When my baby was smaller, I pumped both sides of my breasts during midnight if he only nurse one side. Because i felt that the breast (the side he nursed) was still full. I also read that emptying the breasts will increase milk supply. Subsequently when he was older and he drank more, i would only pump one side if he nursed the other side only. And when he started solids, the milk supply dropped and his demand dropped. He woke up to nurse one side and I stopped pumping as the breast is not that engored any more.
You could try pumping the breast that is unused while baby is nursing on the other. Lots of my friends do that, because it saves time and apparently they can get alot of milk pumping with baby nursing on the other side. When baby breastfeeds, relaxing hormones are released and this helps with the release of the milk during pumping. It takes some practice to balance both baby and pump but once you get the hang of it, works like a dream :)
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If you want to build a stash, you can pump on the other side. Else, just let your supply regulate to meet your baby's demands.