Влияние пространственной структуры молекул фталевых кислот на их адсорбционные свойства

წყლის ორთქლთან ადსორბციის მექანიზმის შესახებ ინფორმაციის მისაღებად ტერეფტალმჟავის და მისი იზომერების ორთოფტალმჟავის და იზოფტალმჟავის მოლეკულების აღნაგობა იყო გამოკვლეული.

Обработка углеродных адсорбентов методом механохимической активации с целью воздействия на теплые туманы

თბილ ნისლებზე ზემოქმედების მიზნით დამუშავებული იქნა ტექნოლოგია და მეთოდიკა წვრილდისპერსული ნახშირბადოვანი ადსორბენტის მასალებად მექანოქიმიური აქტივაციის გზით

Contribution to the study of immune hemolysis by toad complement

EA (sheep erythrocytes carrying rabbit antibody) are lysed by toad complement under optimal conditions which include a low concentration of cells (1.54 x 10*8/ml), a low temperature of incubation (30°C) and the same amounts of Ca++ and Mg++ as required for the titration of guinea-pig complement. Kinetic studies of the role of cations mentioned above in immune lysis by toad C have disclosed a fundamental difference as compared to guinea-pig C. In a limited complement system, the lysis by amphibian C is completely blocked by EDTA, even when the chelating agent is added as late as 15 minutes after zero-time. Inhibition by EGTA is only partial and the findings suggest that Mg++ is required not only at the beginning, but also at late stages of the lytic process. It has been speculated that the activation of amphibian complement proceeds mainly by the alternative pathway.

Adsorció de crom (VI) i crom (III) en solució amb closca de cranc

En l’eliminació del crom en suspensió de les aigües residuals de les indústries es realitzen dos processos: una precipitació en medi àcid on es redueix el crom (VI) a crom (III) en què s’elimina la major part del crom, i el següent tractament es fa per bescanvi iònic o per adsorció. Els adsorbents emprats actualment tenen un elevat cost i s’està estudiant nous adsorbents, com a substituts dels tradicionals, de baix cost. Dins d’aquest adsorbents de baix cost es troben els bioadsorbents, biomaterials amb gran capacitat d’adsorció. L’objectiu del projecte es va centrar en l’estudi de l’adsorció de crom trivalent i hexavalent en solucions aquoses utilitzant com a adsorbent el residu industrial de closca de cranc, provinent d’una indústria alimentària de barretes de cranc

Determinació d'hidrocarburs aromàtics policíclics (PAHs) en mostres de sòls per cromatografia de gasos acoblada a l'espectrometria de masses (GC/MS)

La importància dels Hidrocarburs Aromàtics Policíclics (PAHs) com a contaminants ha estat sempre en debat. Des del moment en què no compleixen els requeriments de persistència, toxicitat i transport a llargues distàncies, no es consideren contaminants orgànics persistents (POPs). En conseqüència, no es troben inclosos dins la llista dels dirty dozen de la Convenció d’Estocolm sobre POPs. A més, ja que el seu alliberament no és intencionat, algunes veus han plantejat la possibilitat d’eliminar o reduir la quantitat d’aquests compostos a l’atmosfera i que arriben també, per deposició, al sòl, sediments, aigües, etc. Tanmateix, segons el Protocol firmat pel Comitè Estats Units-Europa (UNECE), els PAHs haurien d’haver estat inclosos a aquesta llista ja que són productes químics les emissions dels quals haurien de ser minimitzades o previngudes. És per això i l’interès pel medi ambient que dins el projecte Estudi de la influència de contaminants orgànics (BTEX i PAHs) en la mobilitat de metalls pesants en sòls, al qual es vol entendre quin és el mecanisme de transport dels metalls pesants en presència d’aquests contaminants, enfocat sobretot als marges de les carreteres per la combustió de gasolines i l’exhaust dels vehicles, que es justifica aquest treball de recerca. Aquest treball de recerca es basa en la posta a punt d’un mètode d’anàlisi de PAHs mitjançant la Cromatografia de Gasos acoblada a l’Espectrometria de Masses (GC/MS). Cadascun dels mètodes seguits estan reportats a la Environmental Protection Agency dels Estats Units (US EPA), però tot i així cal fer la optimització, realitzant o no, lleus modificacions d’aquests per ajustar-nos a les nostres necessitats específiques. En aquest treball de recerca s’exposen els diferents passos a realitzar un cop feta la presa de mostra fins l’expressió final dels resultats un cop identificats i quantificats els PAHs d’interès presents en una matriu de sòl. Això comprèn la seva extracció inicial mitjançant el Soxhlet, un cleanup posterior a partir tant de l’extracció en fase sòlida (SPE) amb una fase C18 com la cromatografia en columna utilitzant gel de sílice com a adsorbent. Finalment, s’han determinat els paràmetres influents en la separació, identificació i quantificació dels PAHs amb relació a la cromatografia de gasos i la seva detecció per espectrometria de masses.

Estudi del comportament de materials nanoestructurats en el tractament d'aigües contaminades amb arsènic

El SPION (Super Paramagnetic Iron Oxide Nanoparticles) ha estat estudiat com un nou adsorbent per eliminar l’arsènic d’aigües contaminades. Les condicions òptimes de treball es van assolir per un pH de 3,6 i per concentracions inferiors als 100ppm. No es van trobar interferències significatives produïdes pels cations Cu, Ni i Zn en l’adsorció de l’As, sent el fosfat l’anió que més interfereix. Una esponja de cel·lulosa s’ha utilitzat com a suport del SPION, per disminuir les agregacions de les nanopartícules en suspensió i per proporcionar una material adequat per l’adsorció en continu, experiment amb columnes. Així, es va obtenir un augment de la capacitat d’adsorció del SPION per l’As(V), mentre que per l’As(III) continua sent baixa, per tant s’augmenta la selectivitat per l’As(V). Les interferències aniòniques afecten d’igual manera a l’adsorció de l’As(III) i l’As(V) quan l’adsorció és en continu o en discontinu. Els cations metàl·lics no interfereixen en l’adsorció de l’arsènic, a excepció del coure que és adsorbit i porta a la disminució de l’adsorció d’arsènic.

La maladie de Wilson: un caméléon clinique auquel il faut penser [A primer on Wilson disease for the general practitioner].

Wilson disease (WD) is an inherited disorder of hepatic copper excretion leading to toxic accumulation of copper in the liver as well as the brain, cornea, and other organs. The defect is due to mutations of the copper-transporting ATPase ATP7B. Clinical manifestations are highly variable and comprise acute liver failure, chronic hepatitis and cirrhosis as well as neurological or psychiatric symptoms. The Kayser-Fleischer corneal ring is pathognomonic but absent in about 50% of patients with hepatic manifestations alone. A high index of suspicion in clinically compatible situations is key, with a combination of laboratory tests allowing the diagnosis of WD. Treatment is based on the use of chelating agents, D-penicillamine or trientine. Liver transplantation should be considered for patients with acute liver failure or advanced cirrhosis.

Charge dependent substrate activity of C3' and N3 functionalized, organometallic technetium and rhenium-labeled thymidine derivatives toward human thymidine kinase 1.

Human cytosolic thymidine kinase (hTK1) has proven to be a suitable target for the noninvasive imaging of cancer cell proliferation using radiolabeled thymidine analogues such as [(18)F]3'-fluoro-3'-deoxythymidine ([(18)F]FLT). A thymidine analogue for single photon emission computed tomography (SPECT), which incorporates the readily available and inexpensive nuclide technetium-99m, would be of considerable practical interest. hTK1 is known to accommodate modification of the structure of the natural substrate thymidine at the positions N3 and C3' and, to a lesser extent, C5. In this work, we used the copper-catalyzed azide-alkyne cycloaddition to synthesize two series of derivatives in which thymidine is functionalized at either the C3' or N3 position with chelating systems suitable for the M(CO)(3) core (M = (99m)Tc, Re). The click chemistry approach enabled complexes with different structures and overall charges to be synthesized from a common precursor. Using this strategy, the first organometallic hTK1 substrates in which thymidine is modified at the C3' position were identified. Phosphorylation of the organometallic derivatives was measured relative to thymidine. We have shown that the influence of the overall charge of the derivatives is dependent on the position of functionalization. In the case of the C3'-functionalized derivatives, neutral and anionic substrates were most readily phosphorylated (20-28% of the value for the parent ligand thymidine), whereas for the N3-functionalized derivatives, cationic and neutral complexes were apparently better substrates for the enzyme (14-18%) than anionic derivatives (9%).

Cyclododecane exposure in the field of conservation and restoration of art objects

PURPOSE: Recent work practices in the conservation and restoration involve the use of cyclododecane (CDD, CAS 294-62-2) to protect fragile artifacts during their handling or transportation. Little is known about its toxicity, and no previous exposure has been reported. A short field investigation was conducted to characterize the exposure conditions to both CDD vapors and aerosols.METHODS: Measurements were conducted in the laboratory of conservation and restoration of the archeological service in Bern (Switzerland). Three indoor and four outdoor typical work situations, either during brush or spray gun applications, were investigated. Measurements were performed on charcoal adsorbent tube and analyzed by a gas chromatograph equipped with a flame ionization detector.RESULTS: Measurements have been conducted during both brush and spray gun applications. Indoor exposures were of 0.75-15.5 mg/m(3), while outdoors exposures were 19.5-53.9 mg/m(3). Exposures appear to be extremely localized due to both physicochemical properties and application methods of the CDD. Vapor exposure increases dramatically with the confinement of the workplace.CONCLUSION: Preventive measures should be undertaken to limit as much as possible these exposures. Field work in confined areas (ditches, underground) is of particular concern. CDD-coated artifacts or materials should be stored in ventilated areas to avoid delayed exposures. [Authors]

Biosphere/lithosphere interface : microbially-mediated CaCO3 precipitation in hypersaline and freshwater environments

Abstract: Microbial mats very efficiently cycle elements, such as C, 0, N, S and H, which makes them key players of redox processes at the biosphere-lithosphere interface. They are characterized by high metabolic activities and high turnover rates (production and consumption) of biomass, which mainly consists of cell material and of extracellular organic matter (EOM). The EOM forms a matrix, embedding the microbial cells and fulfilling various functions within the microbial mat, including: mat attachment to surfaces; creation of micro-domains within the mat; physical stabilization under hy- drodynamic stress and the protection of the cells in multiple other stress conditions. EOM mainly consists of polysaccharides, amino acids, and a variety of chemical func-tional groups {e.g., -C00H, - SH -OH). These groups strongly bind cations such as Ca2+ and Mg2+ and thus exert a strong control on carbonate mineral formation within the microbial mat. A feedback mechanism between community metabolisms, their prod¬ucts, and the surrounding physicochemical microenvironment thus influences the de¬gree of carbonate saturation favoring either carbonate precipitation or dissolution. We investigated the driving forces and mechanisms of microbialite formation in the Sari ne River, FR, Switzerland, the hypersaline lake, Big Pond, Bahamas and in labo¬ratory experiments. The two fundamentally different natural systems allowed us to compare the geochemical conditions and microbial metabolisms, necessary for car¬bonate formation in microbial mats. Although carbonates are oversaturated in both environments, precipitation does not occur on physicochemical substrates (i.e. out¬side the microbial mats). In the Sarine a high crystal nucleation threshold exceeds the carbonate saturation, despite the high carbonate alkalinity in the water column. Cyanobacterial photosynthesis strongly locally enhances the carbonate alkalinity, whereas the EOM attract and immobilize calcium, which increases the saturation state and finally leads to carbonate precipitation within the EOM (in this case the cyanobacterial sheath) as nucleation template. In Big Pond, the presence of calcium- chelating anions (i.e. sulfate) and EOM, as well as the presence of magnesium, lowers the calcium activity in the water column and mat, and thus inhibits carbonate pre¬cipitation. Coupled with other heterotrophic metabolisms, sulfate reduction uses the EOM as carbon source, degrading it. The resulting EOM consumption creates alkalin¬ity, releases calcium and consumes sulfate in mat-micro domains, which leads to the formation of carbonate layers at the top of the microbial mat. Résumé: Interface biosphère/lithosphère: médiation microbienne de la précipitation de CaC03 dans des environnements en eaux douces et hypersalines Les tapis microbiens engendrent une circulation très efficace des éléments, tels que C, 0, N, S et H, ce qui en fait des acteurs clé pour les processus d'oxydoréduction à l'inter¬face biosphère-lithosphère. Ils sont caractérisés par des taux élevés d'activité méta¬bolique, ainsi que par la production et la consommation de biomasse, principalement constituée de cellules microbiennes et de matière organique extracellulaire (MOE). Dans un tapis microbien, les cellules microbiennes sont enveloppées par une matrice de MOE qui a différentes fonctions dont l'attachement du tapis aux surfaces, la créa¬tion de micro-domaines dans le tapis, la stabilisation physique en situation de stress hydrodynamique, et la protection des cellules dans de multiples autres conditions de stress. La MOE se compose principalement de polysaccharides, d'acides aminés, et d'une variété de groupes fonctionnels chimiques (par exemple, COOH, -SH et -OH). Ces groupes se lient fortement aux cations, tels que Ca2+ et Mg2+, et exercent ainsi un contrôle fort sur la formation de CaC03 dans le tapis microbien. Un mécanisme de rétroaction, entre les métabolismes de la communauté microbienne, leurs produits, et le microenvironnement physico-chimique, influence le degré de saturation de car¬bonate, favorisant soit leur précipitation, soit leur dissolution. Nous avons étudié le moteur et les mécanismes de minéralisation dans des tapis de la Sarine, FR, Suisse et du lac hypersalin, Big Pond, aux Bahamas, ainsi que durant des expériences en laboratoire. Les deux systèmes naturels, fondamentalement dif¬férents, nous ont permis de comparer les conditions géochimiques et les métabolis¬mes nécessaires à la formation des carbonates dans des tapis microbiens. Bien que les carbonates soient sursaturés dans les deux environnements, la précipitation ne se produit pas sur des substrats physico-chimiques (en dehors du tapis microbien). Dans la Sarine, malgré un taux d'alcalinité élevé, les valeurs de seuil pour la nucléa- tion de carbonates sont plus hautes que la saturation du carbonate. La photosynthèse cyanobactérienne augmente localement l'alcalinité, alors que la MOE attire et immo¬bilise le calcium, ce qui augmente l'état de saturation et conduit finalement à la pré¬cipitation des carbonates, en utilisant la MOE comme substrat de nucléation. À Big Pond, la présence de chélateurs de calcium, notamment les anions (p.ex. le sulfate) et la MOE, ainsi que la présence de magnésium, réduit l'activité du calcium et inhibe en conséquence la précipitation des carbonates. Couplée avec d'autres métabolismes hétérotrophes, la réduction des sulfates utilise la MOE comme source de carbone, en la dégradant. Cette consommation de MOE crée l'alcalinité, consomme des sulfates et libère du calcium dans des micro-domaines, conduisant à la formation de couches de carbonates dans le haut du tapis microbien.

Assessment of micronutrient extractants from soils of Paraná, Brazil

In Brazil, plant-available micronutrients in the soil can be determined by several chemical extractants, the most common of which are dilute acid and chelating solutions. The purpose of this study was to assess the extractants 0.1 mol L-1 HCl, Mehlich-1, Mehlich-3 and DTPA for analysis of the micronutrients Cu, Zn, Fe, and Mn in soils from the state of Paraná. In samples from 12 soils (0-20 cm layer), wheat was planted (Triticum aestivum), grown for 42 days after emergence, and then bean (Phaseolus vulgaris) for 38 days. At the end of each planting period, the soil was sampled again. All extractants tested to assess the availability of Cu, Zn, Fe, and Mn correlated with each other. The efficiency of the extractants HCl, Mehlich-3 and DTPA in assessing plant-available Cu was similar, unlike Mehlich-1, which proved less efficient. The extractants HCl, Mehlich-1 and Mehlich-3 were less efficient in estimating plant-available Zn and Fe, and the most indicated extractant is DTPA. The efficiency of the extractants HCl, Mehlich-1, Mehlich-3 and DTPA in assessing plant-available Mn in soils from Paraná was similar.

LAYERED DOUBLE HYDROXIDES: NANOMATERIALS FOR APPLICATIONS IN AGRICULTURE

The current research aims to introduce Layered Double Hydroxides (LDH) as nanomaterials to be used in agriculture, with particular reference to its use as storage and slow release matrix of nutrients and agrochemicals for plant growing. Structural characteristics, main properties, synthesis methods and characterization of LDH were covered in this study. Moreover, some literature data have been reported to demonstrate their potential for storage and slow release of nitrate, phosphate, agrochemicals, besides as being used as adsorbent for the wastewater treatment. This research aims to expand, in near future, the investigation field on these materials, with application in agriculture, increasing the interface between chemistry and agronomy.

Cell death in Leishmania induced by stress and differentiation: programmed cell death or necrosis?

Unicellular organisms, such as the protozoan parasite Leishmania, can be stimulated to show some morphological and biochemical features characteristic of mammalian apoptosis. This study demonstrates that under a variety of stress conditions such as serum deprivation, heat shock and nitric oxide, cell death can be induced leading to genomic DNA fragmentation into oligonucleosomes. DNA fragmentation was observed, without induction, in the infectious stages of the parasite, and correlated with the presence of internucleosomal nuclease activity, visualisation of 45 to 59 kDa nucleases and detection of TUNEL-positive nuclei. DNA fragmentation was not dependent on active effector downstream caspases nor on the lysosomal cathepsin L-like enzymes CPA and CPB. These data are consistent with the presence of a caspase-independent cell death mechanism in Leishmania, induced by stress and differentiation that differs significantly from metazoa.

Relaxivity of Gd-based contrast agents on X nuclei with long intrinsic relaxation times in aqueous solutions.

The relaxivity of commercially available gadolinium (Gd)-based contrast agents was studied for X-nuclei resonances with long intrinsic relaxation times ranging from 6 s to several hundred seconds. Omniscan in pure 13C formic acid had a relaxivity of 2.9 mM(-1) s(-1), whereas its relaxivity on glutamate C1 and C5 in aqueous solution was approximately 0.5 mM(-1) s(-1). Both relaxivities allow the preparation of solutions with a predetermined short T1 and suggest that in vitro substantial sensitivity gains in their measurement can be achieved. 6Li has a long intrinsic relaxation time, on the order of several minutes, which was strongly affected by the contrast agents. Relaxivity ranged from approximately 0.1 mM(-1) s(-1) for Omniscan to 0.3 for Magnevist, whereas the relaxivity of Gd-DOTP was at 11 mM(-1) s(-1), which is two orders of magnitude higher. Overall, these experiments suggest that the presence of 0.1- to 10-microM contrast agents should be detectable, provided sufficient sensitivity is available, such as that afforded by hyperpolarization, recently introduced to in vivo imaging.