$re = '/(?<=^|\s)(@[\w.]+)(?<!\.)/i';
$str = 'Hello, @username
Hello, @username.
Hello, @user.name.
Go to https://google.com/@username
@username says hello.
@user.name says hello.
';
preg_match_all($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