PubMed Health⌕ Search

Biomedical subjects

Stephen A Miller

Publications and source records attributed to Stephen A Miller.

8 recordsLinked to original sources
PubMed2006

An efficient and practical system for the catalytic oxidation of alcohols, aldehydes, and alpha,beta-unsaturated carboxylic acids.

Upon exposure to commercial bleach (approximately 5% aqueous sodium hypochlorite), nickel(II) chloride or nickel(II) acetate is transformed quantitatively into an insoluble nickel species, nickel oxide hydroxide. This material consists of high surface area nanoparticles (ca. 4 nm) and is a useful heterogeneous catalyst for the oxidation of many organic compounds. The oxidation of primary alcohols to carboxylic acids, secondary alcohols to ketones, aldehydes to carboxylic acids, and alpha, beta-unsaturated carboxylic acids to epoxy acids is demonstrated using 2.5 mol % of nickel catalyst and commercial bleach as the terminal oxidant. We demonstrate the controlled and selective oxidation of several organic substrates using this system affording 70-95% isolated yields and 90-100% purity. In most cases, the oxidations can be performed without an organic solvent, making this approach attractive as a "greener" alternative to conventional oxidations.

Journal Article↗
PubMed2005

Ene-diamine versus imine-amine isomeric preferences.

Cyanide-catalyzed aldimine coupling was employed to synthesize compounds with 1,2-ene-diamine and alpha-imine-amine structural motifs: 1,2,N,N'-tetraphenyletheylene-1,2-diamine (13) and (+/-)-2,3-di-(2-hydroxyphenyl)-1,2-dihydroquinoxaline (17), respectively. Single-crystal X-ray diffraction provided solid-state structures and density functional theory calculations were used to probe isomeric preferences within this and the related hydroxy-ketone/ene-diol system. The ene-diamine and imine-amine core structures were calculated (B3LYP/6-311++G(d,p)) to be essentially identical in energy (DeltaG = 0.2 kcal/mol in favor of the imine-amine, within the error of the calculation). However, additional effects-such as pi conjugation-in 13 render an ene-diamine structure that is slightly more stable than the imine-amine tautomer (14) (DeltaG = 0.2-0.7 kcal/mol, within the error of the calculation). In contrast, the intramolecular hydrogen bonding present in 17 significantly favors the imine-amine isomer over the ene-diamine tautomer (18) (DeltaG = 7.2-8.9 kcal/mol). For both 13 and 17, the optimized calculated structures (B3LYP/6-31+G(d')) are identical to those observed by single-crystal X-ray diffraction.

Journal Article↗
PubMed2005

The OH-initiated oxidation of 1,3-butadiene in the presence of O2 and NO: a photolytic route to study isomeric selective reactivity.

We report the study of the isomeric selective OH-initiated oxidation of 1,3-butadiene in the presence of O2 and NO using the LP/LIF technique. The photolysis of monodeuterated 1-iodo-3-buten-2-ol provides only one of the possible OD-butadiene adducts, the minor addition channel product, simplifying the oxidation mechanism. We find, based on analysis of OD time-dependent traces that prompt rearrangement of initial beta-hydroxyalkyl radicals to alpha-hydroxyalkyl radicals occurs in agreement with RRKM/ME theoretical predictions. We report a rate constant of (3.3+/-1.0) x 10(-11) cm3 molecules(-1) s(-1) for deuterium abstraction from the alpha-hydroxyalkyl radical at 298 +/-2 K. Our approach demonstrates the feasibility of isomeric selective kinetic studies of the OH-initiated oxidation of unsaturated hydrocarbons.

Journal Article↗
PubMed2005

Unprecedented syndioselectivity and syndiotactic polyolefin melting temperature: polypropylene and poly(4-methyl-1-pentene) from a highly active, sterically expanded eta1-fluorenyl-eta1-amido zirconium complex.

The structurally unique, sterically expanded eta1-fluorenyl-eta1-amido single-site precatalyst, Me2Si(eta1-N-tBu)(eta1-C29H36)ZrCl2.OEt2 (3), upon activation with methylaluminoxane (MAO), is remarkably active and constitutes the most syndioselective alpha-olefin polymerization catalyst system yet reported. 3/MAO affords as-prepared syndiotactic polypropylene with [rrrr] > 99% and unprecedented melting temperatures for the unannealed (165 degrees C) and annealed (174 degrees C) polymers. The activity of this system is 4 times that of the prototypical syndioselective catalyst Me2C(eta5-C5H4)(eta5-C13H8)ZrCl2/MAO. The high activity and syndioselectivity of 3/MAO can be extended to the production of syndiotactic poly(4-methyl-1-pentene) with a record melting temperature of 215 degrees C and [rrrr] = 97%.

Journal Article↗
PubMed2004

A sterically expanded "constrained geometry catalyst" for highly active olefin polymerization and copolymerization: an unyielding comonomer effect.

The 14 A octamethyloctahydrodibenzofluorene moiety has been incorporated into a sterically expanded constrained geometry catalyst, Me2Si(eta1-C29H36)(eta1-N-tBu)ZrCl2.OEt2 (1). The solid-state structure suggests that the activated olefin polymerization catalyst is quite spatially accessible, rationalizing its extraordinary reactivity toward alpha-olefins. 1/MAO (MAO = methylaluminoxane) can be more reactive toward alpha-olefins than toward ethylene and exhibit activities that are linearly and continuously proportional to 4-methyl-1-pentene or 1-octene concentration in their copolymerizations with ethylene.

Journal Article↗
PubMed2004

Cyanide-catalyzed cyclizations via aldimine coupling.

Aldimine coupling (AIC) is the nitrogen analogue of the benzoin condensation and has been applied to dialdimines, providing the first examples of cyclizations effected by cyanide-catalyzed AIC. Sodium cyanide promoted the facile, intramolecular cyclization of several dialdimines in N,N-dimethylformamide, methanol, or methylene chloride/water (phase-transfer conditions) yielding a variety of six-membered heterocycles. Under aerobic conditions, an oxidative cyclization occurs to provide the diimine heterocycle. Oligomerization was observed with rigid dialdimines for which cyclization was precluded.

Journal Article↗
PubMed2004

Aftershocks driven by a high-pressure CO2 source at depth.

In northern Italy in 1997, two earthquakes of magnitudes 5.7 and 6 (separated by nine hours) marked the beginning of a sequence that lasted more than 30 days, with thousands of aftershocks including four additional events with magnitudes between 5 and 6. This normal-faulting sequence is not well explained with models of elastic stress transfer, particularly the persistence of hanging-wall seismicity that included two events with magnitudes greater than 5. Here we show that this sequence may have been driven by a fluid pressure pulse generated from the coseismic release of a known deep source of trapped high-pressure carbon dioxide (CO2). We find a strong correlation between the high-pressure front and the aftershock hypocentres over a two-week period, using precise hypocentre locations and a simple model of nonlinear diffusion. The triggering amplitude (10-20 MPa) of the pressure pulse overwhelms the typical (0.1-0.2 MPa) range from stress changes in the usual stress triggering models. We propose that aftershocks of large earthquakes in such geologic environments may be driven by the coseismic release of trapped, high-pressure fluids propagating through damaged zones created by the mainshock. This may provide a link between earthquakes, aftershocks, crust/mantle degassing and earthquake-triggered large-scale fluid flow.

Journal Article↗