Abstract
Off-line analytical pyrolysis combined with gas chromatography–mass spectroscopy (GC–MS), directly or after trimethylsilylation, along with infrared spectroscopy and amino acid analysis was applied for the first time to the characterization of the intra-skeletal organic matrix (OM) extracted from four Mediterranean hard corals. They were diverse in growth form and trophic strategy namely Balanophyllia europaea and Leptopsammia pruvoti—solitary corals, only the first having zooxanthelle—and Cladocora caespitosa and Astroides calycularis—colonial corals, only the first with zooxanthelle. Pyrolysis products evolved from OM could be assigned to lipid (e.g. fatty acids, fatty alcohols, monoacylglicerols), protein (e.g. 2,5-diketopiperazines, DKPs) and polysaccharide (e.g. anhydrosugars) precursors. Their quantitative distribution showed for all the species a low protein content with respect to lipids and polysaccharides. A chemometric approach using principal component analysis (PCA) and clustering analysis was applied on OM mean amino acidic compositions. The small compositional diversity across coral species was tentatively related with coral growth form. The presence of N-acetyl glucosamine markers suggested a functional link with other calcified tissues containing chitin. The protein fraction was further investigated using novel DKP markers tentatively identified from analytical pyrolysis of model polar linear dipeptides. Again, no correlation was observed in relation to coral ecology. These analytical results revealed that the bulk structure and composition of OMs among studied corals are similar, as it is the textural organization of the skeleton mineralized units. Therefore, they suggest that coral’s biomineralization is governed by similar macromolecules, and probably mechanisms, independently from their ecology.
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References
Lowenstam HA, Weiner S (1989) On biomineralization. Oxford University Press, Oxford
Addadi L, Joester D, Nudelman F, Weiner S (2006) Chem Eur J 12:981–987
Weiner S, Addadi L (2011) Annu Rev Mater Res 41:21–40
Falini G, Fermani S (2013) Cryst Res Technol 48:864–876
Marin F, Le Roy N, Marie B (2012) Front Biosci 4:1099–1125
Marie B, Jackson DJ, Ramos-Silva P, Zanella-Cleon I, Guichard N, Marin F (2013) FEBS J 280:214–232
Drake JL, Mass T, Haramaty L, Zelzion E, Bhattacharya D, Falkowski PG (2013) Proc Natl Acad Sci U S A 110:2147–2148
Tambutté S, Holcomb SM, Ferrier-Pagès C, Reynaud S, Tambutté É, Zoccola D, Allemand D (2011) J Exp Mar Biol Ecol 408:58–78, and references therein
Goffredo S, Vergni P, Reggi M, Caroselli E, Sparla F, Levy O, Dubinsky Z, Falini G (2011) PLoS ONE 6:e22338
Falini G, Reggi M, Fermani S, Sparla F, Goffredo S, Dubinsky Z, Levi O, Dauphin Y, Cuif JP (2013) J Struct Biol 183:226–238
Mass T, Drake JL, Haramaty L, Kim JD, Zelzion E, Bhattacharya D, Falkowski PG (2013) Curr Biol 23:1126–1131
Mann K, Wilt FH, Poustka AJ (2010) Proteome Sci 8:33
Voorhees KJ, Basile F, Beverly MB, Abbas-Hawks C, Hendricker A, Cody RB, Hadfield TL (1997) J Anal Appl Pyrol 40–41:111–134
Prasad S, Schmidt H, Lampen P, Wang M, Güth R, Rao JV, Smith GB, Eiceman GA (2006) Analyst 131:1216–1225
Schwarzinger C (2005) J Anal Appl Pyrol 74:26–32
Furuhashi T, Schwarzinger C, Miksik I, Smrz M, Beran A (2009) Comp Biochem Phys B 154:351–371
Furuhashi T, Beran A, Blazso M, Czegeny Z, Schwarzinger C (2009) Biosci Biotechnol Biochem 73:93–103
Adamiano A, Bonacchi S, Calonghi N, Fabbri D, Falini G, Fermani S, Genovese D, Kralj D, Montalti M, Džakula N, Prodi L, Sartor G (2012) Chem Eur J 18:14367–14374
NíFhlaithearta S, Ernst SR, Nierop KGJ, de Lange GJ, Reichart GJ (2013) Mar Micropaleontol 102:69–78
Johnstone RAW, Povall TJ (1975) JCS Perkin I, pp:1297–1300
Adamiano A, Fabbri D, Falini G, Belcastro MG (2013) J Anal Appl Pyrol 100:173–180
Stankiewicz BA, Mastalerz M, Hof CHJ, Bierstedt A, Flannery MB, Briggs DEG, Evershed RP (1998) Org Geochem 28:67–76
Chiavari G, Galletti G (1992) J Anal Appl Pyrol 24:123–137
Fabbri D, Adamiano A, Falini G, Mancini I, De Marco R (2012) J Anal Appl Pyrol 95:145–155
Templier J, Gallois N, Derenne S (2013) J Anal Appl Pyrol. doi:10.1016/j.jaap.2013.09.017
Sciutto G, Oliveri P, Prati S, Quaranta M, Lanteri S, Mazzeo R (2013) Anal Bioanal Chem 405:625–633
Xu Y, Cheung W, Winder CL (2010) Anal Bioanal Chem 397:2439–2449
Lu Y, Harrington PB (2010) Anal Bioanal Chem 397:2959–2966
Torri C, Lesci IG, Fabbri D (2009) J Anal Appl Pyrol 85:192–196
Alén R, Kuoppala E, Oesch P (1996) J Anal Appl Pyrol 36:137–148
Fabbri D, Prati S, Vassura I, Chiavari G (2003) J Anal Appl Pyrolysis 68–69:163–171
Abelenda MS, Buurman P, Arbestain MC, Kaal J, Martinez-Cortizas A, Gartzia-Bengoetxea N, Macías F (2011) Eur J Soil Sci 62:834–848
Cao JP, Zhao XY, Morishita K, Wei XY, Takarada T (2010) Bioresour Technol 101:7648–7652
Schlotzhauer WS, Chortyk OT, Austin PR (1976) J Agric Food Chem 24(1):177–180
Ratcliff MA Jr, Medley EE, Simmonds PG (1974) J Org Chem 39:1481–1490
Sharma RK, Chan WG, Wang J, Waymack BE, Wooten JB, Seeman JI, Hajaligol MR (2004) J Anal Appl Pyrol 72:153–163
Schulten HR (1999) J Anal Appl Pyrol 49:385–415
Räisänen U, Pitkänen I, Halttunen H, Hurtta M (2003) J Therm Anal Calorim 72:481–488
Fabbri D, Torri C, Baravelli V (2007) J Anal Appl Pyrol 80:24–29
Gelencsér A, Mészáros T, Blazsó M, Kiss GY, Krivácsy Z, Molnár A, Mészáros E (2000) J Atmos Chem 37:173–183
Casol A, Mirti P, Palla G (1995) Fresenius J Anal Chem 352:372–379
Al-Moghrabi S, Allemand D, Couret JM, Jaubertal J (1995) J Comp Physiol B 165:183–192
Yamashiro H, Hirosuke O, Higa H, Chinen I, Sakai K (1999) Comp Biochem Phys B 122:397–407
Stankiewicz BA, Briggs DEG, Evershed RP, Flannery MB, Wuttke M (1997) Science 276:1541–1543
Schulten HR, Sorge-Lewin C, Schnitzer M (1997) Biol Fertil Soils 24:249–254
Richmond-Aylor A, Bell S, Callery P, Morris K (2007) J Forensic Sci 52:380–382
Smith GG, Reddy GS, Boon JJ (1988) J Chem Soc Perkin Trans II:203–211
Fischer PM (2003) J Pept Sci 9:9–35
Imbs AB (2013) Russ J Mar Biol 39:153–168
Torri C, Soragni E, Prati S, Fabbri D (2013) Microchem J 110:719–725
Gautret P, Cruit JP, Freiwald A (1997) FACIES 36:189–194
Acknowledgments
The research leading to these results has received funding from the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013)/ERC grant agreement no. [249930–CoralWarm: Corals and global warming: the Mediterranean versus the Red Sea]. We deeply thank Gianni Neto for the coral underwater pictures. GF and SF thank the Consorzio Interuniversitario di Ricerca della Chimica dei Metalli nei Sistemi Biologici (CIRC MSB) for the support.
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Adamiano, A., Goffredo, S., Dubinsky, Z. et al. Analytical pyrolysis-based study on intra-skeletal organic matrices from Mediterranean corals. Anal Bioanal Chem 406, 6021–6033 (2014). https://doi.org/10.1007/s00216-014-7995-1
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DOI: https://doi.org/10.1007/s00216-014-7995-1