Mycosporine-like Amino Acids Biosynthesis Research Articles

Genomic Data Reveal Diverse Biological Characteristics of Scleractinian Corals and Promote Effective Coral Reef Conservation.

Reef-building corals (Scleractinia, Anthozoa, Cnidaria) are the keystone organisms of coral reefs, which constitute the most diverse marine ecosystems. Since the first decoded coral genome reported in 2011, about 40 reference genomes are registered as of 2023. Comparative genomic analyses of coral genomes have revealed genomic characters that may underlie unique biological characteristics and coral diversification. These include existence of genes for biosynthesis of mycosporine-like amino acids, loss of an enzyme necessary for cysteine biosynthesis in family Acroporidae, and lineage-specific gene expansions of DMSP lyase-like genes in the genus Acropora. While symbiosis with endosymbiotic photosynthetic dinoflagellates is a common biological feature among reef-building corals, genes associated with the intricate symbiotic relationship encompass not only those shared by many coral species, but also genes that were uniquely duplicated in each coral lineage, suggesting diversified molecular mechanisms of coral-algal symbiosis. Coral genomic data have also enabled detection of hidden, complex population structures of corals, indicating the need for species-specific, local-scale, carefully considered conservation policies for effective maintenance of corals. Consequently, accumulating coral genomic data from a wide range of taxa and from individuals of a species not only promotes deeper understanding of coral reef biodiversity, but also promotes appropriate and effective coral reef conservation. Considering the diverse biological traits of different coral species and accurately understanding population structure and genetic diversity revealed by coral genomic analyses during coral reef restoration planning could enable us to "archive" coral reef environments that are nearly identical to natural coral reefs.

Exploring the Relationship between Biosynthetic Gene Clusters and Constitutive Production of Mycosporine-like Amino Acids in Brazilian Cyanobacteria.

Cyanobacteria are oxygenic phototrophic prokaryotes that have evolved to produce ultraviolet-screening mycosporine-like amino acids (MAAs) to lessen harmful effects from obligatory exposure to solar UV radiation. The cyanobacterial MAA biosynthetic cluster is formed by a gene encoding 2-epi-5-epi-valiolone synthase (EVS) located immediately upstream from an O-methyltransferase (OMT) encoding gene, which together biosynthesize the expected MAA precursor 4-deoxygadusol. Accordingly, these genes are typically absent in non-producers. In this study, the relationship between gene cluster architecture and constitutive production of MAAs was evaluated in cyanobacteria isolated from various Brazilian biomes. Constitutive production of MAAs was only detected in strains where genes formed a co-linear cluster. Expectedly, this production was enhanced upon exposure of the strains to UV irradiance and by using distinct culture media. Constitutive production of MAAs was not detected in all other strains and, unexpectedly, production could not be induced by exposure to UV irradiation or changing growth media. Other photoprotection strategies which might be employed by these MAA non-producing strains are discussed. The evolutionary and ecological significance of gene order conservation warrants closer experimentation, which may provide a first insight into regulatory interactions of genes encoding enzymes for MAA biosynthesis.

Genome Mining as an Alternative Way for Screening the Marine Organisms for Their Potential to Produce UV-Absorbing Mycosporine-like Amino Acid

Mycosporine-like amino acids (MAAs) are small molecules with robust ultraviolet (UV)-absorbing capacities and a huge potential to be used as an environmentally friendly natural sunscreen. MAAs, temperature, and light-stable compounds demonstrate powerful photoprotective capacities and the ability to capture light in the UV-A and UV-B ranges without the production of damaging free radicals. The biotechnological uses of these secondary metabolites have been often limited by the small quantities restored from natural resources, variation in MAA expression profiles, and limited success in heterologous expression systems. Overcoming these obstacles requires a better understanding of MAA biosynthesis and its regulatory processes. MAAs are produced to a certain extent via a four-enzyme pathway, including genes encoding enzymes dehydroquinate synthase, enzyme O-methyltransferase, adenosine triphosphate grasp, and a nonribosomal peptide synthetase. However, there are substantial genetic discrepancies in the MAA genetic pathway in different species, suggesting further complexity of this pathway that is yet to be fully explored. In recent years, the application of genome-mining approaches allowed the identification of biosynthetic gene clusters (BGCs) that resulted in the discovery of many new compounds from unconventional sources. This review explores the use of novel genomics tools for linking BGCs and secondary metabolites based on the available omics data, including MAAs, and evaluates the potential of using novel genome-mining tools to reveal a cryptic potential for new bioproduct screening approaches and unrevealing new MAA producers.

In silico analysis of enzymes involved in mycosporine-like amino acids biosynthesis in Euhalothece sp.: Structural and functional characterization

Mycosporine-like amino acids (MAAs) are ultraviolet-absorbing compounds synthesized by photoautotrophic microorganisms such as cyanobacteria. They have applications as UV protectants and antioxidants in the cosmetic and pharmaceutical sectors. To date, >30 different types of MAAs have been identified, having an absorption range between 310 and 365 nm that covers most of the UVR spectrum (~295–400 nm). In the study, MAAs were extracted and partially purified from a euryhaline Euhalothece sp. Thereafter, in silico analysis of the MAAs biosynthetic genes was conducted to determine the physicochemical characteristics, structural properties, functional analysis and homology model. High salinity stress (120 g L−1) significantly enhanced the production of MAAs (~56 %) in Euhalothece sp. Bioinformatics analysis of the genome of Euhalothece sp. revealed a distinctive mys gene cluster that contained six genes (mysA to mysE), compared to four genes commonly found in MAA-producing cyanobacteria. Interestingly, both EEVS and DHQ synthase were present, indicating the potential to synthesize MAAs via both the shikimate and sedoheptulose 7-phosphate pathways. Secondary structure analysis confirmed that in all the biosynthetic enzymes, the major components were the alpha-helices with random coils. This study emphasized the unique genes for MAAs in Euhalothece sp. as well as highlighted the potential metabolite pathways for commercial production. Elucidation of the protein structure, physicochemical properties, and interactions provides scientific insight into the biosynthesis of MAAs from hypersaline cyanobacteria. Additionally, it is essential for determining the applications of these novel photoprotective compounds.

Microalgae as a Source of Mycosporine-like Amino Acids (MAAs); Advances and Future Prospects.

Mycosporine-like amino acids (MAAs), are secondary metabolites, first reported in 1960 and found to be associated with the light-stimulated sporulation in terrestrial fungi. MAAs are nitrogenous, low molecular weight, water soluble compounds, which are highly stable with cyclohexenone or cycloheximine rings to store the free radicals. Microalgae are considered as a good source of different kinds of MAAs, which in turn, has its own applications in various industries due to its UV absorbing, anti-oxidant and therapeutic properties. Microalgae can be easily cultivated and requires a very short generation time, which makes them environment friendly source of biomolecules such as mycosporine-like amino acids. Modifying the cultural conditions along withmanipulation of genes associated with mycosporine-like amino acids biosynthesis can help to enhance MAAs synthesis and, in turn, can make microalgae suitable bio-refinery for large scale MAAs production. This review focuses on properties and therapeutic applications of mycosporine like amino acids derived from microalgae. Further attention is drawn on various culture and genetic engineering approaches to enhance the MAAs production in microalgae.

Light-dependent impact of salinity on the ecophysiology of Synechococcus elongatus PCC 7942: Genetic and comparative protein structure analyses of UV-absorbing mycosporine-like amino acids (MAAs) biosynthesis

Cyanobacteria are subjected to a dynamic light environment in their natural habitat or artificial cultivation system. The fluctuating light environment is associated with increased salinity stress due to the evaporation of the growth medium. Therefore, it is important to understand the physiology of the organisms under a dynamic environment of light and salinity which together affect the fitness and overall performance of the organism. We studied the growth behavior and other physiological parameters of Synechococcus elongatus PCC 7942 in the presence of different NaCl concentrations (0, 50, 100 and 200 mM) and light conditions such as low PAR (LPAR), high PAR (HPAR) and PAR + UVR using diurnal and continuous photoperiods. We also investigated the ability of S. elongatus PCC 7942 to biosynthesize UV-absorbing mycosporine-like amino acids (MAAs) and conducted genetic and comparative protein structure analyses to better understand its biosynthesis. Results obtained suggest that the impact of salinity stress caused by NaCl on growth behavior and physiological parameters such as photosynthetic pigments, the effective quantum yield of PSII and oxidative stress is dependent on the light environment. These parameters were affected differently by the quality and quantity of light and photoperiods, and the negative effect of salinity was alleviated by a high light environment. S. elongatus PCC 7942 does not biosynthesize MAAs due to the absence of MAAs biosynthesizing genes cluster in its genome. Results from genomic and comparative protein structure analyses suggested that DDGS and DHQS enzymes are different and DDGS but not DHQS is required for MAAs biosynthesis. Understanding the light-dependent impact of salinity stress may help in developing strategies for outdoor cultivation of cyanobacteria for bioenergy and valuable chemicals production by balancing absorbed and utilized radiant energy.

Biosynthesis and Heterologous Production of Mycosporine-Like Amino Acid Palythines.

Mycosporine-like amino acids (MAAs) are a family of natural products that are produced by a variety of organisms for protection from ultraviolet damage. In this work, we combined different bioinformatic approaches to assess the distribution of the MAA biosynthesis and identified a putative gene cluster from Nostoc linckia NIES-25 that encodes a short-chain dehydrogenase/reductase and a nonheme iron(II)- and 2-oxoglutarate-dependent oxygenase (MysH) as potential new biosynthetic enzymes. Heterologous expression of refactored gene clusters in E. coli produced two known biosynthetic intermediates, 4-deoxygadusol and mycosporine-glycine, and three disubstituted MAA analogues, porphyra-334, shinorine, and mycosporine-glycine-alanine. Importantly, the disubstituted MAAs were converted into palythines by MysH. Furthermore, biochemical characterization revealed the substrate preference of recombinant MysD, a d-Ala-d-Ala ligase-like enzyme for the formation of disubstituted MAAs. Our study advances the biosynthetic understanding of an important family of natural UV photoprotectants and opens new opportunities to the development of next-generation sunscreens.

Production of porphyra-334 in transgenic lines of Nannochloropsis salina by the expression of mycosporine-like amino acid biosynthetic genes of P. yezoensis

Mycosporine-like amino acids (MAAs) are small secondary metabolites produced by some marine species. These compounds absorb ultraviolet (UV) light, typically between 310 and 362 nm, and protect the producers from UV-associated damage. They also have anti-photoaging, anticancer, and anti-inflammatory properties, which has generated considerable interest in the cosmetic, pharmaceutical, biotechnology, and materials fields. Commercial use has been limited due to its reliance marine organisms for production, resulting in low and inconsistent yields. This study was undertaken to increase production of MAAs. We generated transgenic lines of the Nannochloropsis salina that carry and express the MAA biosynthesis genes from red alga Pyropia yezoensis. We characterized their MAA yield and the properties of MAAs produced by these lines. When exposed to UV light, the transgenic lines generated fewer reactive oxygen species compared to wild-type. The yield of porphyra-334 in one of the transgenic lines was 25 mg g−1 dry cell weight, the greatest reported. We hope these results will support the use of MAAs in numerous applications and increase our understanding of their biosynthetic pathways.

Mycosporine-like amino acid and aromatic amino acid transcriptome response to UV and far-red light in the cyanobacterium Chlorogloeopsis fritschii PCC 6912

The “UV sunscreen” compounds, the mycosporine-like amino acids (MAAs) are widely reported in cyanobacteria and are known to be induced under ultra-violet (UV) light. However, the impact of far red (FR) light on MAA biosynthesis has not been studied. We report results from two experiments measuring transcriptional regulation of MAA and aromatic amino acid pathways in the filamentous cyanobacterium Chlorogloeopsis fritschii PCC 6912. The first experiment, comparing UV with white light, shows the expected upregulation of the characteristic MAA mys gene cluster. The second experiment, comparing FR with white light, shows that three genes of the four mys gene cluster encoding up to mycosporine-glycine are also upregulated under FR light. This is a new discovery. We observed corresponding increases in MAAs under FR light using HPLC analysis. The tryptophan pathway was upregulated under UV, with no change under FR. The tyrosine and phenylalanine pathways were unaltered under both conditions. However, nitrate ABC transporter genes were upregulated under UV and FR light indicating increased nitrogen requirement under both light conditions. The discovery that MAAs are upregulated under FR light supports MAAs playing a role in photon dissipation and thermoregulation with a possible role in contributing to Earth surface temperature regulation.

Klebsormidin A and B, Two New UV-Sunscreen Compounds in Green Microalgal Interfilum and Klebsormidium Species (Streptophyta) From Terrestrial Habitats.

The terrestrial green algal members of the genera Interfilum and Klebsormidium (Klebsormidiophyceae, Streptophyta) are found in biological soil crusts of extreme habitats around the world where they are regularly exposed, among other abiotic stress factors, to high levels of ultraviolet radiation (UVR). As a consequence those species synthesize and accumulate either one or two mycosporine-like amino acids (MAAs), but with a missing structural elucidation up to now. Therefore, in the present study both MAAs were chemically isolated and structurally elucidated. The two new compounds exhibit absorption maxima of 324 nm. MAA 1 has a molecular weight of 467 and MAA 2 of 305, and the latter (MAA 2) was identified as N-(4,5-dihydroxy-5-(hydroxymethyl)-2-methoxy-3-oxocyclohex-1-en-1-yl)-N-methylserine using one- and two-dimensional 1H and 13C-NMR spectroscopy. MAA 1 contains an additional sugar moiety. As trivial names for these two novel MAAs we suggest klebsormidin A and klebsormidin B. Different species from all previously described phylogenetic clades of Klebsormidiophyceae were chemically screened for their MAA composition in aqueous extracts using RP−HPLC and LC−MS. The novel klebsormidin A was present throughout all clades and hence could be suitable as a chemotaxonomic marker. Additionally, controlled UVR−exposure experiments with all investigated species showed that MAA biosynthesis and intracellular enrichment is strongly induced by short wavelengths, supporting the function of these compounds as natural UV−sunscreen as well as explaining the cosmopolitan distribution and ecological success of Interfilum and Klebsormidium in terrestrial habitats.

Temporal variation in pigment and mycosporine-like amino acid composition of the red macroalga Palmaria palmata from Brittany (France): hypothesis on the MAA biosynthesis pathway under high irradiance

Changes in pigment (chlorophyll-a, carotenoids and phycobiliproteins) and mycosporine-like amino acid (MAA) composition were studied in the red edible macroalga Palmaria palmata, harvested between February 2018 and February 2019 at 2 sites from Brittany (France). The results occuring in natural conditions revealed a high seasonal variability that can be related to a combination of environmental parameters, including light, nutrients, temperature, salinity and pH, which may have synergistic or antagonistic effects. A decrease in pigments was observed in summer, matching with the increase in irradiance at the same period. On the contrary, the increase in light from February to May has caused an increase in the total MAA content, confirming the UV-photoprotective role attributed to these compounds. Analysis of the results coupled with the biosynthesis pathway suggests that some MAAs are favoured in the occurrence of high irradiance. In this sense, asterina-330 was synthetized only between March and July and not the rest of the year, supporting its importance in photoprotection. In addition, analysis revealed that nutrient availibility could have a significant influence on MAAs since their synthesis seemed to be limited in summer, despite significant exposure to light. However, this decrease could be due to another potential role of MAAs as a nitrogen source for macroalgae. Thus, the diversity of these compounds and the different synthesis pathways could be explained by different roles including photo-protection and nitrogen source, making MAA multi-purpose protective agents which could play a key role in the adaptation of this species to its changing environment.

Mycosporine-Like Amino Acids: Making the Foundation for Organic Personalised Sunscreens.

The surface of the Earth is exposed to harmful ultraviolet radiation (UVR: 280–400 nm). Prolonged skin exposure to UVR results in DNA damage through oxidative stress due to the production of reactive oxygen species (ROS). Mycosporine-like amino acids (MAAs) are UV-absorbing compounds, found in many marine and freshwater organisms that have been of interest in use for skin protection. MAAs are involved in photoprotection from damaging UVR thanks to their ability to absorb light in both the UV-A (315–400 nm) and UV-B (280–315 nm) range without producing free radicals. In addition, by scavenging ROS, MAAs play an antioxidant role and suppress singlet oxygen-induced damage. Currently, there are over 30 different MAAs found in nature and they are characterised by different antioxidative and UV-absorbing capacities. Depending on the environmental conditions and UV level, up- or downregulation of genes from the MAA biosynthetic pathway results in seasonal fluctuation of the MAA content in aquatic species. This review will provide a summary of the MAA antioxidative and UV-absorbing features, including the genes involved in the MAA biosynthesis. Specifically, regulatory mechanisms involved in MAAs pathways will be evaluated for controlled MAA synthesis, advancing the potential use of MAAs in human skin protection.

Stress tolerance and photoadaptation to solar radiation in Rhodymenia pseudopalmata (Rhodophyta) through mycosporine-like amino acids, phenolic compounds, and pigments in an Integrated Multi-Trophic Aquaculture system

Rhodymenia pseudopalmata lives in the intertidal zone receiving high doses of solar radiation, including the potentially harmful UVR. Previous studies proved it ability to adapt to different artificial light intensities and salinity concentrations. The aim of this study was to describe the differences on the Mycosporine-like amino acids (MAAs), phenolic compounds, and pigments of R. pseudopalmata due to exposure to high solar radiation. Vegetative thalli were exposed to solar radiation using a Solar Exposure Chambers System (SECS) under an Integrated Multi-Trophic Aquaculture (IMTA) approach with marine fish culture. Samples from natural populations in Playa de Carmen, Mexico were included as reference. The biosynthesis of MAAs, and phenolic compounds were stimulated as a response to the stress caused by the exposure to high solar irradiation. Liquid Chromatography-Mass Spectrometry (LC-MS) revealed seven MAAs and their precursor deoxygadusol. Five MAAs were partially characterized through MS2 and fragmentation patterns suggested a common fragmentation pattern pathway. After seven days (D7), the MAAs total content was significant five-fold higher compared to wild populations (0.26 ± 0.1 mg g−1 DW). The Individual composition increased from four MAAs at D0, up to eight at D7, including deoxygadusol, palythene and usujirene, MAAs with high antioxidant activity. At D7, phenolic compounds increased up to 20%, and the 2, 2-diphenyl-1-picrylhydrazyl (DPPH) antioxidant activity reduced the IC50 to 4.0 ± 0.6 mg mL−1. The pigment content, Phycoerythrin (PE):Chl-a, and MAAs:Chl-a ratios might confer a unique photoprotection role from PE and MAAs to Chl-a. Similarly, Fv/Fm which was adapted to the variations of Photosynthetic Active Radiation (PAR) indicated a process of dynamic photoinhibition. Overall, our results evidenced the ability of this species to tolerate the stress to high solar irradiance and suggested the photoadaptation of the thalli. Farming possibilities, expected MAAs productivity, potential applications of MAAs and ecological considerations are also discussed.

Synthesis of mycosporine-like amino acids by a size-fractionated marine phytoplankton community of the arctic beaufort sea

During the RV-ARAON cruise, a comparative study on the biosynthesis of mycosporine-like amino acids (MAAs) was conducted for the size-fractionated phytoplankton of the Beaufort Sea (Arctic). The MAAs contents in the micro-phytoplankton community (>20 μm size) is considerably higher than that observed in the nano- (20–2 μm size) and pico-phytoplankton (<2 μm size) communities. The micro-phytoplankton of the Mackenzie Shelf had a relatively higher Chlorophyll a (Chl a) concentration. Considering the total phytoplankton community, the MAAs concentration as well as net production of individual MAAs (such as shinorine and palythine) were higher at the Mackenzie Shelf rather than at the sites located beyond the Beaufort Sea; precisely, the highest net production rates of shinorine and palythine were 0.211 (±0.02) ng C L−1 d−1 and 0.136 (±0.001) ng C L−1 d−1 respectively (No other MAAs were detected). The micro-phytoplankton used around 0.5% of the total carbon uptake for the synthesis of MAAs. Compared to the smaller phytoplankton community, the micro-phytoplankton utilized more of their energy for the biosynthesis of MAAs; on the other hand, nano- and pico-phytoplankton focused on cellular activity and had poor biosynthesis of MAAs. This clearly indicates the phytoplankton size-dependent variation in the biosynthesis of MAA in the natural phytoplankton community. This study revealed the environmental adaptation of the various sizes of phytoplankton community as well as their physiological response in the Arctic Beaufort Sea.

Two divergent Symbiodinium genomes reveal conservation of a gene cluster for sunscreen biosynthesis and recently lost genes

BackgroundThe marine dinoflagellate, Symbiodinium, is a well-known photosynthetic partner for coral and other diverse, non-photosynthetic hosts in subtropical and tropical shallows, where it comprises an essential component of marine ecosystems. Using molecular phylogenetics, the genus Symbiodinium has been classified into nine major clades, A-I, and one of the reported differences among phenotypes is their capacity to synthesize mycosporine-like amino acids (MAAs), which absorb UV radiation. However, the genetic basis for this difference in synthetic capacity is unknown. To understand genetics underlying Symbiodinium diversity, we report two draft genomes, one from clade A, presumed to have been the earliest branching clade, and the other from clade C, in the terminal branch.ResultsThe nuclear genome of Symbiodinium clade A (SymA) has more gene families than that of clade C, with larger numbers of organelle-related genes, including mitochondrial transcription terminal factor (mTERF) and Rubisco. While clade C (SymC) has fewer gene families, it displays specific expansions of repeat domain-containing genes, such as leucine-rich repeats (LRRs) and retrovirus-related dUTPases. Interestingly, the SymA genome encodes a gene cluster for MAA biosynthesis, potentially transferred from an endosymbiotic red alga (probably of bacterial origin), while SymC has completely lost these genes.ConclusionsOur analysis demonstrates that SymC appears to have evolved by losing gene families, such as the MAA biosynthesis gene cluster. In contrast to the conservation of genes related to photosynthetic ability, the terminal clade has suffered more gene family losses than other clades, suggesting a possible adaptation to symbiosis. Overall, this study implies that Symbiodinium ecology drives acquisition and loss of gene families.

UV-B induced biosynthesis of a novel sunscreen compound in solar radiation and desiccation tolerant cyanobacteria.

The small-molecule sunscreen compounds, mycosporine-like amino acids (MAAs), have strong ultraviolet (UV) absorption and can protect cyanobacteria against UV-B damage. However, the molecular mechanism underlying UV-B signaling and MAA chemical diversity remain largely unclear. Here, we identified a five-gene cluster for MAA biosynthesis in the solar radiation and desiccation tolerant cyanobacterium Nostoc flagelliforme. A LuxR family protein OrrA was identified as a positive UV-B responsive regulator binding to the promoter region of this gene cluster. OrrA functions as an activator mediating the UV-B induced MAA biosynthesis. Overexpression of orrA strengthened its UV-B tolerance during desiccation, and enhanced the photosynthetic recovery upon rehydration. Heterologous expression of this gene cluster in Anabaena PCC 7120 produces the same MAA as that in field samples of N. flagelliforme. The MAA structure is assigned as mycosporine-2-(4-deoxygadusolyl-ornithine) with a molecular weight of 756 Da, the structurally unique MAA compound reported to date. This MAA was catalyzed by mysD-mysC2-mysC1 encoding proteins from 4-deoxygadusol, which was synthesized through the catalysis of mysA-mysB products. Thus, we elucidated the transcriptional mechanism for a novel type MAA biosynthesis in solar radiation and desiccation tolerant cyanobacteria, which shed light on the identification of other components for UV-B signaling in cyanobacteria.

Comparative Profiling and Discovery of Novel Glycosylated Mycosporine-Like Amino Acids in Two Strains of the Cyanobacterium Scytonema cf. crispum.

The mycosporine-like amino acids (MAAs) are a group of small molecules with a diverse ecological distribution among microorganisms. MAAs have a range of physiological functions, including protection against UV radiation, making them important from a biotechnological perspective. In the present study, we identified a putative MAA (mys) gene cluster in two New Zealand isolates of Scytonema cf. crispum (UCFS10 and UCFS15). Homology to "Anabaena-type" mys clusters suggested that this cluster was likely to be involved in shinorine biosynthesis. Surprisingly, high-performance liquid chromatography analysis of S cf. crispum cell extracts revealed a complex MAA profile, including shinorine, palythine-serine, and their hexose-bound variants. It was hypothesized that a short-chain dehydrogenase (UCFS15_00405) encoded by a gene adjacent to the S cf. crispum mys cluster was responsible for the conversion of shinorine to palythine-serine. Heterologous expression of MysABCE and UCFS15_00405 in Escherichia coli resulted in the exclusive production of the parent compound shinorine. Taken together, these results suggest that shinorine biosynthesis in S cf. crispum proceeds via an Anabaena-type mechanism and that the genes responsible for the production of other MAA analogues, including palythine-serine and glycosylated analogues, may be located elsewhere in the genome. Recently, New Zealand isolates of S cf. crispum were linked to the production of paralytic shellfish toxins for the first time, but no other natural products from this species have been reported. Thus, the species was screened for important natural product biosynthesis. The mycosporine-like amino acids (MAAs) are among the strongest absorbers of UV radiation produced in nature. The identification of novel MAAs is important from a biotechnology perspective, as these molecules are able to be utilized as sunscreens. This study has identified two novel MAAs that have provided several new avenues of future research related to MAA genetics and biosynthesis. Further, we have revealed that the genetic basis of MAA biosynthesis may not be clustered on the genome. The identification of the genes responsible for MAA biosynthesis is vital for future genetic engineering.

Genome mining for natural product biosynthetic gene clusters in the Subsection V cyanobacteria.

BackgroundCyanobacteria are well known for the production of a range of secondary metabolites. Whilst recent genome sequencing projects has led to an increase in the number of publically available cyanobacterial genomes, the secondary metabolite potential of many of these organisms remains elusive. Our study focused on the 11 publically available Subsection V cyanobacterial genomes, together with the draft genomes of Westiella intricata UH strain HT-29-1 and Hapalosiphon welwitschii UH strain IC-52-3, for their genetic potential to produce secondary metabolites. The Subsection V cyanobacterial genomes analysed in this study are reported to produce a diverse range of natural products, including the hapalindole-family of compounds, microcystin, hapalosin, mycosporine-like amino acids and hydrocarbons.ResultsA putative gene cluster for the cyclic depsipeptide hapalosin, known to reverse P-glycoprotein multiple drug resistance, was identified within three Subsection V cyanobacterial genomes, including the producing cyanobacterium H. welwitschii UH strain IC-52-3. A number of orphan NRPS/PKS gene clusters and ribosomally-synthesised and post translationally-modified peptide gene clusters (including cyanobactin, microviridin and bacteriocin gene clusters) were identified. Furthermore, gene clusters encoding the biosynthesis of mycosporine-like amino acids, scytonemin, hydrocarbons and terpenes were also identified and compared.ConclusionsGenome mining has revealed the diversity, abundance and complex nature of the secondary metabolite potential of the Subsection V cyanobacteria. This bioinformatic study has identified novel biosynthetic enzymes which have not been associated with gene clusters of known classes of natural products, suggesting that these cyanobacteria potentially produce structurally novel secondary metabolites.Electronic supplementary materialThe online version of this article (doi:10.1186/s12864-015-1855-z) contains supplementary material, which is available to authorized users.

Sun-screening bioactive compounds mycosporine-like amino acids in naturally occurring cyanobacterial biofilms: role in photoprotection.

To investigate the occurrence of UV sunscreening biomolecules and their role in photoprotection in cyanobacterial biofilms growing in brightly lit habitats with high UV fluxes. High performance liquid chromatography with photodiode-array and mass spectrometry revealed the presence of mycosporine-like amino acids (MAAs) shinorine (λ(max) 334 nm, m/z 333), porphyra-334 (λ(max) 334 nm, m/z 347), mycosporine-glycine (λ(max) 310 nm, m/z 246) and palythinol (λ(max) 332 nm, m/z 303). Two unknown MAAs with λ(max) at 320 (m/z 289) and 329 nm (m/z 318) were also found. Biosynthesis of MAAs was found to increase with increase in exposure time under UV radiation. The MAAs from biofilms showed efficient radical scavenging activity as well as photoprotective potential on the survival of UV-treated Escherichia coli cells. Biosynthesis of photoprotectants is an important mechanism to prevent photodamage in Cyanobacteria. UV-induction and photoprotective function of MAAs may facilitate them to perform important ecological functions under harsh environmental conditions. There are very few reports on qualitative and quantitative characterization of different MAAs in cyanobacterial biofilms. Due to strong UV absorption and photoprotective function, MAAs may be used as an active ingredient in cosmetic and other pharmaceutical industries.

O-Methyltransferase is shared between the pentose phosphate and shikimate pathways and is essential for mycosporine-like amino acid biosynthesis in Anabaena variabilis ATCC 29413.

The parent core structure of mycosporine-like amino acids (MAAs) is 4-deoxygadusol, which, in cyanobacteria, is derived from conversion of the pentose phosphate pathway intermediate sedoheptulose 7-phosphate by the enzymes 2-epi-5-epivaliolone synthase (EVS) and O-methyltransferase (OMT). Yet, deletion of the EVS gene from Anabaena variabilis ATCC 29413 was shown to have little effect on MAA production, thus suggesting that its biosynthesis is not exclusive to the pentose phosphate pathway. Herein, we report how, using pathway-specific inhibitors, we demonstrated unequivocally that MAA biosynthesis occurs also via the shikimate pathway. In addition, complete in-frame gene deletion of the OMT gene from A. variabilis ATCC 29413 reveals that, although biochemically distinct, the pentose phosphate and shikimate pathways are inextricably linked to MAA biosynthesis in this cyanobacterium. Furthermore, proteomic data reveal that the shikimate pathway is the predominate route for UV-induced MAA biosynthesis.