Catalytic oxidative cleavage of olefins promoted by osmium tetroxide and hydrogen peroxide

Hydrogen peroxide was employed as the terminal oxidant in the osmium tetroxide mediated oxidative cleavage of olefins, producing the corresponding aldehyde and ketone products. Aryl olefins are cleaved in good to excellent yield regardless of arene electronics. Alkyl olefins cleave in moderate to good yield for di- and tri-substituted alkenes.     

Chlorometallate and palladium cluster complexes of wide-span diimine and diamine ligands

Diimine and diamine ligands that are unable to coordinate to a single metal favour the formation of unusual, high-nuclearity Zn chlorometallate and palladium chloride complexes.     

Continuous Blooming of Convex Polyhedra

We construct the first two continuous bloomings of all convex polyhedra. First, the source unfolding can be continuously bloomed. Second, any unfolding of a convex polyhedron can be refined (further cut, by a linear number of cuts) to have a continuous blooming.     

Application of thermal analysis in preservation and restoration of historic masonry materials

Thermal analysis techniques have been used in characterizing building materials from significant historic properties in the Charleston, South Carolina area. Determining the chemical and physical effects of deterioration resulting from long periods of exposure is a first step in formulating preservation strategies. In this regard, simultaneous thermal analysis coupled with evolved gas analysis has been used to study reactions between air, seawater, and masonry materials. Further, the traditional petrographic identification of mortar composition is greatly facilitated through use of thermal analysis. Simultaneous thermal analysis allows for an exact determination of the calcium carbonate content in mortars as an alternative to the use of an inferred value based on chemical analysis data. The partial dissolution of calcium carbonate in the presence of sea salt is a major deterioration process. Further, natural cements manufactured in the United States are identified, in part, based on their thermogravimetric (TG) traces and their evolved gases. The data indicates that natural cements form some carbonate phases in addition to the major hydrate phases. Clay bricks are found to exhibit interaction with sea water, with uptake of bicarbonate suggested. Additionally, there is evidence of re-hydroxylation in the 160 year old bricks. The bricks made in coastal zones contain a considerable free silica fraction that is composed of a small percentage of cristobalite. The silica content of the clay bricks is seen to result in very high thermal expansion coefficients in the area of 10 × 10⁻⁶ to 12 × 10⁻⁶ K⁻¹. These studies provide guidance in restoration efforts where authenticity of cements is important. In the event that replacement bricks are required, matching the thermal expansion coefficient of the original bricks is a requirement for preservation of the masonry structure.     

DYNGA: a general purpose QM-MM-MD program. I. Application to water

We present a general purpose QM-MM-MD engine (DYNGA) designed to test alternative hybrid Hamiltonians geared towards the treatment of problems of interest in structural biology including the use of experimental data constraints. In this first presentation we use DYNGA to explore the behaviour of a traditional QM-MM approach in the treatment of the water—water interaction. We find the potential energy hypersurface for the water dimer computed with the HF 4–31G*/TIP3P hybrid Hamiltonian tends to be too flat. We also explore the effect of using traditional QM-MM techniques on proton wires and conclude there is a need for improvement, possibly addressed by using polarizable force fields.     

Fitting of transport measurements in polycrystalline La2/3Ca1/3MnO3

Using a previous qualitative explanation to describe the transport properties of polycrystalline La_2/3Ca_1/3MnO₃ thick films, we achieved a good fit of the temperature dependence of the resistance R(T). Depending on the sample, we have observed different metal–insulator (MI) transitions while the magnetic behavior is always similar. Small regions of depleted T_c adjacent to the grain boundary could have an important resistance contribution without affecting the magnetic properties in an appreciable manner. In this work, we achieve a quantitative explanation for the different transport behaviors that we have observed experimentally.     

The structures of some cycloalkane molecular ions by photodissociation and charge-transfer studies in an ICR-spectrometer

The photodissociation spectra of the molecular ions of some cycloalkanes are compared with those of the corresponding acyclic alkanes and alkenes. It is shown that the molecular ions of cyclohexane and cycloheptane are cyclic whereas the cyclopentane ring opens upon ionisation. This conclusion is supported by a study of the charge-transfer equilibria: C₆D₁₂^± + C₆H₁₂ ? C₆D₁₂ + C₆H₁₂^±, C₅D₁₀^± + C₅H₁₀ ? C₅D₁₀ + C₅H₁₀^±. It is furthermore shown that the maxima in the photodissociation spectra of the molecular ions of saturated hydrocarbons correspond to different dissociation processes.     

Diamino-benzo[1,2-d:4,5-d′]bistriazole (DABT), a new useful 1,4-dibenzyne equivalent

The title compound, when treated with two equivalents of lead tetraacetate, is the synthetic equivalent of 1,4-dibenzyne; bis-cycloadducts are formed with dienes and 1,3-dipoles.