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Chemistry 1894

Influence of Configuration on the Action of Enzymes

Emil Fischer

An enzyme cleaves only the molecular shape it fits — like a key in a lock.

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In depth · the introduction

An enzyme is a lock that only one shape of key can open — and Fischer found two enzymes whose keys were mirror images of each other.

The big idea

Enzymes are the cell's tireless workers: each speeds up one particular chemical reaction and almost no other. Emil Fischer asked the obvious, hard question — out of the thousands of molecules around it, how does an enzyme pick the single one it is meant to work on?

He built two sugars that were chemically identical except for the three-dimensional arrangement at one carbon — as alike, and as different, as your left and right hands. Then he handed them to two enzymes. Each enzyme seized only its matching "hand" and split it apart; the mirror-image sugar it ignored completely. The enzyme, in other words, was not reading the chemical formula. It was feeling the shape.

How it came about

By 1894 Fischer was the world's master of sugar chemistry. He had spent a decade painstakingly working out the exact three-dimensional shapes of the sugars — the achievement that would win him the 1902 Nobel Prize — so he was perfectly placed to make two molecules that differed by the smallest possible twist.

He took invertin, an enzyme from yeast, and emulsin, an enzyme from bitter almonds, and tried each on his two near-twin glucosides. Invertin attacked one form and not the other; emulsin did the exact opposite. To capture what he had found, Fischer reached for a homely image that has stuck ever since: enzyme and substrate must fit together "like lock and key."

Why it mattered

This is the seed of molecular recognition — the realisation that life works because molecules know one another by shape. It is why your body can run thousands of precise reactions without their interfering, and it is the founding idea behind modern medicine: nearly every drug is designed as a key, cut to fit one particular protein lock and as few others as possible.

A way to picture it

Think of a key and its lock. A key that is a hair's-breadth wrong — say, the mirror image of the right one — will slide partway in and then jam, opening nothing. Fischer's two sugars were exactly such mirror-image keys, and his two enzymes were the matching locks: each turned for one key only. A left glove on a right hand makes the same point — same fingers, same size, and still it will not fit.

Interactive enzyme specificity: choose invertin or emulsin and an α- or β-glucoside; a matching configuration seats the key in the lock and the bond is cut into glucose and methanol, while a mismatch will not fit at all.

Where it sits

Decades earlier Pasteur had noticed that living things prefer one mirror-form of a molecule over the other, but no one knew why. Fischer turned that hint into a mechanism: recognition by shape. His static lock was later given a flexible hinge by Koshland's "induced fit" (1958), and his binding step was made quantitative by Michaelis and Menten's kinetics in 1913 (also in this Library). From those two sugars runs a straight line to all of structural biology and to today's structure-based drug design.

The original document
Original source text
Emil Fischer · Berichte der deutschen chemischen Gesellschaft 27 (1894): 2985–2993
The question
Having just settled the spatial configurations of the sugars, Fischer asks whether an enzyme can tell those configurations apart — whether the three-dimensional geometry of a molecule, and not merely its composition, governs whether an enzyme will act on it.
The experiment
He prepares the two methyl-D-glucosides that differ only at the anomeric carbon — the α-form and the β-form — and offers each to two enzymes: invertin, from yeast, and emulsin, from bitter almonds. Invertin hydrolyses the α-glucoside but leaves the β untouched; emulsin does exactly the reverse. Each enzyme acts on one configuration and ignores its near-identical twin.
The conclusion — lock and key
Um ein Bild zu gebrauchen, will ich sagen, dass Enzym und Glucosid wie Schloss und Schlüssel zueinander passen müssen, um eine chemische Wirkung aufeinander ausüben zu können.
“To use an image, I will say that enzyme and glucoside must fit one another like lock and key in order to exert a chemical effect upon each other.” Fischer reasons that the enzyme must therefore itself be an asymmetric, optically active substance: its selectivity is a question of shape.
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Berlin · 1894