Chemical and electrochemical synthesis of homopolymer and copolymers of 3‐methoxyethoxythiophene with aniline,thiophene and pyrrole for studies of their gas and vapour sensing

Herein we report chemical and electrochemical formation of poly(3‐methoxyethoxythiophene) and its copolymers with aniline, thiophene and pyrrole which give highly conducting polymeric materials. These are soluble in common organic solvents in the conducting state. The response mechanism of these compounds, to a selection of gases and vapours, was investigated using two techniques: measurement of conductance and mass changes using a four probe method and X‐ray fluorescence (XRF) device, respectively. Prepared films were exposed to hydrogen halides, hydrogen cyanide, halogens, monochloroacetic acid (MCAA), 1‐3‐5 trichloromethylbenzene (TCMB), methylbenzyl bromide (MBB), bromoacetone (BA) and cyanogen bromide (CB). These gas sensors may have advantages compared to other sensors in their ability to operate at room temperature, low concentration, stability in air, sufficient diffusion and their selectivity. Copyright © 2001 John Wiley & Sons, Ltd.     

Zirconium(IV) oxide chloride and anhydrous copper(II) sulfate mediated synthesis of 2‐substituted benzothiazoles

A simple, fast and efficient benign procedure has been developed for one‐pot synthesis of 2‐substituted benzothiazoles in the presence of zirconium(IV) oxide chloride octahydrate (ZrOCl₂·8H₂O) and anhydrous copper(II) sulfate. The reaction of 2‐aminothiophenol with aldehydes and anhydrides was carried out efficiently in solvent‐free conditions with or without microwave irradiation, and adducts were produced in good to excellent yields. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:136–141, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20191     

Thermal performance of poly(ethylene disulfide)/expanded graphite nanocomposites

In this study, the influences of expanded graphite oxide (EG) nanosheets presence with and without surfactant on structural and thermal performance of poly(ethylene disulfide) (PEDS)-based nanocomposites are investigated. Sodium dodecylbenzenesulfonate (SDBS) is used as a surfactant for the preparation of modified-EG nanosheets. The structural, morphological, and thermal properties of prepared nanocomposites are studied using X-ray diffraction (XRD), scanning electron microscopy, and differential scanning calorimetry techniques, respectively. XRD patterns of nanocomposites reveal that a high degree of expanded graphite nanosheets dispersion is achieved with and without surface modification using in situ polymerization method. Moreover, the presence of immobilized polysulfide chains near the interface region of nanosheets is suggested as a possible reason for the observed increase in the number of semi-crystalline organic fractions in the structure of PEDS via EG nanosheets incorporation. In addition, the morphology of SDBS-modified-EG loaded nanocomposite shows a smoother fracture surface than unmodified-nanosheets reinforced nanocomposite. Therefore, more interactions between nanosheets and polysulfide chains are expected in the structure of unmodified-EG reinforced nanocomposite. Moreover, thermal resistance and degradation kinetics of prepared nanocomposites are studied using thermogravimetric analysis results and degradation activation energy calculations, respectively. The required activation energy for the degradation process of SDBS-EG loaded nanocomposite is about 140 kJ mol^?1 lower than the required degradation activation energy of unmodified-nanosheets reinforced nanocomposite.     

Theoretical study of H⋯P and X⋯P interactions of methylphosphines with HSX molecules

Ab initio calculations were used to analyze the interactions between thiohypohalous acids (HSX; X = F, Cl, Br, I) and methylphosphine derivatives (PH _n Me_3?n , n = 0–3) at the MP2/aug-cc-pVDZ level of theory. Interaction of HSX with PH _n Me_3?n leads to both hydrogen bond (HSX–PH _n Me_3?n –HB) as well as halogen bond (HSX–PH _n Me_3?n –XB) complexes. Stabilities of both HB and XB complexes increase with basicity of the phosphines. However, HB complexes of a phosphine molecule with different HSX have the same order of stabilities, but XB complexes of heavier thiohypohalous acids are more stable. Electron densities of complexes were characterized with the atoms in molecules methodology. The charge transfer within dimers was analyzed by means of natural bond orbitals.     

Polyoxomolybdate368 /polyaniline nanocomposite as a novel fiber for solid‐phase microextraction of antidepressant drugs in biological samples

A novel solid‐phase microextraction fiber was synthesized by coating a stainless steel wire with polyoxomolybdate₃₆₈/polyaniline as a sorbent aimed at extraction of amitriptyline, nortriptyline, and doxepin as antidepressant drugs from urine and blood samples. The polyoxomolybdate₃₆₈/polyaniline composite coating was applied using electropolymerization process under constant potential. This composition leads to enhanced extraction efficiency of the fiber. Scanning electron microscopy images show that huge three‐dimensional structures of polyoxomolybdate₃₆₈ in composite induced more non‐smooth and porous fiber. In order to optimize of the extraction process, a series of variables including concentration of the composite materials, coating thickness, pH, extraction time, salt addition, and stirring rate was investigated and optimum conditions were determined. Analysis of surface morphology and chemical composition was performed. High‐performance liquid chromatography was used for separation and evaluation of mentioned antidepressant drugs from the matrixes. The experiments indicated a detection limits of <0.2 ng/L and a linear dynamic range of 0.3–100 ng/L (R² > 0.994). The relative recovery values were found to be in the range of 92–98%. It was concluded that the purposed fiber is highly efficient in analyzing traces of antidepressant drugs in urine and blood.     

Multi-component synthesis of spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-triones using zinc terephthalate metal-organic frameworks

The present article describes an efficient one-pot method for the preparation of spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-indoline]-trione derivatives from a three-component condensation reaction of 1,3-indandione, aromatic amines and isatins in the presence of a zinc terephthalate metal-organic framework Zn (BDC) MOF as the catalyst under solvent-free conditions. High yields, short reaction times, simple workup and environmentally benign procedure are advantages of this protocol. The Zn (BDC) MOF catalyst can be recovered and reused several times without loss of activity. The catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, Fourier transform infra red, X-ray powder diffraction and thermal gravimetric analysis.     

Experimental study of extraction fraction and mass transfer coefficient in a microchannel using butyl acetate/acetic acid/water chemical system

The droplet flow regime in microchannels can increase the mass transfer and chemical reactions considerably. In this work, the mass transfer of immiscible fluids of water as the solvent and butyl acetate containing 5 vol% of acetic acid as the feed is experimentally studied in a vertical flow inside a microchannel with the inner diameter of 8 mm. Effect of total flow velocity, Re number and volumetric flux ratio of two phases (Q_aq/Q_or) on the extraction fraction of acetic acid, mass transfer coefficient and droplet size were investigated. Based on the experiments, increasing the flux ratio can shift the flow regime from the plug to the droplet. Compared to the plug flow, the extraction fraction increased by 2–3 times in the droplet regime, depending on the total velocity, while the average diameter of the droplets decreased. Moreover, with the increase in the total velocity, the extraction fraction is reduced by 22%. However, in the case of the plug flow, the extraction fraction does not change appreciably with the increase in the total flow velocity. The mass transfer coefficient was found to increase monotonously with increasing Re number and an enhancement of 133% was achieved in the droplet flow regime.     

Hydroarylation of cinnamic acid with phenols catalyzed by acidic ionic liquid [H-NMP]HSO<Subscript>4</Subscript>: computational assessment on substituent effect

Hydroarylation of cinnamic acid with different substituted phenols, in the presence of acidic ionic liquid, N-methyl-2-pyrrolidonum hydrosulfate ([H-NMP]HSO₄) gave the corresponding dihydrocoumarins in high yields and excellent selectivity. Among these substituted phenols, while methyl phenol afforded the corresponding dihydrocoumarin, nitrophenol under the same reaction conditions diverted the course of reaction, affording 3-(4-nitrophenyl)-3-phenylpropanoic acids. We investigated this behavior from the energetic and electronic points of view, using quantum chemistry computational methods. In this respect, the electronic energy change values for the conversion reaction of substituted phenyl cinnamate esters to dihydrocoumarin compounds have been obtained via density functional theory calculations. We demonstrated that the conversion reaction in the presence of CH₃ substituent is more favorable energetically than NO₂ substituent. Moreover, we have concentrated on topological analysis of electron density on some key bond and ring critical points and their associated bond paths to assess the conversion of substituted phenyl cinnamate esters to dihydrocoumarins. Our calculated results showed that para-methyl phenyl cinnamate has more of electronic tendency to undergo the intramolecular cyclization step and, consequently, generate the corresponding dihydrocoumarin.     

Adsorption of sodium dodecyl benzene sulfonate onto carbonate rock: Kinetics,equilibrium and mechanistic study

In this study, kinetics, equilibrium, and mechanisms of SDBS adsorption onto carbonate rock in presence/absence of alkaline/electrolyte, which is not well discussed in the available literature, is analyzed through batch experiments. Analysis of kinetic data showed that adsorption rate of SDBS onto carbonate is controlled by both boundary layer and intraparticle diffusion, also adsorption kinetics meets pseudo second-order model. The coefficient of kinetic model is a linear function of initial and equilibrium concentrations. The adsorption isotherm experiences four distinct regions, with a rising trend in the first regions until reaching to a maximum after which decreases slightly, as the fourth region, due to micellar exclusion. The prevailing mechanisms in other regions were also discussed. Presence of alkaline changes adsorption mechanisms, so that adsorption isotherm matches well with the Langmuir model, while presence of electrolyte does not change the adsorption mechanisms, but it lessens repulsion between surfactant heads which results in a slight reduction in amount of CMC. A new three-parameter equilibrium model is presented which considers all prevailing mechanisms, and matches properly with obtained experimental data, especially the decreasing trend of fourth region which is very difficult to predict along with other regions using a unique isotherm model.