I ran into a similar issue with my laptop, and have had some very serious issues.
The upgrade is not so much, it blends certain files, creates some, and hides others.
This has been the best and worst "Upgrade" experience I have ever had with Windows, but it is no where perfect to be sure
Understand that over time you are going to notice more and more odd behavior and anomalies
In order to over come what you are describing, and to get Dexpot to behave, here is what I had to do:
1) If you have Dexpot set to start on login. Turn this off in settings:
2) Log off and login, or better yet; restart your system.
3) Once Windows is completely up and running; Right click on Dexpot (wherever you launch it from) and Run as Administrator
4) Once Dexpot is up and running; Go back into settings and make what ever changes you require. Create a profile if you like, I did
5) Re-Check the start with windows box in settings, if you start Dexpot with windows login.
6) log off and in again, or restart your system.
This corrected all the flaky issues I was having with Dexpot.
This is the operation I had to follow to get Dexpot to work as I needed it to work on an "Upgrade" system from Windows Vista to 7.
There is one other course of actions:
Install Dexpot in a folder that the Dexpot Core files are not UAC monitored.
I created a folder in C: call Program Files (Alternative). I use this file for self contained/Portable programs. It has the advantage of not being monitored by the UAC for Read/Write Operations, but will continued to be monitored by the UAC for operational actions.
Not so sure I suggest this course for the average individual, especially if you are using the UAC for a very secure system. Which I suggest for about 99% of my clients when I build them a custom system or do Tech Support for end users.