Mycosporine-like amino acids from coral dinoflagellates

Coral reefs are one of the most important marine ecosystems, providing habitat for approximately a quarter of all marine organisms. Within the foundation of this ecosystem, reef-building corals form mutualistic symbioses with unicellular photosynthetic dinoflagellates of the genus Symbiodinium. Exposure to UV radiation (UVR) (280 to 400 nm) especially when combined with thermal stress has been recognized as an important abiotic factor leading to the loss of algal symbionts from coral tissue and/or a reduction in their pigment concentration and coral bleaching. UVR may damage biological macromolecules, increase the level of mutagenesis in cells, and destabilize the symbiosis between the coral host and their dinoflagellate symbionts. In nature, corals and other marine organisms are protected from harmful UVR through several important photoprotective mechanisms that include the synthesis of UV-absorbing compounds such as mycosporine-like amino acids (MAAs). MAAs are small (<400-Da), colorless, water-soluble compounds made of a cyclohexenone or cyclohexenimine chromophore that is bound to an amino acid residue or its imino alcohol. These secondary metabolites are natural biological sunscreens characterized by a maximum absorbance in the UVA and UVB ranges of 310 to 362 nm. In addition to their photoprotective role, MAAs act as antioxidants scavenging reactive oxygen species (ROS) and suppressing singlet oxygen-induced damage. It has been proposed that MAAs are synthesized during the first part of the shikimate pathway, and recently, it has been suggested that they are synthesized in the pentose phosphate pathway. The shikimate pathway is not found in animals, but in plants and microbes, it connects the metabolism of carbohydrates to the biosynthesis of aromatic compounds. However, both the complete enzymatic pathway of MAA synthesis and the extent of their regulation by environmental conditions are not known. This minireview discusses the current knowledge of MAA synthesis, illustrates the diversity of MAA functions, and opens new perspectives for future applications of MAAs in biotechnology.     

The giant zooxanthellae-bearing ciliate Maristentor dinoferus (Heterotrichea) is closely related to folliculinidae

The small subunit rDNA sequence of Maristentor dinoferus (Lobban, Schefter, Simpson, Pochon, Pawlowski, and Foissner, 2002) was determined and compared with sequences from other Heterotrichea and Karyorelictea. Maristentor resembles Stentor in basic morphology and had been provisionally assigned to Stentoridae. However, our phylogenetic analyses show that Maristentor is more closely related to Folliculinidae. Our results support the creation of a separate family for Maristentor, Maristentoridae n. fam., and also confirm the phylogenetic grouping of Folliculindae, Stentoridae, Blepharismidae, and Maristentoridae, which we informally call 'stentorids'. Maristentor, rather than Stentor itself, appears to be most significant in understanding the origins of folliculinids from their aloricate ancestors. Our analyses suggest continued uncertainty in the exact placement of the root of heterotrichs with this phylogenetic marker.     

Mycosporine-like amino acids in planktonic organisms living under different UV exposure conditions in Patagonian lakes

Mycosporine-like amino acids (MAAs) were studied in zooplanktonfrom 13 Argentinian lakes covering a broad range in altitude,maximum depth and physico-chemical properties of the water.Four to nine different MAAs (predominantly porphyra-334 andshinorine) were found in the copepods Boeckella gibbosa, B.gracilipes, B. meteoris and Parabroteas sarsi, and in the ciliateStentor amethystinus, while MAAs were undetectable in the cladoceranDaphnia middendorffiana. Among the different copepods, maximumMAA concentrations accounted for 0.25–1.31% of the dryweight, and contents were generally about three to seven times(up to 43 times) higher in the animals living in the clearestlakes compared to those occurring in low-UV systems. This variabilityin the content of MAAs was related to the lake altitude (r²= 0.71), and the fraction of the water column to which 1% ofthe surface UV radiation at 320 nm penetrated (r² = 0.57). Ourdata therefore underscore the role of MAAs as sunscreens todecrease the potential negative effects of solar radiation,but they also indicate that other environmental factors besidesUV transparency play a role in determining MAA concentrations.One lake was selected to obtain additional information on thequalitative composition of MAAs in seston of <100 µmbetween two sampling sites and over a 2 month study period (australsummer). Six different MAAs were detected in the samples, withporphyra-334 and palythine being predominant. In the copepodscollected simultaneously, there was low variation in MAA concentrationsbetween the two sites and over time. Thus, our results suggestthat under similar UV exposure conditions MAA contents of planktonicorganisms show low temporal variation.     

Mycosporine-like amino acids in Antarctic sea ice algae,and their response to UVB radiation

Mycosporine like amino acids (MAAs) were detected in low concentration in sea ice algae growing in situ at Cape Evans, Antarctica. Four areas of sea ice were covered with plastics of different UV absorption exposing the bottom- ice algal community to a range of UV doses for a period of 15 days. Algae were exposed to visible radiation only; visible + UV radiation; and visible + enhanced UV radiation. MAA content per cell at the start of the experiment was low in snow-covered plots but higher in samples from ice with no snow cover. During the study period, the MAA content per cell reduced in all treatments, but the rate of this decline was less under both ambient UV and visible radiation than under snow covered plots. While low doses of UVB radiation may have stimulated some MAA production (or at least slowed its loss), relatively high doses of UVB radiation resulted in almost complete loss of MAAs from ice algal cells. Despite this reduction in MAA content per cell, the diatoms in all samples grew well, and there was no discernible effect on viability. This suggests that MAAs may play a minor role as photoprotectants in sea ice algae. The unique structure of the bottom ice algal community may provide a self-shading effect such that algal cells closest to the surface of the ice contain more MAAs than those below them and confer a degree of protection on the community as a whole.     

Possible roles of sulfur-containing amino acids in a chemoautotrophic bacterium-mollusc symbiosis

Invertebrate hosts of chemoautotrophic symbionts face the unique challenge of supplying their symbionts with hydrogen sulfide while avoiding its toxic effects. The sulfur-containing free amino acids taurine and thiotaurine may function in sulfide detoxification by serving as sulfur storage compounds or as transport compounds between symbiont and host. After sulfide exposure, both taurine and thiotaurine levels increased in the gill tissues of the symbiotic coastal bivalve Solemya velum. Inhibition of prokaryotic metabolism with chloramphenicol, inhibition of eukaryotic metabolism with cycloheximide, and inhibition of ammonia assimilation with methionine sulfoximine reduced levels of sulfur-containing amino acids. Chloramphenicol treatment inhibited the removal of sulfide from the medium. In the absence of metabolic inhibitors, estimated rates of sulfide incorporation into taurine and thiotaurine accounted for nearly half of the sulfide removed from the medium. In contrast, amino acid levels in the nonsymbiotic, sulfide-tolerant molluscs Geukensia demissa and Yoldia limatula did not change after sulfide exposure. These findings suggest that sulfur-containing amino acids function in sulfide detoxification in symbiotic invertebrates, and that this process depends upon ammonia assimilation and symbiont metabolic capabilities.     

Mycosporine-like amino acids in azooxanthellate and zooxanthellate early developmental stages of the soft coral Heteroxenia fuscescens

The ontogenetic changes of MAAs in the soft coral Heteroxenia fuscescens was studied in relation to their symbiotic state (azooxanthellate vs. zooxanthellate) under different temperature conditions in the Gulf of Eilat, northern Red Sea. The HPLC chromatograms for extracts of the planulae, azoo- and zooxanthellate primary polyps of H. fuscescens from all dates of collection yielded a single peak at 320 nm that has been identified as the compound palythine. Concentration of palythine in planulae at 23 °C was 7.57 ± 1 nmol mg^− 1 protein and at 28 °C reached 17.29 ± 1 nmol × mg^− 1 protein. Concentration of palythine in azooxanthellate primary polyps was 16.4 ± 3 nmol × mg^− 1 protein and 28.37 ± 2.8 nmol × mg^− 1 protein at 23 °C and 28 °C respectively. The palythine concentration for zooxanthellate primary polyps at 23 °C was 13 ± 3 nmol × mg^− 1 protein and at 28 °C 32.7 ± 2 nmol mg^− 1 protein. Palythine concentrations were significantly higher at 28 °C in the different animal groups and correlated linearly with the ambient collection temperature. This study shows for the first time that UVR and temperature act synergistically and affect the MAA levels of early life-history stages of soft corals.     

Mycosporine-like amino acids protect the copepod Boeckella titicacae (Harding) against high levels of solar UVR

Studies were conducted in Lake Titicaca, Bolivia (16°S,69°W, 3810 m a.s.l.) to determine the effects of solar ultravioletradiation (UVR; 280–400 nm) and the protective role ofmycosporine-like amino acids (MAAs) in the calanoid copepodBoeckella titicacae (Harding). Zooplankton samples were takenfrom two different radiation environments: Lake Titicaca anda tank with running lake water, which was covered with layersof neutral-density screen for over a year, receiving ~10% ofincident radiation. Samples collected from the lake had significantlyhigher amounts of MAAs compared with those from the tank. Duringshort-term experiments (6–8 h incubations; six radiationtreatments using sharp cut-off Schott filters), significantlyhigher mortality was observed in B. titicacae from the tankthan from the lake. The higher sensitivity of B. titicacae containinglow amounts of MAAs (compared with specimens collected fromthe lake) was assessed through the determination of biologicalweighting functions (BWFs). A 3-day-long experiment performedwith specimens collected from the lake indicated an increasein mortality as a function of UVR exposure, reaching valuesas high as 70% at the end of day 3 for those individuals thatreceived full radiation compared with <10% for those thatreceived only photosynthetically active radiation (PAR; 400–700nm). Concomitantly, a reduction in the concentration of UV-absorbingcompounds as a function of UVR dose and decreasing wavelengthwas determined. The relatively high UVR dose threshold for mortality(~300 kJ m^–2), as well as a comparison with related species,demonstrated the high resistance of B. titicacae to UVR. Ourresults indicate that this resistance is provided by the presenceof protective compounds, i.e. MAAs, which were efficiently bioaccumulatedthrough the diet.     

Mycosporine-like amino acids (MAAs): chemical structure, biosynthesis and significance as UV-absorbing/screening compounds

Continuous depletion of the stratospheric ozone layer has resulted in an increase in ultraviolet-B (UV-B; 280-315 nm) radiation on the earth's surface which inhibits photochemical and photobiological processes. However, certain photosynthetic organisms have evolved mechanisms to counteract the toxicity of ultraviolet or high photosynthetically active radiation by synthesizing the UV-absorbing/screening compounds, such as mycosporine-like amino acids (MAAs) and scytonemin besides the repair of UV-induced damage of DNA and accumulation of carotenoids and detoxifying enzymes or radical quenchers and antioxidants. Chemical structure of various MAAs, their possible biochemical routes of synthesis and role as photoprotective compounds in various organisms are discussed.     

Mycosporine-like amino acids (MAAs) profile of a rice-field cyanobacterium Anabaena doliolum as influenced by PAR and UVR

The mycosporine-like amino acid (MAA) profile of a rice-field cyanobacterium, Anabaena doliolum, was studied under PAR and PAR + UVR conditions. The high-performance liquid chromatographic analysis of water-soluble compounds reveals the biosynthesis of three MAAs, mycosporine-glycine (lambda (max) = 310 nm), porphyra-334 (lambda (max) = 334 nm) and shinorine (lambda (max) = 334 nm), with retention times of 4.1, 3.5 and 2.3 min, respectively. This is the first report for the occurrence of mycosporine-glycine and porphyra-334 in addition to shinorine in Anabaena strains studied so far. The results indicate that mycosporine-glycine (monosubstituted) acts as a precursor for the biosynthesis of the bisubstituted MAAs shinorine and porphyra-334. Mycosporine-glycine was under constitutive control while porphyra-334 and shinorine were induced by UV-B radiation, indicating the involvement of UV-regulated enzymes in the biotransformation of MAAs. It seems that A. doliolum is able to protect its cell machinery from UVR by synthesizing a complex set of MAAs and thus is able to survive successfully during the summer in its natural brightly lit habitats.     

Cluster dynamics in Maristentor dinoferus,a gregarious benthic ciliate with zooxanthellae and a hypericin-like pigment,in relation to biofilm grazing by the fish Ctenochaetus striatus

The large symbiotic ciliate Maristentor dinoferus (Heterotrichida: Maristentoridae) has an abundant, potentially toxic pigment that makes the cells look black, and it forms clusters making it easy to see in the field. In situ observations of vast Maristentor populations during three bloom years provided insights into the behavioral ecology of the Maristentor holobiont and circumstantial evidence for feeding deterrence. Maristentor migrated onto limestone tiles that were also suitable for development of biofilm, which was consumed by the fish Ctenochaetus striatus. We photodocumented several aspects of Maristentor movement in situ, including a diurnal rhythm of dispersal and re-clustering in the morning, a period of “cocktail party dynamics” that resulted in larger, fewer clusters over the afternoon, and responses to two different disturbances: (1) rapid dispersal–re-clustering when tiles were moved; and (2) swimming off the surface and photoaccumulating on the brightest and highest part of a container when Maristentor was enclosed. Although Maristentor is considered benthic, its abilities to swim rapidly, to photoaccumulate, and to form clusters hanging from a water surface hint that they may also exist in the hyponeuston. Although interaction between Maristentor and Ctenochaetus may not be common, it indicated ways in which the behavior of Maristentor could help defend it from grazing. First, during the morning diaspora and re-clustering, which coincided with a period when Ctenochaetus was not feeding, Maristentor tended to accumulate on thinner biofilm, including edges and previously-grazed areas. Secondly, analysis of bite marks suggested that this fish tended not to select thin biofilm and that, despite rapid feeding, it tended to avoid larger Maristentor clusters.     

Role of rhizobial biosynthetic pathways of amino acids,nucleotide bases and vitamins in symbiosis

Rhizobia require the availability of 20 amino acids for the establishment of effective symbiosis with legumes. Some of these amino acids are synthesized by rhizobium, whereas the remaining are supplied by the host plant. The supply from plant appears to be plant-type specific. Alfalfa provides arginine, cysteine, isoleucine, valine and tryptophan, and cowpea and soybean provide histidine. The production of ornithine and anthranilic acid, the intermediates in the biosynthetic pathways of arginine and tryptophan, respectively, seems to be essential for effective symbiosis of Sinorhizobium meliloti with alfalfa. The expression of ilvC gene of S. meliloti is required for induction of nodules on the roots of alfalfa plants. An undiminished metabolic flow through the rhizobial pathways for the synthesis of purines and pyrimidines and the synthesis of biotin, nicotinic acid, riboflavin and thiamine by rhizobium appear to be requirements for normal symbiosis. To the best of our knowledge, this is the first review article on the role of rhizobial biosynthetic pathways of amino acids, nucleotide bases and vitamins in rhizobium-legume symbiosis. The scientific developments of about 35 years in this field have been reviewed.     

Transformation of some hydroxy amino acids to other amino acids

It has been observed that -hydroxy--amino acids are transformed into other amino acids, when heated in dilute solutions with phosphorous acid, phosphoric acid or their ammonium salts. It has been shown that as in the case of previously reported glycine-aldehyde reactions, glycine also reacts with acetone to give -hydroxyvaline under prebiologically feasible conditions. It is suggested, therefore, that the formation of -hydroxy--amino acids and their transformation to other amino acids may have been a pathway for the synthesis of amino acids under primitive earth conditions.     

Effects of branched-chain amino acids on plasma amino acids in amyotrophic lateral sclerosis

Summary Although the cause of amyotrophic lateral sclerosis (ALS) remains unknown, biological findings suggest that the excitatory amino acid glutamate contributes to the pathogenesis of ALS. In previous studies of ALS, the therapeutic effect of the branched-chain amino acids (BCAAs) leucine, valine and isoleucine has been evaluated. The present study aimed at investigating the acute effect of BCAAs on plasma glutamate levels in ALS patients. Following two oral doses of BCAAs, significantly increased plasma levels were seen for valine (500%), isoleucine (1,377%) and leucine (927%), however the plasma level of glutamate was not affected. The plasma level of several other amino acids (tryptophan, tyrosine, phenylalanine and methionine) were found decreased after oral BCAAs, which may indicate a diminution in the rate of degradation of muscle protein and/or an increase in tissue disposal of amino acids.