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Let's say you take two existing drugs that they have been patented already (and may or may not have expired). You add them in a mixture of specific ratio without changing their chemical structure. You clinically test them for a particular disorder and let's say you find that your mixture has a significant therapeutic advantage. This advantage may or may not be due to any complex synergy, it could only be due to the mere fact that you co-administer them.

Would your mixture be patentable in the above scenario? Are there any prerequisites or potential pitfalls (e.g. the previous individual patents need to have expired)?

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I would guess so. You can even get a new patent on an existing drug for use on a different disease. It would help if the mechanism for the synergy was not an obvious thing to someone skilled in the art of drug development or use. The existing patents, perhaps on the manufacturing of the drugs might keep you from being able to market the combination without a license.

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