Molecule of the Week: BPO

The major ingredient in many acne treatments is benzoyl peroxide (BPO). Did you ever wonder how it works?

BPO is a member of a larger class of compounds called peroxides, which are characterized by an oxygen-oxygen single bond (you may be familiar with hydrogen peroxide, which is the simplest member of this family). A common property among peroxides is a relatively low bond dissociation energy associated with the oxygen-oxygen single bond (51 kcal/mol for hydrogen peroxide). This weak bond easily dissociates to form two radical species, which can undergo subsequent reactions with other chemicals present in the surrounding environment.

The efficacy of BPO stems mainly through its ability to induce breakdown of the outer layer(s) of skin (termed "desquamation" in the medical community). It acts by breaking up the structural proteins (keratins) in the affected area. Once absorbed by the skin, BPO is converted to benzoic acid, presumably via hydrogen abstraction from the keratins.

Photochemistry and Skin Cancer

Did you ever wonder why light from the sun (ultraviolet light) damages your skin and can cause skin cancer?

Ultraviolet (UV) radiation has wavelengths in the range of 200 nm to 300 nm. If you recall the relationship between energy and frequency, E=hv, where v=c/wavelength and c=the speed of light, then we can see that the energy of UV light can range from about 95 kcal/mol to 143 kcal/mol.

Energies in this range are sufficient to induce electronic absorption in molecules. Common organic molecules contain bonds that can be broken with the amount of energy contained in UV light.

One reaction in particular that is driven by UV light is the [2+2] cycloaddition of two thymine molecules in DNA. As you may already know, DNA is composed of two strands of connected nucleotides. Each nucleotide is made up of a nitrogen-containing heterocycle (cytosine, guanine, thymine or adenine), a sugar, and a phosphate group, which links each nucleotide to the next one in a long chain of nucleotides.
Since thymine has a double bond, it can undergo a reaction known as "cycloaddition," in which two double bonds connect with each other to form a four-membered ring (cyclobutane). As you can see below, this is a significant change! Anything that significantly alters the structure of your DNA can have drastic consequences on a number of different processes in your body.The [2+2] cycloaddition of thymine is only one of many reactions that can occur in the presence of high energy UV radiation. So wear your sunscreen!

An Introduction to Eutectic Points

Did you ever wonder why grinding two solids together sometimes produces a liquid?

Depending on the relative amounts of each component in a mixture, the melting point varies. The lowest temperature (as a function of mixture composition) at which the mixture melts is referred to as the "eutectic temperature" from the Greek word for "easily melted." The temperature and composition associated with the eutectic reaction are collectively called the "eutectic point."

(salt-less icy road image complements of Creative Commons)

Eutectic points are exploited in various ways. You are probably familiar with many of them already! For example, during the winter people often sprinkle salt (sodium chloride) over the roads in order to decrease the melting/freezing point of ice. So if the temperature outside is 0°C, the water present on the road will not freeze. The eutectic temperature of water and salt is -21.1°C (for 76.7% water and 23.3% salt), so it would have to be much colder outside for a significant amount of ice to develop on the road. Various other solids can be mixed with water to decrease its freezing point as well!

But why does mixing two solids together always result in a decreased melting/freezing point rather than an increased melting/freezing point?

It doesn't! Take, for example, a 1:1 mixture of mesitylene and hexafluorobenzene, which melts at 34°C (1). The melting point of benzene is 5°C, while the melting point of mesitylene is -44.8°C. In this case, we see an increase in the melting point on mixing two substances together!

It is believed that a complex is formed between hexafluorobenzene and mesitylene. The complex is thought to be a "Lewis base - Lewis acid" type complex, in which one component (electron-rich mesitylene) supplies charge to the other component (electron-deficient hexafluorobenzene). Hexafluorobenzene is so electron-deficient due to the strong electron-withdrawing nature of the fluorine substituent, which is the most electronegative element.

[1] Patrick, C. R.; Prosser, G. S. Nature, 1960, 187, 1021.