What’s Your Favorite Phosphate Polymer?

February 9th, 2007

I realize that posting a picture of an old bottle is not the most original idea for a blog post, but I can’t resist. I recently came across the following reagent in our bioroom:

That’s a whole kilogram of white, powdery RNA. Countless yeast cells gave their lives so that their nucelic acids could hydrolyze in our stockroom. The bottle is quite possibly a relic of my boss’s tenure at MIT (pre-1982). This particular RNA has an associated CAS number (63231-63-0), and the MSDS says it has a shelf life of three years. Oh well. I used it anyway, because I’m cheap and impatient.

I’m interested in finding a commercially-available polymer that contains phosphate. Is there anything besides RNA, DNA, and polyphosphates that I don’t know about? Any help is appreciated.

Previous Comments

  1. Mitch Says:
    February 9th, 2007 at 3:39 am If you place it on a hotplate and heat it up, will it polymerize or would it stay a powdery mess?


  2. milkshake Says:
    February 9th, 2007 at 3:49 am Casein is full of phosphotyrosines (as Ca salt). If you bind out the calcium (by adding lemon) or if you cleave off phosphates with chymosine, the milk protein will precipitate out…
  3. Paul Says:
    February 9th, 2007 at 5:15 am I think it was powdery to begin with. I’m not sure why the shelf life is only three years–nothing obvious besides slow oxidation or hydrolysis comes to mind. I bet the vast majority of this stuff is what it is supposed to be.
  4. excimer Says:
    February 9th, 2007 at 9:55 am I’m sure you can buy phosphorylated polystyrene somewhere… I don’t know where (aldrich?) but it must be pretty easy to make.
  5. joel Says:
    February 9th, 2007 at 11:52 am You could search for dental bond.

    Or, better, you could really impress George and get ahold of some phosphated silicone polyethers. Siltech sells them.

  6. Uncle Al Says:
    February 9th, 2007 at 12:43 pm Take a poly(vinyl alcohol) copolymer and phosphorylate it, P(III) hookup to P(V) product via aqueous triiodide oxidation being a nice path.

    Take an omega-hydroxyalkyl phosphate or phosphonate ester, make the (meth)acrylate, free radial polymerize (ethyl acetate, ~0.1-0.5% VAZO 88, vacuum ampoule; ramp up the waterbath temp to 70 C over a day or two and let sit hot for a week; half life of 10 hours at 88 C.) AIBN sucks for cage recombination and toxic recombination product. If you want spacing or dilution, copolymerize with methyl (meth)acrylate. Methacrylates are glassy, acrylates are rubbery/gooey.

    Patience with the polymerization or you will get crappy MW (chain recombination instead of growth) and suddenly messily eaten by the Trommsdorff effect. No oxygen or other polymerization inhibitors in there.


    If you like inorganic, zirconium phosphate or synthetic zirconium phosphonates. Just about any phosphonic acid or mixture thereof will give you graphitic zirconium phosphonate. The odd groups out sit in the interlammellar gaps, alternately pointing up and down. It’s scut lab synthesis but you *will* need a fumehood.

  7. milkshake Says:
    February 9th, 2007 at 1:22 pm One thing you can do is to take ethanolamine-O-phosphate (buy or make by dehydratation of ethanolamine with 85% H3PO4 – very easy prep). Make disodium salt of it and take some reactive polymer (they sell poly-maleinanhydride, for example) and couple the two together.
  8. Uncle Al Says:
    February 9th, 2007 at 5:49 pm Aldrich: poly(styrene-co-maleic anhydride), poly(methyl vinyl ether-alt-maleic anhydride), poly(maleic anhydride-alt-1-octadecene). Those are reasonably cheap (hair gel goo as the salts). Take ethanolamine-O-phosphate in N-methylpyrrolidinone to make the amidic acid. Doctor knife onto glass plates, desolvate in an oven, dehydrate to the imide films. Or dehydrate in solution with azeotropic removal of water. Look up the synthesis of Kapton and such.

    Basionic BC 01 (1-ethyl-3-methylimidazolium acetate) can dissolve 25 wt-% of cellulose (cotton). Phosphorylate it in solution.

    JACS 124 4974 (2002)

    Start with a soluble cellulose like methyl, ethyl, hydroxypropyl, carboxymethyl… Cellulose dissolves in (LiSCN or LiCl)/DMF, doesn’t it? Here’s something to shiver your timbers: US Pat. 4480091. N-methylmorpholine-N-oxide dissolves cellulose (Lyocel process) but higher temps boom boom the solvent.

  9. Paul Says:
    February 9th, 2007 at 10:55 pm Thanks, everyone. I’ll acknowledge you guys if it makes it anywhere.
  10. milkshake Says:
    February 10th, 2007 at 4:30 am I realized I had a procedure for ethanolamine-O-phosphate in my old thesis:

    In a 1L round flask, 95g of 85% H3PO4 (808 mmol) plus ice (100g) mixture was combined with ethanolamine 50g (819 mmol) with stirring (exothermic). The resulting solution was heated on oil bath at 185C under water-aspirator vacuum (20 Torr). After 3 hours, when the foaming ceased, the flask was cooled and 1 mL of water was added along the flask wall. The crystallization was induced by cratching the flask wall with a spatula. The mixture was left to crystallize at +5C in a fridge for 6 hours, the precipitated solid was collected by a fast filtration using a large coarse-porosity fritted Buchner funnel. The obtained crude solid product was dissolved in water 150mL. Two small spoons of charcoal were added, the mix was gently refluxed for 10 min, cooled, filtered. The obtained pale yellow filtrates were diluted with hot ethanol to the point of cloudiness. The mixture was allowed to crystallize in a fridge overnight. The crystallized product was collected by filtration, dried by suction and on highvac. Y=57.6g (50.5%) of a pale-yellow crystalline solid, m.p. 230-234C(dec.)

    I think this procedure came from the old Houben-Weyl german monography

    In next step I used it for making N-palmitoylethanolamine-O-phosphoric acid Ba salt (0 to RT, THF-water-NaOH, palmitoyl chloride at 0C to RT, then BaCl2 at 70C)

  11. Paul Says:
    February 10th, 2007 at 4:33 am Cool, thanks. That procedure should be immediately co-posted to Org Prep Daily. The ghost of Woodward demands it!
  12. milkshake Says:
    February 10th, 2007 at 7:06 am OK, it is there now. Also, I have to apologize – there is an omissilon in the procedure that I posted here in the comment section – when I was translationg it I have inadverently skipped the part when you concentrate the ethanolamine-phosphoric acid aqueous solution on rotavap (before dehydrating it on oil bath).
  13. Wolfie Says:
    February 13th, 2007 at 2:42 am I have one for you. Polyphosphazene. If you consider the P=N bonds as two hydrolyzed and then reconfirmed P-O bonds, it works.

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