biomass yields was obtained at higher concentrations. The best concentration was 0.5 g/l where glucosamine yield was 0.37 g/l (11 % of the biomass). At this phosphate concentration, ethanol and biomass yields were 360 and 76 g/kg glucose, respectively. On average, proteins comprised 51.5 % of the biomass. Glycerol was the second important metabolite during the fermentation by the fungus which appeared at lower yields (20–34 g/kg glucose).     

Ligandless dispersive liquid-liquid microextraction for the separation of trace amounts of silver ions in water samples and flame atomic absorption spectrometry determination

In this article, a new ligandless dispersive liquid-liquid microextraction method has been developed for preconcentration of trace quantities of silver as a prior step to its determination by flame atomic absorption spectrometry. In the proposed approach, carbon tetrachloride and ethanol were used as extraction and dispersive solvents. Several factors that may be affected on the extraction process, like, extraction solvent, disperser solvent, the volume of extraction and disperser solvent, pH of the aqueous solution and extraction time were optimized. Under the optimal conditions, the calibration curve was linear in the range of 5.0 ng mL⁻¹ to 2.0 μg mL⁻¹ of silver with R² = 0.9995 (n = 9) and detection limit based on three times the standard deviation of the blank (3S_b) was 1.2 ng mL⁻¹ in original solution. The relative standard deviation for eight replicate determination of 0.5 μg mL⁻¹ silver was ±1.5%. The high efficiency of dispersive liquid-liquid microextraction to carry out the determination of silver in complex matrices was demonstrated. The proposed method has been applied for determination of trace amount of silver in standard and water samples with satisfactory results.     

Effect of preparation variables on morphology and pure water permeation flux through asymmetric cellulose acetate membranes

In this study, cellulose acetate (CA) ultrafiltration (UF) membranes were prepared using the phase inversion method. Effects of CA and polyethylene glycol (PEG) concentrations in the casting solution and coagulation bath temperature (CBT) on morphology of the synthesized membranes were investigated. Based on L₉ orthogonal array of Taguchi experimental design 18 membranes were synthesized (with two replications) and pure water permeation flux through them were measured. It was found out that increasing PEG concentration in the casting solution and CBT, accelerate diffusional exchange rate of solvent 1-methyl-2-pyrrolidone (NMP) and nonsolvent (water) and consequently facilitate formation of macrovoids in the membrane structure. Increasing CA concentration, however, slows down the demixing process. This prevents instantaneous growth of nucleuses in the membrane structure. Hence, a large number of small nucleuses are created and distributed throughout the polymer film and denser membranes are synthesized. Rate of water flux through the synthesized membranes is directly dependent on the size and number of macrovoids in the membrane structure. Thus, maximum value of flux is obtained at the highest levels of PEG concentration and CBT (10 wt.% and 23 °C, respectively) and the lowest level of CA concentration (13.5 wt.%). Analysis of variance (ANOVA) showed that all parameters have significant effects on the response. However, CBT is the less influential factor than CA and PEG concentrations on the response (flux).     

Solubility of hydrocarbons in water: Experimental measurements and modeling using a group contribution with association equation of state (GCA-EoS)

In this communication, new experimental data on the solubility of n-hexane, cyclo-hexane and iso-octane in pure water are reported. The data have been measured using a static-analytic technique that takes advantage of a Rolsi™ sampling device in the temperature range of 298–353 K and at pressures up to 0.5 MPa. The experimental data measured in this work at 298 K have been compared with some selected data from the literature and good agreement is found. A group contribution plus association equation of state, namely the GCA-EoS, is used to model the phase equilibrium of water + hydrocarbon (C₂ to n-C₆, cy-C₆, i-C₄ and i-C₈) system. The predictions of the model are found in good agreement with the experimental data measured in this work and some selected data from the literature.     

Solid Phase Extraction and Simultaneous Spectrophotometric Determination of Trace Amounts of Copper and Iron Using Mixture of Ligands

 A novel sensitive and simple method for rapid and selective extraction, preconcentration and determination of iron (as its bathophenanthroline complex) and copper (as its neocuproine complex) using octadecyl silica cartridges and dual wavelength spectrophotometry is presented. The dual wavelength method (533 nm for the iron-bathophenanthroline and 454 nm for the copper-neocuproine as the analytical wavelength) is used to eliminate spectral interferences. Extraction efficiency and the influence of flow rates of sample solution and eluent, pH, amount of neocuproine, bathophenanthroline and hydroxylamine hydrochloride, type and least amount of eluent for elution of iron and copper complexes from cartridge, break-through volume and limit of detection are evaluated. The effects of various cationic and anionic interferences on percent recovery of iron and copper are also studied. Extraction efficiencies >95% are obtained by elution of cartridges with minimal amount of organic solvent. Iron and copper were determined in the range of 3–100 ng mL⁻¹. The limits of detection are 0.98 and 1.13 ng mL⁻¹ for iron and copper, respectively. The proposed method is applied successfully to the determination of both analytes in river, tap and well water samples. Author for correspondence. E-mail: yyamini@modares.ac.ir Received September 18, 2002; accepted December 12, 2002 Published online May 5, 2003     

Benign synthesis of carboxamide ligands,H2Me2bqb and H2Me2bpb. Preparation,characterization and electrochemistry of Ni(II) complexes: The crystal structure of [Ni(Me2bqb)]

A novel and highly efficient approach for the synthesis of H₂Me₂bqb and H₂Me₂bpb using ionic liquid as an environmentally benign reaction medium has been developed, eliminating the need for the pyridine as a toxic solvent. The Ni(II) complex of the dianionic ligand Me₂bqb²⁻, [Me₂bqb²⁻ = 1,2-bis(quinoline-2-carboxamide)-4,5-dimethyl-benzene dianion], has been synthesized and characterized by elemental analyses and spectroscopic methods, and the crystal and molecular structure of [Ni(Me₂bqb)] (1), has been determined by X-ray crystallography. The complex exhibits distorted square-planar NiN₄ coordination geometry with two short and two long Ni–N bonds (Ni–N ∼1.85 and ∼1.96 Å, respectively). The electrochemical behavior of [Ni(Me₂bqb)] (1), has been studied by cyclic voltammetry and compared with the analogous complex, [Ni(Me₂bpb)] (2).     

TiO2 as a Reusable Catalyst for the One‐Pot Synthesis of 3,4‐Dihydropyrimidin‐2(1H)‐ones under Solvent‐Free Conditions

An efficient solvent‐free method for the synthesis of various 3,4‐dihydropyrimidin‐2(1H)‐ones using TiO₂ as a recyclable heterogeneous catalyst is described. Compared to known methods, satisfactory results are obtained with excellent yields, short reaction times, and simplicity in the experimental procedure.     

Design and optimization of on-chip capillary electrophoresis

We present a systematic, experimentally validated method of designing electrokinetic injections for on-chip capillary electrophoresis applications. This method can be used to predict point-wise and charge-coupled device (CCD)-imaged electropherograms using estimates of species mobilities, diffusivities and initial sample plug parameters. A simple Taylor dispersion model is used to characterize electrophoretic separations in terms of resolution and signal-to-noise ratio (SNR). Detection convolutions using Gaussian and Boxcar detector response functions are used to relate optimal conditions for resolution and signal as a function of relevant system parameters including electroosmotic mobility, sample injection length, detector length scale, and the length-to-detector. Analytical solutions show a tradeoff between signal-to-noise ratio and resolution with respect to dimensionless injection width and length to the detector. In contrast, there is no tradeoff with respect to the Peclet number as increases in Peclet number favor both SNR and separation solution (R). We validate our model with quantitative epifluorescence visualizations of electrophoretic separation experiments in a simple cross channel microchip. For the pure advection regime of dispersion, we use numerical simulations of the transient convective diffusion processes associated with electrokinetics together with an optimization algorithm to design a voltage control scheme which produces an injection plug that has minimal advective dispersion. We also validate this optimal injection scheme using fluorescence visualizations. These validations show that optimized voltage scheme produces injections with a standard deviation less than one-fifth of the width of the microchannel.