21-letter word
buckminsterfullerenes
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methionylglutaminylarginyltyrosylglutamylseryllleucylpheny
supercalifragilisticexpialidocious.
Kennethrobertofitzwaterayjameseepatriciacashiichelsayybrianaeasthamaiecaittlinapaigerboothean.
Bellybuttons would be the longest word I can think of beginning with a 'b' and ending in an 's'.
Could be whatchamacallit, 15 letters.