You need to escape your string, you are looking for:
a.Replace("\\\"", "\"");
That should do it!
NOTE
Please note - just calling replace creates a NEW STRING VALUE it does not edit the original string. If you want to use this string you can do the replace inline or you can assign back to the original value like so:
a = a.Replace("\\\"", "\"");
That could also be another issue you are having!