Aplysioviolin

Last updated
Aplysioviolin
Aplysioviolin.svg
Identifiers
3D model (JSmol)
ChemSpider
PubChem CID
  • InChI=1S/C34H40N4O6/c1-8-21-20(6)33(42)38-28(21)15-26-18(4)23(10-12-31(39)40)29(36-26)16-30-24(11-13-32(41)44-7)19(5)25(35-30)14-27-17(3)22(9-2)34(43)37-27/h8-9,15-16,20,27,35-36H,2,10-14H2,1,3-7H3,(H,37,43)(H,39,40)/b21-8+,26-15?,29-16?/t20-,27-/m1/s1
    Key: QTKXLHIVFZPNBG-YLZFFTCBSA-N
  • CC=C1C(C(=O)N=C1C=C2C(=C(C(=CC3=C(C(=C(N3)CC4C(=C(C(=O)N4)C=C)C)C)CCC(=O)OC)N2)CCC(=O)O)C)C
Properties
C34H40N4O6
Molar mass 600.716 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Aplysia californica secreting ink containing aplysioviolin. Aplysia californica.jpg
Aplysia californica secreting ink containing aplysioviolin.

Aplysioviolin is a purple-colored molecule secreted by sea hares of the genera Aplysia and Dolabella to deter predators. [1] Aplysioviolin is a chemodeterrent, serving to dispel predators on olfactory and gustatory levels as well as by temporarily blinding predators with the molecule's dark color. Aplysioviolin is an important component of secreted ink and is strongly implicated in the sea hares' predatory escape mechanism. While the ink mixture as a whole may produce dangerous hydrogen peroxide and is relatively acidic, the aplysioviolin component alone has not been shown to produce human toxicity. [1]

Contents

Biosynthetic origin

Aplysioviolin is a metabolic product of Aplysia californica species of sea hare, and is a major component to its ink mixture. Sea hares first consume red algae as nutriment, and extract from it the light-harvesting pigment phycoerythrin, cleaving it to separate the red-colored chromophore phycoerythrobilin from its covalently-bound protein structure. The sea hare then methylates one of phycoerythrobilin's two carboxylic acid functional groups to form aplysioviolin, which is concentrated and then stored in the ink gland. [2]

Chemical mechanism for aplysioviolin biosynthesis. An enzyme provides a methyl group that the right-sided hydroxyl selectively attacks, forming the methyl-ester moiety that characterizes aplysioviolin. APV Mech.jpg
Chemical mechanism for aplysioviolin biosynthesis. An enzyme provides a methyl group that the right-sided hydroxyl selectively attacks, forming the methyl-ester moiety that characterizes aplysioviolin.

Mechanism of action

Aplysioviolin, when squirted or otherwise exposed to predators, causes avoidance behavior that allows the sea hare to escape from being eaten. While its effects on predatory behavior have been investigated, the precise enzymatic targets of aplysioviolin are as of yet unknown. The behavioral effects of aplysioviolin have been especially characterized in blue crabs, whose feeding behavior is relatively easy to observe. In addition however, aplysioviolin has been shown to deter the approach of spiny lobsters, sea catfish, and other fish and crustacean species. [2] The sea anemone Anthopleura sola has also been shown to retract its feeding protrusions when exposed to aplysioviolin. [3] Aplysioviolin is known to be the major chemodeterrent compound in Aplysia but it is not the only one; both opaline and phycoerythrobilin have been shown to carry chemodeterrant effects, although they are less potent than aplysioviolin. Concentrations of aplysioviolin and phycoerythrobilin in ink are dependent on species: one study showed a 9:1 ratio (27 mg/mL and 3 mg/mL) of aplysioviolin to phycoerythrobilin in A. californica, and a 3.4:1 ratio (2.4 mg/mL and 0.7 mg/mL) for A. dactylomela. Aplysioviolin is often released with escapin in ink, which catalyzes conversion of ink metabolites into hydrogen peroxide, which is an additional deterrent of predators. [1]

History

Aplysioviolin, along with the other components of sea hare ink, has been utilized as a dye since antiquity. Aplysioviolin in particular has been implicated in classical-age dyeing, and has recently been the subject of investigation as the ancient tekhelet (תְּכֵלֶת) dye of Hebrew and other Mediterranean civilizations, [4] though it remains one of several possible historical contenders. Aplysioviolin was first specifically isolated and characterized as a pH-dependent color-changing zoochrome by Lederer & Huttrer in 1942. [5] A first structure was proposed by Rüdiger in 1967 [6] using a chromic-acid based microdegredation technique. This technique was similarly applied in the years following to characterize the structures of the related compounds phycoerythrobilin and phycocyanobilin. [7] The 1967 proposed structure was later modified to remove an angular hydroxyl group at the 7' position, and the final structure was given by Rüdiger & O'Carra in 1969. [8]

Diagram of Rudiger's two structural elucidations of aplysioviolin. Note the difference between the -OH and -H functional groups on the 7' carbon. APV Rudiger.jpg
Diagram of Rüdiger's two structural elucidations of aplysioviolin. Note the difference between the -OH and -H functional groups on the 7' carbon.

Human applications

The principal application of aplysioviolin has been historically in dyeing textiles. Aplysioviolin, in contrast to other more widely-used dyes, is considered a light-sensitive arylmethane dye, and is thus known for fading over time. Other pigments have been similarly extracted from marine animals, including Tyrian purple (6,6-dibromoindigo), from Murex purpuream shellfish, and additionally used as dyes.

Aplysioviolin has seen renewed interest in recent years due to its application to medicine and optical microscopy. Especially given its chirality, aplysioviolin and other natural compounds may serve as useful tools for stereoselective drug production and directed optical polarization. Within the past decade, aplysioviolin has additionally been hypothesized to confer medical pharmacodynamic effects. While as of yet uncharacterized in humans, the bioactive effects seen in fish are hypothesized to be recapitulated in some form in mammalian organisms. [9]

Related Research Articles

<span class="mw-page-title-main">Tyrian purple</span> Natural dye extracted from Murex sea snails

Tyrian purple, also known as, royal purple, imperial purple, or imperial dye, is a reddish-purple natural dye. The name Tyrian refers to Tyre, Lebanon. It is secreted by several species of predatory sea snails in the family Muricidae, rock snails originally known by the name 'Murex'. In ancient times, extracting this dye involved tens of thousands of snails and substantial labor, and as a result, the dye was highly valued. The colored compound is 6,6′-dibromoindigo.

<span class="mw-page-title-main">California sea hare</span> Species of gastropod

The California sea hare is a species of sea slug in the sea hare family, Aplysiidae. It is found in the Pacific Ocean, off the coast of California in the United States and northwestern Mexico.

<span class="mw-page-title-main">Anaspidea</span> Clade of gastropods

The clade Anaspidea, commonly known as sea hares, are medium-sized to very large opisthobranch gastropod molluscs with a soft internal shell made of protein. These are marine gastropod molluscs in the superfamilies Aplysioidea and Akeroidea.

<span class="mw-page-title-main">Sea slug</span> Group of marine invertebrates with varying levels of resemblance to terrestrial slugs

Sea slug is a common name for some marine invertebrates with varying levels of resemblance to terrestrial slugs. Most creatures known as sea slugs are gastropods, i.e. they are sea snails that over evolutionary time have either completely lost their shells, or have seemingly lost their shells due to having a greatly reduced or internal shell. The name "sea slug" is most often applied to nudibranchs, as well as to a paraphyletic set of other marine gastropods without obvious shells.

The Aplysia gill and siphon withdrawal reflex (GSWR) is an involuntary, defensive reflex of the sea hare Aplysia californica, a large shell-less sea snail or sea slug. This reflex causes the sea hare's delicate siphon and gill to be retracted when the animal is disturbed. Aplysia californica is used in neuroscience research for studies of the cellular basis of behavior including: habituation, dishabituation, and sensitization, because of the simplicity and relatively large size of the underlying neural circuitry.

<i>Hexaplex trunculus</i> Species of gastropod

Hexaplex trunculus is a medium-sized sea snail, a marine gastropod mollusk in the family Muricidae, the murex shells or rock snails. It is included in the subgenus Trunculariopsis.

<span class="mw-page-title-main">Aplysiidae</span> Family of gastropods

Aplysiidae is the only family in the superfamily Aplysioidea, within the clade Anaspidea. These animals are commonly called sea hares because, unlike most sea slugs, they are often quite large, and when they are underwater, their rounded body shape and the long rhinophores on their heads mean that their overall shape resembles that of a sitting rabbit or hare. Sea hares are however sea snails with shells reduced to a small plate hidden between the parapodia, and some species are extremely large. The Californian black sea hare, Aplysia vaccaria is arguably the largest living gastropod species, and is certainly the largest living heterobranch gastropod.

<i>Aplysia</i> Genus of sea slugs

Aplysia is a genus of medium-sized to extremely large sea slugs, specifically sea hares, which are a kind of marine gastropod mollusk.

<i>Tekhelet</i> A blue dye mentioned in the Hebrew Bible and prized by ancient Mediterranean civilizations

Tekhelet is a highly valued dye described as "blue-violet”, “blue”, or "turquoise" that held great significance in ancient Mediterranean civilizations. In the Hebrew Bible and Jewish tradition, tekhelet was used to color the clothing of the High Priest, the tapestries in the Tabernacle, and the tzitzit (fringes) attached to the corners of four-cornered garments, including the tallit. The mention of tekhelet is particularly notable in the third paragraph of the Shema, referencing Numbers 15:37–41.

<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">Rhinophore</span> Anatomy of groups of marine gastropods

A rhinophore is one of a pair of chemosensory club-shaped, rod-shaped or ear-like structures which are the most prominent part of the external head anatomy in sea slugs, marine gastropod opisthobranch mollusks such as the nudibranchs, sea hares (Aplysiomorpha), and sap-sucking sea slugs (Sacoglossa).

<i>Aplysia dactylomela</i> Species of gastropod

Aplysia dactylomela, the spotted sea hare, is a species of large sea slug, a marine opisthobranch gastropod in the family Aplysiidae, the sea hares.

<span class="mw-page-title-main">Cephalopod ink</span> Dark pigment released by cephalopods

Cephalopod ink is a dark-coloured or luminous ink released into water by most species of cephalopod, usually as an escape mechanism. All cephalopods, with the exception of the Nautilidae and the Cirrina, are able to release ink to confuse predators.

<i>Aplysia punctata</i> Species of gastropod

The spotted sea hare is a species of sea slug in the family Aplysiidae, the sea hares. It reaches a length of up to 20 cm (7.9 in) and is found in the northeast Atlantic, ranging from Greenland and Norway to the Mediterranean Sea.

<i>Aplysia vaccaria</i> Species of gastropod

Aplysia vaccaria, also known as the black sea hare and California black sea hare, is a species of extremely large sea slug, a marine, opisthobranch, gastropod mollusk in the family Aplysiidae. It is the largest sea slug species.

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

Chemical defense is a strategy employed by many organisms to avoid consumption by producing toxic or repellent metabolites or chemical warnings which incite defensive behavioral changes. The production of defensive chemicals occurs in plants, fungi, and bacteria, as well as invertebrate and vertebrate animals. The class of chemicals produced by organisms that are considered defensive may be considered in a strict sense to only apply to those aiding an organism in escaping herbivory or predation. However, the distinction between types of chemical interaction is subjective and defensive chemicals may also be considered to protect against reduced fitness by pests, parasites, and competitors. Repellent rather than toxic metabolites are allomones, a sub category signaling metabolites known as semiochemicals. Many chemicals used for defensive purposes are secondary metabolites derived from primary metabolites which serve a physiological purpose in the organism. Secondary metabolites produced by plants are consumed and sequestered by a variety of arthropods and, in turn, toxins found in some amphibians, snakes, and even birds can be traced back to arthropod prey. There are a variety of special cases for considering mammalian antipredatory adaptations as chemical defenses as well.

<span class="mw-page-title-main">Pain in invertebrates</span> Contentious issue

Pain in invertebrates is a contentious issue. Although there are numerous definitions of pain, almost all involve two key components. First, nociception is required. This is the ability to detect noxious stimuli which evokes a reflex response that moves the entire animal, or the affected part of its body, away from the source of the stimulus. The concept of nociception does not necessarily imply any adverse, subjective feeling; it is a reflex action. The second component is the experience of "pain" itself, or suffering—i.e., the internal, emotional interpretation of the nociceptive experience. Pain is therefore a private, emotional experience. Pain cannot be directly measured in other animals, including other humans; responses to putatively painful stimuli can be measured, but not the experience itself. To address this problem when assessing the capacity of other species to experience pain, argument-by-analogy is used. This is based on the principle that if a non-human animal's responses to stimuli are similar to those of humans, it is likely to have had an analogous experience. It has been argued that if a pin is stuck in a chimpanzee's finger and they rapidly withdraw their hand, then argument-by-analogy implies that like humans, they felt pain. It has been questioned why the inference does not then follow that a cockroach experiences pain when it writhes after being stuck with a pin. This argument-by-analogy approach to the concept of pain in invertebrates has been followed by others.

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

Phagomimicry is a defensive behaviour of sea hares, in which the animal ejects a mixture of chemicals, which mimic food, and overwhelm the senses of their predator, giving the sea hare a chance to escape. The typical defence response of the sea hare to a predator is to release two chemicals - ink from the ink gland and opaline from the opaline gland. While ink creates a dark, diffuse cloud in the water which disrupts the sensory perception of the predator by acting as a smokescreen and as a decoy, the opaline, which affects the senses dealing with feeding, causes the predator to instinctively attack the cloud of chemicals as if it were indeed food. This ink is able to mimic food by having a high concentration of amino acids and other compounds that are normally found in food, and the attack behaviour of the predator allows the sea-hares the opportunity to escape.

<span class="mw-page-title-main">Opaline gland</span> Defensive gland in sea hares

Sea hares are gastropods without hard shells, using their specialized ink as their main defensive mechanism instead. Their ink has several purposes, most of which have a chemical basis. For one, the ink serves to cloud the predator's vision as well as halt their senses temporarily. In addition, the chemicals in the ink mimic food. Their skin and digestive tract are toxic to predators as well. They are also seen to change their feeding behaviours in response to averse stimuli.

<i>Aplysia gigantea</i> Species of mollusc in the family Aplysiidae

Aplysia gigantea is a species of sea slug, a shell-less marine gastropod mollusk in the family Aplysiidae. The species was first described in the Journal of the Malacological Society of Australia in 1869. A. gigantea is also known more commonly as the sea hare due to their posterior chemosensory tentacles resembling a hare's ear. A. gigantea is the largest known species in Australia of the opisthobranch genus. The species is known to have toxic effects on terrestrial organisms, particularly domestic dogs. Exposure to this species with dogs has been associated with the development of neurotoxicosis, with symptoms ranging from respiratory distress to tremors, muscle fasciculations, and seizures.

References

  1. 1 2 3 Kamio, Michiya; Grimes, Tiphani; Hutchins, Melissa; Van Dam, Robyn; Derby, Charles (July 2010). "The purple pigment aplysioviolin in sea hare ink deters predatory blue crabs through their chemical senses". Animal Behaviour. 80 (1): 89–100. doi:10.1016/j.anbehav.2010.04.003. S2CID   53162083.
  2. 1 2 Derby, Charles; Aggio, Juan (1 November 2011). "The Neuroecology of Chemical Defenses". Integrative and Comparative Biology. 51 (5): 771–780. doi: 10.1093/icb/icr063 . PMID   21705367.
  3. Kamio, Michiya; Derby, Charles D. (10 May 2017). "Finding food: how marine invertebrates use chemical cues to track and select food". Natural Product Reports. 34 (5): 514–528. doi:10.1039/c6np00121a. ISSN   1460-4752. PMID   28217773.
  4. Kitrossky, Levi. "Do We Know Tekhelet?" (PDF). Retrieved 24 April 2018.
  5. Needham, Arthur E. (1974). The Significance of Zoochromes. Heidelberg: Springer-Verlag. p. 78. ISBN   978-3-642-80768-8.
  6. Rüdiger, Wolfhart (February 1967). "On the defensive dyes in Aplysia species. I. Aplysioviolin, a new bile pigment". Hoppe-Seyler's Zeitschrift für Physiologische Chemie. 348 (2): 129–38. doi:10.1515/bchm2.1967.348.1.129. PMID   6033876.
  7. RÜDIGER, WOLFHART; CARRA, PÁDRAIG Ó; HEOCHA, COLM Ó (September 1967). "Structure of Phycoerythrobilin and Phycocyanobilin". Nature. 215 (5109): 1477–1478. Bibcode:1967Natur.215.1477R. doi:10.1038/2151477a0. ISSN   0028-0836. PMID   6052748. S2CID   4221727.
  8. Rüdiger, Wolfhart; O'Carra, Pádraig (1969). "Studies on the Structures and Apoprotein Linkages of the Phycobilins". European Journal of Biochemistry. 7 (4): 509–516. doi:10.1111/j.1432-1033.1969.tb19637.x. PMID   5776242.
  9. Nusnbaum, Matthew (18 April 2011). Chemical Defenses of Aplysia Californica and Sensory Processing by Predatory Fishes (PhD thesis). Georgia State University. S2CID   83074451.