TEMPO‐Mediated Emulsion Polymerization

While miniemulsion polymerization has proven to be well‐suited for conducting living/controlled radical polymerizations, emulsion polymerizations have proven to be far more challenging. Ab initio emulsion polymerizations, in which monomer droplets are present during polymerization, have thus far not been successful with TEMPO‐mediated polymerizations, as a result of colloidal instability and coagulum formation. By selectively inhibiting polymerization in the monomer droplets, it is demonstrated that droplet polymerization is responsible for the formation of large (>1 µm) particles that can lead to coagulum formation. Furthermore, we show that coagulum‐free latexes can be produced using a TEMPO‐mediated ab initio emulsion polymerization by suppressing droplet polymerization.

     

Determination of tamoxifen and metabolites in mouse fetal tissue using nonaqueous capillary electrophoresis

Tamoxifen (TAM), an antiestrogen, has been approved for use by women at risk for developing hormone-dependent breast cancer. Administration of TAM to pregnant CD-1 mice apparently results in reproductive tract toxicity in female offspring. However, there is little or no data describing potential TAM-induced fetal toxicity to women who may become pregnant while receiving prophylactic TAM treatment. In support of the National Toxicology Program's characterization of reproductive and developmental effects of TAM, the present work describes a capillary electrophoresis (CE)-based analytical technique used for detection of TAM and two major metabolites, N-desmethyltamoxifen (DMT), and 4-hydroxytamoxifen (4-HT) in CD-1 mouse fetal tissue. TAM-derived material was extracted from CD-1 mouse fetuses 2-12 h following TAM administration (100 mg/kg) to dams on gestation day 16. The presence of TAM, DMT, and 4-HT was confirmed in the solvent extracts by nonaqueous CE. The limit of detection of TAM by UV absorption was approximately 675 amol at a signal-to-noise ratio of 2:1. This work demonstrates both transplacental transport of TAM in CD-1 mice and a sensitive analytical technique for detecting low concentrations of TAM and similar compounds in biological tissues.     

Self-assembly of nanoparticles on the surface of ionic crystals: Structural properties

With a suitable combination of ligand-stabilised nanoparticle suspension and ionic salt solutions, it is possible to produce microcrystals that are coated with nanoparticles. The self-assembly process of coating microcrystals by gold nanoparticles (NP) is mediated by the crystal lattice. This is the so-called CLAMS process - a generic process for self-organisation of nanoparticles on the surface of crystals [M. Murugeshan, D. Cunningham, J.-L. Martnez-Albertos, R. Vrcelj, B.D. Moore, Chem. Commun. (2005) 2677]. We are exploring here the structural properties of these self-assembled structures by using different imaging techniques.     

Testing membership in matroid polyhedra

Given a matroid M on E and a nonnegative real vector x=(x_j:j∈E), a fundamental problem is to determine whether x is in the convex hull P of (incidence vectors of) independent sets of M. An algorithm is described for solving this problem for which the amount of computation is bounded by a polynomial in |E|, independently of x, allowing as steps tests of independence in M and additions, subtractions, and comparisons of numbers. In case x ∈ P, the algorithm finds an explicit representation for x which has additional nice properties; in case x ? P it finds a most-violated inequality of the system defining P. The same technique is applied to the problem of finding a maximum component-sum vector in the intersection of two matroid polyhedra and a box.     

On submodular function minimization

Earlier work of Bixby, Cunningham, and Topkis is extended to give a combinatorial algorithm for the problem of minimizing a submodular function, for which the amount of work is bounded by a polynomial in the size of the underlying set and the largest function value (not its length). Research partially supported by a grant from the Natural Sciences and Engineering Research Council of Canada.     

Principally Unimodular Skew-Symmetric Matrices

principally unimodular (PU) if every principal submatrix has determinant 0 or ±1. Let A be a symmetric (0, 1)-matrix, with a zero diagonal. A PU-orientation of A is a skew-symmetric signing of A that is PU. If A′ is a PU-orientation of A, then, by a certain decomposition of A, we can construct every PU-orientation of A from A′. This construction is based on the fact that the PU-orientations of indecomposable matrices are unique up to negation and multiplication of certain rows and corresponding columns by −1. This generalizes the well-known result of Camion, that if a (0, 1)-matrix can be signed to be totally unimodular then the signing is unique up to multiplying certain rows and columns by −1. Camion's result is an easy but crucial step in proving Tutte's famous excluded minor characterization of totally unimodular matrices. Received: May 17, 1996