Chemical Signaling Processes in the Marine Environment1

Marquez, Gian Powell Bontigao

THU MS 220

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1 A term paper submitted in partial fulfillment of the requirements in MS 220 Chemical Oceanography under Dr. Maria Lourdes San Diego-McGlone. 1st semester, 2008-2009.

ABSTRACT

Chemical signals are widely used throughout animal kingdom. These chemicals are called secondary metabolites or natural products since its production is not essential for cellular function. In the marine world, organisms used chemical signals as feeding deterrent, feeding attractant, alarm signals, courtship, and habitat selection signals for their survival. The successful transmission of this chemical signal in the marine environment while maintaining its efficacy and consistency is the greatest challenge brought to marine organisms. The unique but diverse chemical composition and hydrodynamics present in marine system limits the success of transmission of this chemical signals. Although the physical characteristics of water such as turbulent mixing, molecular diffusion and advection, greatly influence the transport of chemical signals, the interaction of chemical properties of seawater in the chemical structure of the signals are the main concern of this study. In order to lessen the effect of the chemical properties of the environment to the chemical signals, organisms modify the structure of their released signal substances. The hydrophilicity or hydrophobicity of the signal, the incorporation of novel compounds and the unique combination of common chemical substances those are readily present in the environment are some of the modification made by organism to their chemical signals. Some of the other adaptations of organisms in order to reduce the degradation effect of environment to their signals are the incorporation of their chemicals in their body and the synthesis of their signal substances at right moment and timing. Furthermore, some of the different marine natural products, their production mechanism, effect, and structure have been discussed, with the emphasis of its transmission.
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INTRODUCTION Biological processes is mostly mediated by chemical signals including but not limited to courting behavior and survival adaptation (Atema, 1995). According to Gershenzon and Dudareva (2007), chemical signals are secondary metabolites which are commonly known as natural products- carbonbased structured compounds that are not essential to organisms fundamental cellular activities. Organisms may directly or indirectly produce chemical signals. These chemical signals may serve as mediator between the conspecifics, predator-prey, and organism-habitat interactions. In the marine environment, the detection, dispersal and temporal processes of chemical signals are mainly influenced by the chemical and hydrodynamics, as well as, the biological factors present (Zimmer & Butman, 2000).

Understanding the effect of chemical properties and compositions of the environment to these chemical substances which is being transmitted to its target organism can give us insight on how marine organisms preferred specific chemical structures to maintain the consistency and efficacy of their chemical signals. Objectives of the Study The general objective of the study is to define the chemical signaling processes in the marine environment. It specifically aims to:
1. Identify the different use of marine natural products in chemical signaling processes, and; 2. Discuss the biochemical and physiological regulation of the environment and organisms, respectively, in the chemical signal for successful and efficient transmission to target organisms.

REVIEW OF LITERATURE Role of Marine natural products on Chemical Signaling Processes Diverse natural products produced either directly or indirectly have been used as a feeding deterrent (Zimmer & Ferrer, 2007; Zimmer & Butman, 2000; Matz et al., 2008; Kubanek et al., 2003; Gershenzon et al., 2007; Derby, 2007; Paul et al., 2007; Cohen et al., 2008), feeding attractant, (Derby, 2007; Gershenzon et al., 2007; Zimmer & Butman, 2000), alarm (Zimmer & Butman, 2000; Derby, 2007), courtship and fertilization (Derby, 2007; Gershenzon et al., 2007; Atema, 1995; Zimmer & Butman, 2000), and habitat selection signals (Cohen et al., 2008; Zimmer & Butman, 2000) by marine organisms. Feeding-deterrent secondary metabolites as well as feeding-attractant and alarm chemical signals are mainly involved in the predator-prey interaction. Feeding-deterrent producing organisms protected themselves from predator by becoming unpalatable, through either synthesizing fatal toxin, imparting bitter taste substance in their body or producing indigestible constituents in their structures (Zimmer & Butman, 2000). In general, as Zimmer and Butman (2000) cited the study of Hay and Fenical (1988), Paul (1992) and Pawlik (1993) stated that, Feeding-deterrent substances produced by marine organisms such as sedentary animals, microbes, and plants are primarily water insoluble which instead of releasing in the environment is imparted within the body structure. These substances could be in the form of acetogenins, alkaloids, halogenated hydrocarbons, polyphenols, or terpenes. Feeding-attractant secondary metabolites, on the other hand, could be amino acids, quaternary ammonium bases, nucleotides and nucleosides, or organic acids (Zimmer & Butman, 2000). According to Charles Derby (2007), the presence of feeding stimulant, taurine, in the ink-opaline secretion of sea hare (Aplysia californica) induced phagomimicry behavior to predatory spiny lobster (Panulirus interruptus). The spiny lobster is deceived by the secretion, stimulating its ingestive and appetitive action behavior, believing that the secretion was food. Furthermore, the experimental simulation of amino acids escaping out from wounded and decaying prey showed positive attraction response to mud snails (Ilyanassa obsoleta) (Zimmer &

Butman, 2000). In the study of Snyder and Snyder (1971), Atema and Stenzler (1977), Wyatt (2003), and Jacobsen and Stabell (2004), as cited by Charles Derby (2007), it was mentioned that organisms when attacked by predators release chemical signals for defense, either from damaged tissue or body secretion. In some organisms, the released chemicals is associated with alarm signals to warn near conspecifics to avoid danger. These alarm signals may induce burrowing and escape behavioral response. Tetrodotoxin (TTX) is the substance secreted on skin by the adult California newt (Taricha torosa) that serves as its defense. This TTX secretion also acts as an odor-transported alarm signals for the larval conspecifics for possible danger (Ferrer & Zimmer, 2007). Another chemical substance that acts as alarm signals to sea anemone is anthopleurine (Zimmer & Butman, 2000). While the presence of nucleosides uridine and cytidine, and the base uracil in the ink-opaline secretion of Aplysia californica served as an alarm signal. The courtship and fertilization signal of marine organisms were also mediated by chemicals. Zimmer and Butman (2000) cited the study of Maier and Muller (1986), Boland (1995), Zeeck et al. (1994), Hardege et al. (1996), Dulka et al. (1987), and Sorensen (1992) that in brown algae and polychaete worms, hydrocarbons and terpenes are the principal chemical signals for attracting mate while female fish of some species attract mature male by steroid hormones and their metabolites production during their ovulation period. Arginine or lysine at the carboxy terminal end of small peptides signals the Rhithropanopeus harrisii (mud crab) to discharge and spread their brooded embryos. On the other hand, the chemical recognition mechanisms in fertilization of other marine organisms are commonly present in the surface membrane of eggs and sperm cells. Primarily, glycoprotein present in the egg vetilline envelope acts as the receptor of sperm acrosomal protein bindin (Ulrich et al., 1998) and lysin (Kesge et al., 2000) of sea urchins and abalone, respectively, for binding and fusion, while, surface glycoproteins on the female body of rotifers attach to specific receptor proteins on the corona of male which is important to species specificity (Joanidopoulos & Marwan, 2001). Moreover, the small peptides released by oyster (Crassostrea virginica) are being utilized by its conspecific larvae for settling (Zimmer & Butman, 2000). The Caribbean sponges, Erylus formosus and Ectyoplasia ferox produced triterpene glycosides to inhibit microbial colonization and other growth competing sponges (Taylor et al., 2007; Kubanek et al., 2003). In

the study of Zimmer and Butman, they cited the works of Burke (1984), Morse and Morse (1984), and Zimmer-Faust and Tamburri (1994) wherein small peptides released by the adult or by the plant-preferred juvenile food signal the larval settlement of abalone, oyster, and sand dollar. Specifically, the primary response of oyster larvae is to swim to the already oyster-colonized area then attaches itself to the suitable substrate. Habitat selection signals have diverse use in the marine environment causing negative and positive response to organisms such as settlement of larvae, inhibiting the growth of microbial pathogens or competitors, and the regulation of substrate colonization of other marine organisms (Zimmer & Butman, 2000).

Restrictions to chemical signals in the marine environment Marine environment presents several limitations- biochemical composition and hydrodynamicsto chemical signals. The identification of novel compounds or mixture of compounds as chemical cues in spite the presence of naturally occurring identical substance and the recognition of information imparted in the identified cues are the main mechanisms involved in chemical signal detection (Atema, 1995). Chemicals found in the ocean are the nutrients and ions, and some of the chemical substances that most believed to influence the chemical signals were carbohydrates, fatty acids, humic acids, organic nitrogen bases, proteins, and peptides (Zimmer & Butman, 2000). The utilization of organic compounds by living organisms or inanimate materials such as sediments, suspended particulate matter, or high-molecularmass polymers could alter the concentration and distribution of an organic-based chemical signal therefore decreasing its effectiveness (Browne & Zimmer-Faust, 1998). Furthermore, some hydrodynamic elements of ocean that constraints the success of chemical transmission are the speed of flow of water current, advection, and turbulent mixing (Zimmer & Butman, 2000). The behavior, timing, and mechanism of transmission of organisms that produce the chemical signal as well as the chemosensory organ of the target organisms affect the chemical signaling processes. Though the factors mentioned are all important in chemical signaling processes, the effect of chemical composition of ocean and some

important interaction of hydrodynamics that dictates the chemical structure of chemical signals are emphasized.

SUMMARY AND DISCUSSION Since ocean is an aqueous solution and mixture, organisms favored hydrophilic chemical signals. These water soluble signals could easily be transported through molecular diffusion but this is constrained by time and stronger hydrodynamic elements. Therefore, in the region where strong hydrodynamic elements are present such as turbulent flow or advection, hydrophobic chemical signals were preferred by organisms to specifically use the fluid flow for transport. Another method which sea anemone used in the production of anthopleurine- an alarm chemical signal- is by producing unique substrate for each signal. The use of polymer such as peptides in chemical signals is known in the marine world. Aside from being hydrophilic, there are 20 coded amino acids present in eukaryotic organisms that can be utilized to form peptides of different combination sequences (as few as 5 amino acids) encoding unique information for each sequence. Although the unique molecular weight of amino acid sequence is recognized by mud snail to determine the chemical cues, the physical transport and release of this substance influence much of the behavior of the organism (Zimmer & Butman, 2000). This is mainly due to the possible bacterial degradation to organic compounds released. Since marine bacteria utilize the peptide chemical cues as food, the perception of this chemical cue is highly dependent on its rate of distribution and transport (Browne & Zimmer-Faust, 1998). Certain concentration of chemical signals is needed to be identified as cue from its environmental concentration level. Some organisms counteract rapid dilution of chemical cue by imparting the cue to a carrier substance which is mostly synthesized at the same time as the cue. This could be observed in the inking of cephalopod wherein dopamine and dopa are present as an alarm signal. The dopamine is adsorbed by the melanin- a reducing agent which is abundant in ink and responsible for the black coloration- to prevent rapid dilution while other effects of melanin to dopa and dopamine are by stabilizing them through prevention of their oxidation by the reactive oxygen species (Derby, 2007).

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