Mushroom Coral as a Sunscreen

In an episode of Man vs. Wild that I was watching, a Mushroom Coral's mucus was used as a sunscreen, so me as a chemist interested in cosmetics, I wanted to know what photoprotecting chemicals were in this mucus.  The coral Fungia fungites and a couple other species gained this ability to protect themselves because they would grow in shallow water of the Adaman Sea where a lot of UV radiation penetrates through the clear water.  First looking at this ability one would expect the coral to synthesize these molecules, but it turns out that the culprits are tiny symbiotic dinoflagellates. In a paper from 1999 by Brown¹ studying the makeup of the mucus required for photoprotection, they look at the concentration of xanthophylls in the mucus, the primary photoprotector. Their study looked at how the concentrations of xanthophylls varried throughout the day, and showed that it is best to harvest the mucus at noon when the xanthophylls are at their peak concentration.

So finally to the chemistry of all of this. The molecule shown above is called diatoxanthin, which is a type of xanthophylls, and this is the molecule mostly responsible for filtering out the harmful rays.  So how does this happen? Well molecules and atoms absorb light one way or another through absorbing the photons, resulting in electron excitation, and in this case, the molecule absorbs in the UV portion of the electromagnetic spectrum. So what happens after the diatoxanthin molecules become excited? Well biology has found a solution for that, which has been named the Xanthophyll Cycle. It's job is to convert all the used up diatoxanthin back into diatoxanthin.

References:
1. Fitt, W. K., R. P. Dunne, S. W. Gibb, D. G. Cummings, I. Ambarsari, B. E. Brown, and M. E. Warner. "Diurnal Changes in Photochemical Efficiency and Xanthophyll Concentrations in Shallow Water Reef Corals : Evidence for Photoinhibition and Photoprotection." Coral Reefs (1999): 99-105.

Hydrangeas and their Variety of Colour

Hydrangeas (Hydrangea macrophylla) have been known to form in a range of colours, from red, to purple, to blue, with having nothing to do with the genetics of the plant. So, if this colour difference isn't due to the genes, it must be due to certain environmental factors, and as it turns out, it is all to do with the pH and other properties of the soil. The more acidic the soil, and the greater [Al³⁺] in the soil, the more blue the sepals of the hydrangea will become. So why is this? Let's start with looking at the pigments which govern the colour of the sepals. The major pigment found in Hydrangeas (along with a number of other plants) is called Myrtillin, also known as delphinidin 3-glucoside, which is part of a group of molecules called anthocyanin.

But odly, this molecule assumes a red colour in acidic conditions and blue in basic conditions¹ (opposite to that of the soil conditions) and the pH within the sepals is usually slightly acidic, with little variation, so the blue colouring must have something to do with the Al³⁺. Through much research, Kondo et al. ², came up with a model proposing that the aluminum acts as a bridge to coordinate the Myrtillin to other copigments pigments known as acylquinic acids, which produces this blue colour.

While this is how the blue colour is formed, it can be safely assumed that the red colour is merely caused by Myrtillin by itself without any co-pigments or metal chelation.  A question which hasn't been answered yet is what the pH of the soil has to do with all of this.  The low pH allows there to be more free aluminum ions within the soil, to allow there to be more [Al³⁺] taken up into the plant.

References:
Second figure from 1.
1. K. Yoshida, M. Mori and T. Kondo, Nat. Prod. Rep., 2009, 26, 884–915.
2. T. Kondo, Y. Toyama-Kato and K. Yoshida, Tetrahedron Lett., 2005, 46, 6645–6649.

Why are Flamingos Pink?

This is a question that many children will ask their parents at some point, and if the child is chemically literate this is what the parents could tell them.  Flamingos primarily eat crustaceans and algae from their aquatic environment, which we usually see them standing in, and in their food, there is what is known as carotenoid pigments. Carotenoids are made from fats, and the incorporated into the chloroplasts of algae to serve as light absorbing pigment.  Then the algae get eaten by the crustaceans or flamingos, the carotenoids get passed on into these animals.  Usually when a molecule is eaten, it breaks down, but something such as a pigment will absorb into your bloodstream and not break down, so when a flamingo eats these, the pigments enter the blood stream and then eventually come out in their feathers.  Now for flamingos, the primary pigments which get absorbed and end up in their feathers, are Canthaxanthin (the molecule below), astaxanthin and  phoenicoxanthin ¹. Canthaxanthin is a molecule which gives of a bright violet colour when it is crystallized  but when it is incorporated into flamingo feathers, it is diluted to give a vibrant pink.

References:
1. Fox, D., and T. Hopkins. "Comparative Metabolic Fractionation of Carotenoids in Three Flamingo Species." Comparative Biochemistry and Physiology 17.3 (1966): 841-56.

Egyptian Blue: Calcium Copper Silicate

In a recent article by Scientific American, a story is told of Calcium Copper Silicate (Egyptian Blue) being the first artificial pigment made by humans, and soon to be utilized, once again, as a nano ink for biomedical imaging.  I'm not going to go over the details of the article, but I will present some background information of this soft blue colour.

Being the first recorded synthetic pigment, you may ask how it was originally synthesized.  The first procedures, in 3000 B.C., involves the heating of sand, calcium carbonate, copper, and an alkali substance to obtain this blue pigment having a composition of CaCuSi₄O₁₀.  The reaction below is a general understanding of the reaction, where the molecules can be variable in a number of different ways.

Cu₂CO₃(OH)₂ + 8SiO₂ + 2CaCO₃ → 2CaCuSi₄O₁₀ + 3CO₂ + H₂O

The blue colour comes from the absorption of the copper, which can range from the blue, seen above, to a much darker blue, depending on how pure the mixture is. But what wasn't known at that time, was that when irradiated with visible light, the compound emits IR photons, which is the property that will conduct the imaging technologies.

References:
Via: Scientific American
Wikipedia