Photoprotection

Photoprotection is a group of mechanisms that help living organisms cope with molecular damage caused by sunlight. Plants and other oxygenic phototrophs have developed a suite of photoprotective mechanisms to prevent photoinhibition and oxidative stress caused by excess or fluctuating light conditions. Humans and other animals have also developed photoprotective mechanisms to avoid UV photodamage to the skin, prevent DNA damage, and minimize the downstream effects of oxidative stress.

Photoprotection in Plants

In organisms that perform oxygenic photosynthesis, excess light may lead to photoinhibition, or photoinactivation of the reaction centers, a process that does not necessarily involve chemical damage. When photosynthetic antenna pigments such as chlorophyll are excited by light absorption, unproductive reactions may occur by charge transfer to molecules with unpaired electrons. Because oxygenic phototrophs generate O2 as a byproduct from the photocatalyzed splitting of water (H2O), photosynthetic organisms have a particular risk of forming reactive oxygen species.

Therefore, a diverse suite of mechanisms have developed in photosynthetic organisms to mitigate these potential threats, which become exacerbated under high irradiance, fluctuating light conditions, in adverse environmental conditions such as cold or drought, and while experiencing nutrient deficiencies which cause an imbalance between energetic sinks and sources.

In eukaryotic phototrophs, these mechanisms include non-photochemical quenching mechanisms such as the xanthophyll cycle, biochemical pathways which serve as "relief valves", structural rearragements of the complexes in the photosynthetic apparatus, and use of antioxidant molecules. Higher plants sometimes employ strategies such as reorientation of leaf axes to minimize incident light striking the surface. Mechanisms may also act on a longer time-scale, such as up-regulation of stress response proteins or down-regulation of pigment biosynthesis, although these processes are better characterized as "photoacclimatization" processes.

Cyanobacteria possess some unique strategies for photoprotection which have not been identified in plants nor in algae.[1] For example, most cyanobacteria possess an Orange Carotenoid Protein (OCP), which serves as a novel form of non-photochemical quenching.[2] Another unique, albeit poorly-understood, cyanobacterial strategy involves the IsiA chlorophyll-binding protein, which can aggregate with carotenoids and form rings around the PSI reaction center complexes to aid in photoprotective energy dissipation.[3] Some other cyanobacterial strategies may involve state-transitions of the phycobilisome antenna complex[4] , photoreduction of water with the Flavodiiron proteins,[5] and futile cycling of CO2[6] .

Photoprotection in Humans

Photoprotection of the human skin is achieved by extremely efficient internal conversion of DNA, proteins and melanin. Internal conversion is a photochemical process that converts the energy of the UV photon into small, harmless amounts of heat. If the energy of the UV photon were not transformed into heat, then it would lead to the generation of free radicals or other harmful reactive chemical species (e.g. singlet oxygen, or hydroxyl radical).

In DNA this photoprotective mechanism evolved four billion years ago at the dawn of life.[7] The purpose of this extremely efficient photoprotective mechanism is to prevent direct DNA damage and indirect DNA damage. The ultrafast internal conversion of DNA reduces the excited state lifetime of DNA to only a few femtoseconds (10−15s)—this way the excited DNA does not have enough time to react with other molecules.

For melanin this mechanism has developed later in the course of evolution. Melanin is such an efficient photoprotective substance that it dissipates more than 99.9% of the absorbed UV radiation as heat. [8] This means that less than 0.1% of the excited melanin molecules will undergo harmful chemical reactions or produce free radicals.

Artificial melanin

The cosmetic industry claims that the UV filter acts as an "artificial melanin". But those artificial substances used in sunscreens do not efficiently dissipate the energy of the UV photon as heat. Instead these substances have a very long excited state lifetime. [9]
In fact, the substances used in sunscreens are often used as photosensitizers in chemical reactions. (see Benzophenone).

This discrepancy between melanin and sunscreen ingredients is one of the reasons for the increased melanoma risk that can be found in sunscreen users compared to non-users. (see sunscreen) Oxybenzone, titanium oxide and octyl methoxycinnamate are photoprotective agents used in many sunscreens, providing broad-spectrum UV coverage, including UVB and short-wave UVA rays.[10][11]

UV-absorber other names percentage of molecules that dissipate the photon energy (quantum yield: Φ ) [9]
molecules not dissipating the energy quickly
DNA > 99.9% < 0.1%
natural melanin > 99.9% < 0.1%
2-phenylbenzimidazole-5-sulfonic acid PBSA, Eusolex 232, Parsol HS,
2-ethylhexyl 4-dimethylaminobenzoate Padimate-O, oxtyldimethyl PABA, OD-PABA 0.1 = 10% 90%
4-Methylbenzylidene camphor (4-MBC), (MBC), Parsol 5000, Eusolex 6300 0.3 = 30% 70%
4-tert-butyl-4-methoxydibenzoyl-methane (BM-DBM), Avobenzone, Parsol 1789, Eusolex 9020
Menthyl Anthranilate (MA), Menthyl-2-aminobenzoate, meradimate 0.6 = 60% 40%
Ethylhexyl methoxycinnamate (2-EHMC), (EHMC), EMC, Octyl methoxycinnamate, OMC, Eusolex 2292, Parsol 0.81 = 81% 19%

See also

References

  1. ↑ Bailey, Shaun; Grossman, Arthur (2008). "Photoprotection in Cyanobacteria: Regulation of Light Harvesting". Photochemistry and Photobiology 84: 1410–1420. doi:10.1111/j.175-1097.2008.00453.x.
  2. ↑ Kirilovsky, Diana; Kerfeld, Cheryl A. (2013). "The Orange Carotenoid Protein: a blue-green light photoactive protein". Photochemical & Photobiological Sciences0 12: 1135–1143. doi:10.1039/C3PP25406B.
  3. ↑ Berera, Rudi; van Stokkum, Ivo H.M.; d'Haene, Sandrine; Kennis, John T.M.; van Grondelle, Rienk; Dekker, Jan P. (2009). "A Mechanism of Energy Dissipation in Cyanobacteria". Biophysical Journal 96 (6): 2261–2267. doi:10.1016/j.bpj.2008.12.3905. ISSN 0006-3495.
  4. ↑ Dong, Chunxia; Tang, Aihui; Zhao, Jindong; Mullineaux, Conrad W.; Shen, Gaozhong; Bryant, Donald A. (2009). "ApcD is necessary for efficient energy transfer from phycobilisomes to photosystem I and helps to prevent photoinhibition in the cyanobacterium Synechococcus sp. PCC 7002". Biochimica et Biophysica Acta (BBA) - Bioenergetics 1787 (9): 1122–1128. doi:10.1016/j.bbabio.2009.04.007. ISSN 0005-2728.
  5. ↑ Allahverdiyeva, Y.; Mustila, H.; Ermakova, M.; Bersanini, L.; Richaud, P.; Ajlani, G.; Battchikova, N.; Cournac, L.; Aro, E.-M. (2013). "Flavodiiron proteins Flv1 and Flv3 enable cyanobacterial growth and photosynthesis under fluctuating light". Proceedings of the National Academy of Sciences 110 (10): 4111–4116. doi:10.1073/pnas.1221194110. ISSN 0027-8424.
  6. ↑ Tchernov, Dan; Silverman, Jack; Luz, Boaz; Reinhold, Leonora; Kaplan, Aaron (2003). Photosynthesis Research 77 (2/3): 95–103. doi:10.1023/A:1025869600935. ISSN 0166-8595. Missing or empty |title= (help)
  7. ↑ "ultrafast internal conversion of DNA". Retrieved 2008-02-13.
  8. ↑ Meredith, Paul; Riesz, Jennifer (2004). "Radiative Relaxation Quantum Yields for Synthetic Eumelanin". Photochemistry and photobiology 79 (2): 211–216. doi:10.1111/j.1751-1097.2004.tb00012.x. ISSN 0031-8655. PMID 15068035.
  9. 1 2 Cantrell, Ann; McGarvey, David J; (2001). "3(Sun Protection in Man)". Comprehensive Series in Photosciences 495: 497–519. CAN 137:43484.
  10. ↑ Burnett, M. E. and Wang, S. Q. (2011), Current sunscreen controversies: a critical review. Photodermatology, Photoimmunology & Photomedicine, 27: 58–67
  11. ↑ Serpone N, Salinaro A, Emeline AV, Horikoshi S, Hidaka H, Zhao JC. 2002. An in vitro systematic spectroscopic examination of the photostabilities of a random set of commercial sunscreen lotions and their chemical UVB/UVA active agents. Photochemical & Photobiological Sciences 1(12): 970-981.
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