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# The string these literals produce don't contains any "\".
my $string = "my string with \ and / slashes."; 
...
# It works.
$string =~ s/\Q$substring\E/\"$substring\"/gi;
print("$string\n");

my string with  and / slashes.
with  and / slashes
...
with \ and / slashes

my string "with \ and / slashes".