The sign bit is the most significant bit on any two's-complement machine (like the x86), and thus will be in the last byte in a little-endian format
Just cause i didn't want to be the one not including ASCII art... :)
/---------------first byte ------------\ /--------------second byte-------------\
+-------------------------------------------------------------------------------+
| 0 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 |
+-------------------------------------------------------------------------------+
sign bit -----^
Bits are basically "backwards" from how most people think about them, which is why the high byte is last. But it's all consistent, and "bit 15" comes after "bit 0" just like other addresses work. You don't have to do any bit twiddling, because the hardware talks in terms of bytes at all but the lowest levels -- so when you read a byte, it looks just like you'd expect. Just look at the most significant bit of your word, or the last byte of it (if you're reading a byte at a time), and there's your sign bit.
Note, though, that two's complement doesn't exactly designate a particular bit as the "sign bit". That's just a very convenient side effect of how the numbers are represented. For 16-bit numbers, -x is equal to 65536-x rather than 32768+x (which would be the case if the upper bit were strictly the sign).