That is awesome background and great response Just what I was after.
Just an update, I in fact did failover to my secondary node, update the iSCSI settings on my primary node, re synced and failed back to the primary.
Then put each of my VM host machines into maintenance mode (in a DR config meant they migrated all running VM's to my other hosts). Adjusted the iSCSI settings in ESXi and brought the host back online, repeated this for all my hosts.
It has made a VERY noticeable difference to my whole VM setup. "by the seat of your pants feel" things are remarkable more snappy in there response inside the VM guests.
Now the last step for me is the tweak on drbd, as I have BBU controllers on each node (disable barrier checks etc). But I think this one will have to be a complete outage to do.