Bacterial biosensors for measuring availability of environmental pollutants

Abstract: Traditionally, pollution risk assessment is based on the measurement of a pollutant's total concentration in a sample. The toxicity of a given pollutant in the environment, however, is tightly linked to its bioavailability, which may differ significantly from the total amount. Physico-chemical and biological parameters strongly influence pollutant fate in terms of leaching, sequestration and biodegradation. Bacterial sensorreporters, which consist of living micro-organisms genetically engineered to produce specific output in response to target chemicals, offer an interesting alternative to monitoring approaches. Bacterial sensor-reporters detect bioavailable and/or bioaccessible compound fractions in samples. Currently, a variety of environmental pollutants can be targeted by specific biosensor-reporters. Although most of such strains are still confined to the lab, several recent reports have demonstrated utility of bacterial sensing-reporting in the field, with method detection limits in the nanomolar range. This review illustrates the general design principles for bacterial sensor-reporters, presents an overview of the existing biosensor-reporter strains with emphasis on organic compound detection. A specific focus throughout is on the concepts of bioavailability and bioaccessibility, and how bacteria-based sensing-reporting systems can help to improve our basic understanding of the different processes at work.

Boron mobility in eucalyptus clones

Understanding the magnitude of B mobility in eucalyptus may help to select clones that are more efficient for B use and to design new practices of B fertilization. This study consisted of five experiments with three eucalyptus clones (129, 57 and 58) where the response to and mobility of B were evaluated. Results indicated that clone 129 was less sensitive to B deficiency than clones 68 and 57, apparently due to its ability to translocate B previously absorbed via root systems to younger tissues when B in solution became limiting. Translocation also occurred when B was applied as boric acid only once to a single mature leaf, resulting in higher B concentration in roots, stems and younger leaves. The growth of B-deficient plants was also recovere by a single foliar application of B to a mature leaf. This mobility was greater, when foliar-applied B was supplied in complexed (boric acid + manitol) than in non-complexed form (boric acid alone). When the root system of clone 129 was split in two solution compartments, B supplied to one root compartment was translocated to the shoot and back to the roots in the other compartment, improving the B status and growth. Thus, it appears that B is relatively mobile in eucalyptus, especially in clone 129, and its higher mobility could be due to the presence of an organic compound such as manitol, able to complex B.

Bemisia tabaci, Brevicoryne brassicae and Thrips tabaci abundance on Brassica oleracea var. acephala

Kale Brassica oleracea var. acephala is attacked by whitefly Bemisia tabaci, aphid Brevicoryne brassicae and Thrips tabaci. One of the main reasons for extensive insecticide application is the lack of information about factors that control insect population. The objectives of this study were to investigate the relationships between predators and parasitoids, organic compound leaves, levels of leaf nitrogen and potassium, total rainfall, relative humidity, sunlight and median temperature on the abundance of whitefly, aphid, and thrips in kale genotype "Talo Roxo". The beating tray method, direct counting and magnifying lens were used to estimate the number of these pests, predators and parasitoids. Median temperature, sunlight and relative humidity correlated to the amount of leaf nonacosane, which in turn was associated with aphids population increase. A tendency in the reduction of aphids and thrips populations with increase in total rainfall was observed. The whitefly can be a harmful pest in kale producing regions of higher temperature and smaller rainfall. In regions which present moderate temperature, where there is a high incidence of aphids, genotype with low leaf wax content should be chosen. Natural enemies, especially the parasitoid Adialytus spp., can control agents of the aphids population in kale.

Towards desired crystalline product properties: In-situ monitoring of batch crystallization

The objective of industrial crystallization is to obtain a crystalline product which has the desired crystal size distribution, mean crystal size, crystal shape, purity, polymorphic and pseudopolymorphic form. Effective control of the product quality requires an understanding of the thermodynamics of the crystallizing system and the effects of operation parameters on the crystalline product properties. Therefore, obtaining reliable in-line information about crystal properties and supersaturation, which is the driving force of crystallization, would be very advantageous. Advanced techniques, such asRaman spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and in-line imaging techniques, offer great potential for obtaining reliable information during crystallization, and thus giving a better understanding of the fundamental mechanisms (nucleation and crystal growth) involved. In the present work, the relative stability of anhydrate and dihydrate carbamazepine in mixed solvents containing water and ethanol were investigated. The kinetics of the solvent mediated phase transformation of the anhydrate to hydrate in the mixed solvents was studied using an in-line Raman immersion probe. The effects of the operation parameters in terms of solvent composition, temperature and the use of certain additives on the phase transformation kineticswere explored. Comparison of the off-line measured solute concentration and the solid-phase composition measured by in-line Raman spectroscopy allowedthe identification of the fundamental processes during the phase transformation. The effects of thermodynamic and kinetic factors on the anhydrate/hydrate phase of carbamazepine crystals during cooling crystallization were also investigated. The effect of certain additives on the batch cooling crystallization of potassium dihydrogen phosphate (KDP) wasinvestigated. The crystal growth rate of a certain crystal face was determined from images taken with an in-line video microscope. An in-line image processing method was developed to characterize the size and shape of thecrystals. An ATR FTIR and a laser reflection particle size analyzer were used to study the effects of cooling modes and seeding parameters onthe final crystal size distribution of an organic compound C15. Based on the obtained results, an operation condition was proposed which gives improved product property in terms of increased mean crystal size and narrowersize distribution.

Datação da fração humina da matéria orgânica do solo e sua comparação com idades 14C de carvões fósseis

The radiocarbon dating of the soil organic matter (SOM) is a polemic subject, due mainly to the complexity of the formation of the soils and to the variable contamination from several sources. Soil samples from 4 different Brazilian localities were submitted to physical and chemical pre-treatment for the extraction of humin fraction, which is the most stable organic compound and theoretically the oldest and representative of the age of the SOM. The radiocarbon dating obtained from the total SOM and their humin fractions are compared to the 14C ages from buried charcoals at similar depths. The radiocarbon ages obtained from such charcoals are, in most of the cases, concordant within the experimental errors of those obtained on humin fractions, or are in average 10% higher, with one exception. Thus, the ages on humin fractions could be assumed as the minimum ages for the associated soils, while the results obtained on total SOM, even at depths until 200 cm, exhibit pronounced contamination effect by modern carbon, rejuvenating their ages.

Bioenergiaa ja ravinteita kasvi- ja eläinperäisistä sivuainevirroista Parikkalassa

Euroopan unionissa pyritään lisäämään uusiutuvien energialähteiden käyttöä. Tämän työn tavoitteena oli selvittää Parikkalan kunnan alueella muodostuvat biomassat sekä tutkia niiden hyötykäyttömahdollisuuksia sähkön, lämmön sekä lannoitteiden tuotannossa. Käsiteltäviä biomassoja ovat eläintilojen lietteet ja lannat, biojätteet ja yhdyskuntalietteet, vesistöjen kunnostuksessa syntyvät biomassat sekä peltobiomassat ja metsäbiomassa. Mädätyksen kannalta olennaisinta on materiaalien kosteus ja haihtuvan orgaanisen aineksen pitoisuus sekä siitä saatava biokaasumäärä. Poltossa polttoaineen kuiva-aineen lämpöarvo ja kosteus määrittelevät saadun hyödyn. Kompostoinnissa on tärkeää huolehtia riittävästä ilman saannista ja riittävästä viipymäajasta. Hyödynnettäessä biokaasua sähkön ja lämmön yhteistuotannossa on tärkeää löytää hyötykäyttö myös muodostuvalle lämmölle. Poltosta saatavan tuhkan hyötykäyttö onnistuu metsälannoitteena, kun poltetaan turvetta tai puuta. Kompostia voidaan hyödyntää maanparannusaineena. Parikkalan alueella tarkasteltiin biomassojen nykyistä ja mahdollista tulevaa hyötykäyttöä. Tarkastelu tehtiin skenaarioiden avulla. Skenaarioihin kuuluvat mädätyksen ja polton maksimipotentiaalit sekä keskitetyn ja hajautetun käsittelyn skenaariot. Alueelta on saatavissa paljon biomassoja, joista massaltaan suurin on eläintilojen lannat. Alueella on hankaluutena löytää sopiva kulutuskohde biokaasusta tuotetulle lämmölle, mutta sopivana kohteena voisi toimia alueella oleva suuri sikala tai lämpökeskukset.

Esquema para interpretação de espectros de substâncias orgânicas na região do infravermelho

This article decribes a simple and systematic method to interpret an infrared spectrum using a flow chart to elucidate the structure of a simple organic compound. It is aimed at undergraduate courses of organic chemistry to make beginners proficient. The proposed flow chart for infrared spectrum interpretation and characterization of organic compounds is suitable for theoretical and experimental courses.

Métodos simples de formação de monocristal de substância orgânica para estudo estrutural por difração de raios X

This work presents three operationally simple laboratory protocols for monocrystal growth of small-molecule organic compounds, which have been applied with success in the last ten years for the formation of single crystals for X-ray structural studies. In addition, five structure hints were formulated as general guidelines for selecting a small-molecule organic compound as a candidate for monocrystal growth: molecular weight >200 D, melting point >100 ºC, two or more aromatic rings in the structure, at least two sites for intermolecular hydrogen bond formation, and a halogen or other heavy atom in the structure.

Furfural - da biomassa ao laboratório de química orgânica

The goal of this manuscript is provide to students of Chemistry and related areas an alternative experiment in which they can obtain a compound and learn to observe and interpret properties and predict organic structure by obtaining furfural from biomass. Furfural is an organic compound, obtained through acid hydrolysis of pentosans, commonly used in the chemical and pharmaceutical industries. Students are guided to get furfural through extractive procedures and chemical reactions adapted to semi-micro laboratory scale. Characterization of furfural was done by chemical tests and physical properties. Identification was accomplished by a series of spectroscopic and spectrometric techniques.

OXIDACIÓN ELECTROQUÍMICA DE LAMBDACIALOTRINA SOBRE ELECTRODOS DE PBO2-BI

The electrochemical oxidation of lambdacyhalotrin in a triton X-100 water solution on a PbO2-Bi electrode has been studied. It was discovered that electrocatalytic degradation proceeded through the Langmuir-Hinshelwood (L-H) mechanism. The Langmuir adsorption equilibrium constant of the organic compound on the PbO2-Bi surface (0.67 (±0.02) mg-1L) and the L-H maximum reaction rate for lambdacyhalotrin oxidation (0.040 (±0.002) mg L-1 min-1) was also determined on the basis of kinetic data. Oxidation/mineralization was tested at electrode potential higher than 2.3 V vs. Ag/AgCl, in this conditions the higher degradation percent of 85 (±4) % has been obtained.

Substrate with Organosuper® for cucumber seedlings formation in protected environments and polystyrene trays

Culture environments, trays and doses of organic compost were evaluated in the formation of cucumber seedlings (Cucumis sativus L.). Five environmental conditions were tested: (A1) a greenhouse with height of 2.5 m, covered with polyethylene film, (A2) nursery with height of 2.5 m, monofilament fabric, 50% shading, (A3) nursery with height of 2.5 m, heat-reflective screen, 50% shading, (A4) nursery with a height of 1.8 m, covered with coconut tree straw and (A5) greenhouse with height of 4.0 m, covered with polyethylene film, with zenith opening and thermo-reflective cloth under the plastic. Trays of 72 (R1) and 128 (R2) cells were filled with 93% soil and 7% organic compound (S1), 86% soil and 14% organic compound (S2) and 79% soil and 21% organic compound (S3). It was used a randomized design in split-split-plot scheme, with five replicates (environments x trays x substrates). The greenhouses provide the best environments for the formation of cucumber seedlings. A tray of 72 cells is the best container, promoting more vigorous seedlings in substrate with soil and 7 or 14% organic compound.

Nitrogen fertilization by deep-bedding swine production and its effects on the properties of a Quartzarenic Neosol

The objective of this study was to evaluate the effects of the nitrogen fertilization in the form of swine deep bed in the properties of a quartz-sand neosol. The organic compound used was the deep bed made with rice hulls, from a commercial swine finishing system farm. Deep bed samples have been collected at various points in the installation in order to obtain a representative composite sample which has been fractionated in a 2.0 mm sieve and submitted to a 50-day maturation period. Then, agronomic value analyses were done. The experimental design was completely randomized. The treatments consisted of 0; 75; 150 and 300 mg dm-3 of N doses of deep bed as well as an additional treatment with ammonium sulfate at a 150 mg dm-3 of N. The experimental period in the greenhouse was 45 days, where the soil was cultivated with maize. After the experiment completion, further soil properties analyses were done. From the results, it was noted that the organic fertilization with deep bed provided a significant increase in the levels of potassium, in the sum of the bases, in the effective CEC, in the CEC at pH 7.0 and in the percentage of saturation.

Nitrogen fertilization by deep bedding swine production and its effects on dry matter production and accumulation of nutrients by maize

The goal of this study was to evaluate the nitrogen fertilization as deep litter for pigs in order to produce biomass and accumulate nutrients by the corn. A deep litter made of rice husk as organic compound, from a commercial pig farm during finishing phase, was used. After three consecutive batches of pigs, the deep litter was subjected to a maturation period of 50 days, and samples of this material were taken for analysis of agronomic value. The experimental design was completely randomized with five replicates. The treatments consisted of doses of 0, 75, 150 and 300mg dm-3 of N of deep litter, as well as an additional treatment with ammonium sulfate, with a dosage of 150mg dm-3 of N. After 45 days, corn plants were harvested in order to evaluate the total dry weight and nutrient concentrations of their aerial parts. Dry matter increases were found with more application of deep litter. Regarding control fertilization, the use of increasing dosages of deep litter allowed accumulation of K, reduced the availability of P, Ca, Mg, Zn and B and did not alter the concentrations of N, Cu, Fe and Mn.

α-Pinene oxide and verbenol oxide isomerizations over heterogeneous catalysts

Terpenes are a valuable natural resource for the production of fine chemicals. Turpentine, obtained from biomass and also as a side product of softwood industry, is rich in monoterpenes such as α-pinene and β-pinene, which are widely used as raw materials in the synthesis of flavors, fragrances and pharmaceutical compounds. The rearrangement of their epoxides has been thoroughly studied in recent years, as a method to obtain compounds which are further used in the fine chemical industry. The industrially most desired products of α-pinene oxide isomerization are campholenic aldehyde and trans-carveol. Campholenic aldehyde is an intermediate for the manufacture of sandalwood-like fragrances such as santalol. Trans-carveol is an expensive constituent of the Valencia orange essence oil used in perfume bases and food flavor composition. Furthermore it has been found to exhibit chemoprevention of mammary carcinogenesis. A wide range of iron and ceria supported catalysts were prepared, characterized and tested for α-pinene oxide isomerization in order to selective synthesis of above mentioned products. The highest catalytic activity in the preparation of campholenic aldehyde over iron modified catalysts using toluene as a solvent at 70 °C (total conversion of α-pinene oxide with a selectivity of 66 % to the desired aldehyde) was achieved in the presence of Fe-MCM-41. Furthermore, Fe-MCM-41 catalyst was successfully regenerated without deterioration of catalytic activity and selectivity. The most active catalysts in the synthesis of trans-carveol from α-pinene oxide over iron and ceria modified catalysts in N,N-dimethylacetamide as a solvent at 140 °C (total conversion of α-pinene oxide with selectivity 43 % to trans-carveol) were Fe-Beta-300 and Ce-Si-MCM-41. These catalysts were further tested for an analogous reaction, namely verbenol oxide isomerization. Verbenone is another natural organic compound which can be found in a variety of plants or synthesized by allylic oxidation of α-pinene. An interesting product which is synthesized from verbenone is (1R,2R,6S)-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol. It has been discovered that this diol possesses potent anti-Parkinson activity. The most effective way leading to desired diol starts from verbenone and includes three stages: epoxidation of verbenone to verbenone oxide, reduction of verbenone oxide and subsequent isomerization of obtained verbenol oxide, which is analogous to isomerization of α-pinene oxide. In the research focused on the last step of these synthesis, high selectivity (82 %) to desired diol was achieved in the isomerization of verbenol oxide at a conversion level of 96 % in N,N-dimethylacetamide at 140 °C using iron modified zeolite, Fe-Beta-300. This reaction displayed surprisingly high selectivity, which has not been achieved yet. The possibility of the reuse of heterogeneous catalysts without activity loss was demonstrated.

Kaasukromatografi-massaspektrometrin käyttö haihtuvien orgaanisten yhdisteiden analytiikassa ja kynureniinipolun kuuden metaboliitin analysointi solunäytteistä

Haihtuvat orgaaniset yhdisteet (eng. volatile organic compound, VOC) ovat yksi yleisimmistä ja laajimmalle levinneistä ympäristökontaminaattiryhmistä. VOC- yhdisteryhmän yhdisteet ovat määritelmän mukaisesti haihtuvia, molekyylimassaltaan pieniä (16-250 Da) yhdisteitä, joista suurin osa on joko haitallisia tai myrkyllisiä. VOC- yhdisteet pääasiallisesti emittoituvat ympäristöön ihmisen toiminnasta johtuen (teollisuus, autot, maatalous) ja päätyvät luonnossa vesistöihin ja maaperään. Ihmisille haitallisten ominaisuuksien lisäksi, VOC-yhdisteet vaikuttavat esimerkiksi ilmaston lämpenemiseen ja savusumujen syntyyn. Edellä mainittujen ominaisuuksien vuoksi on tärkeää analysoida VOC-yhdisteiden pitoisuuksia. Haihtuvien orgaanisten yhdisteiden ryhmän laajuus, ja fysikaalisten sekä kemiallisten ominaisuuksien (poolisuus, höyrynpaine, vesiliukoisuus) erot asettavat haastetta niiden analysointiin. Yleisimmin VOC-yhdisteitä analysoidaan kaasukromatografia- massaspektrometrin avulla. Pro gradu -tutkielman kirjallisessa osassa käydään läpi VOC-yhdisteiden analytiikassa käytettyjä erilaisia GC-MS-laitekokonaisuuksia ja niiden ominaisuuksia. Lisäksi keskitytään VOC-yhdisteiden erilaisiin näytteenkäsittelymenetelmiin vesi-, maa- ja sedimettinäytteissä. Kokeellisessa osassa analysoitiin kuutta kynureniinipolun metaboliittia solunäytteistä. Kynureniinipolku on nisäkkäillä tärkein tryptofaanin katabolinen polku. Kynureniinipolku aktivoituu entsymaattisesti esimerkiksi tulehdusten, hermostoa rappeuttavien prosessien ja immuunivasteen aikana. Kynureniinipolun yhdisteiden uskotaan lisäävän solun toksisuutta, mutta parantavan sen kykyä lisääntyä ja vähentävän solukuolleisuutta. Esimerkiksi 3-hydroksikynureniinin lisääntynyt määrä on yhdistetty hermostoperäisiin sairauksiin, kuten Huntingtonin- ja Parkinsonin tautiin. Kokeellisessa osassa luotiin yhdistespesifinen MRM-menetelmä, ultra korkean erotuskyvyn nestekromatografi-sähkösumutusionisaatio- kolmoiskvadrupolimassaspektrometrille. Luodulla ja optimoidulla menetelmällä kvantitoitiin soluviljelmänäytteistä samanaikaisesti L-kynureniini-, kynureniinihappo-, 3-hydroksikynureniini-, antraniilihappo-, 3-hydroksiantraniilihappo-, sekä kinoliinihappo-pitoisuudet sisäisen- ja ulkoisen standardin menetelmällä. Solunäytteiden päämetaboliiteiksi havaittiin kynureniini, kunyreniinihappo, sekä antraniilihappo. Ainoastaan 3-hydroksikynureniinihappoa ja kinoliinihappoa ei havaittu yhdestäkään näytteestä.