Living in Argentina I'd tell you it's a difficult thing. Something similar (although not that bad) happened here not long ago.
The things I could tell you worked here are really specific like knowing a guy that transfers money from here to the US, no receipts since it's not really a transfer (nor exactly legal). You gave someone he knew 100USD cash in the US, he gave your friend 95USD cash here. When someone wanted to do the same thing the other way around it worked mostly on the same way, but with a different cut.
Other than taking cash with you while visiting, sending it with someone you know that it's traveling there, or maybe bitcoin or similar as suggested (our price difference wasn't that big, so bitcoin buy/sell spread didn't make it convenient to send money that way).
The best thing I could suggest you is to search for someone who is Venezuelan near where you live, or any kind of community of Latin Americans, (or maybe look for Venezuelan Facebook groups) and ask them what methods work the best, I don't think you'll find tons of Venezuelans over here.
Since you seem to live near MIT and Harvard you could ask around if there's a Hispanic club or anything like that and ask for anyone from Venezuela that might me able to help you.
Good luck sending that help!