Axially perpendicular offset Raman scheme for reproducible measurement of housed samples in a noncircular container under variation of container orientation.

An axially perpendicular offset (APO) scheme that is able to directly acquire reproducible Raman spectra of samples contained in an oval container under variation of container orientation has been demonstrated. This scheme utilized an axially perpendicular geometry between the laser illumination and the Raman photon detection, namely, irradiation through a sidewall of the container and gathering of the Raman photon just beneath the container. In the case of either backscattering or transmission measurements, Raman sampling volumes for an internal sample vary when the orientation of an oval container changes; therefore, the Raman intensities of acquired spectra are inconsistent. The generated Raman photons traverse the same bottom of the container in the APO scheme; the Raman sampling volumes can be relatively more consistent under the same situation. For evaluation, the backscattering, transmission, and APO schemes were simultaneously employed to measure alcohol gel samples contained in an oval polypropylene container at five different orientations and then the accuracies of the determination of the alcohol concentrations were compared. The APO scheme provided the most reproducible spectra, yielding the best accuracy when the axial offset distance was 10 mm. Monte Carlo simulations were performed to study the characteristics of photon propagation in the APO scheme and to explain the origin of the optimal offset distance that was observed. In addition, the utility of the APO scheme was further demonstrated by analyzing samples in a circular glass container.