The most obvious effects of too much sun exposure are cosmetic¹, like wrinkled and rough skin. Some damage, however, goes deeper -- ultraviolet light can damage DNA² and cause proteins in the body to break down into smaller, sometimes harmful pieces that may also damage DNA, increasing the risk of skin cancer and cataracts³. Understanding the specific pathways by which this degradation⁴ occurs is an important step in developing protective mechanisms⁵ against it. Researchers from the École Polytechnique Fédérale de Lausanne (EPFL) in Switzerland have shown that certain peptides (small proteins) degrade under UV light by first passing through a triplet quantum state, a reactive arrangement that can cause greater damage than fragmentation alone.

 

Their results, described in a paper appearing this week in The Journal of Chemical Physics, from AIP Publishing, explore this pathway of protein degradation and could facilitate the development of better UV protection mechanisms.

 

The researchers took gas-phase peptides containing tyrosine or phenylalanine, light-absorbing amino acids found throughout our bodies, and subjected them to ultraviolet laser radiation. Then, they used ultraviolet-infrared spectroscopy to examine the resulting structural⁶ changes over time. They found that instead of immediately degrading once excited, some of the molecules⁸ formed intermediate triplet states.

 

Normally, electron spins are paired -- if two electrons are present, one spin points one direction and the other points the opposite direction. But under certain conditions, the spin of one of the electrons can flip⁹ so that they both point in the same direction. This arrangement is known as a triplet state.

 

Because electronic configurations¹⁰ can affect how a molecule⁷ will react, knowing that it passes through a triplet state can provide additional insight into the potential consequences of photodamage for these molecules.

 

"Triplet states are long-lived and can be involved in harmful chemical reactions," said chemical physicist¹¹ Aleksandra Zabuga, an author of the new paper. "Long-lived" is relative -- they still only last from microseconds to milliseconds -- but it does give them a greater opportunity to do damage.

 

"During that time the triplet species may transfer their energy to nearby oxygen and produce highly reactive singlet oxygen or other free radicals¹². These radicals can in turn move around the cell and cause DNA damage that is much more dangerous than the fragmentation of peptides," she said.

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