Ummm, why would you want PDF's? it's an inferior filetype for this task but if you do want PDF's you can find all the Oriely books online for free. Also, videos would be a very hard way to learn to code.
And VB.NET? You're paying to teach this? it's probably the easiest language i can think of...
Also, i thought i would help some people not waste there money on this guy that's clearly just trying to take it...
http://visual*basic.about.c*m/od/vbnetbeginnerbooks/The_VBNET_Books_for_Beginners.htm // You can pirate these online if you're into that.
http://www.startvb*dotnet.c*m/forms/default.aspx //A quick google search bought up some free stuff, there is better out there but i really don't have time, i'm late for work!
http://uk.you*tube.c*m/watch?v=e80rW9FeSVY //Oh, just to prove a point.
VB.NET is a BAD languge to start with, bad syntax and whatnot, it will give you bad programming habbits for when you want to move onto a proper language (C for example.)
Also, one on one support? why one on one when you can use a coding forum and get the help of lots of people?