Cyberlipid

 

 

UBIQUINONES

 


These molecules are also known as coenzyme Q or mitoquinones. They are involved in electron transport in mitochondrial preparations playing an essential role in the oxidation of succinate or NADH via the cytochrome system. They serves not only as a coenzyme but also, in their reduced forms, as antioxidants. They are synthesized de novo in all animal tissues and cannot thus be regarded as vitamins. Ubiquinones are present in all aerobic organisms, plants, animals (the name ubiquinone was proposed with reference to their ubiquitous occurrence) and bacteria, but are absent from Gram-positive eubacteria and the archaebacteria. They were discovered by the Morton’s group (Biochem J 1955, 59, 558) in animal fat but their quinonoid structure was revealed by Crane two years later (Biochim Biophys Acta 1957, 25, 220) in extracts from beef heart mitochondria. The compound had a 2,3-dimethoxy-5-methylbenzoquinone nucleus and a side chain of 10 
isoprenoid units and was referred to as coenzyme Q 10 . Later, homologues with 6, 7, 8 and 9 units were isolated from other organisms, bacteria or higher organisms. The main form in man has 10 units but in rat has 9 units. Another system of nomenclature is used: ubiquinone(x) in which x designates the total number of carbon atoms in the side chain, it can be a multiple of 5. Thus, coenzyme Q10 is also named ubiquinone (50). Ubiquinone became the “official” name of the compound in 1975 (IUPAC-IUB commission).
Recent review: “Biochemical, physiological and medical aspects of ubiquinone function” by Ernster L et al. (Biochim Biophys Acta 1995, 1271, 195).

 

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Ubiquinones accept one electron and are transformed into semiquinone radicals (UQH°) or two electrons to give ubiquinol (UQH2)

 

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Coenzyme Q is reducible by sodium dithionite or borohydride to its hydroquinone form, and can in turn be reoxidized to the quinone by Ag2O or more slowly by oxygen. The absorption spectra of the two forms are shown below. The quinone form has a strong absorption band at 275 nm which disappears in the reduced form.

 

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Ubiquinone-9: MW 794     Ubiquinone-10: MW 862
Ubiquinones are readily destroyed by heating in alkali , but in the presence of pyrogallol the destruction is minimized.

Idebenone is a synthetic analogue of coenzyme Q10 which has antioxidant properties.Iinitially developed by Takeda Pharmaceutical Company for the treatment of Alzheimer’s disease. it was investigated by the Swiss company Santhera Pharmaceuticals for the treatment of neuromuscular diseases. Several indications have been approveed in some countries and many research are in progress in various nervous pathologies (treatment of neurodegenerative diseases) and skin disorders (Montenegro L et al., Nanomaterials 2018, 8(2). pii: E87). 

 

Idebenone

 

A new quinone compound with estrogenic properties has been isolated from yam tuber (Dioscorea alata) (Cheng WY et al., J Agric Food Chem 2007, 55, 7350). This product was identified as hydro-Q9 chromene, a derivative of coenzyme Q9.

 

hydro-Q9 chromene
Hydro-Q9 chromene

 

The presence of that biologically active compound in yam extract likely provides basic evidence for a part of its beneficial effect for menopausal women.


 

PLASTOQUINONES

 

 

A substituted quinone was isolated in a lipid extract of lucerne by Kofler in 1946. The discovery of ubiquinone and of its role in mitochondrial electron transport stimulated studies of related substances. Crane FL (1959) suggested that this quinone was called plastoquinone because it appeared concentrated in the chloroplasts of higher plants. Rapidly, it appeared that plastoquinone plays a role analogous to that of ubiquinone in mitochondria but associated with the transformation of light into chemical energy. They are also present in algae and cyanobacteria.
The elucidation of the structure of plastoquinone was that of a 2,3-dimethyl-1,4-benzoquinone with a C45 side chain related to the isoprenoid alcohol, solanesol.

There are several plastoquinones with side chains of different length in position 5. They are designated as plastoquinone-n where n is the number of carbon atoms in the side chain or better as PQ-n where n indicates the number of isoprenoid units. n varies from 6 to 9.

 

 

Plastoquinone is a yellow crystalline solid (PQ-9 has a MW of 748) soluble in most organic solvents. It has a characteristic UV spectrum with a maximum at 255 nm (molar abs. coeff.: 15700). On reduction (with sodium borohydride) a single maximum of lower intensity at 290 nm (molar abs. coeff.: 3440) is observed.

 

 

Several plastoquinone and plastohydroquinone analogues have been described in brown algae (Reddy P et al., Phytochemistry 2009, 70, 250). They differ primarily in the linear terpene chain moiety which has hydroxy and carbonyl groups in various positions. As an example, we give below the structures of the simplest (sargaquinone) and one of the most complex (fallaquinone) described in Sargassum fallax.

 

 Sargaquinone

Fallaquinone

 

Many of these molecules displayed significant antioxidant, potent antiviral or moderate antitumour activities.

 

 

HETEROCYCLIC QUINONES

 


Various heterocyclic quinones have been described in sulphur-oxidizing archaebacteria, the benzothiophenoquinones.

 

 

Several species of these quinones are present with menaquinones in the same bacteria. R1 may be -CH3 or -SCH3, and R2 is an isoprenoid chain, saturated or mono6unsaturated, with 3 to 6 isoprenoid units.

 

 

ALKYL HYDROQUINONES

 

 

tert-Butylhydroquinone is a synthetic aromatic organic compound which is a derivative of hydroquinone, substituted with a tert-butyl group. In foods, It is used as an antioxidant to preserve unsaturated vegetable oils and many edible animal fats. It can be combined with other preservatives such as butylated hydroxyanisole. As a food additive, its E number is E319. While it has been determined as safe to consume at the concentration allowed in foods, a number of studies have shown that prolonged exposure to very high doses of butylhydroquinone may be carcinogenic.

 


tert-Butylhydroquinone

 


Several alkylated hydroquinones have been described in vegetals.

As an example, we give below the common structure of cytotoxic compounds discovered in Tapirira guianensis, a tall tree from Mexico to Brazil, used as folk medicine (m = 8 and n = 5) (David JM et al., J Nat Prod 1998, 61, 287) and in Lannea welwitschii (lanneaquinol with m = 6 and n = 7) (Groweiss A et al., J Nat prod 1997, 60, 116). 

 

 

These two products displayed cytotoxic activity against human prostate cancer.

 

A large number of linear polyprenylhydroquinones (plastoquinones without methyl groups) have been isolated from sponges, especially from the Irciniidae family. Biological studies conducted on several of these molecules showed them to have a moderate antibacterial, antiviral, and anti-inflammatory activity. These linear polyprenylhydroquinones could be further divided in two main groups with polyprenylhydroquinones sulfates (De Rosa S et al., J Nat Prod 1995, 58, 1450) and hydroxylated polyprenylhydroquinones (Abed C et al., Mar Drugs 2011, 9, 1210).

 

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