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Does anyone know what size nut I need to replace this on the back of a Shimano 105 rim brake caliper?

I can’t help you with the nut but from that photograph your rim is very worn and needs checking professionally. Worn rims and high pressure tyres are a safety concern, if you’re lucky you’ll get a warning when your brakes start rubbing, if you’re unlucky the rim will go pop and the tyre deflate rapidly. I’ve seen plenty of examples where the rim has split, in some cases cutting the rider from the razor sharp shards of metal. Please get it checked.
your rim is very worn and needs checking professionally
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Ossify: thanks for that - I've got to admit to having been a bit lazy and hoping that someone already knew the measurements 🙂 I'll measure it up tonight
Wheelsonfire1: interesting - it's an el-cheapo from Superstar which I've used through 3 winters (all conditions), and at a guess approx 4-5k miles. I guess you might be right.
Well, they do seem to come in pairs. But, it has to be said, seem a bit like a design afterthought.

This is a very worn rim that demonstrates how the pressure from the tyre acts on the wall of the rim with potentially catastrophic consequences!
I may have exploded a rear rim on my commuter - used to get just 18 months from a rim on the rear.
I may have exploded a rear rim on my commuter – used to get just 18 months from a rim on the rear.
I had that on my Surly. The reason was that I was using the Tektro cantilever brakes which squealed like and absolute banshee. I got used to only using my front brake in emergencies and when I wanted to let people know I was annoyed at their driving/walking, relying on the rear brake for all other braking.
I switched to Vs after I realised replacing rear rims was going to be a twice a year job if I carried on like that.
That's a very worrying photo that wheelsonfire posted - had me rushing off and checking all my rims asap...then I remembered they're all disc brakes now!