Fluorosugar chain termination agents as probes of the sequence specificity of a carbohydrate polymerase

Naturally occurring carbohydrate polymers are ubiquitous. They are assembled by polymerizing glycosyltransferases, which can generate polysaccharide products with repeating sequence patterns. The fidelity of enzymes of this class is unknown. We report a method for testing the fidelity of carbohydrate polymerase pattern deposition: we synthesized fluorosugar donors and used them as chain termination agents. The requisite nucleotide fluorosugars could be produced from a single intermediate using the Jacobsen catalyst in a kinetically controlled separation of diastereomers. The resulting fluorosugar donors were used by the galactofuranosyltransferase GlfT2 from Mycobacterium tuberculosis, and the data indicate that this enzyme mediates the cell wall galactan production through a sequence-specific polymerization.     

Magnetic click colloidal assembly

We introduce a new class of spherical colloids that reversibly self-assemble into well-defined nonlinear structures by virtue of "magnetic patches". This assembly is driven by tunable magnetostatic binding forces that originate from microscopic permanent magnets embedded underneath the surface of the particles. The resulting clusters form spontaneously in the absence of external magnetizing fields, and their geometry is determined by an interplay between magnetic, steric, and electrostatic interactions. Imposing an external magnetic field enables the clusters to unbind or change their geometry allowing, in principle, the creation of materials with a reconfigurable structural arrangement.     

Synthesis and Photophysical Properties of a Series of Cyclopenta[b]naphthalene Solvatochromic Fluorophores

The synthesis and photophysical properties of a series of naphthalene-containing solvatochromic fluorophores are described within. These novel fluorophores are prepared using a microwave-assisted dehydrogenative Diels-Alder reaction of styrene, followed by a palladium-catalyzed cross coupling reaction to install an electron donating amine group. The new fluorophores are structurally related to Prodan. Photophysical properties of the new fluorophores were studied and intriguing solvatochromic behavior was observed. For most of these fluorophores, high quantum yields (60-99%) were observed in methylene chloride in addition to large Stokes shifts (95-226 nm) in this same solvent. As the solvent polarity increased, so did the observed Stokes shift with one derivative displaying a Stokes shift of ～300 nm in ethanol. All fluorophore emission maxima, and nearly all absorption maxima were significantly red-shifted when compared to Prodan. Shifting the absorption and emission maxima of a fluorophore into the visible region increases its utility in biological applications. Moreover, the cyclopentane portion of the fluorophore structure provides an attachment point for biomolecules that will minimize disruptions of the photophysical properties.     

Mechanistic insight on the catecholase activity of dinuclear copper complexes with distant metal centers

The catecholase activity of two dinuclear Cu(II) complexes with distant metal centers is discussed together with solid state and solution studies. The crystal structure for one of them, [Cu(2)(diep)(H(2)O)(4)](ClO(4))(4)·2H(2)O, is described, showing the two copper ions are 7.457 ? apart and in a square pyramidal coordination. Both complexes display a weak antiferromagnetic coupling in the solid state that is manifest in the dimer EPR spectra obtained in frozen solution. The pH-potentiometric speciation performed in 1:1 MeOH-H(2)O allowed the assignment of hydrolyzed copper species as those catalytically active in the oxidation of 3,5-di-tert-butylcatechol (DTBC). The kinetic measurements led us to propose behavior consistent with Michaelis-Menten plus a linear dependence of the initial rate on [DTBC]. This can be associated with the presence of more than one catalytically active species, which is consistent with the evidence of several differently hydrolyzed species shown in the predominance diagrams. Product characterization studies led to establishing the formation of hydrogen peroxide during the catalytic cycle, while semiquinone and superoxide radicals were detected by EPR spectroscopy, supporting one-electron transference at each of the copper centers.     

Raman spectroscopic characterization of the magnesium content in amorphous calcium carbonates

A series of Mg‐bearing synthetic amorphous calcium carbonates (ACC) were characterized by Raman spectroscopy. The spectra showed a systematic increase in the carbonate ν₁ peak position from the control samples that contained 0.0 mol % MgCO₃ to samples that contained up to 43 mol % MgCO₃. The relationship is best described by the function: mol % MgCO₃ = (ν₁ – 1079.66) / 0.2017. The Mg content is equally well‐predicted by a correlation with the instrumentally corrected ν₁ full width at half maximum that is quantified by: mol % MgCO₃ = (ν₁ – 23.26) / 0.1969. An analysis of the Raman data collected for ACC combined with insights from crystalline materials suggests that compositional dependencies arise from changes in the local metal–oxygen bonds as Mg substitutes for Ca. The calibrations described here provide a rapid and nondestructive means of determining the Mg content of ACC, with additional advantages of minimal sample preparation and a high degree of lateral spatial resolution (approximately 1 µm). This method may be appropriate for investigations of heterogeneous samples such as biominerals. Copyright © 2011 John Wiley & Sons, Ltd.     

Foundations for a Theory of Complex Matroids

We explore a combinatorial theory of linear dependency in complex space, complex matroids, with foundations analogous to those for oriented matroids. We give multiple equivalent axiomatizations of complex matroids, showing that this theory captures properties of linear dependency, orthogonality, and determinants over ? in much the same way that oriented matroids capture the same properties over ?. In addition, our complex matroids come with a canonical S ¹ action analogous to the action of ?^? on a complex vector space. Our phirotopes (analogs of determinants) are the same as those studied previously by Below, Krummeck, and Richter-Gebert (Discrete and Computational Geometry, Springer, pp.?203?C233, 2003) and Delucchi (Diploma Thesis, ETH Zurich, 2003). We further show that complex matroids cannot have vector axioms analogous to those for oriented matroids.     

Homotopy Sphere Representations for Matroids

For any rank r oriented matroid M, a construction is given of a ??topological representation?? of M by an arrangement of homotopy spheres in a simplicial complex which is homotopy equivalent to S ^r?C1 . The construction is completely explicit and depends only on a choice of maximal flag in M. If M is orientable, then all Folkman-Lawrence representations of all orientations of M embed in this representation in a homotopically nice way.     

Pollution control quasi-equilibrium problems with joint implementation of environmental projects

In this paper, we show how one of the Kyoto Protocol mechanisms, the so-called joint implementation in environmental projects, can be transformed into and studied as an infinite-dimensional quasi-variational inequality. Specifically, we examine the situation in which different countries attempt to fulfill Kyoto commitments by investing in emission reduction or emission removal projects in countries where the abatement costs are lower. We derive the equilibrium conditions and prove their characterization in terms of an infinite-dimensional quasi-variational inequality problem. Finally, we discuss the existence of solutions.