Unimolecular dissociation of the CH3OCO radical: an intermediate in the CH3O + CO reaction

This work investigates the unimolecular dissociation of the methoxycarbonyl, CH(3)OCO, radical. Photolysis of methyl chloroformate at 193 nm produces nascent CH(3)OCO radicals with a distribution of internal energies, determined by the velocities of the momentum-matched Cl atoms, that spans the theoretically predicted barriers to the CH(3)O + CO and CH(3) + CO(2) product channels. Both electronic ground- and excited-state radicals undergo competitive dissociation to both product channels. The experimental product branching to CH(3) + CO(2) from the ground-state radical, about 70%, is orders of magnitude larger than Rice-Ramsperger-Kassel-Marcus (RRKM)-predicted branching, suggesting that previously calculated barriers to the CH(3)OCO --> CH(3) + CO(2) reaction are dramatically in error. Our electronic structure calculations reveal that the cis conformer of the transition state leading to the CH(3) + CO(2) product channel has a much lower barrier than the trans transition state. RRKM calculations using this cis transition state give product branching in agreement with the experimental branching. The data also suggest that our experiments produce a low-lying excited state of the CH(3)OCO radical and give an upper limit to its adiabatic excitation energy of 55 kcal/mol.     

New air-stable catalysts for general and efficient suzuki-miyaura cross-coupling reactions of heteroaryl chlorides

[reaction: see text] New air-stable PdCl(2){P(t)Bu(2)(p-R-Ph)}(2) (R = H, NMe(2), CF(3),) complexes represent simple, general, and efficient catalysts for the Suzuki-Miyaura cross-coupling reactions of aryl halides including five-membered heteroaryl halides and heteroatom-substituted six-membered heteroaryl chlorides with a diverse range of arylboronic acids. High product yields (89-99% isolated yields) and turn-over-numbers (10,000 TON) are observed.     

Orthogonal polynomials for refinable linear functionals

A refinable linear functional is one that can be expressed as a convex combination and defined by a finite number of mask coefficients of certain stretched and shifted replicas of itself. The notion generalizes an integral weighted by a refinable function. The key to calculating a Gaussian quadrature formula for such a functional is to find the three-term recursion coefficients for the polynomials orthogonal with respect to that functional. We show how to obtain the recursion coefficients by using only the mask coefficients, and without the aid of modified moments. Our result implies the existence of the corresponding refinable functional whenever the mask coefficients are nonnegative, even when the same mask does not define a refinable function. The algorithm requires rational operations and, thus, can in principle deliver exact results. Numerical evidence suggests that it is also effective in floating-point arithmetic.

     

Surface modification of poly(methyl methacrylate) for improved adsorption of wall coating polymers for microchip electrophoresis

The development of rapid and simple wall coating strategies for high-efficiency electrophoretic separation of DNA is of crucial importance for the successful implementation of miniaturized polymeric DNA analysis systems. In this report, we characterize and compare different methods for the chemical modification of poly(methyl methacrylate) (PMMA) surfaces for the application of wall coating polymers. PMMA surfaces coated with 40 mol% diethylacrylamide and 60 mol% dimethylacrylamide are compared to the PMMA surfaces first oxidized and then coated with hydroxypropylmethyl-cellulose or poly(vinyl alcohol) (PVA). PMMA oxidation was accomplished with UV/ozone or an aqueous solution of HNO(3) to yield hydrogen-bond donors for the spontaneous adsorption of the coating polymers. Contact angle measurements of UV/ozone exposed PMMA surfaces indicate increase in hydrophilicity, and polymer coated surfaces show a strong dependence on the coating polymer and the oxidation method. Fast and repeatable electrophoretic separations of a 10-base and 20-base DNA ladder were performed in PMMA micro CE devices. All analyses were completed in less than 10 min, resulting in the number of theoretical plates as high as 583 000 in a 7.7 cm long separation channel. The duration of UV/ozone treatment was found to have a considerable impact on separation performance. The microchips irradiated with UV for 10 min and coated with PVA as well as the microchips treated with HNO(3) and coated with HPMC were found to have the best separation performance. These results demonstrate facile and robust methods for the surface modification of PMMA enabling low-cost single use devices for electrophoretic DNA separations.     

The interval number of a complete multipartite graph

The interval number of a graph G, denoted i(G), is the least positive integer t for which G is the intersection graph of a family of sets each of which is the union of at most t closed intervals of the real line $\text{R}$. Trotter and Harary showed that the interval number of the complete bipartite graph K(m,n) is $\text{?}\text{(mn + 1)}\text{(m + n)}\text{?}$. Matthews showed that the interval number of the complete multipartite graph K(n₁,n₂,…,n_p) was the same as the interval number of K(n₁,n₂) when n₁ = n₂ = ? = n_p. Trotter and Hopkins showed that i(K(n₁,n₂,…,n_p)) ≤ 1 + i(K(n₁,n₂)) whenever p ≥ 2 and n₁≥n₂≥ ? ≥n_p. West showed that for each n ≥ 3, there exists a constant c_n so that if p ≥ c_n,n₁ = n²?n ?1, and n₂ = n₃ = ? n_p = n, then i(K(n₁,n₂,…,n_p) = 1 + i(K(n₁, n₂)). In view of these results, it is natural to consider the problem of determining those pairs (n₁,n₂) with n₁ ≥ n₂ so that i(K(n₂,…,n_p)) = i(K(n₁,n₂)) whenever p ≥ 2 and n₂ ≥ n₃ ≥ ? ≥ n_p. In this paper, we present constructions utilizing Eulerian circuits in directed graphs to show that the only exceptional pairs are (n² ? n ? 1, n) for n ≥ 3 and (7,5).     

Nuclear-magnetic-resonance shielding constants calculated by pseudospectral methods

We have developed an algorithm based upon pseudospectral (PS) ab initio electronic structure methods for evaluating nuclear magnetic shielding constants using gauge-including atomic orbitals (GIAOs) in the spin-restricted and spin-unrestricted formalisms of Hartree-Fock (HF) theory and density-functional theory (DFT). The nuclear magnetic shielding constants for both 1H and 13C calculated using PS methodology for 21 small molecules have absolute mean errors of less than 0.3 ppm in comparison with analytic integral results. CPU timing comparisons between PS methods and conventional methods carried out for seven large molecules ranging from 510 to 1285 basis functions demonstrate that the PS methods are an order of magnitude more efficient than the conventional methods. PS-HF was between 9 and 26 times faster than conventional integral technology, and PS-DFT (Becke three-parameter Lee-Yang-Parr) was between 6 and 21 times faster.