2,3-Bis(phenylsulfonyl)-1,3-butadiene: Substrate for Michael Donor/Acceptors in a Novel Synthesis of Fused Cyclopentenes

The reaction of 2,3-bis(phenylsulfonyl)-1,3-butadiene with the anion of various 1-substituted dimethyl 1-pentenedioates has been investigated with the purpose of devising a tandem conjugate addition-[3 + 2]-anionic cyclization route for the synthesis of bicyclo[3.3.0]octenes. The reaction proceeds with complete stereospecificity as was evidenced by treating (E)- and (Z)-dimethyl (3-cyano-2-propenyl)propanedioate with NaH in the presence of the bis(phenylsulfonyl)diene. In both cases only a single cycloadduct was obtained with no detectable signs of the other diastereomer. The overall process involves a series of three sequential conjugate additions followed by benzenesulfinate ion ejection. The success of the method is dependent on the electrophilicity of the proximal pi-bond. When 2-((5-oxo-2,5-dihydrofuranyl)methyl)malonic acid dimethyl ester was used, a mixture of the tricyclic adduct as well as an allene was obtained. In this case, elimination of the benzenesulfinate group from the initially formed sulfone-stabilized carbanion is competitive with the intramolecular [3 + 2]-annulation process. The base-induced reaction of dimethyl 2-(methoxycarbonyl)-2-pentenedioate with the bis(phenylsulfonyl)diene was also studied. Even though the position of the acceptor moiety on the pi-bond was altered, the tandem Michael reaction sequence still occurs. The course of the reaction is dependent upon the length of the tether as well as the relative placement of the electron-withdrawing group on the olefin. Reaction with gamma-substituted beta,gamma-alkenyl derivatives leads to bicyclo[3.3.0]octenes, whereas beta-substituted beta,gamma-alkenyl reagents provide bicyclo[3.3.0]octenes derived from a novel alpha-elimination reaction.     

The effects of an electric field on an autocatalytic ionic reaction in a system with high ionic strength

The effects of an applied electric field on an ionic autocatalyticreaction with a quadratic rate law are considered, where thereacting species, A⁺ and B⁺, are present in a system which alsoincludes non-reacting species C^- and D⁺. The conditions areestablished under which the general terms which describe theelectric field effects in the reaction-diffusion equations canbe simplified to those used in previous studies, where theseeffects are modelled by linear advection terms. The resultingequations are then studied in detail by first obtaining conditionsfor the existence of travelling waves of permanent form. Thisdiscussion shows that _B, the ratio of the diffusion coefficientsof B⁺ and A⁺, is a critical parameter, with different formsof behaviour arising for _B < 1 and _B > 1. This analysisis augmented by obtaining solutions valid for large times andlarge values of (the dirnensionless applied field). Numericalsolutions of initial-value problems are obtained for a rangeof values of and _B, guided by and interpreted through the analysispreviously obtained. These numerical integrations show the formationof reaction fronts, with the possibility of greatly increasedreaction rates caused by the applied electric field, as wellas propagating electrophoretic fronts in B⁺ being formed incases where a reaction front is also initiated. There is alsothe possibility of separate electrophoretic fronts in A⁺ andB⁺ being formed, which become increasingly separated as timeincreases with the reaction being completely inhibited.     

Zero-order release formulations using a novel cellulose ester

New carboxymethylcellulose esters were developed with useful properties for oral dosage forms in drug delivery. Normally, commercial cellulose esters are used as the major excipients in oral dosage forms as a coating or a membrane. In applications involving compression tablets, cellulose esters are usually mixed with other more hydrophilic matrix components to facilitate dissolution of the active. In the present study, novel cellulose esters were single component matrix resins. Pharmaceutical actives were cryogenically ground as a physical blend or an amorphous blend with the polymer. Subsequently, tablets were made by direct compression using a single tablet press, or capsules were made by filling them with the ground material. Dissolution tests were completed on the solid dosage forms at pH 1.2, 4.5, 6.8 or 7.4 in a United States Pharmacopeia (USP) II device to determine the release profiles for up to 24 h. Carboxymethylcellulose esters provide an excellent matrix for controlling both the rate of release and the pH at which pharmaceutical actives release into the aqueous environment. When used in suitable quantities, dictated by the active of interest, carboxymethylcellulose acetate butyrate provided zero-order release over sustained time up to 24 h.     

Resilience in reaction-diffusion systems

Reaction-diffusion systems with zero-flux Neumann boundariesare widely used to model various kinds of interaction in, forexample, the scientific fields of ecology, biology, chemistry,medicine and industry. The physical systems within these fieldsare often known to be (conditionally or unconditionally) resilientwith respect to shocks, disturbances or catastrophies in theimmediate environment. In order to be good mathematical modelsof such situations the reaction-diffusion systems must havethe same resilient or asymptotic behaviour as that of the physicalsituation. Three fundamentally different kinds of reaction termsare usually distinguished according to the entry signs of thereaction Jacobian: mutualism, mixed (predator-prey) interactionand competition. The asymptotic stability (in the Poincarésense) of mutualistic systems has already been studied extensively,but the results cannot be generalized (globally) to the othertwo fundamental types, which are not order-preserving. A partial(local) generalization is, however given here for these twotypes, involving simple Jacobian inequalities and knowledge(often prompted by the underlying physical situation) of invariantsets in solution space. The return time of resilient systemsand the approach rate of asymptotically stable solutions arealso estimated.     

A solution-adaptive mesh procedure for predicting confined explosions

Explosion hazards constitute a significant practical problem for industry. In response to the need for better-resolved predictions for confined explosions, and particularly with a view to advancing safety cases for offshore oil and gas rigs, an existing unstructured, adaptive mesh, finite volume Reynolds-averaged Navier–Stokes computational fluid dynamics code (originally developed to handle non-combusting turbomachinery flows) has been modified to include a one-equation, eddy break-up combustion model. Two benefits accrue from the use of unstructured, solution-adaptive meshes: first, great geometrical flexibility is possible; second, automatic mesh adaptation allows computational effort to be focused on important or interesting areas of the flow by enhancing mesh resolution only where it is required. In the work reported here, the mesh was adaptively refined to achieve flame front capture, and it is shown that this results in a 10%–33% CPU saving for two-dimensional calculations and a saving of between 57% and 70% for three-dimensional calculations. The geometry of the three-dimensional calculations was relatively simple, and it may be expected that the use of unstructured meshes for truly complex geometries will result in CPU savings sufficient to allow an order-of-magnitude increase in either complexity or resolution. © 1998 John Wiley & Sons, Ltd.     

The photocurrent response of human cones is fast and monophasic

Background  

The precise form of the light response of human cone photoreceptors in vivo has not been established with certainty. To investigate the response shape we compare the predictions of a recent model of transduction in primate cone photoreceptors with measurements extracted from human cones using the paired-flash electroretinogram method. As a check, we also compare the predictions with previous single-cell measurements of ground squirrel cone responses.     

A versatile charged particle activation technique for the analysis of the noble metals

The general usefulness of neutron activation analysis (NAA) for samples containing the platinum group elements (PGE) and Au, either as major or trace consituents, is discussed. Charged particle activation is shown to be a viable or complementary alternative. Proton (6–10 MeV) and alpha particle (9–15 MeV) beams, produced in a Tandem van de Graaff accelerater, have been established to be the most effective choice. By taking advantage of the Coulomb Barrier Effect and the fact that many charged particle induced reactions have relatively large threshold values, the same instrumental technique can be applied, with minor modifications, to a wide range of materials.