As far as I am concerned, mashing out when done properly is effectively pasteurisation. In fact, from my experiments with sour mashing, 50C is enough to kill most of the wild bugs on grain. I tend to think any spontaneous ferment after that is due to grain dust, etc dropping in on the cool-down.
There is a school of thought that day-after boiling results in a poorer break, as some of the proteins and tannins have had time to oxidise and form polymers. The effect, however, is fairly slight.