On 03.07.2017 19:01, Otto Stolz via Unicode wrote:
Since German ist the only language using “ß” (if I am not mistaken), […]

Some old Sorbian (blackletter) orthographies also employed the ß. It was also 
used at the beginning of words where it was capitalised to Sſ at the beginning 
of sentences or similar. I am not aware of all-caps being used (which was very 
rare in blackletter in general).

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