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Penicillin was accidentally discovered as a mold.
The first I can't answer... it's likely to be a herbal Chinese remedy, though quinine (used since 1600's) would be in the running too (found in tree bark).
Here's a list of other drugs accidentally found or invented
http://en.wikipedia.org/wiki/Serendipity#Pharmacology
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∙ 12y ago
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When was Egyptian medicine invented?
When Egyptians invented medicine
Why did the sumerians invented glass?
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Coke was invented by a pharmacist who accidentally added carbonated water to his medicine syrup to create somewhat of a HAPPY accident :D
What year was post it notes invented?
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