In the first issue, Spider-Man inadvertently lets slip that he knows Mary Jane:
Mary Jane: Hey, how'd you know where I live? Spider-Man: (obviously covering) Uh... it... it's one of my special powers. (long, skeptical pause) Spider-Man: (embarrassed) Igottago.
In general whenever Spider-Man appears. Example is when he and Electro were fighting, Electro told Spidey to die. Spidey just said that Electro's mask makes him look like a doofus.
In Issue #13 of the first volume, Gwen Stacy happens to get caught up in a battle between Spider-Man and Sandman, and after it's finished calls up Mary-Jane to tell her all about it. However, whilst the action is exactly what you would see in any standard Spider-Man comic, the captions — and dialogue — are all exactly what they would be like if the action was being described and narrated by an excited, slightly hyperactive and breathless teenage girl, thus resulting in beautiful moments like:
Caption:And so they're fighting, right? And [Spider-Man's] all — Spider-Man: Hey, look at me! I'm Spider-Man! I'm cool! Caption:— and the other dude's all — Sandman: Yeah, whatever, loser. Spider-Man: I'm gonna jump right through you — even though it's gross — 'cause I'm all awesome and stuff! Hey Sandman, why do we keep fighting all the time? Sandman: Endangering the lives of innocent people is funner than anything! Duh! Spider-Man: That's right! I forgot! LOL!