Hi Jeet,
I am also looking for the same solution as I need to do this for the application that I am working on. I am also generating the PDF and user can then print it.
As you are saying that already developed apps are printing without using intermediate PC. But while searching over the net I came around an application which is useful for printing for Epson
http://mobile.eurosmartz.com/products/print.html
There it is mentioned by the company it self that "Install “Print” on your iPhone, download the free WePrint software for your desktop/laptop computer and then you can print directly from your iPhone."
Also there is another application on iTunes called "PrinterShare- print from iPhone to anywhere". There also they mentioned that computer connected to printer needs the PrinterShare software.
So I think there is a mediator present in these printings.
Let me know if you find some more information on this topic, as this is very new and clients are asking to avail this facility in there applications.
If you come to know any sample application
Regards,
Vishal.