An ex vivo headspace gas chromatography-mass spectrometry method for the determination of short-chain siloxanes in silicon oil tamponades used in ophthalmic surgery.

Being able to facilitate retinal reattachment by preventing water migration into the subretinal space, silicone oils are widely used as long-term intraocular tamponade to treat cases of retinal detachment. Various commercial tamponades constituted by linear polydimethylsiloxane polymers with different molecular weights and cyclic impurities are available. In this study, for the first time, an untargeted headspace-gas-chromatography-mass spectrometry (HS-GC-MS) method was developed to identify low-molecular weight contaminants in three different types of silicone oil tamponades, namely Siluron 2000, RS-OIL ECS5000 and Densiron Xtra. Both commercial and post-operative tamponades were analysed to screen for the different classes of compounds present in the samples. The most abundant classes were short-chain siloxanes, fluorinated compounds, and hydrocarbons. To quantify the siloxanes present in the samples, a targeted HS-GS-MS was optimized using a central composite design and validated according to guidelines for bioanalytical methods. Lower limits of quantification in the low μg/L range, good precision with RSD% < 12% and accuracy with recovery rates in the 81 ( ± 7) - 96 ( ± 4) % range were achieved. Short-chain siloxanes were quantified in both commercial and post-operative tamponades, being the RS-OIL ECS5000 characterized by the highest concentration levels of the investigated analytes. By contrast, Densiron Xtra tamponades showed the lowest amount of short-chain siloxanes, observing a general decrease in their concentration levels according to the residence time in the eyes.