The absorption and fluorescence sensing properties of liquid-immersed exposed-core microstructured optical fibers are explored for the regime where these structures act as supported nanowires with direct access to the sensing environment. For absorption-based sensing we demonstrate that the amount of power propagating in the sensing region of the exposed-core fiber can compete with that of traditional MOFs. For fluorescence-based sensing, we see that in addition to the enhanced fluorescence capture efficiency already predicted for small-core, high refractive index contrast fibers, an improvement of up to 29% can be gained by using liquid-immersed exposed-core fibers. Additionally, calculation of the losses associated with interfaces between filled and unfilled sections predict significant benefit in using high refractive index substrate glasses for liquid-immersed exposed-core fiber sensing. This work demonstrates that, for fiber dimensions of interest, the exposed-core fiber is an attractive new sensor technology.