$re = '/(?:[BR]?|(?<!L)C)REF|^(?!\|)/';
$str = 'XYZ:MUMBAI UNIVERSITYCREF:PUNE UNIVERSITYBREF:DADAR UNIVERSITYRREF:KOLHAPUR UNIVERCITY LLCREF:SOLAPUR UNIVERSITY
';
$subst = "|\g<0>";
$result = preg_replace($re, $subst, $str);
echo "The result of the substitution is ".$result;
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