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Dunnt know if u r still interested in this question.
the TCA circle was proprosed by Krebs. but actually, the specific research of the mechanisms were done by other scienstists such as Maritus & Knoop who showed that citrate could be formed nonenzymatically from OAA and pyruvate with H2O2 in basic medium. it was already "common sense" to the scienstists at that time that the cirtrate->isocitrate->alpha-ketoglutarate->succinate->fumarate->malate->OAA.
But a small amount of any of the intermediate would result in increasing the total reaction significantly. So Krebs proprosed the TCA cycle by closing the rxn: pyruvate + OAA->citrate + CO2
that is what i learnt from a gentle professor from India. Guess you may find almost the same info from the text book. (any biochemistry book will give detailed info on it)
hope this will do a little for you.
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