Nullification, the theory that states may invalidate federal law they declare unconstitutional, was first proposed in 1798. Since that time, attempts by state to engage in Nullification have been declared unconstitutional in 1809, 1813, 1819, 1821, 1824, 1832, 1842, 1859, 1958, and 1960. So yeah, the Supreme Court is pretty sure Nullification isn’t constitutional.