Array
(
[0] => Array
(
[file] => /var/websites/example.com/assets/images/200px/1419050406e6648e1c766551a0ffc91380fd6ff3406002011-10-233750.
// your array
$array = array(...);
// will be used to store md5 hashes
$md5 = array();
// walk through array
foreach ($array as $key => $arr) {
// have we already seen this md5 hash?
if (in_array($arr['md5'], $md5)){
// remove element
unset($array[$key]);
}else {
// keep element, but add it's md5
$md5[] = $arr['md5'];
}
}