Chlorophyll
Chlorophyll is a green photosynthetic pigment found in plants, algae, and cyanobacteria. Its name is derived from ancient Greek: chloros = green and phyllon = leaf. Chlorophyll absorbs mostly in the blue and to a lesser extent red portions of the electromagnetic spectrum, hence its intense green colour.
Chlorophyll and photosynthesis
In plant photosynthesis, incoming light is absorbed by chlorophyll and other accessory pigments in the antenna complexes of photosystem I and photosystem II. The antenna pigments are predominantly chlorophyll α, chlorophyll b and carotenoids; their absorption spectrums are non-overlapping, to broaden the range of light that can be absorbed for photosynthesis. The carotenoids have another role as an antioxidant, to prevent photo-oxidative damage to the chlorophyll molecules.
Each antenna complex has between 250 and 400 pigment molecules, and the energy they absorb is shuttled by resonance energy transfer to a specialized chlorophyll α at the reaction center of each photosystem. When either of the two chorophyll α molecules at the reaction center absorb energy, an electron is excited and transferred to an electron-acceptor molecule, leaving an electron hole in the donor chlorophyll. In a poorly-understood reaction, electrons from water are oxidized, the hole is filled, and diatomic oxygen is produced. The resulting chemical energy is then captured in the form of ATP and NADPH, and is ultimately used to convert carbon dioxide (CO2) to carbohydrates. This CO2 fixation process results in the conversion of 3% to 6% of total solar radiation, with a theoretical maximum efficiency of 11%. [1]
The photosystem reaction centers consist of a pair of chlorophyll α molecules that are characterised by their specific absorption maximum. The chorophyll α of photosystem I is designated P700, and the one from photosystem II is designated P680. The P is short for pigment, and the number is the specific absorption peak in nanometers for the chlorophyll molecules in each reaction center.
Chlorophyll α is common to all eukaryotic photosynthetic organisms, and, due to its central role in the reaction center, is essential for photosynthesis. The accessory pigments such as chlorophyll b and carotenoids are not essential. Some algae, such as brown algae and diatoms, use chlorophyll c as a substitute for chlorophyll b. Historically, red algae have been assumed to have chlorophyll d, although it could not be isolated from all species. This puzzle has recently been resolved, since the chlorophyll d is actually from an epiphytic cyanobacterium (Acaryochloris marina) that lives on the red algae. These cyanobacteria have a ratio of chlorophyll d: chlorophyll α of approximately 30:1, and represent a rare example of a photosystem with chlorophyll d at the reaction center of the photosystem. All other known eukaryotes and cyanobacteria use chlorophyll α.
Other chemical variations of chlorophyll are found in photosynthetic bacteria, other than cyanobacteria. Purple bacteria use bacteriochlorophyll, which absorbs infrared light between 800nm - 900nm, and the green sulphur bacteria chlorobium chlorophyll.
Chemical structure
Chlorophyll is a chlorin pigment, which is structurally similar to porphyrin pigments such as heme. At the center of the porphyrin ring is a magnesium ion. This has various side chains, usually including a long phytyl chain. There are a few different forms that occur naturally:
| Chlorophyll α | Chlorophyll b | Chlorophyll c1 | Chlorophyll c2 | Chlorophyll d | |
|---|---|---|---|---|---|
| Molecular formula | C55H72O5N4Mg | C55H70O6N4Mg | C35H30O5N4Mg | C35H28O5N4Mg | C54H70O6N4Mg |
| C3 group | -CH=CH2 | -CH=CH2 | -CH=CH2 | -CH=CH2 | -CHO |
| C7 group | -CH3 | -CHO | -CH3 | -CH3 | -CH3 |
| C8 group | -CH2CH3 | -CH2CH3 | -CH2CH3 | -CH=CH2 | -CH2CH3 |
| C17 group | -CH2CH2COO-Phytyl | -CH2CH2COO-Phytyl | -CH=CHCOOH | -CH=CHCOOH | -CH2CH2COO-Phytyl |
| C17-C18 bond | Single | Single | Double | Double | Single |
| Occurrence | Universal | Mostly in land plants | Various algae | Various algae | cyanobacteria |
 Common structure of chlorophyll α, b and d
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 Common structure of chlorophyll c1, and c2
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Evidence for chlorophyll
Chlorophyll can be shown to be vital for photosynthesis by destarching a leaf from a variegated plant and exposing it to light for several hours. (Variegated leaves have green areas that contain chlorophyll and white areas that have none.) When tested with iodine solution, a colour change revealing the presence of starch occurs only in regions of the leaf that were green and therefore contained chlorophyll. This shows that photosynthesis does not occur in areas where chlorophyll is absent, and constitutes evidence that the presence of chlorophyll is a requirement for photosynthesis.