Development of a Surface-Enhanced Raman Spectroscopic Methodology to Detect Immobilized Organic Materials in Biogeological Contexts.

The likelihood of finding intact cellular structures on the surface or in the near subsurface of the martian regolith is slim, due in part to the intense bombardment of the surface by ionizing radiation from outer space. Given that this radiation is predicted to be so intense that it would render a living cell inactive within minutes, it is logical to search for evidence of microbial life by looking for molecules produced by the breakdown of cellular matter. This "pool" of molecules, known as biomarkers, consists of a range of species with various functionalities that make them likely to interact with minerals in the martian regolith. Raman spectroscopy, a molecularly specific analysis method utilized for detecting organic biomarkers among inorganic geomaterials, suffers from low signal intensity when the concentration of organics is as low as it appears to be on the martian surface. This article describes the utility of a surface-enhanced Raman spectroscopy (SERS) method used to detect extremely low levels of biomarkers that were passively adhered to mineral surfaces in a method that represents how this interaction would take place in a natural environment on Mars. The methodology showed promise for the detection of multiple classes of biomarkers.

Investigation of polymorphic transitions of piracetam induced during wet granulation.

Piracetam was investigated as a model API which is known to exhibit a number of different polymorphic forms. It is freely soluble in water so the possibility exists for polymorphic transformations to occur during wet granulation. Analysis of the polymorphic form present during lab-scale wet granulation, using water as a granulation liquid, was studied with powder X-ray diffraction and Raman spectroscopy as off-line and inline analysis tools respectively. Different excipients with a range of hydrophilicities, aqueous solubilities and molecular weights were investigated to examine their influence on these solution-mediated polymorphic transitions and experimental results were rationalised using molecular modelling. Our results indicated that as an increasing amount of water was added to the as-received piracetam FIII, a greater amount of the API dissolved which recrystallised upon drying to the metastable FII(6.403) via a monohydrate intermediary. Molecular level analysis revealed that the observed preferential transformation of monohydrate to FII is linked with a greater structural similarity between the monohydrate and FII polymorph in comparison to FIII. The application of Raman spectroscopy as a process analytical technology (PAT) tool to monitor the granulation process for the production of the monohydrate intermediate as a precursor to the undesirable metastable form was demonstrated.