Perylene synthesis by the parallel cycloaromatization of adjacent enediynes

As part of an investigation into new synthetic routes to poly(peri-naphthalene), the synthesis and cycloaromatization of tetraethynylbiphenyls is described. The temperature-dependent cyclization of biphenyls containing unsubstituted alkynes provides the desired perylene in good yield.     

Polymer-coated ferromagnetic colloids from well-defined macromolecular surfactants and assembly into nanoparticle chains

A novel synthetic route to polymer-coated ferromagnetic colloids of metallic cobalt has been developed. Well-defined end-functional polystyrenes were synthesized using controlled radical polymerization and used as surfactants in the thermolysis of dicobaltoctacarbonyl to afford uniform ferromagnetic nanoparticles. The presence of the polymer shell enabled prolonged colloidal stability of dispersions in a wide range of organic solvents and formed glassy encapsulating coatings around ferromagnetic cores in the solid state. These polymer-coated colloids assembled into robust, micron-sized nanoparticle chains when cast onto supporting surfaces due to dipolar associations of magnetic cores. Hierarchical assemblies were also prepared by blending polystyrene-coated cobalt colloids with larger silica beads.     

Tuning "kappticity" of tripodal ligands

The synthesis and structural characterization of a series of tripodal tris(phosphine) ligands, containing SiMe2 elbow groups, is described. The significant steric congestion in these ligands, due to the silylmethyl substituents, is manifest both in the solid-state structures and in the solution NMR spectra of the free ligands. Variable temperature 1H{31P} NMR studies of one of the ligands, CH3C(SiMe2PEt2)3 (4b) gave an estimated barrier to rotation around the Si-Capical bonds of approximately 10.4 kcal mol(-1). Octahedral kappa2- and kappa3-molybdenum complexes of these ligands also demonstrate the impact of the additional bulk imparted by the SiMe2 substituents, and the high Lewis basicity of these phosphines, with subtle changes at the apical and phosphine substituents changing the overall coordination chemistry observed.     

One-Dimensional Numerical Algorithms for Gradient Flows in the p-Wasserstein Spaces

We numerically approximate, on the real line, solutions to a large class of parabolic partial differential equations which are “gradient flows” of some energy functionals with respect to the L ^p -Wasserstein metrics for all p>1. Our method relies on variational principles involving the optimal transport problem with general strictly convex cost functions.     

Osmotic force resisting chain insertion in a colloidal suspension

We consider the problem of inserting a stiff chain into a colloidal suspension of particles that interact with it through excluded volume forces. The free energy of insertion is associated with the work of creating a cavity devoid of colloid and sufficiently large to accommodate the chain. The corresponding work per unit length is the force that resists the entry of the chain into the colloidal suspension. In the case of a hard sphere fluid, this work can be calculated straightforwardly within the scaled particle theory; for solutions of flexible polymers, on the other hand, we employ simple scaling arguments. The forces computed in these ways are shown, for nanometer chain and colloid diameters, to be of the order of tens of pN for solution volume fractions of a few tenths. These magnitudes are argued to be important for biophysical processes such as the ejection of DNA from viral capsids into the cell cytoplasm. Received 18 December 2002 Published online: 16 April 2003 RID="a" ID="a"e-mail: castel@chem.ucla.edu RID="b" ID="b"Present address: Courant Institute of Mathematical Sciences, NYU, New York, New York 10012, USA     

Additive NMR chemical shift parameters for deshielded methine protons

The use of additive parameters for the prediction of NMR chemical shifts is widely practised. However, no correlations are available for highly deshielded methine protons. In this work, methine chemical shifts have been studied using both multiple linear regression analysis and Simplex function minimization in an effort to determine under what limiting circumstances the additivity of shift parameters can be expected to apply. As expected, it was not possible to explain satisfactorily all methine shifts with a single set of substituent parameters. However, if only the deshielded cases were considered (H—CXYZ, where at least two of the three groups X, Y, and Z are electron-withdrawing), a much better set of parameters could be determined. Using a data set of 440 of these deshielded methine shifts, involving 31 different substituents, a standard error of estimate of 0.20 ppm is found for protons spread between 3.0 and 7.5 ppm.     

The first three anisotropy constants of nickel

The technique of ferromagnetic resonance at 23 GHz has been used to determine the first three anisotropy constants of pure Ni down to 4.2K. A temperature and orientation dependent linewidth has also been observed.     

Measurement of day and night neutrino energy spectra at SNO and constraints on neutrino mixing parameters

The Sudbury Neutrino Observatory (SNO) has measured day and night solar neutrino energy spectra and rates. For charged current events, assuming an undistorted 8B spectrum, the night minus day rate is 14.0%+/-6.3%(+1.5%)(-1.4%) of the average rate. If the total flux of active neutrinos is additionally constrained to have no asymmetry, the nu(e) asymmetry is found to be 7.0%+/-4.9%(+1.3%)(-1.2%). A global solar neutrino analysis in terms of matter-enhanced oscillations of two active flavors strongly favors the large mixing angle solution.