Think about what “big endian” and “little end” mean.
Memory is a sequence (or on more interesting machines, several sequences) of bytes. For elements whose size is two or more bytes, the bytes of the element can be stored in memory in different orders, and the two most obvious orders are called the "big end" and "small end" (if you have three or more bytes, that is, more than two possible byte orders, and in any case, who says that int bits, for example, cannot be distributed across several bytes in a chaotic but fixed order?)
But for a sequence of bytes, the byte order is the byte order. The "big end" and "small end" are determined by the fact that the bits of the larger element are located in the byte array. For a sequence of bytes, they are stored in the order in which they are stored - there is no way for any other order. It’s like asking “could the numbers 1, 2, 3, 4 be something other than the numbers 1, 2, 3, 4?”, And, of course, they cannot.
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