Synthesis of a novel C2-aryl substituted 1,2-unsaturated pyrrolobenzodiazepine

A novel C2-aryl 1,2-unsaturated PBD (14) has been prepared via an enol triflate intermediate (8). The regiochemistry of triflation is dependent upon the point at which the reaction is performed during the synthetic route.     

Finite covers of random 3-manifolds

A 3-manifold is Haken if it contains a topologically essential surface. The Virtual Haken Conjecture posits that every irreducible 3-manifold with infinite fundamental group has a finite cover which is Haken. In this paper, we study random 3-manifolds and their finite covers in an attempt to shed light on this difficult question. In particular, we consider random Heegaard splittings by gluing two handlebodies by the result of a random walk in the mapping class group of a surface. For this model of random 3-manifold, we are able to compute the probabilities that the resulting manifolds have finite covers of particular kinds. Our results contrast with the analogous probabilities for groups coming from random balanced presentations, giving quantitative theorems to the effect that 3-manifold groups have many more finite quotients than random groups. The next natural question is whether these covers have positive betti number. For abelian covers of a fixed type over 3-manifolds of Heegaard genus 2, we show that the probability of positive betti number is 0.In fact, many of these questions boil down to questions about the mapping class group. We are led to consider the action of the mapping class group of a surface Σ on the set of quotients π₁(Σ)→Q. If Q is a simple group, we show that if the genus of Σ is large, then this action is very mixing. In particular, the action factors through the alternating group of each orbit. This is analogous to Goldman’s theorem that the action of the mapping class group on the SU(2) character variety is ergodic. Mathematics Subject Classification (2000) 57M50, 57N10     

Nucleation and crystal growth of copper(II) 8-hydroxyquinolinate precipitated from mixed solvents

The precipitation kinetics of copper(II) 8-hydroxyquinolinate, formed in water-acetone mixtures, have been studied in a stop-flow apparatus by spectrophotometric techniques. Three factors are found to be important in improving the physical characteristics of crystals precipitated from mixed solvents. Supersaturation and growth rate can be controlled uniformly by slow rate of change in solvent composition; the presence of acetone significantly reduces the number of effective nuclei; thirdly, large amounts of organic solvent cause a change in the crystal form and its growth mechanism. At room temperature, copper(II) 8-hydroxyquinolinate is precipitated as a dihydrate from water-acetone mixtures containing 0-60% acetone, and the crystal growth is limited by a diffusion-controlled process. Anhydrous copper(II) 8-hydroxyquinolinate is formed in 70% acetone solutions by a surface-controlled reaction.     

Co-existence of long- and short-range magnetic correlations in holmium-erbium superlattices

The effect of competing crystal-field anisotropies on magnetic order has been investigated in a series of Ho/Er superlattices using a combination of x-ray and neutron scattering techniques. For temperatures in the interval T_N(Er)≤T≤T_N(Ho) the Ho basal-plane order propagates coherently through the paramagnetic Er over a typical length scale of 1000 Å. At low temperatures the Ho moments retain their bulk-like helical configuration, whereas the magnetic structure in the Er blocks has both basal-plane and c-axis components. Below T_N(Er), the coherence length of the basal-plane order decreases on cooling, while the longitudinal component of the Er moments fails to order across the Ho block. It is argued that these results require an extension of current models of indirect exchange in superlattices to explicitly include the superlattice band structure.     

Synthesis and characterization of magnetic Co nanoparticles: A comparison study of three different capping surfactants

This paper compares the performance of three long-chain acids—oleic and elaidic (both olefinic) and stearic (aliphatic)—as a capping agent in the synthesis of magnetic Co nanoparticles. The particles were formed through thermal decomposition of dicobalt octacarbonyl in toluene in the presence of the long-chain acid, and characterized by TEM, high-resolution TEM, and SQUID measurements. Infrared spectra revealed that some of the added olefinic acid was transformed from cis- to trans-configuration (for oleic acid) or from trans- to cis- (for elaidic acid) to facilitate the formation of a densely packed monolayer on the surface of Co nanoparticles. As compared to aliphatic acids, olefinic acids are advantageous for dense packing on small particles with high surface curvatures due to a bent shape of the cis-isomer. The presence of an olefinic acid is able to control particle growth, stabilize the colloidal suspension, and prevent the final product from oxidation by air. Our results indicate that oleic acid, elaidic acid, and a mixture of oleic/stearic acids or elaidic/stearic acids have roughly the same performance in serving as a capping agent for the synthesis of Co nanoparticles with a spherical shape and narrow size distribution.     

The bicritical phase diagram of two-dimensional antiferromagnets with and without random fields

Neutron scattering measurements have been made of the phase diagrams of the nearly two-demensional antiferromagnets Rb₂MnF₄ and Rb₂Mn_0.7Mg_0.3F₄ in a magnetic field applied along thec-axis. In Rb₂MnF₄ there is at low temperatures a spin-flop phase at fields above 5.5 T which has long range order. The observation of true long range order rather than the algebraic decay of the order characteristic of the two-dimensional XY model is presumably due to subtle anisotropy effects in the plane as well as weak three-dimensional coupling. The phase boundaries of the uniaxial and transverse phases are shown to be consistent with renormalization group predictions for two-dimensional systems. The two lines become exponentially close to each other at low temperatures. The weak three-dimensional coupling moves the bicritical point fromT=0 to a non-zero temperature. The situation is more complex in Rb₂Mn_0.7Mg_0.3F₄ because of Ising random field effects. At low fields we observe typical random field metastable behavior with a sharp metastability boundary and a gange of length scales which are time independent below that boundary. At higher fields there are substantial uniaxial fluctuations. The transverse phase boundary and the metastability line appear to intercept atT=0 showing that the random field fluctuations do have a large effect on the phase diagram. The theory of the phase diagrams has been extended to include the random field fluctuations and good agreement is obtained with the observed transverse phase boundary. Unfortunately, there is as yet no theory of the metastable uniaxial phase with which to compare our results.