Elucidating the structures of powerful fish toxins from algal blooms.

While I tend to focus my growing environmental paranoia on the accelerating and on going destruction of the planetary atmosphere, we are making huge "progress" (Thinkprogress) at destroying the other fluid phase that is responsible for life on this planet, specifically surface water bodies, even one very, very, very, very large surface water body, our planetary oceans.

Of course, the interaction of these two phases makes some of the destruction interrelated, for instance, the acidification of the oceans because of the release of the dangerous fossil fuel waste carbon dioxide into our favorite waste dump, the atmosphere, or the release of vast quantities of the highly neurotoxic element mercury from coal (and to a lesser extent dangerous natural gas) burning while we all wait, like Godot, for the grand Greenpeace inspired so called "renewable energy" nirvana that never comes.

Another mechanism by which we are destroying the oceans is by eutrophication, which is the result of the release of vast quantities of fixed nitrogen, ammoniacal compounds, nitrates and related compounds and mobilized phosphorous. This important effect has, for one example, destroyed huge swathes of increasingly destroyed Gulf of Mexico near the mouth of the Mississippi River because of our need for corn for um, food, and of course, the all important goal of serving our most important master and God, the automobile, which requires us to produce huge amounts of "renewable" ethanol, even as we hem and haw into the even more absurd "electric car" era.

I feel wonderful, all "renewally." You can be very popular if you're "renewally," but unpopular if you question this assumption about the form of energy abandoned in the early 19th century because most people lived short, miserable lives of dire poverty.

We're, um, rich today, at least the top billion or so of us.

Eutrophication's mechanism involves the explosive growth of algae, and often, besides depleting oxygen in waters, this algae generates highly toxic "natural" compounds.

We love "natural" stuff on this planet, to the point we're willing to kill ourselves.

A recent event along these lines was the microcystin poisoning of the water supply of several major Ohio cities two years ago because of an algae bloom, resulting in the shutting of the water supply of Toledo.

The toxin that shut off Toledo’s water? The feds don’t make you test for it.

Microcystin is a very interesting complex compound.

All this comes to mind because I happened to stumble upon a very interesting and fun paper in the primary scientific literature concerning a algal ichthyotoxins, Prymnesins.

The paper is interesting to analytical chemists, because of the wonderful 2D and 3D NMR experiments performed on a remarkably high field instrument operating at 800 MHz in a 18.7 Tesla magnetic field.

When I was a kid, I was real excited when I could get access to a 300 MHz instrument. Kids today have it wonderful, or would have it wonderful, if we hadn't done so much to kill their planet for them because we were so certain that wind and solar "could" provide all of their energy after we're all dead and they're living in a nirvana we never actually constructed, but were absolutely certain they would construct, unless of course, they're all wiped out because we were, um, wrong.

That's their problem, not ours.

I'm no longer an NMR kind of guy by the way; I'm more of a mass spec kind of guy, and there's some very nice high resolution mass spec work in this paper on the structural elucidation.

Here's a graphic with the structure of prymnesins superimposed over a 1D NMR and 3D NMR spectra:



This is an incredibly complex molecule, and apparently, the biochemical synthesis doesn't involve all that much sugar chemistry, despite the fused pyranosyl rings hydroxy functionalized rings. I'm inspired to look up the biosynthetic references just for fun. Those triple bonds on the side chain are relatively rare in biomolecules, which makes them also interesting.

Here's an excerpt from the introduction: