Acetylation of Alcohols Catalyzed by Dodeca-tungsto(molybdo)phosphoric acid

Summary. Acetylation of primary, secondary, and tertiary alcohols was carried out in some refluxing alkyl acetates and in two carboxylic acids with the participation of catalytic amounts of H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₁₄P₅W₃₀O₁₁₀ with good yields and high stereo(regio)specificity under mild reaction condition. H₃PW₁₂O₄₀ and H₃PMo₁₂O₄₀ have also shown excellent reactivity in the formylation of 1-butanol with ethyl formate at room temperature and in short reaction times. Heteropolyacid catalysts could be separated after a simple work up and reused for several times.     

Spectrophotometric study of Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) complexes with some crown ethers in dimethylsulphoxide solution using murexide as a metallochromic indicator

The complexation reactions between Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions and benzo-15-crown-5, dicyclohexyl-18-crown-6, dibenzo-18-crown-6 and 1,10-diaza-18-crown-6 have been studied in dimethylsulphoxide solution at 25 degrees by means of a competitive spectrophotometric method using murexide as a metallochromic indicator. With the exception of Pb(II)(benzo-15-croqn-5)(2) the stoichiometry of the resulting complexes was found to be 1:1. The formation constants of the complexes were determined, and found to follow the Irving-Williams rule for the cations of the first transition series. It was found that the metal ion-18-crown interactions are strongly dependent on the nature of the substituents on the ring.     

Quasicontinuum multiscale modeling of the effect of rough surface on nanoindentation behavior

Roughness of surface has as an important influence on identifying the mechanical behavior and performance of crystalline metals. In this study, nanoindentation simulations are conducted by the two dimensional quasicontinuum method to determine the load–penetration response and the critical load associated with the onset of plasticity in rough surfaces of a face-centered cubic single crystal copper. The arithmetic roughness index, ranging between 2 and 13 Å, is used to specify the roughness of surface. Results of indentation with different roughnesses are in good agreement with previous studies for the indenter size of 10–140 Å. The resultant load–penetration scattering, which stems from the roughness, indicates different dislocation nucleation steps, different subsequent dislocations intervals and varying stiffness values of samples. It can be concluded that the surface roughness has a significant effect on the first dislocation emission because of the indenter position and surface interactions beneath it. Moreover, the critical penetration depth for the first dislocation emission increases by the increase of the contact area between the indenter and surface.

     

A Simple Synthesis of Stable 1,4-Diionic Pyridinium Betaines

Summary.  Protonation of the reactive intermediate produced in the reaction between pyridine and dialkyl acetylenedicarboxylates by strong CH-acids such as N,N′-dimethylbarbituric acid, Meldrum’s acid, or indane-1,3-dione leads to a vinylpyridinium cation which undergoes an addition reaction with the enolate anion of the CH-acid to produce stable 1,4-diionic pyridinium betaines in good yields. Corresponding author. E-mail: isayavar@yahoo.com Received February 5, 2002. Accepted (revised) March 12, 2002     

Synthesis of stable ketenimines via a four-component reaction

Abstract  

An efficient one-pot synthesis of ketenimine derivatives is described. It involves a four-component reaction between benzylamines, 2,2-dichloroethanoyl chloride, alkyl isocyanide, and dialkyl acetylenedicarboxylates under mild conditions at ambient temperature.     

Nanostructured conducting molecularly imprinted polymer for selective extraction of salicylate from urine and serum samples by electrochemically controlled solid-phase micro-extraction

Overoxidized polypyrrole (OPPy) films templated with salicylate (SA) have been utilized as conducting molecular imprinted polymers (CMIPs) for potential-induced selective solid-phase micro-extraction processes. Various important fabrication factors for controlling the performance of the OPPy films have been investigated using fluorescence spectrometry. Several key parameters such as applied potential for uptake, release, pH of uptake and release solution were varied to achieve the optimum micro-extraction procedure. The film template with SA exhibited excellent selectivity over some interference. The calibration graphs were linear in the ranges of 5×10(-8) to 5×10(-4) and 1.2×10(-6) to 5×10(-4)mol mL(-1) and the detection limit was 4×10(-8) mol L(-1). The OPPy film as the solid-phase micro-extraction absorbent has been applied for the selective clean-up and quantification of trace amounts of SA from physiological samples. The results of scanning electron microscopy (SEM) have confirmed the nano-structure morphologies of the films.     

Toluene chemiresistor sensor based on nano-porous toluene-imprinted polymer

In this work, the application of molecularly imprinted polymer (MIP) as the recognition element of a chemiresistor sensor was introduced. Toluene-imprinted polymer and non-imprinted polymer (NIP) were synthesized and then mixed with carbon black powder in the presence of melted n-eicosane as the binder agent. The obtained composites were applied for the construction of chemiresistor sensors. The sensor, fabricated with toluene-imprinted polymer, showed a significant response towards toluene. Moreover, the response of the NIP-based (polymer synthesized without solvent) chemiresistor sensor was very small and negligible. The components of the MIP-based sensing composite were found to strongly influence the sensor sensitivity. Response surface experimental design methodology was applied to optimize the important parameters of the proposed sensor. Cross-sensitivity of the MIP-based chemiresistor sensor for different vapours was investigated and a satisfactory result was found for toluene vapour recognition. It was shown that the sensor response to toluene concentration in air was linear in the concentration range of 3.8 to 46.4?ppm. The detection limit and relative standard deviation (for five separate determinations) of the designed sensor were calculated equal to 0.8?ppm and 5.6%, respectively.     

Synthesis of 4,5-Dialkyl 1-Isopropyl 3-Isopropoxy1 H -Pyrazole-1,4,5-tricarboxylate by Using Mitsunobu Chemistry

4,5-dialkyl 1-isopropyl 3-isopropoxy-1H-pyrazole-1,4,5-tricarboxylate was obtained in an excellent yield from the reaction of dialkyl acetylenedicarboxylates and diisopropyl azodicarboxylate in the presence of triphenylphosphine in dry dichloromethane. This reaction provides a useful synthetic route to highly functionalized pyrazoles.