Bacteriochlorophyll

Last updated
Bacteriochlorophyll a
BacterioChlorophyll a.svg
Names
IUPAC name
[methyl (3S,4S,13R,14R,21R)-9-acetyl-14-ethyl-4,8,13,18-tetramethyl-20-oxo-3-(3-oxo-3-([(2E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-yl]oxy)propyl)-13,14-dihydrophorbine-21-carboxylatato(2−)-kappa4N23,N24,N25,N26]magnesium
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
KEGG
PubChem CID
  • InChI=1S/C55H75N4O6.Mg/c1-13-39-34(7)41-29-46-48(38(11)60)36(9)43(57-46)27-42-35(8)40(52(58-42)50-51(55(63)64-12)54(62)49-37(10)44(59-53(49)50)28-45(39)56-41)23-24-47(61)65-26-25-33(6)22-16-21-32(5)20-15-19-31(4)18-14-17-30(2)3;/h25,27-32,34-35,39-40,51H,13-24,26H2,1-12H3,(H-,56,57,58,59,60,62);/q-1;+2/p-1/b33-25+;/t31-,32-,34-,35+,39-,40+,51-;/m1./s1 Yes check.svgY[ EBI ]
    Key: DSJXIQQMORJERS-AGGZHOMASA-M
  • CC[C@@H]1[C@@H](C)C2=N/C/1=C\c3c(C)c4C(=O)[C@H](C(=O)OC)\C\5=C/6\N=C(\C=C\7/N([Mg]n3c45)\C(=C/2)\C(=C7C)C(=O)C)[C@@H](C)[C@@H]6CCC(=O)OC\C=C(/C)\CCC[C@H](C)CCC[C@H](C)CCCC(C)C
Properties
MgC55H74N4O6
Molar mass 911.524 g·mol−1
AppearanceLight green to blue-green powder
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Bacteriochlorophylls (BChl) are photosynthetic pigments that occur in various phototrophic bacteria. They were discovered by C. B. van Niel in 1932. [1] They are related to chlorophylls, which are the primary pigments in plants, algae, and cyanobacteria. Organisms that contain bacteriochlorophyll conduct photosynthesis to sustain their energy requirements, but the process is anoxygenic and does not produce oxygen as a byproduct. They use wavelengths of light not absorbed by plants or cyanobacteria. Replacement of Mg 2+ with protons gives bacteriophaeophytin (BPh), the phaeophytin form.

Contents

List of major bacteriochlorophylls
PigmentTaxain vivo infrared absorption maximum (nm)
BChl a Purple bacteria, Heliobacteria, Green Sulfur Bacteria, Chloroflexota, Chloracidobacterium thermophilum [2] 805, 830–890
BChl b Purple bacteria 835–850, 1020–1040
BChl c Green sulfur bacteria, Chloroflexota, C. thermophilum , [2] C. tepidum 745–755
BChl d Green sulfur bacteria 705–740
BChl e Green sulfur bacteria 719–726
BChl f(Discovered by mutation of BChl e synthesis by analogy to BChl c/d. Not evolutionarily favorable.) [3] 700–710
BChl g Heliobacteria 670, 788

Structure

Chemical structures comparing porphin, chlorin, bacteriochlorin, and isobacteriochlorin. Note relocation of C=C double bond between the two bacteriochlorin isomers. There are two p electrons (symbolized by p e ) for every double bond in the macrocycle. Porphyrin, chlorin, bacteriochlorins.png
Chemical structures comparing porphin, chlorin, bacteriochlorin, and isobacteriochlorin. Note relocation of C=C double bond between the two bacteriochlorin isomers. There are two π electrons (symbolized by π e ) for every double bond in the macrocycle.

Bacteriochlorophylls a, b, and g are bacteriochlorins, meaning their molecules have a bacteriochlorin macrocycle ring with two reduced pyrrole rings (B and D). Bacteriochlorophylls c, d, e, and f are chlorins, meaning their molecules have a chlorin macrocycle ring with one reduced pyrrole ring (D). [4]

Bacteriochlorophylls c to f occur in the form of closely related homologs with different alkyl groups attached to pyrrole rings B and C and are illustrated above in their simplest versions, esterified with the sesquiterpene alcohol farnesol. [5] Most of the variation occurs in the 8 and 12 positions and can be attributed to methyltransferase variation. [6] BChl cS is a term for 8-ethyl,12-methyl homolog of BChl c. [7]

Bacteriochlorophyll g has a vinyl group in ring (A), at position 8. [8]

Biosynthesis

The common biosynthetic precursor for bacteriochlorophylls is chlorophyllide a Chlorophyllide a.svg
The common biosynthetic precursor for bacteriochlorophylls is chlorophyllide a

There are a large number of known bacteriochlorophylls [4] [9] but all have features in common since the biosynthetic pathway involves chlorophyllide a (Chlide a) as an intermediate. [10]

Chlorin-cored BChls (c to f) are produced by a series of enzymatic modifications on the sidechain of Chlide a, much like how Chl b, d, e are made. The bacteriochlorin-cored BChls a, b, g require a unique step to reduce the double bound between C7 and C8, which is performed by Chlorophyllide a reductase (COR). [9]

Isobacteriochlorins, in contrast, are biosynthesised from uroporphyrinogen III in a separate pathway that leads, for example, to siroheme, cofactor F430 and cobalamin. The common intermediate is sirohydrochlorin. [11]

Related Research Articles

<span class="mw-page-title-main">Chlorophyll</span> Green pigments found in plants, algae and bacteria

Chlorophyll is any of several related green pigments found in cyanobacteria and in the chloroplasts of algae and plants. Its name is derived from the Greek words χλωρός, khloros and φύλλον, phyllon ("leaf"). Chlorophyll allow plants to absorb energy from light.

Pyrrole is a heterocyclic, aromatic, organic compound, a five-membered ring with the formula C4H4NH. It is a colorless volatile liquid that darkens readily upon exposure to air. Substituted derivatives are also called pyrroles, e.g., N-methylpyrrole, C4H4NCH3. Porphobilinogen, a trisubstituted pyrrole, is the biosynthetic precursor to many natural products such as heme.

<span class="mw-page-title-main">Chlorin</span> Chemical compound

In organic chemistry, chlorins are tetrapyrrole pigments that are partially hydrogenated porphyrins. The parent chlorin is an unstable compound which undergoes air oxidation to porphine. The name chlorin derives from chlorophyll. Chlorophylls are magnesium-containing chlorins and occur as photosynthetic pigments in chloroplasts. The term "chlorin" strictly speaking refers to only compounds with the same ring oxidation state as chlorophyll.

<span class="mw-page-title-main">Green sulfur bacteria</span> Family of bacteria

The green sulfur bacteria are a phylum, Chlorobiota, of obligately anaerobic photoautotrophic bacteria that metabolize sulfur.

Chlorophyll <i>a</i> Chemical compound

Chlorophyll a is a specific form of chlorophyll used in oxygenic photosynthesis. It absorbs most energy from wavelengths of violet-blue and orange-red light, and it is a poor absorber of green and near-green portions of the spectrum. Chlorophyll does not reflect light but chlorophyll-containing tissues appear green because green light is diffusively reflected by structures like cell walls. This photosynthetic pigment is essential for photosynthesis in eukaryotes, cyanobacteria and prochlorophytes because of its role as primary electron donor in the electron transport chain. Chlorophyll a also transfers resonance energy in the antenna complex, ending in the reaction center where specific chlorophylls P680 and P700 are located.

<span class="mw-page-title-main">Purple bacteria</span> Group of phototrophic bacteria

Purple bacteria or purple photosynthetic bacteria are Gram-negative proteobacteria that are phototrophic, capable of producing their own food via photosynthesis. They are pigmented with bacteriochlorophyll a or b, together with various carotenoids, which give them colours ranging between purple, red, brown, and orange. They may be divided into two groups – purple sulfur bacteria and purple non-sulfur bacteria. Purple bacteria are anoxygenic phototrophs widely spread in nature, but especially in aquatic environments, where there are anoxic conditions that favor the synthesis of their pigments.

<span class="mw-page-title-main">Chromatiaceae</span> Family of purple sulfur bacteria

The Chromatiaceae are one of the two families of purple sulfur bacteria, together with the Ectothiorhodospiraceae. They belong to the order Chromatiales of the class Gammaproteobacteria, which is composed by unicellular Gram-negative organisms. Most of the species are photolithoautotrophs and conduct an anoxygenic photosynthesis, but there are also representatives capable of growing under dark and/or microaerobic conditions as either chemolithoautotrophs or chemoorganoheterotrophs.

Photoheterotrophs are heterotrophic phototrophs—that is, they are organisms that use light for energy, but cannot use carbon dioxide as their sole carbon source. Consequently, they use organic compounds from the environment to satisfy their carbon requirements; these compounds include carbohydrates, fatty acids, and alcohols. Examples of photoheterotrophic organisms include purple non-sulfur bacteria, green non-sulfur bacteria, and heliobacteria. These microorganisms are ubiquitous in aquatic habitats, occupy unique niche-spaces, and contribute to global biogeochemical cycling. Recent research has also indicated that the oriental hornet and some aphids may be able to use light to supplement their energy supply.

Tetrapyrroles are a class of chemical compounds that contain four pyrrole or pyrrole-like rings. The pyrrole/pyrrole derivatives are linked by, in either a linear or a cyclic fashion. Pyrroles are a five-atom ring with four carbon atoms and one nitrogen atom. Tetrapyrroles are common cofactors in biochemistry and their biosynthesis and degradation feature prominently in the chemistry of life.

Chlorophyll <i>b</i> Chemical compound

Chlorophyll b is a form of chlorophyll. Chlorophyll b helps in photosynthesis by absorbing light energy. It is more soluble than chlorophyll a in polar solvents because of its carbonyl group. Its color is green, and it primarily absorbs blue light.

<span class="mw-page-title-main">Chlorosome</span>

A chlorosome is a photosynthetic antenna complex found in green sulfur bacteria (GSB) and many green non-sulfur bacteria (GNsB), together known as green bacteria. They differ from other antenna complexes by their large size and lack of protein matrix supporting the photosynthetic pigments. Green sulfur bacteria are a group of organisms that generally live in extremely low-light environments, such as at depths of 100 metres in the Black Sea. The ability to capture light energy and rapidly deliver it to where it needs to go is essential to these bacteria, some of which see only a few photons of light per chlorophyll per day. To achieve this, the bacteria contain chlorosome structures, which contain up to 250,000 chlorophyll molecules. Chlorosomes are ellipsoidal bodies, in GSB their length varies from 100 to 200 nm, width of 50-100 nm and height of 15 – 30 nm, in GNsB the chlorosomes are somewhat smaller.

<span class="mw-page-title-main">Protochlorophyllide reductase</span>

In enzymology, protochlorophyllide reductases (POR) are enzymes that catalyze the conversion from protochlorophyllide to chlorophyllide a. They are oxidoreductases participating in the biosynthetic pathway to chlorophylls.

<span class="mw-page-title-main">Antenna complex in purple bacteria</span>

The antenna complex in purple photosynthetic bacteria are protein complexes responsible for the transfer of solar energy to the photosynthetic reaction centre. Purple bacteria, particularly Rhodopseudomonas acidophila of purple non-sulfur bacteria, have been one of the main groups of organisms used to study bacterial antenna complexes so much is known about this group's photosynthetic components. It is one of the many independent types of light-harvesting complex used by various photosynthetic organisms.

Chlorophyll c refers to forms of chlorophyll found in certain marine algae, including the photosynthetic Chromista and dinoflagellates. These pigments are characterized by their unusual chemical structure, with a porphyrin as opposed to the chlorin as the core; they also do not have an isoprenoid tail. Both these features stand out from the other chlorophylls commonly found in algae and plants.

<span class="mw-page-title-main">Anoxygenic photosynthesis</span> Process used by obligate anaerobes

Anoxygenic photosynthesis is a special form of photosynthesis used by some bacteria and archaea, which differs from the better known oxygenic photosynthesis in plants in the reductant used and the byproduct generated.

Aerobic anoxygenic phototrophic bacteria (AAPBs) are Alphaproteobacteria and Gammaproteobacteria that are obligate aerobes that capture energy from light by anoxygenic photosynthesis. Anoxygenic photosynthesis is the phototrophic process where light energy is captured and stored as ATP. The production of oxygen is non-existent and, therefore, water is not used as an electron donor. They are widely distributed marine bacteria that may constitute over 10% of the open ocean microbial community. They can be particularly abundant in oligotrophic conditions where they were found to be 24% of the community. Aerobic anoxygenic phototrophic bacteria are photoheterotrophic (phototroph) microbes that exist in a variety of aquatic environments. Most are obligately aerobic, meaning they require oxygen to grow. One aspect of these bacteria is that they, unlike other similar bacteria, are unable to utilize BChl (bacteriochlorophyll) for anaerobic growth. The only photosynthetic pigment that exists in AAPB is BChl-a. Anaerobic phototrophic bacteria, on the contrary, can contain numerous species of photosynthetic pigments like bacteriochlorophyll-a. These bacteria can be isolated using carotenoid presence and medias containing organic compounds. Predation, as well as the availability of phosphorus and light, have been shown to be important factors that influence AAPB growth in their natural environments. AAPBs are thought to play an important role in carbon cycling by relying on organic matter substrates and acting as sinks for dissolved organic carbon. There is still a knowledge gap in research areas regarding the abundance and genetic diversity of AAPB, as well as the environmental variables that regulate these two properties.

Chlorobaculum tepidum, previously known as Chlorobium tepidum, is an anaerobic, thermophilic green sulfur bacteria first isolated from New Zealand. Its cells are gram-negative and non-motile rods of variable length. They contain chlorosomes and bacteriochlorophyll a and c.

<span class="mw-page-title-main">Chlorophyllide</span> Chemical compound

Chlorophyllide a and Chlorophyllide b are the biosynthetic precursors of chlorophyll a and chlorophyll b respectively. Their propionic acid groups are converted to phytyl esters by the enzyme chlorophyll synthase in the final step of the pathway. Thus the main interest in these chemical compounds has been in the study of chlorophyll biosynthesis in plants, algae and cyanobacteria. Chlorophyllide a is also an intermediate in the biosynthesis of bacteriochlorophylls.

Chlorobactane is the diagenetic product of an aromatic carotenoid produced uniquely by green-pigmented green sulfur bacteria (GSB) in the order Chlorobiales. Observed in organic matter as far back as the Paleoproterozoic, its identity as a diagnostic biomarker has been used to interpret ancient environments.

<span class="mw-page-title-main">Chlorophyllide a reductase</span> Enzyme

Chlorophyllide a reductase (EC 1.3.7.15), also known as COR, is an enzyme with systematic name bacteriochlorophyllide-a:ferredoxin 7,8-oxidoreductase. It catalyses the following chemical reaction

References

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  2. 1 2 Bryant DA, et al. (2007-07-27), "Candidatus Chloracidobacterium thermophilum: An Aerobic Phototrophic Acidobacterium", Science, 317 (5837): 523–526, Bibcode:2007Sci...317..523B, doi:10.1126/science.1143236, PMID   17656724, S2CID   20419870
  3. Vogl K, et al. (2012-08-10). "Bacteriochlorophyll f: properties of chlorosomes containing the "forbidden chlorophyll"". Front. Microbiol. 3: article 298, pages 1–12. doi: 10.3389/fmicb.2012.00298 . PMC   3415949 . PMID   22908012.
  4. 1 2 Senge, Mathias O.; Smith, Kevin M. (2004). "Biosynthesis and Structures of the Bacteriochlorophylls". Anoxygenic Photosynthetic Bacteria. Advances in Photosynthesis and Respiration. Vol. 2. pp. 137–151. doi:10.1007/0-306-47954-0_8. ISBN   0-7923-3681-X.
  5. Harada, Jiro; Shibata, Yutaka; Teramura, Misato; Mizoguchi, Tadashi; Kinoshita, Yusuke; Yamamoto, Ken; Tamiaki, Hitoshi (2018). "In Vivo Energy Transfer from Bacteriochlorophyll c , d , e , or f to Bacteriochlorophyll a in Wild-Type and Mutant Cells of the Green Sulfur Bacterium Chlorobaculum limnaeum". ChemPhotoChem. 2 (3): 190–195. doi:10.1002/cptc.201700164.
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  7. Gloe, A; Risch, N (1 August 1978). "Bacteriochlorophyll cs, a new bacteriochlorophyll from Chloroflexus aurantiacus". Archives of Microbiology. 118 (2): 153–6. doi:10.1007/BF00415723. PMID   697505. S2CID   20011765.
  8. Tsukatani, Yusuke; Yamamoto, Haruki; Mizoguchi, Tadashi; Fujita, Yuichi; Tamiaki, Hitoshi (2013). "Completion of biosynthetic pathways for bacteriochlorophyll g in Heliobacterium modesticaldum: The C8-ethylidene group formation". Biochimica et Biophysica Acta (BBA) - Bioenergetics. 1827 (10): 1200–1204. doi: 10.1016/j.bbabio.2013.06.007 . PMID   23820336.
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  10. Willows, Robert D. (2003). "Biosynthesis of chlorophylls from protoporphyrin IX". Natural Product Reports. 20 (6): 327–341. doi:10.1039/B110549N. PMID   12828371.
  11. Battersby, Alan R. (2000). "Tetrapyrroles: The pigments of life: A Millennium review". Natural Product Reports. 17 (6): 507–526. doi:10.1039/B002635M. PMID   11152419.