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Naphthoquinones of the spinochrome class: occurrence, isolation, biosynthesis and biomedical applications.
Hou Y
,
Vasileva EA
,
Carne A
,
McConnell M
,
El-Din A Bekhit A
,
Mishchenko NP
.
Abstract
Quinones are widespread in nature and have been found in plants, fungi and bacteria, as well as in members of the animal kingdom. More than forty closely related naphthoquinones have been found in echinoderms, mainly in sea urchins but occasionally in brittle stars, sea stars and starfish. This review aims to examine controversial issues on the chemistry, biosynthesis, functions, stability and application aspects of the spinochrome class, a prominent group of secondary metabolites found in sea urchins. The emphasis of this review is on the isolation and structure of these compounds, together with evaluation of their relevant biological activities, source organisms, the location of origin and methods used for isolation and identification. In addition, the studies of their biosynthesis and ecological function, stability and chemical synthesis have been highlighted. This review aims to establish a focus for future spinochrome research and its potential for benefiting human health and well-being.
Fig. 1. Polyketide pathway of spinochrome biogenesis.
Fig. 2. Summary of extraction, purification and identification methods for spinochrome pigments from sea urchin shells and spines.
Scheme 1. Synthesis of spinochromes as described by Singh et al.90 Reagents and conditions: (i) AlCl3–NaCl, 195 °C; (ii) MeONa, MeOH, reflux; (iii) conc. HBr, reflux.
Scheme 2. Synthesis of spinochrome E (6) as described by Borisova and Anufriev.94 Reagents and conditions: (i) (EtO)3CH, reflux; (ii) NaNO2, EtOH, H2O, heating; (iii) Na2S2O4, H2O; (iv) AlCl3, PhNO2, heating, then 5% HCl, heating.
Scheme 3. Synthesis of echinamines A (30) and B (31) as described by Pokhilo et al.95 Reagents and conditions: (i) NaN3, DMSO, 50 °C, then H2O; (ii) HBr-HOAc, reflux.
Scheme 4. Synthesis of bis(trihydroxynaphthazarin) (23).98 Reagents and conditions: (i) MeNH2·HCl, EtOH, heating 4 h; (ii) AlCl3, PhNO2, 70 °C, 12 h.
Scheme 5. Synthesis of echinochrome A (1) as described by Peña-Cabrera and Liebeskind.99
Agafonova,
Evaluation of effects of histochrome and mexidol on structural and functional characteristics of the brain in senescence-accelerated OXYS rats by magnetic resonance imaging.
2011, Pubmed
Agafonova,
Evaluation of effects of histochrome and mexidol on structural and functional characteristics of the brain in senescence-accelerated OXYS rats by magnetic resonance imaging.
2011,
Pubmed
Agafonova,
Assessment of Nephroprotective Potential of Histochrome during Induced Arterial Hypertension.
2015,
Pubmed
Anderson,
Distribution of spinochrome pigments in echinoids.
1969,
Pubmed
,
Echinobase
Anufriev VPh,
Synthesis of some hydroxynaphthazarins and their cardioprotective effects under ischemia-reperfusion in vivo.
1998,
Pubmed
Branco,
The impact of rising sea temperature on innate immune parameters in the tropical subtidal sea urchin Lytechinus variegatus and the intertidal sea urchin Echinometra lucunter.
2013,
Pubmed
,
Echinobase
Brasseur,
The Roles of Spinochromes in Four Shallow Water Tropical Sea Urchins and Their Potential as Bioactive Pharmacological Agents.
2017,
Pubmed
,
Echinobase
Calestani,
Isolation of pigment cell specific genes in the sea urchin embryo by differential macroarray screening.
2003,
Pubmed
,
Echinobase
Egorov,
[Histochrome, a new antioxidant, in the treatment of ocular diseases].
1999,
Pubmed
GOODWIN,
A study of the pigments of the sea-urchins, Echinus esculentus L. and Paracentrotus lividus Lamarck.
1950,
Pubmed
,
Echinobase
Haug,
Antibacterial activity in Strongylocentrotus droebachiensis (Echinoidea), Cucumaria frondosa (Holothuroidea), and Asterias rubens (Asteroidea).
2002,
Pubmed
,
Echinobase
Herrmann,
THE SHIKIMATE PATHWAY.
1999,
Pubmed
Hou,
Naphthoquinones of the spinochrome class: occurrence, isolation, biosynthesis and biomedical applications.
2018,
Pubmed
Jeong,
Echinochrome A protects mitochondrial function in cardiomyocytes against cardiotoxic drugs.
2014,
Pubmed
,
Echinobase
Kim,
Echinochrome A regulates phosphorylation of phospholamban Ser16 and Thr17 suppressing cardiac SERCA2A Ca²⁺ reuptake.
2015,
Pubmed
,
Echinobase
Kominami,
Behavior of pigment cells in gastrula-stage embryos of Hemicentrotus pulcherrimus and Scaphechinus mirabilis.
2001,
Pubmed
,
Echinobase
Kuzuya,
Inhibition of dopamine-beta-hydroxylase by spinochrome A and echinochrome A, naphthoquinone pigments of echinoids.
1973,
Pubmed
,
Echinobase
Lebed'ko,
Effect of Antioxidant Echinochrome A on Bleomycin-Induced Pulmonary Fibrosis.
2015,
Pubmed
Lebedev,
How do calcium ions induce free radical oxidation of hydroxy-1,4-naphthoquinone? Ca2+ stabilizes the naphthosemiquinone anion-radical of echinochrome A.
2003,
Pubmed
,
Echinobase
Lebedev,
Antioxidant properties, autooxidation, and mutagenic activity of echinochrome a compared with its etherified derivative.
2001,
Pubmed
Lee,
Acetylcholinesterase inhibitory activity of pigment echinochrome A from sea urchin Scaphechinus mirabilis.
2014,
Pubmed
,
Echinobase
Mischenko,
Echinamines A and B, first aminated hydroxynaphthazarins from the sea urchin Scaphechinus mirabilis.
2005,
Pubmed
,
Echinobase
Mizutani,
Inhibition of tyrosine hydroxylase by naphthoquinone pigments of echinoids.
1972,
Pubmed
,
Echinobase
Mohamed,
Mechanisms of echinochrome potency in modulating diabetic complications in liver.
2016,
Pubmed
,
Echinobase
Natori,
The structures of mompain and deoxyhelicobasidin and the biosynthesis of helicobasidin, quinonoid metabolites of Helicobasidium mompa Tanaka.
1967,
Pubmed
Peña-Cabrera,
Squaric acid ester-based total synthesis of echinochrome A.
2002,
Pubmed
,
Echinobase
Pinsino,
Sea urchin immune cells as sentinels of environmental stress.
2015,
Pubmed
,
Echinobase
Pokhilo,
Synthesis of echinamines A and B, the first aminated hydroxynaphthazarins produced by the sea urchin Scaphechinus mirabilis and its analogues.
2006,
Pubmed
,
Echinobase
Pokhilo,
Synthesis, Cytotoxic and Contraceptive Activity of 6,8,9-Trihydroxy-2-methyl-2H-naphtho[2,3-b]pyran-5,10-dione, a Pigment of Echinothrix diadema, and its Analogs.
2015,
Pubmed
,
Echinobase
Pozharitskaya,
Antiallergic effects of pigments isolated from green sea urchin (Strongylocentrotus droebachiensis) shells.
2013,
Pubmed
,
Echinobase
Salaque,
[On the biosynthesis of echinochrome A by the sea urchin Arbacia pustulosa].
1967,
Pubmed
,
Echinobase
Seo,
Echinochrome A Improves Exercise Capacity during Short-Term Endurance Training in Rats.
2015,
Pubmed
,
Echinobase
Shestak,
Preparative production of spinochrome E, a pigment of different sea urchin species.
2014,
Pubmed
,
Echinobase
Shikov,
The offline combination of thin-layer chromatography and high-performance liquid chromatography with diode array detection and micrOTOF-Q mass spectrometry for the separation and identification of spinochromes from sea urchin (Strongylocentrotus droebachiensis) shells.
2011,
Pubmed
,
Echinobase
Shikov,
Comparative stability of dimeric and monomeric pigments extracted from sea urchin Strongylocentrotus droebachiensis.
2017,
Pubmed
,
Echinobase
Singh,
The synthesis of spinochromes A, C, D, and E.
1965,
Pubmed
Stekhova,
[Antimicrobial activity of polyhydroxynaphthoquinones from sea urchins].
1988,
Pubmed
,
Echinobase
Suh,
Hypoxia-modulated gene expression profiling in sea urchin (Strongylocentrotus nudus) immune cells.
2014,
Pubmed
,
Echinobase
Tyler,
Crystalline Echinochrome and Spinochrome: Their Failure to Stimulate the Respiration of Eggs and of Sperm of Strongylocentrotus.
1939,
Pubmed
,
Echinobase
Vasileva,
New Aminonaphthoquinone from the Sea Urchins Strongylocentrotus pallidus and Mesocentrotus nudus.
2016,
Pubmed
,
Echinobase
Vasileva,
Diversity of Polyhydroxynaphthoquinone Pigments in North Pacific Sea Urchins.
2017,
Pubmed
,
Echinobase
WHITE,
THE FUNCTION OF 2-DEMETHYL VITAMIN K2 IN THE ELECTRON TRANSPORT SYSTEM OF HEMOPHILUS PARAINFLUENZAE.
1965,
Pubmed