An assessment of the technique of simultaneous cooling in conjunction with microwave heating for organic synthesis

In the light of the controversy in the area and since reports using simultaneous cooling in conjunction with microwave heating are appearing in the literature, we were keen to assess the methodology, looking at temperature measurement issues as well as the use of the technique in three classes of reaction, namely a Heck coupling, a Diels-Alder cycloaddition and a Michael addition. We present our initial findings here.     

Kinetics of dispersion polymerization: Effect of medium composition

The effect of the medium composition (monomer and solvent) on the kinetics of dispersion polymerization of methyl methacrylate (MMA) was studied via reaction calorimetry. It was found that increasing the monomer concentration increased the reaction rate; the exponent of the dependency of the initial reaction rate on the MMA concentration was found to be 0.93. Narrow particle size distributions were achieved at the lower monomer concentrations (0.24–0.81 mol/L) and a minimum size (2.45 μm) was found at an intermediate concentration (0.44 mol/L). The average molecular weight of the PMMA increased and the molecular weight distribution broadened with increasing monomer concentration. During a dispersion polymerization, the MMA concentration was found to decrease linearly with conversion in both phases, whereas the ratio of concentrations in the particles and continuous phase ([M]_p/[M]_c) remained constant (0.47) with partitioning favoring the continuous phase. The average number of free radicals per particle in MMA dispersion polymerization was estimated to be high from the nucleation stage onward (>5000). The increasing rate during the first ～ 40% conversion was primarily caused by the increasing volume of the polymer particle phase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3638–3647, 2008     

Littlewood–Richardson polynomials

We introduce a family of rings of symmetric functions depending on an infinite sequence of parameters. A distinguished basis of such a ring is comprised by analogues of the Schur functions. The corresponding structure coefficients are polynomials in the parameters which we call the Littlewood–Richardson polynomials. We give a combinatorial rule for their calculation by modifying an earlier result of B. Sagan and the author. The new rule provides a formula for these polynomials which is positive in the sense of W. Graham. We apply this formula for the calculation of the product of equivariant Schubert classes on Grassmannians which implies a stability property of the structure coefficients. The first manifestly positive formula for such an expansion was given by A. Knutson and T. Tao by using combinatorics of puzzles while the stability property was not apparent from that formula. We also use the Littlewood–Richardson polynomials to describe the multiplication rule in the algebra of the Casimir elements for the general linear Lie algebra in the basis of the quantum immanants constructed by A. Okounkov and G. Olshanski.     

Chiral pool based synthesis of pyrrolidinium ionic liquids

Chiral ionic liquids show promising applications in various different fields. A series of pyrrolidinium-based chiral ionic liquids bearing a chiral cation, a chiral anion or both was prepared in good yields using an efficient, economic and simple pathway. The chirality was introduced using (l)-lactate and (l)-menthol derivatives. The resultant chiral compounds were characterized by both spectroscopy and polarimetry. We envision that these new chiral compounds can serve as effective reaction media and chiral catalysts for asymmetric reactions, which are presently being investigated in our lab.     

On manifolds of initial conditions leading to intersection of orbits of satellites with planet under weak gravitational perturbations

We consider the problem of initial conditions that lead to the intersection of a satellite orbit with planetocentric sphere of a radius R. The problem is considered in frame of the satellite version of the double-averaged restricted three body problem with taking into account gravitational perturbations caused by the polar oblateness of the planet. For some integrable cases we provide the boundaries of the manifolds of the initial orbital elements leading (or not leading) to the intersection of the satellite orbit with the planet surface.     

Formation of dislocation loops during He clustering in bcc Fe

The clustering of helium in bcc (body centered cubic) iron and the growth of a helium bubble are simulated at the atomistic level for the helium-rich vacancy-poor condition. It is shown that a ? 111 dislocation loop is formed as a sequential collection of 111 crowdions, the latter being the most stable self-interstitial atom configuration in the presence of a He cluster.     

Every group is a maximal subgroup of a naturally occurring free idempotent generated semigroup

The study of the free idempotent generated semigroup IG(E) over a biordered set E has recently received a deal of attention. Let G be a group, let \(n\in\mathbb{N}\) with n≥3 and let E be the biordered set of idempotents of the wreath product \(G\wr \mathcal{T}_{n}\) . We show, in a transparent way, that for e∈E lying in the minimal ideal of \(G\wr\mathcal{T}_{n}\) , the maximal subgroup of e in IG(E) is isomorphic to G. It is known that \(G\wr\mathcal{T}_{n}\) is the endomorphism monoid End F _n (G) of the rank n free G-act F _n (G). Our work is therefore analogous to that of Brittenham, Margolis and Meakin for rank 1 idempotents in full linear monoids. As a corollary we obtain the result of Gray and Ru?kuc that any group can occur as a maximal subgroup of some free idempotent generated semigroup. Unlike their proof, ours involves a natural biordered set and very little machinery.     

Overlap Cycles for Steiner Quadruple Systems

Steiner quadruple systems are set systems in which every triple is contained in a unique quadruple. It is well known that Steiner quadruple systems of order v, or SQS(v), exist if and only if . Universal cycles, introduced by Chung, Diaconis, and Graham in 1992, are a type of cyclic Gray code. Overlap cycles are generalizations of universal cycles that were introduced in 2010 by Godbole, et al. Using Hanani's SQS constructions, we show that for every with there exists an SQS(v) that admits a 1‐overlap cycle.