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Sure, each column gets a className made of the 'yui-dt-col-' prefix plus a sanitized version of the column key (some questionable characters are replaced by underscores). So, you could use css to change that. However, defining a thicker border for that column on its own won't help much. Borders are already defined in the DataTable so you need to override those definitions and overriding them will require some reading:

http://www.satyam.com.ar/yui/widgetstyles.html