VOB is short of DVD Video Object developed to save all audio and video data of MPEG2. It includes many data streams of video, audio and subtitles. Vob mainly contains 2 types of data: simple data including files, catalogues and its each version and complicated data like branch, labeling and record of incidents, etc., whose structures and formats are determined by vob Schema.

To synchronize/sync vob file, you may first install a DVD player based on Microsoft DirectShow technology on your Windows. VISTA has bundled vob decoder. 

Download Audio Video Synchronizer which can synchronize/sync audio/video of vob file. Click the Options button, select Output Format with WMV. If the vob files are protected or encrypted, the synchronization will fail.

MPE is a kind of mpeg file extension.  Install the proper mpeg decoder first, then you can sync mpe.