Spheroidene

Last updated
all-trans-spheroidene
Spheroidene.svg
Names
IUPAC name
(3E)-1-Methoxy-3,4-didehydro-1,2,7',8'-tetrahydro-ψ,ψ-carotene
Systematic IUPAC name
(6E,10E,12E,14E,16E,18E,20E,22E,24E,26E,28E)-31-methoxy-2,6,10,14,19,23,27,31-octamethyldotriaconta-2,6,10,12,14,16,18,20,22,24,26,28-dodecaene
Other names
  • Pigment Y
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
KEGG
MeSH spheroidene
PubChem CID
  • Key: FJOCMTHZSURUFA-AXYGSFPTSA-N
  • InChI=1S/C41H60O/c1-34(2)20-14-23-37(5)26-17-29-38(6)27-15-24-35(3)21-12-13-22-36(4)25-16-28-39(7)30-18-31-40(8)32-19-33-41(9,10)42-11/h12-13,15-16,18-22,24-28,30-32H,14,17,23,29,33H2,1-11H3/b13-12+,24-15+,25-16+,30-18+,32-19+,35-21+,36-22+,37-26+,38-27+,39-28+,40-31+
  • CC(=CCC/C(=C/CC/C(=C/C=C/C(=C/C=C/C=C(\C)/C=C/C=C(\C)/C=C/C=C(\C)/C=C/CC(C)(C)OC)/C)/C)/C)C
Properties
C41H60O
Molar mass 568.930 g·mol−1
Melting point 135–138 °C (275–280 °F; 408–411 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Spheroidene is a carotenoid pigment. It is a component of the photosynthetic reaction center of certain purple bacteria of the Rhodospirillaceae family, including Rhodobacter sphaeroides and Rhodopseudomonas sphaeroides . [1] [2] Like other carotenoids, it is a tetraterpenoid. In purified form, it is a brick-red solid soluble in benzene. [2]

Contents

Spheroidene was discovered by microbiologist C. B. van Niel, who named it "pigment Y". It was renamed by Basil Weedon, who was the first to prepare it synthetically, and to determine its structure, in the mid-1960s. [2]

Function

Spheroidene is bound to the type II photosynthetic reaction center of purple bacteria, and together with the bacteriochlorophyll forms part of the light-harvesting complex. Spheroidene has two major functions in the complex. First, it absorbs visible light in the blue-green part of the visible spectrum (320–500 nm), [2] where bacteriochlorophyll has little absorbance. It then transfers energy to the bacteriochlorophyll via singlet–singlet energy transfer. In this manner the reaction center is able to harness more of the visible light spectrum than would be possible with bacteriochlorophyll alone. [3] Second, spheroidene quenches excited singlet states of bacteriochlorophyll by forming a stable triplet state. This quenching helps to prevent the formation of harmful singlet oxygen. [4] [5] Other functions of spheroidene may include scavenging of singlet oxygen, nonradiative dissipation of excess light energy, and structural stabilization of the photosystem proteins. [4]

Spheroidene is thought to exist as the 15,15'-cis isomer, and not the all-trans isomer commonly shown in the literature, in native photosynthetic reaction centers. [6]

Biosynthesis

The proteins involved in spheroidene biosynthesis are encoded by a gene cluster. [7] Geranylgeranyl pyrophosphate (GGPP) is the precursor to spheroidene and the other carotenoids; two molecules of GGPP condense to form the symmetric tetraterpene phytoene. This molecule then undergoes three desaturations to form neurosporene, which is then hydroxylated, desaturated again, and methoxylated to produce spheroidene. In some species, spheroidene is further oxygenated to produce the ketone spheroidenone. [5]

See also

Related Research Articles

<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.

<span class="mw-page-title-main">Carotenoid</span> Class of chemical compounds; yellow, orange or red plant pigments

Carotenoids are yellow, orange, and red organic pigments that are produced by plants and algae, as well as several bacteria, archaea, and fungi. Carotenoids give the characteristic color to pumpkins, carrots, parsnips, corn, tomatoes, canaries, flamingos, salmon, lobster, shrimp, and daffodils. Over 1,100 identified carotenoids can be further categorized into two classes – xanthophylls and carotenes.

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

Bacteriochlorophylls (BChl) are photosynthetic pigments that occur in various phototrophic bacteria. They were discovered by C. B. van Niel in 1932. 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 Mg2+ with protons gives bacteriophaeophytin (BPh), the phaeophytin form.

<span class="mw-page-title-main">Photosystem</span> Structural units of protein involved in photosynthesis

Photosystems are functional and structural units of protein complexes involved in photosynthesis. Together they carry out the primary photochemistry of photosynthesis: the absorption of light and the transfer of energy and electrons. Photosystems are found in the thylakoid membranes of plants, algae, and cyanobacteria. These membranes are located inside the chloroplasts of plants and algae, and in the cytoplasmic membrane of photosynthetic bacteria. There are two kinds of photosystems: PSI and PSII.

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">Photosynthetic reaction centre</span> Molecular unit responsible for absorbing light in photosynthesis

A photosynthetic reaction center is a complex of several proteins, pigments and other co-factors that together execute the primary energy conversion reactions of photosynthesis. Molecular excitations, either originating directly from sunlight or transferred as excitation energy via light-harvesting antenna systems, give rise to electron transfer reactions along the path of a series of protein-bound co-factors. These co-factors are light-absorbing molecules (also named chromophores or pigments) such as chlorophyll and pheophytin, as well as quinones. The energy of the photon is used to excite an electron of a pigment. The free energy created is then used, via a chain of nearby electron acceptors, for a transfer of hydrogen atoms (as protons and electrons) from H2O or hydrogen sulfide towards carbon dioxide, eventually producing glucose. These electron transfer steps ultimately result in the conversion of the energy of photons to chemical energy.

A light-harvesting complex consists of a number of chromophores which are complex subunit proteins that may be part of a larger super complex of a photosystem, the functional unit in photosynthesis. It is used by plants and photosynthetic bacteria to collect more of the incoming light than would be captured by the photosynthetic reaction center alone. The light which is captured by the chromophores is capable of exciting molecules from their ground state to a higher energy state, known as the excited state. This excited state does not last very long and is known to be short-lived.

<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.

Photoprotection is the biochemical process that helps 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.

Tetraterpenes are terpenes consisting of eight isoprene units and have the molecular formula C40H64. Tetraterpenoids (including many carotenoids) are tetraterpenes that have been chemically modified, as indicated by the presence of oxygen-containing functional groups.

<span class="mw-page-title-main">Biological pigment</span> Substances produced by living organisms

Biological pigments, also known simply as pigments or biochromes, are substances produced by living organisms that have a color resulting from selective color absorption. Biological pigments include plant pigments and flower pigments. Many biological structures, such as skin, eyes, feathers, fur and hair contain pigments such as melanin in specialized cells called chromatophores. In some species, pigments accrue over very long periods during an individual's lifespan.

<span class="mw-page-title-main">Photosynthetic reaction centre protein family</span>

Photosynthetic reaction centre proteins are main protein components of photosynthetic reaction centres (RCs) of bacteria and plants. They are transmembrane proteins embedded in the chloroplast thylakoid or bacterial cell membrane.

<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.

Rhodobacter sphaeroides is a kind of purple bacterium; a group of bacteria that can obtain energy through photosynthesis. Its best growth conditions are anaerobic phototrophy and aerobic chemoheterotrophy in the absence of light. R. sphaeroides is also able to fix nitrogen. It is remarkably metabolically diverse, as it is able to grow heterotrophically via fermentation and aerobic and anaerobic respiration. Such a metabolic versatility has motivated the investigation of R. sphaeroides as a microbial cell factory for biotechnological applications.

<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.

<span class="mw-page-title-main">Orange carotenoid protein</span>

Orange carotenoid protein (OCP) is a water-soluble protein which plays a role in photoprotection in diverse cyanobacteria. It is the only photoactive protein known to use a carotenoid as the photoresponsive chromophore. The protein consists of two domains, with a single keto-carotenoid molecule non-covalently bound between the two domains. It is a very efficient quencher of excitation energy absorbed by the primary light-harvesting antenna complexes of cyanobacteria, the phycobilisomes. The quenching is induced by blue-green light. It is also capable of preventing oxidative damage by directly scavenging singlet oxygen (1O2).

<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.

Light harvesting materials harvest solar energy that can then be converted into chemical energy through photochemical processes. Synthetic light harvesting materials are inspired by photosynthetic biological systems such as light harvesting complexes and pigments that are present in plants and some photosynthetic bacteria. The dynamic and efficient antenna complexes that are present in photosynthetic organisms has inspired the design of synthetic light harvesting materials that mimic light harvesting machinery in biological systems. Examples of synthetic light harvesting materials are dendrimers, porphyrin arrays and assemblies, organic gels, biosynthetic and synthetic peptides, organic-inorganic hybrid materials, and semiconductor materials. Synthetic and biosynthetic light harvesting materials have applications in photovoltaics, photocatalysis, and photopolymerization.

<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

  1. Harrison, D.M. (1986). "The biosynthesis of carotenoids". Natural Product Reports. 3 (3): 205–215. doi:10.1039/np9860300205. PMID   3534642.
  2. 1 2 3 4 Barber, M.S.; Jackman, L.M.; Manchand, P.S.; Weedon, B.C.L. (1966). "Carotenoids and related compounds. Part XVI. Structural and synthetic studies on spirilloxanthin, chloroxanthin, spheroidene, and spheroidenone". Journal of the Chemical Society C: 2166–2176. doi:10.1039/j39660002166.
  3. Hashimoto, Hideki; Uragami, Chiasa; Cogdell, Richard J. (2016). "Carotenoids and Photosynthesis". Carotenoids in Nature. Subcellular Biochemistry. Vol. 79. pp. 111–139. doi:10.1007/978-3-319-39126-7_4. ISBN   978-3-319-39124-3. PMID   27485220.
  4. 1 2 Frank, Harry A.; Cogdell, Richard J. (1996). "Carotenoids in photosynthesis". Photochemistry and Photobiology. 63 (3): 257–264. doi:10.1111/j.1751-1097.1996.tb03022.x. ISSN   0031-8655. PMID   8881328. S2CID   1900488.
  5. 1 2 Maresca, Julia A.; Graham, Joel E.; Bryant, Donald A. (2008). "The biochemical basis for structural diversity in the carotenoids of chlorophototrophic bacteria". Photosynthesis Research. 97 (2): 121–140. doi:10.1007/s11120-008-9312-3. PMID   18535920. S2CID   2056720.
  6. Mathies, Guinevere; van Hemert, Marc C.; Gast, Peter; Gupta, Karthick B. Sai Sankar; Frank, Harry A.; Lugtenburg, Johan; Groenen, Edgar J.J. (2011). "Configuration of spheroidene in the photosynthetic reaction center of Rhodobacter spheroides: A comparison of wild-type and reconstituted R26". Journal of Physical Chemistry A. 115 (34): 9552–9556. Bibcode:2011JPCA..115.9552M. doi:10.1021/jp112413d. hdl: 1887/3570972 . ISSN   1089-5639. PMID   21604722.
  7. Naylor, Grant William; Addlesee, Hugh Alistair; Gibson, Lucien Charles Donald; Hunter, Christopher Neil (1999). "The photosynthesis gene cluster of Rhodobacter sphaeroides". Photosynthesis Research. 62 (2–3): 121–139. doi:10.1023/A:1006350405674. ISSN   0166-8595. S2CID   20340930.