A new polymorph of tetraphenyldiboroxane

A new polymorph of tetraphenyldiboroxane [or oxybis(diphenylborane)], C₂₄H₂₀B₂O, (Ia), has been found. It is monoclinic, like the already known form, (Ib), and can be refined in the same space group, namely P2₁/c, or in the equivalent setting P2₁/n. The molecular conformations of the two polymorphs differ in the rotations of two of the phenyl rings about the B—C bonds, leading to markedly different packing patterns and cell dimensions.     

Asymmetric hydrogenation of alkyl(vinyl)thioethers: a promising approach to α-chiral thioethers

This paper describes the enantioselective hydrogenation of vinylthioethers. We show that thioether derivatives of maleic esters can be hydrogenated with full conversion and up to 60% ee, and that α-thioether cinnamic acids can be hydrogenated in 51% ee with modest conversion.     

A Metropolis Monte Carlo Implementation of Bayesian Time-Domain Parameter Estimation: Application to Coupling Constant Estimation from Antiphase Multiplets

The Bayesian perspective on statistics asserts that it makes sense to speak of a probability of an unknown parameter having a particular value. Given a model for an observed, noise-corrupted signal, we may use Bayesian methods to estimate not only the most probable value for each parameter but also their distributions. We present an implementation of the Bayesian parameter estimation formalism developed by G. L. Bretthorst (1990,J. Magn. Reson.88, 533) using the Metropolis Monte Carlo sampling algorithm to perform the parameter and error estimation. This allows us to make very few assumptions about the shape of the posterior distribution, and allows the easy introduction of prior knowledge about constraints among the model parameters. We present evidence that the error estimates obtained in this manner are realistic, and that the Monte Carlo approach can be used to accurately estimate coupling constants from antiphase doublets in synthetic and experimental data.     

Determination of the Tolman cone angle from crystallographic parameters and a statistical analysis using the crystallographic data base

Summary A new method of evaluating the Tolman cone angle from X-ray structural data available from the Cambridge Crystallographic Data Base has been developed and a statistical analysis of the cone angles of the phosphines PPh₃, PMe₂Ph, PMePh₂, PMe₃, PEt₃ and PCy₃ (Cy = cyclohexyl) in transition metal complexes has been completed.     

A goal programming approach to strategic resource allocation in acute care hospitals

This paper describes a methodology for allocating resources in hospitals. The methodology uses two linear goal-programming models. One model sets case mix and volume for physicians, while holding service costs fixed; the other translates case mix decisions into a commensurate set of practice changes for physicians. The models allow decision makers to set case mix and case costs in such a way that the institution is able to break even, while preserving physician income and minimizing disturbance to practice. The models also permit investigation of trade-offs between case mix and physician practice parameters. Results are presented from a decision-making scenario facing the surgical division of Toronto's Mount Sinai Hospital after the announcement of a 3-year, 18% reduction in funding.     

Noise-induced asymptotic periodicity in a piecewise linear map

We examine asymptotically periodic density evolution in one-dimensional maps perturbed by noise, associating the macroscopic state of these dynamical systems with a phase space density. For asymptotically periodic systems density evolution becomes periodic in time, as do some macroscopic properties calculated from them. The general formalism of asymptotic periodicity is examined and used to calculate time correlations along trajectories of these maps as well as their limiting conditional entropy. The time correlation is shown to naturally decouple into periodic and stochastic components. Finally, asymptotic periodicity is studied in a noise-perturbed piecewise linear map, focusing on how the variation of noise amplitude can cause a transition from asymptotic periodicity to asymptotic stability in the density evolution of this system.     

Finite Abelian actions on surfaces

Edmonds showed that two free orientation preserving smooth actions φ₁ and φ₂ of a finite Abelian group G on a closed connected oriented smooth surface M are equivalent by an equivariant orientation preserving diffeomorphism iff they have the same bordism class [M,φ₁]=[M,φ₂] in the oriented bordism group Ω₂(G) of the group G. In this paper, we compute the bordism class [M,φ] for any such action of G on M and we determine for a given M, the bordism classes in Ω₂(G) that are representable by such actions of G on M. This will enable us to obtain a formula for the number of inequivalent such actions of G on M. We also determine the “weak” equivalence classes of such actions of G on M when all the p-Sylow subgroups of G are homocyclic (i.e. of the form n(Z/pαZ)).     

Nitroxide‐mediated radical polymerization of 2‐(dimethylamino)ethyl acrylate and its sequential block copolymerization with styrene and N‐butyl acrylate

Nitroxide‐mediated radical polymerization (NMRP) of 2‐(dimethylamino)ethyl acrylate (DMAEA) was carried out at 100–120 °C, initiated by MONAMS, an alkoxyamine based on N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethylpropyl)nitroxide, SG1. Controlled polymerization can be achieved by the addition of free SG1 (the initial molar ratio of SG1 to MONAMS ranged from 0.06 to 0.12), giving a linear first‐order kinetic plot up to 55–70% conversion depending on the reaction conditions. The molecular weights show a near linear increase with conversion; however, they deviate to some extent with theoretical values. SG1‐mediated polymerization of DMAEA at 112 °C is also controlled in organic solvents (N,N‐dimethylformide, anisole, xylene). Polymerization rate increases with increasing solvent polarity. Chain transfer to polymer produces ～1 mol % branches in bulk and 1.2–1.9 mol % in organic solvents, typical of those for acrylates. From poly(styrene) (pS) and poly(n‐butyl acrylate) (pBA) macroinitiators, amphiphilic di‐ and triblock copolymers p(S‐b‐DMAEA), p(DMAEA‐b‐S‐b‐DMAEA), p(BA‐b‐DMAEA), and p(DMAEA‐b‐BA‐b‐DMAEA) were synthesized via NMRP at 110 °C. Polymers were characterized by GPC, NMR, surface tension measurements, and DSC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 414–426, 2006