There are no programs that I know of that will allow you to edit mobi's on-the-fly. Basically because all of the details of the mobi format are not known (it's proprietary).
If the Calibre to epub->Sigil edit->Calibre to mobi approach is less than satisfactory, you can try unpacking the mobi with mobiunpack.py (search these forums for a download link), editing the source and converting it back to a mobi with MobiPocket Creator or Kindlegen.
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