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Treatment of the sides of the mouth may affect nearby muscles that can produce an unwanted effect such as an unequal smile or difficulty in pursing the mouth on that side. If you have a droopy corner of the mouth, then the depressor anguli oris (DAO) muscle can be injected to help lift these corners, but the injection site is close to the jaw margin, not a the corner of the mouth.
Yes, you can use Botox to correct a variety of conditions around the mouth and lips, such as a gummy smile, smoker's lines, drooping mouth, uneven lips, etc. However, it takes a great deal of experience to inject in this area and get a good outcome. Take your time finding an expert injector. I hope this helps.
Botulinum Toxin (Dysport and Botox) is not a filler around the mouth but may ease the "lipstick" lines that appear with pursing of the lips. It also can ease the muscle which pulls down the corners of the mouth called the Depressor Anguli Oris
Botox (and Dysport) works by relaxing hyperactive muscles that cause wrinkles, such as the vertical lines between the eyebrows from scowling and the crow's feet lines by the eyes from squinting. Dermal fillers such as Restylane and Juvederm are used to fill in furrows, such as the groove that runs from the nose toward the corner of the mouth. Botox may be used for "smoker's lines" since it would relax the muscles of puckering, but it is an advanced application so you need to go to someone experienced.
Botox can be used to inject the depressor anguli oris muscle which pulls the corners of the mouth down. Botox injection would temporarily weaken this muscle and cause the corners of the mouth to come up. This should be performed by a skilled professional as injection in the wrong area can lead to a crooked smile.