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Due to luminescence (i.e fluorescing capability of molecule), which is inherently more sensitive then absorption. Imagine dark stadium, 1 flashlight turns on. You can see it. That's luminescence. Now imagine the stadium with 500 flashlights on and 1 gets turned on. You won't really notice, i.e. less sensitive, like absorption.

In luminescence and spectrofluorometry the background is dark with all the other non-fluorescing molecules. The ones the fluoresce are clearly seen and can be detected to individual molecules.

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