Leonel Pereira

USE OF FTIR, FT-RAMAN AND 13C-NMR SPECTROSCOPY FOR IDENTIFICATION OF SOME SEAWEED PHYCOCOLLOIDS

Many seaweeds produce phycocolloids, stored in the cell wall. Members of the Rhodophyceae produce polysaccharides the main components of which are galactose (galactans)-agar and carrageenan. In addition, alginic acid is extracted from members of the Phaeophyceae. This is a binary polyuronide made up of mannuronic acid and guluronic acid. The wide uses of these phycocolloids are based on their gelling, viscosifying and emulsifying properties, which generate an increasing commercial and scientific interest. In this work, the FTIR and FT-RAMAN spectra of carrageenan and agar, obtained by alkaline extraction from different seaweeds (e.g. Mastocarpus stellatus, Chondrus crispus, Calliblepharis jubata, Chondracanthus acicularis, Chondracanthus teedei and Gracilaria gracilis), were recorded in order to identify the type of phycocolloid produced. The spectra of commercial carrageenan, alginic acid and agar samples (SIGMA and TAAB laboratories) were used as references. Special emphasis was given to the 500-1500 cm(-1) region, which presents several vibrational modes, sensitive to the type of polysaccharide and to the type of glycosidic linkage. The FT-Raman spectra present a higher resolution than FTIR spectra, this allowing the identification of a larger number of characteristic bands. In some cases, phycocolloids can be identified by FT-Raman spectroscopy alone.

Analysis by Vibrational Spectroscopy of Seaweed Polysaccharides with Potential Use in Food, Pharmaceutical, and Cosmetic Industries

Polysaccharides present in several seaweeds (Kappaphycus alvarezii, Calliblepharis jubata, and Chondrus crispus—Gigartinales, Rhodophyta; Gelidium corneum and Pterocladiella capillacea—Gelidiales, Rhodophyta; Laurencia obtusa—Ceramiales, Rhodophyta; Himanthalia elongata, Undaria pinnatifida, Saccorhiza polyschides, Sargassum vulgare, and Padina pavonica—Phaeophyceae, Ochrophyta) are analyzed by spectroscopic techniques. The nature of the polysaccharides (with extraction and without any type of extraction) present in these seaweeds was determined with FTIR-ATR and FT-Raman analysis of extracted phycocolloids and ground dry seaweed.

Chemical composition of red, brown and green macroalgae from Buarcos bay in Central West Coast of Portugal.

Six representative edible seaweeds from the Central West Portuguese Coast, including the less studied Osmundea pinnatifida, were harvested from Buarcos bay, Portugal and their chemical characterization determined. Protein content, total sugar and fat contents ranged between 14.4% and 23.8%, 32.4% and 49.3% and 0.6-3.6%. Highest total phenolic content was observed in Codium tomentosum followed by Sargassum muticum and O. pinnatifida. Fatty acid (FA) composition covered the branched chain C13ai to C22:5 n3 with variable content in n6 and n3 FA; low n6:n3 ratios were observed in O. pinnatifida, Grateloupia turuturu and C. tomentosum. Some seaweed species may be seen as good sources of Ca, K, Mg and Fe, corroborating their good nutritional value. According to FTIR-ATR spectra, G. turuturu was associated with carrageenan seaweed producers whereas Gracilaria gracilis and O. pinnatifida were mostly agar producers. In the brown algae, S. muticum and Saccorhiza polyschides, alginates and fucoidans were the main polysaccharides found.

A comparative analysis of phycocolloids produced by underutilized versus industrially utilized carrageenophytes (Gigartinales, Rhodophyta)

Carrageenan (E-407) and semi-refined carrageenan (E-407a) are some of the main additives used by the food industry for their gelling, emulsifying, thickening, and stabilizing properties. These are natural ingredients, which have been used for decades in food applications and are generally regarded as safe. Internationally, sub-tropical carrageenophytes (e.g., Kappaphycus alvarezii) are cultivated extensively as a source of raw materials for industrial extraction, and their use as potential candidates in integrated multitrophic aquaculture is tentative. We analyzed carrageenan yield (as a percentage of dry weight) and chemical composition (by Fourier transform infrared attenuated total reflection and Fourier transform-Raman) of extracts produced by several carrageenophytes (Gigartinales, Rhodophyta), from different origins, e.g., K. alvarezii (Tanzania, Indonesia, the Philippines, Panama, and Mexico), Kappaphycus striatum (Madagascar), Eucheuma denticulatum (Tanzania, the Philippines, and Madagascar), Betaphycus gelatinum (the Philippines), Chondracanthus chamissoi, and Sarcothalia crispata (Chile). For comparison, some underutilized carrageenophytes were also analyzed, e.g., Chondrus crispus, Mastocarpus stellatus, Gigartina pistillata, Chondracanthus teedei var. lusitanicus, Chondracanthus acicularis, Calliblepharis jubata, Gymnogongrus crenulatus, and Ahnfeltiopsis devoniensis (Portuguese carrageenophytes). The main findings were that the highest carrageenan yield was obtained from K. striatum (Madagascar) with 75.6 (percent dry weight (% DW)); B. gelatinum and K. alvarezii (both from the Philippines) had yields of 71.0% and 68.0% (% DW), respectively; and G. pistillata (Portugal) 65.4% (% DW). Spectroscopic analysis of the phycocolloids allowed determination of a wide range of carrageenan types, e.g., pure iota carrageenan, several kappa–iota hybrid carrageenans with different iota/kappa ratios, and kappa–beta, xi–theta, and xi–lambda hybrid carrageenans.

Carrageenophytes of occidental Portuguese coast: 1-spectroscopic analysis in eight carrageenophytes from Buarcos bay

Infrared and Raman spectroscopic analysis of the carrageenan (alkaline extraction) in eight species (representing seven genera and four families) of Gigartinales, in different reproductive phases from Buarcos bay (Figueira da Foz, Portugal), were studied. Female gametophytes and non-fertile thalli samples of Chondrus crispus, Mastocarpus stellatus, Chondracanthus teedei var. lusitanicus, Gigartina pistillata and Chondracanthus acicularis present a kappa-carrageenan profile or varying degrees of a kappa-iota hybrid. The presence of kappa-iota hybrid carrageenan in C. teedei var. lusitanicus was confirmed by 13C NMR. The carrageenans extracted from Gymnogongrus crenulatus and Ahnfeltiopsis devoniensis are constituted mainly by iota-carrageenan but seasonal variations in the nature of carrageenans are present. lambda-Family carrageenans were found in tetrasporophytes of C. crispus, M. stellatus, C. teedei var. lusitanicus, C. acicularis and G. pistillata. Calliblepharis jubata presents carrageenans of iota-type in all reproductive stages.

Impact of enzyme- and ultrasound-assisted extraction methods on biological properties of red, brown, and green seaweeds from the central west coast of Portugal.

Seaweeds are an excellent source of bioactive compounds, and therefore the use of sustainable and food compatible extraction methods such as enzyme-assisted (EAE) and ultrasound-assisted extraction were applied on Sargassum muticum, Osmundea pinnatifida, and Codium tomentosum. Extracts were evaluated for proximate characterization and biological properties. Higher extraction yields were observed for C. tomentosum EAE (48-62%; p < 0.05 for Cellulase and Viscozyme), followed by O. pinnatifida (49-55%; p < 0.05 except Alcalase) and S. muticum (26-31%; p < 0.05). S. muticum extracts presented the highest nitrogen (25 ± 2 mg/glyoph extract) and total phenolics (261 ± 37 μgcatechol equiv/glyoph extract) contents, whereas higher sugars (78 ± 14 mgglucose equiv/glyoph extract) including sulfated polysaccharide (44 ± 8 mgNa2SO4 acid/glyoph extract) contents characterized O. pinnatifida extracts. A higher effect on hydroxyl-radical scavenging activity (35-50%) was observed for all extracts, whereas S. muticum Alcalase and C. tomentosum Cellulase extracts exhibited higher prebiotic activity than fructooligosaccharides. O. pinnatifida and C. tomentosum EAE showed inhibitory potential against α-glucosidase (38-49%).

Population studies and carrageenan properties of Chondracanthus teedei var. lusitanicus (Gigartinaceae, Rhodophyta)

Features of an intertidal population of Chondracanthus teedei var. lusitanicus, which occurs in sandy basins on rocky shores of part of the Portuguese coast (Buarcos, Figueira da Foz), were studied over one year. Biomass and plant size showed a small increase in early spring (April), a marked increase in early summer (June/July) and were at a minimum in late summer. There was generally more tetrasporophytes (4–32.5%) than female gametophytes (3–29%), which contrasts with other geographical regions where C. teedei populations have been studied, such as Brazil and France. However, non-fructified thalli predominated throughout the year. Phycocolloid extracts were compared for the various stages using spectroscopic methods (FTIR, FT-Raman, 1H- and 13C-NMR). These showed a hybrid carrageenan belonging to the lambda family in the tetrasporophyte and a hybrid kappa-iota-mu-nu carrageenan in the female gametophyte and non-fructified thalli. The average phycocolloid content was 34.9% dry weight, with a maximum of 43.6% in July. The combination of high available biomass and phycocolloid content makes this species a potentially important source of kappa/iota hybrid carrageenan in Portugal additional to the traditionally harvested carrageenophytes.

Population Studies and Carrageenan Properties in Eight Gigartinales (Rhodophyta) from Western Coast of Portugal

Eight carrageenophytes, representing seven genera and three families of Gigartinales (Florideophyceae), were studied for 15 months. The reproductive status, dry weight, and carrageenan content have been followed by a monthly random sampling. The highest carrageenan yields were found in Chondracanthus acicularis (61.1%), Gigartina pistillata (59.7%), and Chondracanthus teedei var. lusitanicus (58.0%). Species of Cystocloniaceae family produces predominantly iota-carrageenans; Gigartinaceae family produces hybrid kappa-iota carrageenans (gametophytic plants) and lambda-family carrageenans (sporophytic plants); Phyllophoraceae family produces kappa-iota-hybrid carrageenans. Quadrate destructive sampling method was used to determine the biomass and line transect. Quadrate nondestructive sampling method, applied along a perpendicular transect to the shoreline, was used to calculate the carrageenophytes cover in two periods: autumn/winter and spring/summer. The highest cover and biomass were found in Chondrus crispus (3.75%–570 g/m2), Chondracanthus acicularis (3.45%–99 g/m2), Chondracanthus teedei var. lusitanicus (2.45%–207.5 g/m2), and Mastocarpus stellatus (2.02%–520 g/m2).

Marine algae : biodiversity, taxonomy, environmental assessment, and biotechnology

Marine algae: General aspects (taxonomy, biology, field and lab techniques). Marine macro algae communities under natural conditions: Problems and possible approaches for the establishment of reference conditions. The multi-facets of opportunistic macroalgae: A brief review. Marine macroalgae and assessment of ecological conditions. Exotic and invasive species: Case studies. Marine algae as carbon sinks and allies to combat global warming. Marine micro algae (toxic algae). Review of marine algae as a source of bioactive metabolites. Analysis by vibrational spectroscopy of seaweed with potential use in food, pharmaceutical, and cosmetic industries. Marine algae culture: techniques, uses, perspectives. Cultivation problems and the impacts of a commercial extract of the brown seaweed Ascophyllum nodosum. Marine algae and the global food industry. Marine algae and human health. Applications of macro algae in animal feeds. Marine algae vs biofuels. Economically successful histories of macro algae uses. Internet information resources for marine algae.

Edible seaweeds of the world

Introduction - Role of Algae in Nature, Main Taxonomic Groups of Marine Algae, Importance of Algae for Mankind (Historical Overview), Marine Algae and Health. Seaweed and the Food Industry - Phycocolloids, Agar, Alginate, Carrageenan. Nutritional Composition of Edible Seaweed - Carbohydrates, Lipids, Proteins, Vitamins, Minerals. Edible Marine Algae Listed by Geographic Region - North Atlantic (Europe and North America) Chlorophyta, Ochrophyta (Phaeophyceae), Rhodophyta. South Atlantic (Africa and South America) Chlorophyta, Ochrophyta, Rhodophyta. Pacific West, Northwest and Southwest (Alaska, California, Mexico, Chile) Chlorophyta, Ochrophyta, Rhodophyta. Pacific Islands (Micronesia, Polynesia, Melanesia) and Hawaii Chlorophyta, Ochrophyta, Rhodophyta. East Asia (China, Japan, Korea) Chlorophyta, Ochrophyta, Rhodophyta. Indo-Pacific (China, Indochina, Philippines, Indonesia, Australia, New Zealand) Chlorophyta, Ochrophyta, Rhodophyta. Bibliography. Index of Species. Index of Common Names. Index of illustrations/photos. Glossary.