The Flemish Primitives: Glowing lollipops (part 4)

Bruce Bryan demonstrated a glowing cocktail drink (top left), and tempted us with fluorescent cake frosting (top right). The chocolate surprise boxes included a lollipop (bottom left) and I was quite busy sucking the lollipop, listening to the translation of the Belgian/French/Spanish contributions, taking notes and photographing at the same time (bottom right).

The chocolate surprise box was one of the highlights at The Flemish Primitives that I’ve blogged about three times already. As I promised you in the last post I’d come back to the lollipop that was included in the box. Between chocolates number 2 and 3 Bruce Bryan entered the stage. The lights went off, we were instructed to suck intensely on the lollipos and then – when I took the lollipop out of my mouth it was glowing! I was sitting in the front row, but as I turned around I saw a fully packed auditorium of people sticking out their glowing tongues and holding a glowing lollipop in their hands. The only sound you could hear was a whispering choir of “wows”. That was quite amazing!

Bruce Bryan is a medical doctor by profession but he now spends most of his time trying to secure funding for his inventions related to bioluminescence. His primary invention is related to the use of green fluorescent proteins in combination with luciferin/luciferases as tumor markers by combining them with appropriate antibodies. I’m not able to explain the details, but you can find more information on Bruce’s homepage. The take home message is that it for instance can improve cancer surgery by litterarily being a “guiding light” for the surgeon.

Bioluminescence is emission of light by living organisms. Glow worms (which include Fire flies) and dinoflagellates are among the best known. Most dinoflagellates are marine plankton and they glow when the water is disturbed, for instance by waves crushing onto the shore or by the propeller of an outboard motor. Sitting in a small motorized boat, crusing through water that is glowing is truly amazing – I got to experience this some years ago! And the chemistry behind is also fascinating – I’ve included a little about that at the end of the post.


A lollipop submerged in a glass with hot water which makes it glow even brighter (yet still requiring 8 seconds of exposure time!).

I had a quick chat with Bruce Bryan in the break following his presentation and he was so kind to give me two lollipops to take home. Of the glowing kind, yes. That’s how I got the pictures in this post. He suggested that I hold a lollipop under hot running water and then spray the water clinging to the lollipop on a wall in a dark bathroom. – You’ll see the universe open up in front of you, Bruce told me enthusiastically. I tried it and you can see a picture below.

Unfortunately it has been hard to find funding for further development and FDA approval of the isolated luciferin/luciferase complexes of use in food. In fact, during his presentation Bruce showed us a slide with the following text:

(…) These “colorants” are not FDA approved and may not be by the patent expiration (10 years) if some broader shoulders don’t get involved. Optimistic estimates are 2 1/2 years and $5 million dollars to get these products approved. (…) we’ve cloned six genes, spent a lot on collection, have put our life savings and mortgages into making rapid chip based diagnostic and cancer imaging applications possible! Tragically we have not had ANY corporate interest.

Considering this it might be true what he jokingly said about the lollipops perhaps being the most expensive candy ever made :) Even ideas such as “Bud light” or “Pepsi light” (yes, that kind of light) were turned down by the respective companies. The only products to appear so far are various toy items which are available online through Biotoy. Bruce has also set up the companies Prolume, Biolume and Nanolight to further develop and market the technology. His own homepage also has some info and the full text of the patents is easily found with a google search.


The lollipops (top left) I got from Bruce were of a different kind than those in the chocolate surprise box. A nice “stars of the universe” effect was achieved by dipping the lollipop in water and spraying the bathroom wall (top right). The bottom pictures shows my glowing tongue and the lollipop (sorry for the blurry picture – exposure time is 1 second at ISO 1600).

The chemistry behind the glowing lollipops is fascinating. What is required is a luciferin and luciferase. These are not specific compounds but rather generic terms. Luciferin is a compound which acts as a substrate for the reaction that generates light (see list of luciferins) and luciferase is an enzyme which catalyzes the reaction. One of the most common luciferins is coentelerazine (shown in the figure below). In the presence of a suitable luciferase and oxygen it is oxidized to coenteleramide. The important thing here is that coenteleramide exists in an excited (energy rich) state. To get rid of the excess energy it emits a photon which we see as light. In the process the substrate (or fuel if you like) is used up and must be provided continously for constant light production. The enzyme luciferase is unchanged by the reaction and can be reused. Further information on coelenterazine chemistry and bioluminescence can be found in the book “Bioluminescence” by Osamu Shimomura who was awarded the 2008 Nobel prize in chemistry (together with Martin Chalfie and Roger Tsien) for the discovery of green fluorescent protein.


In the presence of a luciferase and oxygen coentelerazine is oxidized to coenteleramide in an excited state. As coenteleramide reverts back to it’s ground state it emits light. The part of the coentelerazine molecule where the changes occur is indicated with blue color. The cartoon representation of luciferase is taken from Wikimedia Commons.

Update:
Bruce Bryan generously sent me a pack of different glowing candies and lollipops with different tastes and colors. IMO this surely has a market potential!

The label of the green and white lollipops reads: “Ingredients: Sucrose, corn Syrup, Tapioca & Chicory root starch, salt, natural and artificial flavors, 5 mg Renilla Luciferase protein and less than 0.2 mg Coelenterazine a naturally occurring anti-oxidant found in many fish”

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Comments

  1. nova Says:

    this is very cool – any word of the potential side effects of ingesting luciferin/luciferase?

  2. Erik Says:

    What about flavour/taste? Are the luciferins and luciferases taste and odourless? What did the lollipops taste?

  3. Martin Lersch Says:

    nova: The fact that the luciferin/luciferase have not been FDA isn’t that important. It only means no one has forked out the $5 million to start the registration process. However, luciferin and luciferase are sold for “consumption” with all the appropriate warnings from the biotoy.com website. You can read more on their safety page. The compounds do not show acute oral toxicity, skin iritaion, eye iritation, nor subactute oral toxicity. An Ames test of the luciferin used was negative for mutagenicity.

    From a general viewpoint the luciferases are present at a very low concentration so I wouldn’t be concerned about that. The luciferin (the “fuel”) is present at a somewhat higher concentration. But from a risk perspective I believe luciferin and luciferase are quite harmless, simply because you’d never eat this every day. Saturated fats, salt, alcohol etc. are a lot more threatening from a health perspective!

    Erik: Good question – I actually forgot to mention that (which says a lot). The ones included in the box had a strange taste, not very sweet or lollipoppy, perhaps a little like medicine, but they glowing really bright. The ones I got to take home were of a different, less glowing kind. The taste was reminiscent of a toothpaste which was OK, but they would never become my favorite kind of lollipop if I were to judge by taste…

  4. Katie Says:

    sweet!! to bad it’s not FDA approved and ready to sell to the public I would totally by some of that candy. :P

  5. little chef Says:

    That’s great!!!Do you think it’s possible to use Luciferin-Luciferase in others Kitchen preparation?…I’m thinking about a glowing sauce for a cake!!!

  6. Chemist Says:

    “The fact that the luciferin/luciferase have not been FDA isn’t that important. It only means no one has forked out the $5 million to start the registration process.” Eh… I beg to differ. The process is quite stringent precisely because of the need to protect public health, and sometimes some health-related suprises can come out of the required testing.

    “From a general viewpoint the luciferases are present at a very low concentration so I wouldn’t be concerned about that. ” You’re confusing mass with activity. The toxicity is determined by the mass and activity, and the exposure time. Last time I checked it doesn’t take a lot of arsenic to kill someone.

    Maybe these compounds are safe… or maybe they aren’t. That’s what testing is for, there are serious reasons for it, and you’re being a bit flippant about it.

  7. Martin Lersch Says:

    I agree – and it’s not my intention to make fun of FDA or the registration process at this point, but one should consider the amount consumed and take that into the over all risk asessment. Luciferin/luciferase will never become a staple food so to say – it’s something you’ll try a couple of times, and that’s it. The company checked luciferin/luciferase for acute toxicity, so I belive your comparison with arsenic or other poisons is a little far fetched. I’m not into the toxicology terminology regarding activity, but as a chemist I know that “there are no toxic compounds, only toxic doses”. So – since there is no acute toxicity, several people have actually tasted the lollipops without experiencing any problems, and this is something you are likely to try a couple of times only – your total exposure to luciferin/luciferase is so low that the resulting risk is practically non-existant.

  8. Chemist Says:

    “So – since there is no acute toxicity, several people have actually tasted the lollipops without experiencing any problems, and this is something you are likely to try a couple of times only – your total exposure to luciferin/luciferase is so low that the resulting risk is practically non-existant.”

    It is impossible to make that statement without enough test subjects, because it’s well known from drug testing that it can take thousands of people before the adverse effects become clear.

    I understand your point, in general, but I am being hard on you precisely because the devil is in the details with these things. If only 1 in 1000 people are affected, would you still want to be that 1 person? The point is that risks need to be better quantified before public consumption, precisely so we know where we stand. It’s fine to say “risks are low if you want to go ahead and try something uncertified”, it’s not fine to say “the fact that the luciferin/luciferase have not been FDA certified isn’t that important”.

  9. Bruce Bryan, MD Says:

    Dear Martin,
    Without a doubt you have done the best reporting of anyone ever; you provide precise and accurate information about the product.

    Some new developments: NBC news report on luciferase-biochip based rapid diagnostics:
    http://www.9news.com/life/programming/shows/evenings/article.aspx?storyid=108571&catid=510
    (click on the video in the right upper corner)

    Readers need to remember that these light emtting and green fluorescent proteins have been cloned into every cell of whole, pigs, dogs, cats, monkeys, rats, rabbits, and used in countless experiments with direct intravenous injections that would amount to 1/3-1 gram of the potent part of the chemistry I.V. PUSH and these animals do not seem to be affected or harmed by it. The dose in our latest lollipops is 0.2 milligrams/lollipop. We have not made them professionally and have not formulated the taste and flavoring. Taste any pure flavor, synthetic or extract, and you may not be happy with the result….however I agree the lollipop needs professional formulation.

    My family, ages 4, 6, 18, 20, 22, and myself have been consuming these candies for years. I have inhaled grams of the materials sprayed by airbrush in small dark rooms to clone these genes. No, it will not intoxicate you in any way…sorry…nor is it addictive in any way.

    The fact that the metabolites and active ingredients are present in Herring, Squid, Sardines, Shrimp, and other edible species should be considered when comparing it to Arsenic toxicity. I am not the inventor of this, Mother Nature devised this chemistry, I only copied her beauty.

    To repeat myself, Martin, great job, precise in every detail many thanks! We will never understand why an August Busch III or William Wrigley III would not jump on this after seeing it themselves…alas, their companies are no longer owned by their founder families, that should say a lot in and of itself.

    It saddens me to no end that Americans and the American inventiveness, risk taking, and desire to be the first is no longer…our greatest universities are 60% Asian. While we sit in our complacency, playing computer games, and our corporate management is playing derivative paper games…making fraudulent money without working for it, others are out there running in the lead, bringing real products and developing new technology…God Bless them everyone no matter where from!

    The newer lollipops are much better….write me for some samples…www.biolume.com

    Bruce

  10. Martin Lersch Says:

    Bruce: Thank you for your kind comments! I was wondering: is there any chance that luciferin/luciferase could achieve a GRAS status? BTW I’m pleased to hear that you’ve done some development regarding the taste of lollipops :)

  11. Glowing lollipops « Cakehead Loves Evil Says:

    [...] } It is amazing where a degree in PhD in organometallic chemistry will get you – namely this glow in the dark drink, cakefrosting and [...]

  12. Jet the student Says:

    i think it should get a permit… Because is it dilicious os dangerous? or both? Hmm alot of testing should be dne first before I would try the product.