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In the same vein, does anyone have good links / articles to help someone who knows the basics of PHP/MySQL (like me) learn about larger apps?
This isn't an answer to your question exactly but you should definitely check this out if you're interested in large scale web app architecture. If you want to know about really big apps work look to Amazon:
# More than 55 million active customer accounts.
# More than 1 million active retail partners worldwide.
# Between 100-150 services are accessed to build a page.
...
It grew. For years the scaling efforts at Amazon focused on making the back-end databases scale to hold more items, more customers, more orders, and to support multiple international sites. In 2001 it became clear that the front-end application couldn't scale anymore. The databases were split into small parts and around each part and created a services interface that was the only way to access the data.
There are a lot of other articles on that site also.
