No. It's technically the OS that recognizes the RAM, if the OS only sees 3.5 gb, the program will only see 3.5gb. Plus a 32 bit OS won't run a 64 bit program (a 64 bit OS will run a 32 bit program though).
On the subject, if you have a 32 bit OS and Photoshop 32 bit, and your computer has 4 gb of RAM, you still won't be able to use all of it, and Photoshop will only address about 2.6 gb or so. There's a simple fix for this called the "3 gb switch". If you enable it, The OS will be able to use more of the RAM, meaning more of it will also be available to Photoshop (up to about 3.5 gb or so). If you don't enable it, no matter how much RAM you have, you're not using but a little more than half of it. Google 3 gb switch to find out how to enable it, it takes no more than 5 minutes.