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Niall,
With the live view on the Canon cameras, they generally have Exposure Simulation on which shows on the back LCD what the exposure will be like. So to get the alignment stars to be visible, try bumping the ISO to as high as you can (say 3200) and the shutter speed to something like 20 or 30 seconds.
I do that on my 40D and the alignment stars for my mount can be seen on live view on the camera.
Gus.
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