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This is a little more complicated than a straightforward yes or no. Smell in general is the result of a rather complicated physicochemical process in the nose. It is possible for substances that are not very similar chemically to produce quite similar smells, and it's equally possible for substances that are almost identical chemically to produce quite different smells. One good example is carvone: R-(-)-carvone smells like spearment, while S-(+)-carvone, chemically identical except for being the mirror image, smells like caraway.

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