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For internet URLs, you can get half way there by making Maxthon or Opera your default browser to cause UR to open externally in that browser.
For local file items, use the item's Explorer context menu (Item | Show Explorer Menu or Ctrl+right-click or Ctrl+E). On XP, the menu has an Open With option where you can choose which program to open in (it also remembers previously chosen applications for that file type).
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