Initially, they looked at the electron, which had just been discovered. Physicists noticed that when a charged particle (like the electron) moves, it makes a magnetic field.
This magnetic field then pushes back on the particle, making it harder to get the particle moving faster.
It's the same effect as if the electron had some kind of hard-to-push mass stuff to it, which gave physicists the first idea that mass and energy (in this case, the energy of the magnetic field) could be more than just two different things.
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It was the positron, the first predicted particle of antimatter. In 1932, Caltech physicist Carl Anderson discovered the particle, and later physicists spotted the annihilation process Dirac had predicted as well.
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