This is for an older version of Cassandra. Keys are now treated as default hexadecimal bytes, so you need to:
set User[utf8('jsmith')]['first'] = 'John';
or do:
assume User keys as utf8;
set User['jsmith']['first'] = 'John';
Or, as noted in the document in the document:
. Cassandra 0.8, _validation_class :
update column family User with key_validation_class=UTF8Type;