Clarification of "256 bit word" semantics.

EVM has "256bit words". Some cases treat strings shorter than 32 bytes (156 bits) as left-justified ascii (packed into the most significant bytes of the word).

Does this mean that the word value of the string '*' is equivalent to: 42 << 148 ?

Note that the RLP encoding of the single ASCII character '*' is two bytes, whereas the RLP encoding of 42 << 148 is different. Are there important edge cases for security and correctness where the EVM word semantics and RLP encodings don't quite match up?
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