Active Sync Attachment limit Increase will override organization wide settings or not ?

Hello Folks, 

We recently changed the Active Sync Attachment limit to 50 MB from 10 MB in web.config file , but some how we are not able to send the messages over 35 MB is that due to that as our organization attachment limit size which is 35 MB. ?

Will internally also organization wide setting will applied or only when any email will send or receive from internet.

Thanks