Haha, it is not only a question of a structure layer ... no !
It is a combination of vignetting, saturation, desaturation, color balance, color shifting, tint and all this color stuff. It is possible to do this in photoshop and as well in LR or any other more sophisticated PP Software .... depends only on your skill and patience or your will to open your wallet: Such sets or action can be bougth as well...
see more of my work on http://www.klaweide.de ( some NSFW )
would u mind to tell me what is color shifting, tint in photoshop CS5 ?
i usually worked with Vignetting, saturation, color balance and selection color, but very hard to get this effects. pls advice