Extração e purificação de clorofila a, da alga Spirulina maxima: um experimento para os cursos de química

This work describes a simple and economical experiment for the extraction and purification of chlorophyll a from Spirulina maxima. Extraction and purification of natural compounds can be considered one of the most illustrative experiments that can be performed in Organic Chemistry courses. Particularly, the chromatography of dyes and pigments allows students to have a better comprehension of the chromatography separations. These compounds represent an important class of organic pigments applied in pharmaceutical, cosmetic, detergent compositions, and various other fields and can be extracted from plants and algae. To extract, separate and purify chlorophyll a from associated pigments such as xanthophylls, carotenes, and pheophytins, very costly processes are reported. The present approach is perfectly adequate for use in Chemistry experiments for undergraduate students.

Carotenoids production: microorganisms as source of natural dyes

Carotenoids are natural dyes synthesized by plants, algae and microorganisms. Application in many sectors can be found, as food dyeing and supplementation, pharmaceuticals, cosmetics and animal feed. Recent investigations have shown their ability to reduce the risks for many degenerative diseases like cancer, heart diseases, cataract and macular degeneration. An advantage of microbial carotenoids is the fact that the cultivation in controlled conditions is not dependent of climate, season or soil composition. In this review the advances in bio-production of carotenoids are presented, discussing the main factors that influence the microbial production of these dyes in different systems.

Química e sustentabilidade: novas fronteiras em biocombustíveis

This contribution discusses the state of the art and the challenges in producing biofuels, as well as the need to develop chemical conversion processes of CO2 in Brazil. Biofuels are sustainable alternatives to fossil fuels for providing energy, whilst minimizing the effects of CO2 emissions into the atmosphere. Ethanol from fermentation of simple sugars and biodiesel produced from oils and fats are the first-generation of biofuels available in the country. However, they are preferentially produced from edible feedstocks (sugar cane and vegetable oils), which limits the expansion of national production. In addition, environmental issues, as well as political and societal pressures, have promoted the development of 2nd and 3rd generation biofuels. These biofuels are based on lignocellulosic biomass from agricultural waste and wood processing, and on algae, respectively. Cellulosic ethanol, from fermentation of cellulose-derived sugars, and hydrocarbons in the range of liquid fuels (gasoline, jet, and diesel fuels) produced through thermochemical conversion processes are considered biofuels of the new generation. Nevertheless, the available 2nd and 3rd generation biofuels, and those under development, have to be subsidized for inclusion in the consumer market. Therefore, one of the greatest challenges in the biofuels area is their competitive large-scale production in relation to fossil fuels. Owing to this, fossil fuels, based on petroleum, coal and natural gas, will be around for many years to come. Thus, it is necessary to utilize the inevitable CO2 released by the combustion processes in a rational and economical way. Chemical transformation processes of CO2 into methanol, hydrocarbons and organic carbonates are attractive and relatively easy to implement in the short-to-medium terms. However, the low reactivity of CO2 and the thermodynamic limitations in terms of conversion and yield of products remain challenges to be overcome in the development of sustainable CO2 conversion processes.

Química Sem Fronteiras: o desafio da energia

Coal, natural gas and petroleum-based liquid fuels are still the most widely used energy sources in modern society. The current scenario contrasts with the foreseen shortage of petroleum that was spread out in the beginning of the XXI century, when the concept of "energy security" emerged as an urgent agenda to ensure a good balance between energy supply and demand. Much beyond protecting refineries and oil ducts from terrorist attacks, these issues soon developed to a portfolio of measures related to process sustainability, involving at least three fundamental dimensions: (a) the need for technological breakthroughs to improve energy production worldwide; (b) the improvement of energy efficiency in all sectors of modern society; and (c) the increase of the social perception that education is a key-word towards a better use of our energy resources. Together with these technological, economic or social issues, "energy security" is also strongly influenced by environmental issues involving greenhouse gas emissions, loss of biodiversity in environmentally sensitive areas, pollution and poor solid waste management. For these and other reasons, the implementation of more sustainable practices in our currently available industrial facilities and the search for alternative energy sources that could partly replace the fossil fuels became a major priority throughout the world. Regarding fossil fuels, the main technological bottlenecks are related to the exploitation of less accessible petroleum resources such as those in the pre-salt layer, ranging from the proper characterization of these deep-water oil reservoirs, the development of lighter and more efficient equipment for both exploration and exploitation, the optimization of the drilling techniques, the achievement of further improvements in production yields and the establishment of specialized training programs for the technical staff. The production of natural gas from shale is also emerging in several countries but its production in large scale has several problems ranging from the unavoidable environmental impact of shale mining as well as to the bad consequences of its large scale exploitation in the past. The large scale use of coal has similar environmental problems, which are aggravated by difficulties in its proper characterization. Also, the mitigation of harmful gases and particulate matter that are released as a result of combustion is still depending on the development of new gas cleaning technologies including more efficient catalysts to improve its emission profile. On the other hand, biofuels are still struggling to fulfill their role in reducing our high dependence on fossil fuels. Fatty acid alkyl esters (biodiesel) from vegetable oils and ethanol from cane sucrose and corn starch are mature technologies whose market share is partially limited by the availability of their raw materials. For this reason, there has been a great effort to develop "second-generation" technologies to produce methanol, ethanol, butanol, biodiesel, biogas (methane), bio-oils, syngas and synthetic fuels from lower grade renewable feedstocks such as lignocellulosic materials whose consumption would not interfere with the rather sensitive issues of food security. Advanced fermentation processes are envisaged as "third generation" technologies and these are primarily linked to the use of algae feedstocks as well as other organisms that could produce biofuels or simply provide microbial biomass for the processes listed above. Due to the complexity and cost of their production chain, "third generation" technologies usually aim at high value added biofuels such as biojet fuel, biohydrogen and hydrocarbons with a fuel performance similar to diesel or gasoline, situations in which the use of genetically modified organisms is usually required. In general, the main challenges in this field could be summarized as follows: (a) the need for prospecting alternative sources of biomass that are not linked to the food chain; (b) the intensive use of green chemistry principles in our current industrial activities; (c) the development of mature technologies for the production of second and third generation biofuels; (d) the development of safe bioprocesses that are based on environmentally benign microorganisms; (e) the scale-up of potential technologies to a suitable demonstration scale; and (f) the full understanding of the technological and environmental implications of the food vs. fuel debate. On the basis of these, the main objective of this article is to stimulate the discussion and help the decision making regarding "energy security" issues and their challenges for modern society, in such a way to encourage the participation of the Brazilian Chemistry community in the design of a road map for a safer, sustainable and prosper future for our nation.

Tehokalastuksen vaikutukset Lappajärvessä : Kalastus elinkeinoksi Lappajärvellä -hankkeen vuosien 2001-2006 seurannan loppuraportti

Lappajärven, Etelä-Pohjanmaan suurimman järven, ekologinen tila on heikentynyt ja se luokitellaan nykyisin tyydyttäväksi. Rehevöityminen, 1990-luvun muikkukato ja yhteiskunnan rakennemuutos ovat vähentäneet kalastajien ja kalansaaliin määrää. Ammattikalastuksen edellytysten parantamiseksi toteutettiin vuosina 2001–2004 ”Kalastus elinkeinoksi Lappajärvellä” – hanke. Hankkeen vaikutuksia kalastoon ja järven ekosysteemiin seurattiin vuosina 2001–2006. Kokonaissaalis vuosina 2001–2004 oli 1655 tonnia (n. 29 kg/ha/vuosi). Vaikka saalistavoitetta (2100 tn) ei täysin saavutettu, oli hankkeella runsaasti myönteisiä, joskin osin vähäisiä tai epävarmoja vaikutuksia järven tilaan ja kalastoon. Kalastajien yksikkösaaliit etenkin kuhan ja isokokoisen ahvenen osalta nousivat hankkeen alussa. Loppuvuosina yksikkösaaliiden kehitys oli osittain ristiriitaista. Ulapan taloudellisesti vähempiarvoinen kalasto, varsinkin kuorekanta harveni selvästi. Muikku puolestaan lisääntyi ja pysyi runsaana. Kuhan ja isokokoisen ahvenen lisääntymistä selittivät pääosin lämpimät kesät ja kuhan onnistuneet istutukset. Petokalat, etenkin kuha, voivat osaltaan säädellä Lappajärven ulapan planktonsyöjäkalojen kantoja ja toisaalta estää särjen siirtymistä ulapalle. Tehokalastuksen loputtua alkoi näkyä merkkejä kalakantojen palautumisesta takaisin kohti lähtötilannetta. Rantavyöhykkeellä hankkeen vaikutukset jäivät selvästi vähäisemmiksi kuin ulapalla. Eläinplankton lisääntyi hieman ylemmissä vesikerroksissa, mutta tilanne alkoi palautua ennalleen hankkeen jälkeen. Sinileväkukinnot vaikuttivat vähentyneen hankkeen aikana, tosin kukintojen voimakas vaihtelu vaikeutti arviointia. Tehokalastus ja vesiensuojelun tehostuminen vähensivät fosforipitoisuuksia, tosin myös vähäsateiset vuodet vaikuttivat vähenemiseen. Pitoisuuksien lasku jatkui hankkeen jälkeen. Hanketta edeltänyt klorofyllipitoisuuksien kasvusuuntaus pysähtyi ja pitoisuustaso vakiintui. Tehokalastus pienensi klorofylli/fosfori-suhdetta ja vähensi sisäistä kuormitusta, mutta vaikutus alkoi heiketä hankkeen loputtua. Typpipitoisuuksiin, veden väriin tai näkösyvyyteen kalastus ei vaikuttanut. Tehokalastuksella voidaan parantaa Lappajärven tilaa, mutta kalastuksen on oltava jatkuvaa. Saalistavoitteeksi voisi riittää n. 20-30 kg/ha vuodessa, mutta samalla on jatkettava ulkoisen kuormituksen vähentämistä. Kalastuksen tulisi kohdistua arvokalojen lisäksi myös vähempiarvoisiin kalalajeihin ja samalla on tuettava petokalakantojen vahvistumista.

Temporal and spatial variations in the structure of macroalgal communities associated with mangrove trees of Ilha do Cardoso, São Paulo state, Brazil

Temporal and spatial variations in species composition and vertical distribution of macroalgal communities growing on mangrove trees were analyzed bimonthly in the Ilha do Cardoso State Park, São Paulo state (25°03'S and 47°55'W), Southeastern Brazil. The macroalgal communities from mangroves of Perequê and Sítio Grande rivers comprised 10 and 18 taxa respectively. Bostrychia radicans (Mont.) Mont. and B. calliptera (Mont.) Mont. were the predominant taxa, present almost throughout the year and in all the sites studied. The species composition of macroalgal communities from both mangroves presented temporal and spatial variations related to environmental factors. The highest number of taxa was observed during colder, drier months, coinciding with the highest means of high water neap and short periods of continuous emersion (April to August). Some mangrove algae such as B. calliptera, Rhizoclonium spp., Caloglossa spp., and Boodleopsis pusilla (Collins) W. Taylor, Joly et Bernatowicz showed a high degree of tolerance to desiccation, being able to tolerate continuous emersion up to six days. The spatial variations in species composition were related to light, as observed in Catenella caespitosa (Withering) L. Irvine, which occurred in well-lit sites. No pattern of vertical zonation was observed, since Rhizoclonium spp., B. radicans, and B. calliptera occur over the entire vertical range. Variations in the range of vertical distribution of macroalgae of Perequê mangrove were mainly related to the variations in the tidal levels (mean high water neap and/or mean high water spring) while those observed in Sítio Grande mangrove were related to salinity variations, except for B. calliptera and Caloglossa spp. related to tidal levels and high irradiance, respectively.

Ecological distribution of Cyanophyceae in lotic ecosystems of São Paulo State

A hundred seventy two stream reaches from six distinct natural regions (parts of biomes or geological areas) in São Paulo State (Atlantic Rainforest, Cerrado, Hard Water regions, Northwest region, Subtropical Rainforest, and Tropical Rainforest) were searched for the most representative macroscopic Cyanophyceae of phytobenthic communities. Selected ecological parameters were analyzed in each stream segment: conductance, current velocity, oxygen saturation, pH, turbidity, and water temperature. Algal abundance was evaluated as percentage cover. Thirthy four cyanophyte taxa were identified and Phormidium retzii was the most widespread species throughout the State, occurring in all studied regions, except in hard water areas, and was negatively correlated to conductance. The subtropical Rainforest region presented the highest mean species richness per site, whereas the tropical Rainforest region had the highest abundance (percentage cover) of blue-green algae. Correlation tests revealed that conductance was significantly and negatively related to variations in abundance and richness of cyanophyte in streams of São Paulo State. This relationship probably reflects the ability of blue-green algae to grow at medium to low ion content and to take advantage under nutrient stress conditions.

Similarity among periphyton algal communities in a lentic-lotic gradient of the upper Paraná river floodplain, Brazil

Floristic comparison of periphyton communities from three systems with different hydrodynamic regimes (lentic, semilotic, and lotic) was carried out during high and low water periods on the Upper Paraná River floodplain. For each period and system, glass slides were sampled every two days during 18-day periods, and Eichhornia azurea Kunth petioles were sampled three times. A total of 228 species was collected, representing 12 classes, mainly diatoms and desmids. The highest species-richness was found in communities from lentic system and during high water. Species richness in the lotic system was more stable over succession and hydrological periods. Algal taxonomic structure in river community was clearly separated from the other two systems, with 43% of similarity level. The hydrological period was next in importance, followed last by the substratum type, with communities associated at 65-78% similarity levels, depending on system and hydrological period. The type of system, but not the water levels,was the main factor that influenced community richness, followed by disturbances caused by flood pulses and the operation of reservoirs upstream. The periphyton on artificial and natural substrata presented high degree of similarity.

Purification and characterisation of a lectin from the red marine alga Pterocladiella capillacea (S.G. Gmel.) Santel. & Hommers.

A lectin present in the marine red alga Pterocladiella capillacea was purified and characterised by extraction of soluble proteins (crude extract) in 20 mM Tris-HCl buffer, pH 7.5. Among the analysed erythrocytes (human blood group A, B and O and the animals ox, goat, chicken and rabbit) the lectin agglutinated specifically rabbit erythrocytes. The hemagglutinating activity assay showed that the lectin was not dependent on divalent cations and was shown to be inhibited by the glycoproteins avidin and mucin. The purification procedure was conduced by precipitation of the crude extract with 80% saturation ammonium sulfate (F0/80) followed by affinity chromatography on guar-gum column. The lectin of P. capillacea was purified 14.5 fold and had a recovery of 27.4% of the original total specific activity present in the crude extract. The absence of carbohydrate suggested that the lectin is not a glycoprotein. The molecular mass of P. capillacea lectin, determined by gel filtration, was 5.8 kDa. SDS-PAGE in the presence of ß-mercaptoethanol gave one band, indicating that the native lectin is a monomeric protein. The activation energy of denaturation process (D G') was calculated to be 106.87 kJ . mol-1 at 70 ºC.

Temporal dynamics of two species of Chaetophoraceae (Chlorophyta) in tropical streams of São Paulo State, Southeastern Brazil

Temporal dynamics of the chaetophoracean green algae Chaetophora elegans (Roth) C.A. Agardh and Stigeoclonium amoenum Kützing populations was investigated biweekly during late autumn trhough early spring (April to October) in two tropical streams from northwestern São Paulo State, southeastern Brazil. Abundances of one population of each species was evaluated by the quadrat technique in terms of percent cover and frequency. The fluctuations were related to the following stream variables: temperature, turbidity, specific conductance, pH, oxygen saturation, depth, substratum type, current velocity, irradiance and nutrients. Percent cover and frequency of C. elegans had lower values throughout the study period and was positively correlated to rainfall. Other correlations (i.e. positive of percent cover with depth and current velocity and negative with irradiance) were consistently found, reinforcing the strong influence of rainfall. On the other hand, percent cover and frequency of S. amoenum had higher values, with maximum growth from June to September. Percent cover was negatively correlated to rainfall. Results suggest the precipitation regime as the most important driving force to temporal changes in both populations, but playing different roles in each one. The gelatinous thallus of C. elegans seem to be favored by the increment of current velocity, since higher flows can improve the nutrient uptake by means of reduction in diffusion shell without promoting excessive drag force. In contrast, tufts of S. amoenum are, presumably, more exposed to drag force, and, consequently, more susceptible to mechanical damage effects due to higher current velocities.

Taxonomy and distribution of the green algal genus Halimeda (Bryopsidales, Chlorophyta) in Brazil

Halimeda is a genus of calcified coenocytic green algae with a well known ecological importance in some tropical areas. Bleached calcified segments of Halimeda may accumulate in large deposits of economic potential as is the case in the northeastern coast of Brazil. In a survey of the genus in Brazil based on recent collections and examination of abundant material deposited on Brazilian herbaria we identified seven species: Halimeda cuneata Hering, H. discoidea Decaisne, H. gracilis Harvey ex J. Agardh, H. incrassata (Ellis) Lamouroux, H. opuntia (Linnaeus) Lamouroux, H. simulans Howe and H. tuna (Ellis & Solander) Lamouroux. These species are described in detail, with emphasis on diagnostic characters. Our study has shown that the shape and size of the utricula in surface view, under scanning electron microscopy, can be utilized to discriminate some species. Fertile specimens of Halimeda cuneata and H. discoidea are reported for the first time in the region. Data on vertical and geographical distribution are presented for each species and the southern limit of the genus in the western Atlantic was extended.

Morphology and reproduction of Predaea feldmannii Børgesen (Nemastomataceae, Rhodophyta), an uncommon species from Brazil

The coast of Espirito Santo State is located in a biogeographic transition zone presenting high diversity. A renewed interest in this region occurred in the 1990s, resulting in various new records and new species descriptions added to the Brazilian marine flora. The study of the infralitoral of this region is just beginning, and a detailed exploration with use of Scuba diving is revealing a flora containing many little-known taxa, particularly of red algae. As a first result, Predaea feldmannii Børgesen is being described for the Brazilian coast. The occurrence of the genus Predaea in Brazil has been considered with restriction since representatives of this genus had been referred only once by Howe & Taylor in 1931, being first considered as Platoma. The occurrence of Predaea in Brazil is now confirmed, and its vegetative and reproductive structures are described in detail. Predaea feldmannii can be recognized by having gonimoblast initial formed on a bulge of the connecting filament, cortical filaments of nearly equal lengths, lack of gland cells, dense clusters of nutritive cells borne only on cells immediatelly contiguous to the auxiliary cell, and a three-celled carpogonial branch.

Genus Bourrellyodesmus (Desmidiaceae, Zygnemaphyceae) in the state of São Paulo, Brazil

Floristic survey of genus Bourrellyodesmus (Desmidiaceae, Zygnemaphyceae) was based on 149 sample units, 76 of which were already deposited at the Herbário Científico do Estado "Maria Eneyda P. Kauffmann Fidalgo" (SP) of the Instituto de Botânica, Secretaria do Meio Ambiente do Estado de São Paulo, and 73 of which were collected during 2000-2001. Two species of Bourrellyodesmus were identified: B. jolyanus (C. Bicudo & Azevedo) C. Bicudo & Compère e B. guarrerae sp. nov.

Sulfated bromophenols from Osmundaria obtusiloba (C. Agardh) R. E. Norris (Rhodophyta, Ceramiales)

Two new sulfated oligobromophenols from the marine red algae Osmundaria obtusiloba, 4-(1'-potassium sulfate, 2,3-dibromo, 1',4,5-trihydroxybenzyl) - 4''-(1'''-potassium sulfate, 2'',3''-dibromo, 1''',4'',5''-trihydroxybenzyl) sulfate and 1'-(2, 3-dibromo, 4-potassium sulfate, 1', 4, 5-trihydroxybenzyl) - 4''-(1''' potassium sulfate, 2'', 3''-dibromo, 1''', 4'', 5'' trihydroxybenzyl) sulfate, are herein reported. Besides them it was obtained 2, 2', 3, 3'-tetrabromo-4, 4', 5, 5'-tetrahydroxydiphenylmethane, 2, 3-dibromo-p-hydroxybenzyl methyl ether (methyl lanosol), dipotassium 2,3-dibromo-5-hydroxybenzyl 1',4-disulfate, 24-methylenecolest-5-en-3-beta-ol and alpha-D-mannopyranosyl-(1->2')-glycerate (digeneaside). The structures were determined by analysis of the spectroscopic data (IR, NMR and MS) and comparison with the literature. The 13CNMR data for dipotassium 2,3-dibromo-5hydroxybenzyl-1',4-disulfate are described here for the first time. The present study also suggests a mild method to isolate and to purify sulfated compounds.

Talousvesilaitoksen saostusvaiheen tehostaminen esihapetuksella – Case Suomen Sokeri Oy:n vedenkäsittely

Diplomityö tehtiin Suomen Sokeri Oy:n vesilaitokselle Vihreän Kemian laboratoriossa. Prosessia tarkasteltiin saostuksen osalta ja tavoitteena oli sen kehittäminen esihapetusmenetelmän tai saostuskemikaalin vaihdon avulla. Tarkastelu tehtiin orgaanisen, kiintoaineksen ja metallien poiston, desinfiointitehon sekä ympäristöystävällisyyden osalta. Potentiaalisia esihapetusmenetelmiä (kaliumpermanganaatti, vetyperoksidi, valokemiallinen, H2O2/UV, valokatalyyttinen, TiO2/UV, H2O2/ultraääni sekä esihapetus peretikkahapolla) tarkasteltiin eri pitoisuuksilla ja tehoilla laboratoriomittakaavassa jar-testin avulla. Saostustehoa testattiin alumiinikloridilla ja ferrisulfaatilla. Raakaveden laadun muutoksia eri vaiheissa seurattiin laboratorioanalyysein. Hapetusmenetelmien desinfiointiteho, vaikutukset syanobakteereihin ja -toksiineihin sekä reaktioissa syntyvät sivutuotteet kartoitettiin teorian perusteella. Työn tuloksien perusteella kaliumpermanganatti, vetyperoksidi erityisesti kehittyneenä hapetustekniikkana sekä valokatalyyttinen menetelmä tehostivat vedenkäsittelyä, mutta koska TiO2/UV- tai ultraäänihapetukselle ei ole vielä olemassa kaupallista sovellusta laitosmittakaavassa niin suositeltavat menetelmät ovat KMnO4- ja H2O2(/UV)-hapetukset jatkotutkimussuositukset huomioiden. Peretikkahappo ei tämän tutkimuksen perusteella vaikuttanut suositeltavalta hapetusmenetelmältä, mutta sen sijaan teorian perusteella potentiaaliselta desinfektioaineelta myös talousvedenpuhdistukseen. Opinnäytetyötä eri hapetusmenetelmien osalta talousvedelle ei ole aiemmin tehty eikä peretikkahappohapetuksesta ole laajalti aiempaa tutkimustietoa. Kokeellisen osuuden tulokset antavat uutta tietoa menetelmien soveltuvuudesta vastaaville laitoksille.