If your DBMS does not impose limitations on which table you select from when you execute an insert, try:
INSERT INTO x_table(instance, user, item)
SELECT 919191, 123, 456
FROM dual
WHERE NOT EXISTS (SELECT * FROM x_table
WHERE user = 123
AND item = 456)
In this, dual
is a table with one row only (found originally in Oracle, now in mysql too). The logic is that the SELECT statement generates a single row of data with the required values, but only when the values are not already found.
Alternatively, look at the MERGE statement.