Splenda (sucralose) starts out it's life as simple table sugar, but it is undergoes a complex chemical process before it ends up in the little yellow packet. All sugars are composed of complexes of carbon, hydrogen, and oxygen in a 1:2:1 ratio. The Spleda-fying process removes 3 oxygen-hydrogen molecules from the sugar and replaces them with chloride ions. Chlorine, as you may know, is a noxious chemical that we tend to associate with acrid city water and an unpleasant burning sensation in the swimming pool, and in it's elemental state, it was kill you, quickly and painfully. However, when this horrid chlorine is bound to sodium (another extremely nasty element that explosively burns when it contacts water), it forms a chemical that we all know and love: table salt. So bollocks on all those wacko websites that rave on and on about the use of "unnatural" cholorine in Splenda; it's a bunch of codswollop. That said, the array of chemicals used to drive the -OH to -Cl substitution reactions are pretty damn noxious; you wouldn't want reach in to a half-baked batch of sucralose for a pinch of sweet in your morning joe. But by the time it reaches your table, it's been thoroughly purified of all the gross stuff.
Anyway, once all the alchemical magic happens, the resulting compound is rendered both 600 times "sweeter" than sugar and biochemically inert. The super-sweetness is the result of the alteration of the shape of the molecule, so that it stimulates "sweet" receptors in your mouth a lot more effectively. The no-cal part comes later. I haven't read the paper on the absorbtion and elimination of sucralose, so I don't know the exact mechanism of action. However, it seems as though it gets absorbed in the gut, rather than being directly excreted like the ill-fated fat-replacement, Olestra. So once it's floating around in your blood, it would seem that the same structural changes that make it more sweet on the tongue make it "invisible" to the bio-machinery that take nutrients in the bloodstream and turn them in to energy, fat, or something else---I'm not certain about this part though. It could just as easily be recognized by the body, but still be "unavailable" because the chlorine bonds require a lot more energy to break than the -OH bond. . .
The only thing that I did learn while looking into this matter (Can anyone guess who has a slow work day today?) is that there are two forms of Splenda out on the market. The stuff from the packet you pour into your coffee is only a tiny fraction Splenda and a lot of tasteless filler, so that you can measure it out like sugar without having your food 600X as sweet as you wanted it; this product is effectively 0 carb and safe for diabetics. The Splenda for Baking, on the other hand, is 1/2 Splenda and 1/2 unmodified sugar. This mix cuts down on the sugar content while maintaining some of the textural characteristics that sugar adds to food---this one could have a big impact on blood sugar levels, depending on how much was ingested; if you're using this product as part of a controled diet, you need to be aware that it doesn't give you carte blanche with the christmas pie.
Also of note, Splenda was legal in Canada for 8 years before the FDA allowed it into the US. So, in addition to thanking our neighbors to the North for most of our gasoline and timber, we should also recognize their contribution as our nation's human test subjects. :-O
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