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I vaguely remember running into an issue with published Word some years ago. Have trawled back through my email and found something. Word has (or at least did in 2013) an odd dependency on the desktop folder in the profile. This was being excluded and causing issues in Word. Not sure if related to your issue, but see this CTX article. https://support.citrix.com/article/CTX130329/error-word-cannot-open-the-existing-file-normal

This also reminds me of a similar issue. I believe @Scott Knights is right on the money. I had blocked certain top-level folders from syncing with the UPM profile and messed up Office apps. We had to get them added back to the profile.