Absolute rate constants and Arrhenius parameters for hydrogen abstractions (from carbon) by the t-butoxyl radical ((t) BuO.) are reported for several hydrocarbons and tertiary amines in solution. Combined with data already in the literature, an analysis of all the available data reveals that most hydrogen abstractions (from carbon) by (t) BuO. are entropy controlled (i.e., TdeltaS > deltaH, in solution at room temperature). For substrates with C-H bond dissociation energies (BDEs) > 92 kcal/mol, the activation energy for hydrogen abstraction decreases with decreasing BDE in accord with the Evans-Polanyi equation, with alpha approximately 0.3. For substrates with C-H BDEs in the range from 79 to 92 kcal/mol, the activation energy does not vary significantly with C-H BDE. The implications of these results in the context of the use of (t) BuO. as a chemical model for reactive oxygen-centered radicals is discussed.

Merocyanine (MC) isomers that are formed after absorption of a UV photon by 1',3'-dihydro-1',3'-3'-trimethyl-6-nitrospiro[2H-1-benzopyran-2',2'-(2H)-indole] were studied. Several, predominantly TTC and TTT, merocyanine isomers are present in toluene solution ("T" and "C" indicate trans and cis conformations of the C-C bonds in the methine bridge). Excitation in the MC visible absorption band (at 490, 550, and 630 nm) with 100 fs laser pulses was used to study MC excited-state dynamics. Internal conversion on the picosecond time scale was found to be the dominant relaxation pathway. Excited-state isomerization reactions were also observed. Excitation at 630 nm (assigned to TTC isomer excitation) leads to formation of a third isomer (either CTC or CTT). Excitation at 490 nm (assigned to TTT isomer excitation) leads to more complex excited-state relaxation, including formation of two isomers: TTC (absorption at 600 nm) and CTC or CTT (absorption at 650 nm).

Low surface energy copoly(imide siloxane)s were generated via condensation polymerization reactions. The generated materials were characterized spectroscopically, thermally, mechanically, and via contact angle goniometry. The decrease in tensile modulus and opaque appearance of copoly(imide siloxane) films indicated phase segregation in the bulk. Preferential surface partitioning of the siloxane moieties was verified by X-ray photoelectron spectroscopy (XPS) and increased advancing water contact angle values (theta(A)). Pristine copoly(imide siloxane) surfaces typically exhibited theta(A) values of 111 degrees and sliding angles from 27 degrees to >60 degrees. The surface properties of these copoly(imide siloxane) films were further altered using laser ablation patterning (frequency-tripled Nd:YAG laser, 355 nm). Laser-etched square pillar arrays (25 microm pillars with 25 microm interspaces) changed theta(A) by up to 64 degrees. Theta(A) values approaching 175 degrees and sliding angles from 1 degree to 15 degrees were observed. ATR-IR spectroscopy and XPS indicated polymer chain scission reactions occurred as a result of laser ablation. Initial particle adhesion studies revealed that the copoly(imide siloxane)s outperformed the corresponding homopolyimides and that laser ablation patterning further enhanced this result.

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