Hello Wasy,
You can include escaped characters like "\06" (without quotes) in your command strings in the Instrument IO Assistant and it will send the value 0x06 to the serial port. You can also use VISA read/write to do this directly in LabVIEW. Note that there is currently an issue with sending a NULL character via the Assistant; if you need to send NULL "\00" characters, use VISA directly.
Hope this helps.
Scott B.
Applications Engineer
National Instruments