Design and synthesis of DNA-tethered ruthenium complexes that self-assemble into linear arrays

Ruthenium(II) bis(terpyridine) complexes have been prepared with two triethylene glycol linkers to which DNA sequences have been attached; hybridization at various complex ratios results in linear arrays of varying lengths.     

Metal-directed self-assembly of bimetallic dithiocarbamate transition metal cryptands and their binding capabilities

A novel family of redox-active dinuclear transition metal based cryptands self-assembled from dithiocarbamate ligands has been synthesised; depending upon the nature of the spacer groups these new cryptand systems have been shown to electrochemically recognise the binding of cations or anions.     

Isobutene polymerization using a chelating diborane co-initiator

Lewis acidic diborane 1 (J. Am. Chem. Soc. 1999, 121, 3244-3245) is highly effective for both proton- and cationogen-initiated isobutene polymerization in hydrocarbon media at low temperature. Reactions of diborane 1 with cumyl chloride and cumyl methyl ether were studied by variable-temperature 1H and 19F NMR spectroscopy. At low temperatures stable ion pairs 2a and 2b are formed; at higher temperatures these ion-pairs form phenyl-1,3,3-trimethylindan (3) with concomitant release of HCl to form 1 in the case of 2a or degradation of the anion (2b). Reaction between Ph3C-Cl and diborane 1 resulted in the generation of an ion-pair 4 consisting of the Ph3C cation very weakly associated with the chelated, mu-Cl counteranion as revealed by X-ray crystallography.     

An analysis of the Rayleigh-Ritz method for approximating eigenspaces

This paper concerns the Rayleigh-Ritz method for computing an approximation to an eigenspace of a general matrix from a subspace that contains an approximation to . The method produces a pair that purports to approximate a pair , where is a basis for and . In this paper we consider the convergence of as the sine of the angle between and approaches zero. It is shown that under a natural hypothesis--called the uniform separation condition--the Ritz pairs converge to the eigenpair . When one is concerned with eigenvalues and eigenvectors, one can compute certain refined Ritz vectors whose convergence is guaranteed, even when the uniform separation condition is not satisfied. An attractive feature of the analysis is that it does not assume that has distinct eigenvalues or is diagonalizable.

     

A statistical process control approach to selecting a warm-up period for a discrete-event simulation

The selection of a warm-up period for a discrete-event simulation continues to be problematic. A variety of selection methods have been devised, and are briefly reviewed. It is apparent that no one method can be recommended above any other. A new approach, based upon the principles of statistical process control, is described (SPC method). Because simulation output data are often highly autocorrelated and potentially non-normal, the batch means method is employed in constructing the control chart. The SPC method is tested on seven data sets and encouraging results are obtained concerning its accuracy. The approach is also discussed with respect to its ease of implementation, simplicity, generality of use and requirements for parameter estimation.     

Shifting the Superparamagnetic Limit of Nanosized Copper Iron Spinel

In this paper we analyze trend of EFG values measured at Cd impurity in a group of semiconducting delafossites with chemical formula CuBO₂ (B = Al, Fe, Cr, Nd). We conclude that this trend reveals one of the most subtle details in electronic spectrum of the compounds: if impurity states are formed within or out of the band gap. In CuAlO₂ and CuFeO₂ the Cd EFG exhibits larger value than in CuCrO₂ and CuNdO₂, when Cd substitutes the Cu atom. This occurs because in the first two compounds the Cd forms shallow band within the gap, and in the second two compounds does not. When Cd occupies the B position it exhibits almost the same EFG in all delafossites. In this case, Cd does not form its states within the gap in none of the compounds. To arrive to these conclusions we analyzed and calculated various systems (Cd-doped CuAlO₂ and CuCrO₂ compounds, fictitious molecules), using the FP-LAPW method.     

Renormalization-group improved calculation of top-quark production near threshold

The top-quark cross section close to threshold in e(+)e(-) annihilation is computed including the summation of logarithms of the velocity at next-to-next-to-leading-logarithmic order in QCD. The remaining theoretical uncertainty in the normalization of the total cross section is at the few-percent level, an order of magnitude smaller than in previous next-to-next-to-leading order calculations. This uncertainty is smaller than the effects of a light standard-model Higgs boson.     

Non-aqueous solvation of n-octanol and ethanol: spectroscopic and computational studies

Raman spectroscopy was used to examine the interactions of the free O-H bonds in n-octanol and ethanol with the organic solvents carbon tetrachloride (CCl(4)), cyclohexane, and benzene. These spectra reveal that the solvents CCl(4) and cyclohexane have a small effect on the free O-H peak of alcohols, whereas benzene as a solvent significantly red-shifts the free O-H band. Calculated spectra were generated via MP2/6-31G* calculations and the B3LYP/6-31+G**//MP2/6-31G*-derived Boltzmann populations of each ethanol complex and are consistent with the experimental results. Additional spectra were calculated using Boltzmann populations derived from single-point energies at the polarizable continuum model (PCM) level with the B3LYP/6-31+G** level of theory to take overall solvent effects into account, and these simulated spectra are also largely consistent with the experimental results. Analysis of the computational results reveals a lengthening of the O-H bond from the O-H interaction with the delocalized electronic structure of benzene as well as a bimodal distribution of the free O-H peak of the alcohol/benzene mixtures due to two distinctly different types of alcohol/benzene complexes.     

Optically pumped nuclear magnetic resonance of semiconductors

Optically pumped NMR (OPNMR) of direct gap and indirect gap semiconductors has been an area of active research interest, motivated by both basic science and technological perspectives. Proposals to enhance and to spatially localize nuclear polarization have stimulated interest in this area. Recent progress in OPNMR has focused on exploring the experimental parameter space in order to elucidate details of the underlying photophysics of optical pumping phenomena. The focus of this review is on recent studies of bulk samples of GaAs and InP, namely, the photon energy dependence, the magnetic field dependence, and the phase dependence of OPNMR resonances. Models for the development of nuclear polarization are discussed.