What makes stain removers work?

Most stain removers are made to breakdown oils and other non-polar substances. Since water is polar, it will only dissolve things that are polar. Stain removers usually contain enzymes that help break-up the things that water can't Specific enzymes will bind to their substrates (The stain) and break them down.

For example, proteases (enzyme) will be use to break proteins (substrate) down. A stain containing protein will be removed easily depending on what the stain contains and what enzymes the stain remover contains.

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