Set Appliance State:

Isolate Mains Power to appliance as per TOPs P4
Set Multimeter to DC Volts Set meter to measure DC Volts
CH Demand
Turn Hot Water Tap On
Isolate mains DHW at boiler isolation valve
Attach black lead to a suitable earth using a crocodile clip
WARNING! - Mains voltage is expected during test follow
TOPs P4 live testing procedure
Mains Power On

Measurement:

Allow the boiler to run in CH mode.
Place the red probe on pin 15 (green) on LV2
Monitor the voltage on the multimeter and open the DHW isolation valve - as the boiler recognises the DHW demand the multimeter display should be seen to fluctuate from 0 - 12 VDC a few times as the mode changes (some multimeters may show 0 - O.L or a negative voltage due to their response time - this is acceptable as are any voltage fluctuations on the multimeter display).
Does the voltage behave as expected?
Note:
The voltage will only be seen to flicker for a few seconds while the PCB switches between modes, repeat test from the start until you are confident of the result.