Mid-infrared optical coherence tomography.

A time domain optical coherence tomography (OCT) system is described that uses mid-infrared light (6-8 microm). To the best of our knowledge, this is the first OCT system that operates in the mid-infrared spectral region. It has been designed to characterize bioengineered tissues in terms of their structure and biochemical composition. The system is based upon a free-space Michelson interferometer with a germanium beam splitter and a liquid nitrogen cooled HgCdTe detector. A key component of this work has been the development of a broadband quantum cascade laser source (InGaAs/AlInAs containing 11 different active regions of the three well vertical transition type) that emits continuously over the 6-8 microm wavelength range. This wavelength range corresponds to the so called "mid-infrared fingerprint region" which exhibits well-defined absorption bands that are specifically attributable to the absorbing molecules. Therefore, this technology provides an opportunity for optical coherence molecular imaging without the need for molecular contrast agents. Preliminary measurements are presented.

Probing the reactivity of photoinitiators for free radical polymerization: time-resolved infrared spectroscopic study of benzoyl radicals.

A series of substituted benzoyl radicals has been generated by laser flash photolysis of alpha-hydroxy ketones, alpha-amino ketones, and acyl and bis(acyl)phosphine oxides, all of which are used commercially as photoinitiators in free radical polymerizations. The benzoyl radicals have been studied by fast time-resolved infrared spectroscopy. The absolute rate constants for their reaction with n-butylacrylate, thiophenol, bromotrichloromethane and oxygen were measured in acetonitrile solution. The rate constants of benzoyl radical addition to n-butylacrylate range from 1.3 x 10(5) to 5.5 x 10(5) M(-1) s(-1) and are about 2 orders of magnitude lower than for the n-butylacrylate addition to the counterradicals that are produced by alpha-cleavage of the investigated ketones. Density functional theoretical calculations have been performed in order to rationalize the observed reactivities of the initiating radicals. Calculations of the phosphorus-centered radicals generated by photolysis of an acyl and bis(acyl)phosphine oxide suggest that P atom Mulliken spin populations are an indicator of the relative reactivities of the phosphorus-centered radicals. The alpha-cleavage of (2,4,6-trimethylbenzoyl)phosphine oxide was studied by picosecond pump-probe and nanosecond step-scan time-resolved infrared spectroscopy. The results support a mechanism in which the alpha-cleavage occurs from the triplet excited state that has a lifetime less than or equal to the singlet excited state.