Is it easy to customize Mastodon front-end or front-page like that ? Any pointers ?
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That instance just has a custom homepage written in React. The actual social UI is normal Mastodon with some color tweaks.
It is possible to use different frontends for Mastodon, though. Web apps like Elk can either run on a dedicated server to log into any Mastodon instance, or can be hosted by instance admins as alternative frontends.