Study of the oxidation of some catechols in the presence of 4‐amino‐3‐thio‐1,2,4‐triazole by digital simulation of cyclic voltammograms

Electrochemical oxidation of catechol and its derivatives ( 1a–d ) has been studied in the presence of 4‐amino‐3‐thio‐1,2,4‐triazole ( 3 ) at various pHs. Some electrochemical techniques such as cyclic voltammetry using the diagnostic criteria derived by Nicholson and Shain for various electrode mechanisms and controlled‐potential coulometry were used. Results indicate the participation of catechols ( 1a–d ) with 3 in an intramolecular cyclization reaction to form the corresponding 1,2,4‐triazino[5,4‐b]‐1,3,4‐thiadiazine derivatives. In various scan rates, based on an electron transfer–chemical reaction–electron transfer–chemical reaction mechanism, the observed homogeneous rate constants (k_obs) for Michael addition reaction were estimated by comparing the experimental cyclic voltammetric responses with the digital simulated results. The oxidation reaction mechanism of catechols ( 1a–d ) in the presence of 4‐amino‐3‐thio‐1,2,4‐triazole ( 3 ) was also studied. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 340–345, 2007     

Kinetic study of the oxidation of some catecholamines by digital simulation of cyclic voltammograms

Electrochemical oxidation of some catecholamines such as dopamine ( 1 ), L ‐dopa ( 2 ), and methyldopa ( 3 ) has been studied in various pH values, using cyclic voltammetry. The results indicate participation of catecholamines ( 1–3 ) in intramolecular cyclization reaction to form the corresponding o‐quinone derivatives ( 1d–3d ). In various pHs, based on ECE mechanism, the observed homogeneous rate constants (k_obs) of cyclization reaction were estimated by comparing the experimental cyclic voltammetric responses with the digital‐simulated results. Also, the cyclization rate constants (k_cyc) were calculated using microscopic acidic dissociation constant of ammonium groups. The significant differences in electrochemical behavior, k_obs and k_cyc, of L ‐dopa ( 2 ) and methyldopa ( 3 ) with dopamine ( 1 ) are due to the effects of the side chain carboxyl group. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 37: 17–24, 2005     

Synthesis of pyranopyrazoles,benzopyrans, amino-2-chromenes and dihydropyrano[<Emphasis Type="Italic">c</Emphasis>]chromenes using ionic liquid with dual Brønsted acidic and Lewis basic sites

An efficient ionic liquid with both Brønsted acidic and Lewis basic sites, namely 1,4-dimethyl-1-(4-sulphobutyl)piperazinium hydrogen sulphate (IL1), was synthesised and characterised. IL1 is a “green”, homogeneous and reusable catalyst for: i) the synthesis of pyranopyrazoles (Va-Vj)and benzopyrans (VIa-VIj and VIIa-VIIf) at ambient temperature under solvent-free conditions and ii) the synthesis of amino-2-chromenes (VIIIa-VIIIi and IXa-IXi) and dihyropyrano[c]chromenes (Xa-Xi) at 80 °C under solvent-free conditions. The reactions were rapid with excellent product yields. In addition, the double Brønsted acid, 1,4-dimethyl-1,4-bis(4-sulphobutyl)piperazinium hydrogen sulphate (IL2), was prepared to evaluate the cooperation efficiency of their Brønsted acidic and Lewis basic sites as compared with the double Brønsted acidic sites in IL1.     

Module derivations on semigroup algebras

We show that for an inverse semigroup S with the set idempotents E acting on S trivially from left and by multiplication from right, any bounded module derivation from \(\ell ^1(S)\) to \(({\ell ^1(S)}/{J})^*=J^{\perp }\) is inner, where J is the closed ideal generated by elements of the form \(\delta _{set}-\delta _{st}\) with \(s,t\in S\) and \(e\in E\).     

Effect of variable viscosity and viscous dissipation on the Hagen‐Poiseuille flow and entropy generation

In this article, the steady‐state flow of a Hagen‐Poiseuille modelin a circular pipe is considered and entropy generation due tofluid friction and heat transfer is examined. Because of variationin fluid viscosity, the entropy generation in the flow varies. Inhis model, Arrhenius law is applied for temperature equation‐dependent viscosity, and the influence of viscosity parameters on the entropy generation number and distribution of temperature and velocity is investigated. The governing momentum and energy equations, which are coupled due to the dissipative term in the energy equation, were solved by analytical techniques. The solutions of equations via perturbation method and homotopy perturbation method are obtained and then compared with those of numerical solutions. It is found that the fluid viscosity influences considerably the temperature distribution in the fluid close to the pipe wall, and increasing pipe wall temperature enhances the rate of entropy generation. © 2009 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 27: 529–540, 2011     

Structural evidence of anomeric effects in the anesthetic isoflurane

The conformational and structural properties of the inhalational anesthetic isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) have been probed in a supersonic jet expansion using Fourier-transform microwave (FT-MW) spectroscopy. Two conformers of the isolated molecule were identified from the rotational spectrum of the parent and several (37)Cl and (13)C isotopologues detected in natural abundance. The two most stable structures of isoflurane are characterized by an anti carbon skeleton (τ(C(1)-C(2)-O-C(3)) = 137.8(11)° or 167.4(19)°), differing in the trans (AT) or gauche (AG) orientation of the difluoromethyl group. The conformational abundances in the jet were estimated from relative intensity measurements as (AT)/(AG) ≈ 3:1. The structural preferences of the molecule have been rationalized with supporting ab initio calculations and natural-bond-orbital (NBO) analysis, which suggest that the molecule is stabilized by hyperconjugative effects. The NBO analysis of donor-acceptor (LP → σ*) interactions showed that these stereoelectronic effects decrease from the AT to AG conformations, so the conformational preferences can be accounted for in terms of the generalized anomeric effect.     

Weak Module Amenability for Semigroup Algebras

We study the weak module amenability of Banach algebras which are Banach module over another Banach algebra with compatible actions. As an example we show that the semigroup algebra of a commutative inverse semigroup is always weakly amenable as a module over the semigroup algebra of its subsemigroup of idempotents.     

The mechanism of reaction of tetraalkyltins with mercuric carboxylates in methanol

In the reaction of mercuric carboxylates with tetraalkyltins in methanol, rate constrants for attack of the species (RCO₂)₂ Hg increase along the series R = t-Bu < Et < Me < Ph < ClCH₂CH₂ < MeOCH₂ < ClCH₂ which suggests an open transition state for these S_E2 substitutions.     

Electrochemical oxidation of catechol in the presence of cyclopentadiene. Investigation of electrochemically induced Diels-Alder reactions

We describe the synthesis and kinetic evaluation of compounds from [4 + 2] alone and [4 + 2] followed by [2 + 2] cycloaddition reactions of electrochemically generated o-benzoquinone with 1,3-cyclopentadiene.     

2-Domination number of generalized Petersen graphs

Let \(G=(V,E)\) be a graph. A subset \(S\subseteq V\) is a k-dominating set of G if each vertex in \(V-S\) is adjacent to at least k vertices in S. The k-domination number of G is the cardinality of the smallest k-dominating set of G. In this paper, we shall prove that the 2-domination number of generalized Petersen graphs \(P(5k+1, 2)\) and \(P(5k+2, 2)\), for \(k>0\), is \(4k+2\) and \(4k+3\), respectively. This proves two conjectures due to Cheng (Ph.D. thesis, National Chiao Tung University, 2013). Moreover, we determine the exact 2-domination number of generalized Petersen graphs P(2k, k) and \(P(5k+4,3)\). Furthermore, we give a good lower and upper bounds on the 2-domination number of generalized Petersen graphs \(P(5k+1, 3), P(5k+2,3)\) and \(P(5k+3, 3).\)