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I managed to break my office PC which is running Windows 7 and, rather than take the fight to the components while they are still more or less able to exercise at least some sort of control over the system while in Windows (even safe mode), I was wondering if effective decontamination can be carried out by booting into a Linux live CD?

Do such tools exist?

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Yes, as long as the live CD you use has software on it capable of finding and removing whatever specific malware you've caught - check to make sure you've got up to date virus definition files, for example.
Or you could boot to a live CD and download something then, while it's running (but obviously would have to re-download every time you boot).
Or get any old live CD and make sure you have all the AV stuff you need on a USB stick.

Have a look at the questions I've linked below, which investigate a similar theme and have several suggestions that I think may already provide a useful answer for you:

http://superuser.com/questions/88924/anti-virus-live-cd

http://superuser.com/questions/130389/live-cd-with-good-anti-virus-software-to-scan-repair-windows

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