Preparation of macroscopic carbon nanohorn-based monoliths in polypropylene tips by medium internal phase emulsion for the determination of parabens in urine samples.

A porous monolithic solid based on single-walled carbon nanohorns dahlia-like structure, produced from a medium internal phase emulsion (MIPE), was prepared in a polypropylene tip using UV energy. Thus, single-walled carbon nanohorns (SWNHs) were added to the organic phase where they polymerized in the presence of a radical initiator. A cross-linker (ethylene dimethacrylate, EDMA) was also used in order to obtain a more robust structure. On the other hand, aqueous phase was the responsible for generating the pores in the final solid being inside the droplets generated by the surfactant (Pluronic L121) used to stabilize the polymerization emulsion. Variables related to the formation of the monolithic phase including the stability and composition of emulsion mixture, size of pores, solvent flow resistance and robustness, were studied in detail. In addition, the potential of the SWNH-monolith as extractant phase was evaluated using parabens as target analytes. The LODs ranged from 1 to 7 μg L, while the linear range was extended up to 5000 μg L. The reproducibility of the extraction procedure with different batches of emulsions was acceptable with RSD values < 16% and one prepared SWNH-tip can be used for more than 100 times without apparent extraction losses. The microextraction unit yielded an enrichment factor of 20 for all analytes (extraction efficiency of 100%), with recovery values between 80% and 116% in human urine samples.