$re = '/(\my_folder\/\w+\.xml)(?![\s\S]*\1)/m';
$str = 'my_folder/foo.xml::someextracontent
my_folder/foo.xml::someextracontent
another_folder/foo.xml::someextracontent
my_folder/bar.xml::someextracontent
my_folder/bar.xml::someextracontent
my_folder/hello.xml::someextracontent';
preg_match_all($re, $str, $matches, PREG_SET_ORDER, 0);
// Print the entire match result
var_dump($matches);
Please keep in mind that these code samples are automatically generated and are not guaranteed to work. If you find any syntax errors, feel free to submit a bug report. For a full regex reference for PHP, please visit: http://php.net/manual/en/ref.pcre.php