Contenu total en éléments traces de sols forestiers du Québec méridional

Les sols forestiers constituent un réservoir considérable d’éléments nutritifs disponibles pour soutenir la productivité forestière. Ces sols contiennent aussi une quantité, encore inconnue à ce jour, d’éléments traces biodisponibles provenant de sources anthropiques ou naturelles. Or, plusieurs de ces éléments recèlent un potentiel toxique pour les organismes vivants. Ainsi, la quantification de la concentration et du contenu total en éléments traces des sols forestiers s’avère nécessaire afin d’évaluer les impacts des perturbations sur la qualité des sols. Les objectifs de ce projet de recherche sont: 1) de mesurer le contenu total en éléments traces en phase solide (Ag, As, Ba, Cd, Ce, Co, Cr, Cu, Mn, Ni, Pb, Rb, Se, Sr, Tl, V, Y, Zn) des divers horizons de sols d’écosystèmes forestiers du Québec méridional; 2) d’établir des liens significatifs entre la fraction soluble dans l’eau des éléments traces et les propriétés des horizons de sols et; 3) d’évaluer le rôle de la proximité d’un centre urbain sur les contenus en éléments traces. Pour répondre à ces objectifs, quatre profils de sols situés dans la région de St-Hippolyte et deux situés dans la région de Montréal furent échantillonnés jusqu'à l'atteinte du matériel parental. Les résultats de ce projet de recherche ont révélé que le contenu total en éléments traces présents dans les profils de sols se retrouve en grande partie dans les fragments grossiers du sol. Il a été démontré que la teneur en carbone organique, les complexes organométalliques et les oxydes de fer et d’aluminium dictent la distribution en profil de la majorité des éléments traces étudiés. Finalement, il fut prouvé que la région de Montréal présente des niveaux de contamination en éléments traces (Ag, As, Ba, Cu, Mn, Pb, Rb, Se, Sr, Tl et Zn) supérieurs à ceux rencontrés dans les Laurentides.

Le rôle du récepteur B1 des kinines dans le développement de la rétinopathie diabétique

La rétinopathie diabétique est associée à plusieurs changements pathologiques du lit vasculaire rétinien, incluant l’ouverture de la barrière hémato-rétinienne, l’inflammation vasculaire et la modification du débit sanguin. Récemment, il a été proposé que le récepteur B1 des kinines, qui est surexprimé dans la rétine diabétique, puisse être impliqué dans le développement de ces altérations vasculaires. Ainsi, cette thèse présente les effets de traitements pharmacologiques avec des antagonistes du récepteur B1 sur la perfusion rétinienne, la perméabilité vasculaire, l’infiltration des leucocytes (leucostasie), l’expression de médiateurs de l’inflammation et la production d’anion superoxyde dans la rétine du rat rendu diabétique avec la streptozotocine (STZ). Les résultats obtenus montrent que l’application oculaire (10 µl d’une solution à 1%, deux fois par jour pendant 7 jours) de LF22-0542, un antagoniste hydrosoluble du récepteur B1, bloque significativement l’hyperperméabilité vasculaire, la leucostasie, le stress oxydatif et l’expression génique de médiateurs de l’inflammation (B1R, iNOS, COX-2, VEGF-R2, IL-1β et HIF-1α) dans la rétine chez le rat à 2 semaines de diabète. L’administration orale (3 mg/kg) d’un antagoniste non-peptidique et sélectif pour le récepteur B1, le SSR240612, entraîne une diminution du débit sanguin rétinien 4 jours après l’induction du diabète mais n’a aucun effet sur la réduction de la perfusion rétinienne à 6 semaines. Le récepteur B1 joue donc un rôle protecteur au tout début du diabète en assurant le maintien d’un débit sanguin normal dans la rétine; un effet qui n’est toutefois pas maintenu pendant la progression du diabète. Ces données présentent ainsi la dualité du récepteur B1 avec des effets à la fois protecteurs et délétères. Elles suggèrent aussi un rôle important pour le récepteur B1 dans l’inflammation rétinienne et le développement des altérations vasculaires. Le récepteur B1 pourrait donc représenter une nouvelle cible thérapeutique pour le traitement de la rétinopathie diabétique.

Développement de nouveaux polymères amphiphiles comme floculants versatiles pour le traitement de l’eau issue de l’industrie pétrolière

Les polymères hydrosolubles sont utilisés dans diverses industries pour permettre la floculation, soit une séparation solide-liquide de particules présentes en suspension colloïdale. Afin de réduire les impacts environnementaux de l’exploitation des sables bitumineux en Alberta, l’industrie est à la recherche de nouveaux moyens et procédés pour traiter les résidus miniers permettant de séparer les matières solides et de récupérer l’eau. L’objectif des travaux présentés est d’améliorer la floculation, la densification et la déshydratation de ces résidus miniers aqueux par de nouveaux polymères synthétiques. Des homopolymères d’acrylamide de différentes masses molaires ont été synthétisés pour étudier l’influence de la masse molaire sur l’efficacité de floculation. Le taux initial de sédimentation (TIS) est le paramètre qui fut utilisé afin de comparer l’efficacité de floculation des différents polymères. Il a été possible de confirmer l’importance de la masse molaire sur l’efficacité de floculation et de déterminer une masse molaire minimale d’environ 6 MDa pour des polyacrylamides, afin d’obtenir l’efficacité de floculation maximale de suspensions colloïdales principalement composées de kaolin. Afin d’étudier l’effet des charges sur l’efficacité de floculation, des polymères anioniques et cationiques ont été synthétisés. Une série de copolymères d’acrylamide et d’acide acrylique ont été synthétisés comme polymères anioniques et deux séries de copolymères ont été synthétisés comme polymères cationiques, soit des copolymères d’acrylamide et de chlorure de diallyldiméthylammonium et des copolymères de 4-vinyl pyridine et de 1-méthyl-4-vinyl pyridinium. Il a été démontré que les charges anioniques des polymères avaient peu d’influence sur l’efficacité de floculation et que leur comportement en présence de sels était différent de ce que prévoyait la littérature. Il a aussi été démontré que les charges cationiques des polymères n’améliorent pas l’efficacité de floculation. Par la suite, des séries de copolymères amphiphiles, avec des monomères d’acrylamide, de N-alkylacrylamides et d’acrylonitrile, ont été synthétisés, pour étudier l’effet du caractère amphiphile sur la déshydratation des résidus miniers. Le pourcentage de déshydratation nette est le paramètre qui fut utilisé afin de comparer l’efficacité de déshydratation des différents polymères. Il a été possible de développer des copolymères amphiphiles qui améliorent l’efficacité de déshydratation par rapport à des homopolymères d’acrylamide. Il ne fut pas possible de déterminer une tendance entre la balance hydrophile/hydrophobe des copolymères amphiphiles et l’efficacité de déshydratation.

Development of Polymer Cement Composites

Research in the field of polymer modified cement has been carried out for the last 70 years or more. Polymers are mostly used to enhance durability and sustainability of cement concrete and in combination with classical construction materials a synergistic effect is obtained. In this work different polymers were added to Portland cement in various proportions and the mechanical and chemical resistance properties of the resultant composites when exposed to chemical environments were studied. Microstructural studies were also carried out to investigate the morphology of the composite and analyse the nature of interactions taking place between the cement and polymer phases. Though most polymers did not improve the compressive strength of the cement paste, it was found that they enhanced the resistance of the virgin cement paste to external chemical environments. The polymers seal the pores in the cement matrix and bridge the microcracks within the composite. Some of the polymers underwent chemical interactions with the cement paste thereby interfering in the hydration of cement. Polymers also decreased the leachability of water soluble components of virgin cement resulting in composites having improved durability. An attempt to correlate the structure of the polymers with the properties of the resultant composites is also presented.

Cadmium Selenide Based Core-Shell Quantum Dots for Biosensing and Imaging Applications

The overall focus of the thesis involves the synthesis and characterization of CdSe QDs overcoated with shell materials for various biological and chemical sensing applications. Second chapter deals with the synthesis and characterization of CdSe and CdSe/ZnS core shell QDs. The primary attention of this work is to develop a simple method based on photoinduced charge transfer to optimize the shell thickness. Synthesis of water soluble CdSe QDs, their cytotoxicity analysis and investigation of nonlinear optical properties form the subject of third chapter. Final chapter deals with development of QD based sensor systems for the selective detection of biologically and environmentally important analytes from aqueous media.

Influence of collagen content on the texture andstorage quality of fish mince basedproducts

Objectives of the present study are to find out the proximate composition of 20 commercially important tropical fish species on the west coast of India. To determine the collagen content in these commercially important fish species and fractionation of collagen into acid soluble collagen (ASC) and hot water soluble (insoluble) collagen (ISC). To classify fishes according to its collagen content and To study the different storage characteristics in the mince based product—surimi, from different species of fishes. The researcher tries to find out a suitable collagen source to incorporate in surimi. and studies the different storage qualities in the mince based product, surimi at different levels of collagen in different species of fishes. The optimum collagen level to get desirable texture and storage quality for mince based product. The researcher aims to develop some products from surimi with desirable level of collagen. And compare the products prepared from surimi of lesser collagen content fish containing desirable level of collagen with surimi prepared with high collagen content fish without collagen. This study gains in importance as there is littleinformation on the collagen content of different species of fishes in India. So far no attempt was made to classify fishes according to its collagen content.

Changes in Biochemical Composition in Indian Major Carps in Relation to size

Total biochemical composition of freshwater major carps, Labeo rohita -(r9hu); Catla catla (catla); Cirrltinus tnrigala (mrigal), in relation to size was evaluated . The water soluble nitrogen fraction constituted about 21% of the tota l nitro gen . Salt so luble fraction constituted 55 - 60% of the total nitrogen. Non-protein nitrogen represented 12% of the total nit rogen in all the cases except mri gal of small size (9.36%). The insoluble connec tive tissu e contributed to 2-3 per cent of tota l nitrogen . The monounsaturated fatty acid s (MUFA) formed 31-39% of the total fatty acids and 60-68% of the MUFA in freshwat er carps was CI 8:1. The esse ntial amino acids contributed to 41 to 51% of the total amino acid s in freshwater major carps. Arom atic amino acid content was sligh tly higher compared to marine fishe s while the proportion of proline was less. Varia tions in compos ition in rela tion to size are discu ssed . The autolytic activi ty was significantly higher in small fish in all the three species

Behaviour of mrigal (cirrihinus mrigala) meat components during the washing process in the preparation of surimi

To elucidate the effect of washing, on flesh components, mrigal flesh was washed through one, two and three washing cycles. Washing resulted in absorption of water (1-3%) and loss of fat (49%). 35% loss of soluble protein (SP) was noticed in the first washing itself and the loss is almost equally shared by the sarcoplasmic (18% of SP) and the myofibrillar proteins (17% of SP). The subsequent washings removed small portions of water-soluble sarcoplasmic proteins resulting in the concentration of myofibrillar proteins. 73% of the soluble protein was retained in the flesh after three washing cycles. The protein had undergone marginal conformational changes as reflected by the decrease in the actomyosin Ca super(2+) ATPase activity The rheological properties of the washed flesh were,however, significantly better than that of the unwashed mince

Design and study of self-assembled functional organic and hybrid systems for biological applications

The focus of self-assembly as a strategy for the synthesis has been confined largely to molecules, because of the importance of manipulating the structure of matter at the molecular scale. We have investigated the influence of temperature and pH, in addition to the concentration of the capping agent used for the formation of the nano-bio conjugates. For example, the formation of the narrower size distribution of the nanoparticles was observed with the increase in the concentration of the protein, which supports the fact that γ-globulin acts both as a controller of nucleation as well as stabiliser. As analyzed through various photophysical, biophysical and microscopic techniques such as TEM, AFM, C-AFM, SEM, DLS, OPM, CD and FTIR, we observed that the initial photoactivation of γ-globulin at pH 12 for 3 h resulted in small protein fibres of ca. Further irradiation for 24 h, led to the formation of selfassembled long fibres of the protein of ca. 5-6 nm and observation of surface plasmon resonance band at around 520 nm with the concomitant quenching of luminescence intensity at 680 nm. The observation of light triggered self-assembly of the protein and its effect on controlling the fate of the anchored nanoparticles can be compared with the naturally occurring process such as photomorphogenesis.Furthermore,our approach offers a way to understand the role played by the self-assembly of the protein in ordering and knock out of the metal nanoparticles and also in the design of nano-biohybrid materials for medicinal and optoelectronic applications. Investigation of the potential applications of NIR absorbing and water soluble squaraine dyes 1-3 for protein labeling and anti-amyloid agents forms the subject matter of the third chapter of the thesis. The study of their interactions with various proteins revealed that 1-3 showed unique interactions towards serum albumins as well as lysozyme. 69%, 71% and 49% in the absorption spectra as well as significant quenching in the fluorescence intensity of the dyes 1-3, respectively. Half-reciprocal analysis of the absorption data and isothermal titration calorimetric (ITC) analysis of the titration experiments gave a 1:1 stoichiometry for the complexes formed between the lysozyme and squaraine dyes with association constants (Kass) in the range 104-105 M-1. We have determined the changes in the free energy (ΔG) for the complex formation and the values are found to be -30.78, -32.31 and -28.58 kJmol-1, respectively for the dyes 1, 2 and 3. Furthermore, we have observed a strong induced CD (ICD) signal corresponding to the squaraine chromophore in the case of the halogenated squaraine dyes 2 and 3 at 636 and 637 nm confirming the complex formation in these cases. To understand the nature of interaction of the squaraine dyes 1-3 with lysozyme, we have investigated the interaction of dyes 1-3 with different amino acids. These results indicated that the dyes 1-3 showed significant interactions with cysteine and glutamic acid which are present in the side chains of lysozyme. In addition the temperature dependent studies have revealed that the interaction of the dye and the lysozyme are irreversible. Furthermore, we have investigated the interactions of these NIR dyes 1-3 with β- amyloid fibres derived from lysozyme to evaluate their potential as inhibitors of this biologically important protein aggregation. These β-amyloid fibrils were insoluble protein aggregates that have been associated with a range of neurodegenerative diseases, including Huntington, Alzheimer’s, Parkinson’s, and Creutzfeldt-Jakob diseases. We have synthesized amyloid fibres from lysozyme through its incubation in acidic solution below pH 4 and by allowing to form amyloid fibres at elevated temperature. To quantify the binding affinities of the squaraine dyes 1-3 with β-amyloids, we have carried out the isothermal titration calorimetric (ITC) measurements. The association constants were determined and are found to be 1.2 × 105, 3.6× 105 and 3.2 × 105 M-1 for the dyes, 1-3, respectively. To gain more insights into the amyloid inhibiting nature of the squaraine dyes under investigations, we have carried out thioflavin assay, CD, isothermal titration calorimetry and microscopic analysis. The addition of the dyes 1-3 (5μM) led to the complete quenching in the apparent thioflavin fluorescence, thereby indicating the destabilization of β-amyloid fibres in the presence of the squaraine dyes. Further, the inhibition of the amyloid fibres by the squaraine dyes 1-3, has been evidenced though the DLS, TEM AFM and SAED, wherein we observed the complete destabilization of the amyloid fibre and transformation of the fibre into spherical particles of ca. These results demonstrate the fact that the squaraine dyes 1-3 can act as protein labeling agents as well as the inhibitors of the protein amyloidogenesis. The last chapter of the thesis describes the synthesis and investigation of selfassembly as well as bio-imaging aspects of a few novel tetraphenylethene conjugates 4-6.Expectedly, these conjugates showed significant solvatochromism and exhibited a hypsochromic shift (negative solvatochromism) as the solvent polarity increased, and these observations were justified though theoretical studies employing the B3LYP/6-31g method. We have investigated the self-assembly properties of these D-A conjugates though variation in the percentage of water in acetonitrile solution due to the formation of nanoaggregates. Further the contour map of the observed fluorescence intensity as a function of the fluorescence excitation and emission wavelength confirmed the formation of J-type aggregates in these cases. To have a better understanding of the type of self-assemblies formed from the TPE conjugates 4-6, we have carried out the morphological analysis through various microscopic techniques such as DLS, SEM and TEM. 70%, we observed rod shape architectures having ~ 780 nm in diameter and ~ 12 μM in length as evidenced through TEM and SEM analysis. We have made similar observations with the dodecyl conjugate 5 at ca. 70% and 50% water/acetonitrile mixtures, the aggregates formed from 4 and 5 were found to be highly crystalline and such structures were transformed to amorphous nature as the water fraction was increased to 99%. To evaluate the potential of the conjugate as bio-imaging agents, we have carried out their in vitro cytotoxicity and cellular uptake studies though MTT assay, flow cytometric and confocal laser scanning microscopic techniques. Thus nanoparticle of these conjugates which exhibited efficient emission, large stoke shift, good stability, biocompatibility and excellent cellular imaging properties can have potential applications for tracking cells as well as in cell-based therapies. In summary we have synthesized novel functional organic chromophores and have studied systematic investigation of self-assembly of these synthetic and biological building blocks under a variety of conditions. The investigation of interaction of water soluble NIR squaraine dyes with lysozyme indicates that these dyes can act as the protein labeling agents and the efficiency of inhibition of β-amyloid indicate, thereby their potential as anti-amyloid agents.

Efficient phosphorus application strategies for increased crop production in sub-Saharan West Africa

Comparable data are lacking from the range of environments found in sub-Saharan West Africa to draw more general conclusions about the relative merits of locally available rockphosphate (RockP) in alleviating phosphorus (P) constraints to crop growth. To fill this gap, a multi-factorial field experiment was conducted over 4 years at eight locations in Niger, Burkina Faso and Togo. These ranged in annual rainfall from 510 to 1300 mm. Crops grown were pearl millet (Pennisetum glaucum L.), sorghum (Sorghum bicolor (L.) Moench) and maize (Zea mays L.) either continuously or in rotation with cowpea (Vigna unguiculata Walp.) and groundnut (Arachis hypogaea L.). Crops were subjected to six P fertiliser treatments comprising RockP and soluble P at different rates and combined with 0 and 60 kg N ha^-1. For legumes, time trend analyses showed P-induced total dry matter (TDM) increases between 28 and 72% only with groundnut. Similarly, rotation-induced raises in cereal TDM compared to cereal monoculture were only observed with groundnut. For cereals, at the same rate of application, RockP was comparable to single superphosphate (SSP) only at two millet sites with topsoil pH-KCl <4.2 and annual average rainfall >600 mm. Across the eight sites NPK placement at 0.4 g P per hill raised average cereal yields between 26 and 220%. This was confirmed in 119 on-farm trials revealing P placement as a promising strategy to overcome P deficiency as the regionally most growth limiting nutrient constraint to cereals.

Surface Functionalization of Monodisperse Magnetic Nanoparticles

We present a systematic methodology to functionalize magnetic nanoparticles through surface-initiated atom-transfer radical polymerization (ATRP). The magnetite nanoparticles are prepared according to the method proposed by Sun et al. (2004), which leads to a monodisperse population of ~ 6 nm particles stabilized by oleic acid. The functionalization of the nanoparticles has been performed by transforming particles into macro-initiators for the ATRP, and to achieve this two different routes have been explored. The first one is the ligand-exchange method, which consists of replacing some oleic acid molecules adsorbed on the particle surface with molecules that act as an initiator for ATRP. The second method consists in using the addition reaction of bromine to the oleic acid double bond, which turns the oleic acid itself into an initiator for the ATRP. We have then grown polymer brushes of a variety of acrylic polymers on the particles, including polyisopropylacrylamide and polyacrylic acid. The nanoparticles so functionalized are water soluble and show responsive behavior: either temperature responsive behavior when polyisopropylacrylamide is grown from the surface or PH responsive in the case of polyacrylic acid. This methodology has potential applications in the control of clustering of magnetic nanoparticles.

Conflicto por el agua: un análisis geopolítico al sistema Tigris-Éufrates. 1990-2003

El interés de este estudio de caso es analizar la situación vivida entre los Estados de la cuenca del Sistema Tigris-Éufrates, un recurso hídrico transfronterizo entre 1990 y el 2003. Se estudia y explica cómo el Interés Nacional de Turquía, Siria e Irak, Estados ribereños del Sistema supuso un obstáculo para la implementación de la Gestión Integrada de Recursos Hídricos sobre la cuenca, al impedir la cooperación y coordinación de las políticas gubernamentales, dificultando la protección de la cuenca y la garantía del acceso al recurso de forma equitativa. Este trabajo se enmarca en los estudios sobre Seguridad Ambiental, particularmente en la teoría de la Escasez Ambiental de Thomas Homer-Dixon y el Grupo de Toronto, referente a la relación entre la escasez de un recurso natural renovable y el surgimiento de un conflicto.

Síntesi, caracterització química i estudi de l'activitat biològica de nous complexos de Pt(II) amb lligands de tipus diaminocarboxílic i els respectius ésters i derivats peptídics

El cisplatí, PtCl2(NH3)2, ha estat una de les drogues més utilitzades en la quimioteràpia del càncer des del descobriment de la seva activitat. Però degut a la seva alta toxicitat i greus efectes secundaris, s'han sintetitzat nous compostos amb la finalitat de reduir aquests inconvenients. En aquest sentit, el treball desenvolupat en aquesta tesi doctoral ha estat la síntesi i caracterització de tretze complexos de Pt(II) amb la finalitat d'estudiar llur activitat antitumoral. Aquests complexos presenten unes característiques estructurals comunes: geometria cis, dos lligands làbils de tipus clorur i un lligand diaminoquelatant derivat dels àcids d,l-2,3-diaminopropiònic (Hdap) i d,l-2,4-diaminobutíric (Hdab). S'han dissenyat unes estratègies sintètiques a partir de les quals els lligands han estat funcionalitzats amb diferents grups de tipus éster, aminoàcid i peptídic: Etdap·2HCl, Etdab·2HCl, [(dap-Metala)·2CF3COOH], [(dab-Metala)·2CF3COOH], [(dap-phe)·2CF3COOH], [(dab-phe)·2CF3COOH], [(dap-Mettrp)·2CF3COOH], [(dab-Mettrp)·2CF3COOH], [(dap-ASTTTNYT-NH2)·2CF3COOH], essent Metala= éster metílic de L-alanina, phe= L-fenilalanina, Mettrp= éster metílic del L-triptofà. Aquests lligands diaminoquelatants s'han utilitzat per sintetitzar els corresponents complexos de Pt(II): PtCl2(Hdap), PtCl2(Hdab), PtCl2(Etdap), PtCl2(Etdab), PtCl2(dap-Metala), PtCl2(dab-Metala), PtCl2(dap-ala), PtCl2(dab-ala), PtCl2(dap-phe), PtCl2(dab-phe), PtCl2(dap-Mettrp), PtCl2(dab-Mettrp), PtCl2(dap-ASTTTNYT-NH2). A través de diferents tècniques i assaigs biològics (dicroisme circular, electroforesi en gel d'agarosa, microscopia de forces atòmiques, citometria de flux, assaigs de proliferació cel·lular) s'ha pogut demostrar l'activitat antitumoral d'aquests compostos. A través de la tècnica de dicroisme circular (DC) s'ha pogut demostrar que els lligands lliures no interaccionen covalentment amb el DNA de Calf Thymus i no modifiquen l'estructura secundària de la doble hèlix. En canvi, els respectius complexos han demostrat tenir capacitat per interaccionar amb el DNA i modificar la seva estructura secundària. Els complexos PtCl2(Hdap), PtCl2(Hdab) i PtCl2(dab-phe) mostren un comportament similar al cisplatí, generant adductes cis-bifuncionals que distorcionen la doble hèlix de forma no desnaturalitzant amb obertura de la doble cadena. Els complexos PtCl2(Etdap), PtCl2(Etdab), PtCl2(dap-ala), PtCl2(dab-ala), PtCl2(dap-Metala), PtCl2(dab-Metala), PtCl2(dap-phe), PtCl2(dap-ASTTTNYT-NH2) quan interaccionen amb el DNA generen un canvi en la conformació del DNA de la forma B a la forma C, produint-se un augment de la curvatura de l'hèlix per rotació de les bases nitrogenades. En aquests estudis s'ha comprovat que l'estructura del complex influeix en l'efecte generat sobre l'estructura secundària de l'àcid nucleic. En primer lloc, existeix una diferència en el comportament en funció del tamany del lligand diaminoquelatant, de manera que els complexos amb el lligand (dab) provoquen un efecte més remarcable. També s'observa aquest canvi de comportament al passar dels complexos que tenen el grup funcional esterificat als que el tenen protonat. D'aquesta manera, s'observa un major efecte sobre l'estructura secundària del DNA en aquells complexos que tenen el lligand diaminoquelatant de tres metilens (dab) i amb el grup carboxilat terminal protonat. Per tal de modelitzar la interacció d'aquests complexos amb el DNA, s'ha estudiat la interacció d'aquests compostos de Pt(II) amb 5'-GMP a través de RMN-1H, observant la variació dels senyals corresponents al H8 de 5'-GMP. Així s'ha pogut demostrar que aquests compostos interaccionen amb la 5'-GMP a través d'un enllaç covalent Pt-N7, de la mateixa manera a com interacciona el cisplatí. A través d'electroforesi en gel d'agarosa i microscopia de forces atòmiques (AFM) s'ha pogut determinar l'efecte que generen els lligands lliures i els respectius complexos de Pt(II) sobre l'estructura terciària del plasmidi pBR322. Els lligands provoquen un augment de l'agregació de les molècules de DNA i un lleuger augment de la compactació de l'estructura terciària. Aquests resultats s'atribueixen a la capacitat d'aquests compostos a interaccionar per pont d'hidrogen amb el DNA. Els corresponents complexos de Pt(II) provoquen un augment de l'agregació i una important compactació, degut per una banda a la capacitat de l'àtom de Pt a interaccionar covalentment amb el DNA, i per altra banda, a la capacitat del lligand a interaccionar per pont d'hidrogen amb l'àcid nucleic. Finalment s'ha estudiat l'activitat citotòxica d'aquests complexos de Pt(II) en diferents línies cel·lulars: A431 (línia de carcinoma epidermoide), HeLa (línia de carcinoma de coll d'úter) i HL-60 (línia promielocítica de leucèmia). Els complexos moderadament solubles en aigua, PtCl2(Hdap), PtCl2(Hdab), PtCl2(dap-ala), PtCl2(dab-ala), PtCl2(dap-phe) i PtCl2(dab-phe), han demostrat ser actius. L'activitat depèn de la concentració de complex, del temps d'incubació i de la línia cel·lular. Per temps d'incubació alts i concentracions de complex elevades s'observa la màxima activitat. Els complexos de l'alanina, PtCl2(dap-ala) i PtCl2(dab-ala), són els que mostren més activitat, mentre que els compostos de la fenilalanina són els menys actius, degut probablement a la voluminositat del lligand, la qual pot impedir o dificultar el transport del compost a través de la membrana cel·lular. L'activitat citotòxica dels complexos insolubles en aigua, PtCl2(Etdap) i PtCl2(Etdab), queda bloquejada per l'elevada concentració de DMSO (12%) necessària per solubilitzar els compostos. Aquests resultats permeten deduir que la presència d'un 12% de DMSO anul·la l'activitat d'aquests complexos, ja que el DMSO pot coordinar-se amb el Pt ocupant les posicions làbils del complex i evitant que es pugui coordinar amb el DNA. Els assaigs de proliferació cel·lular del complex PtCl2(dap-ASTTTNYT-NH2) i del pèptid lliure ASTTTNYT-NH2 han demostrat que ambdós compostos són actius. Tot i això, l'activitat del complex és superior a la del pèptid lliure, ja que el Pt pot interaccionar covalentment amb el DNA i augmentar l'efecte citotòxic. Per tant, el complex presenta un lligand portador biològicament actiu que pot transportar el metall a través de la membrana cel·lular i facilitar així la seva interacció amb el DNA. A través de la tècnica de citometria de flux s'ha comprovat que en tots els casos la mort cel·lular produïda pels complexos ha estat per apoptosi. Per últim, s'ha sintetitzat i caracteritzat un complex trinuclear de Pt(II), {[Pt(Me2Bpy)2][PtCl2(Me2Bpy)]2}, essent Me2Bpy= 4,4'-dimetil-2,2'-dipiridil. La resolució de la seva estructura per difracció de Raig-X ha permès determinar l'existència d'una interacció intramolecular Pt-Pt de 3.474 Å.

Microbial and biochemical soil quality indicators and their potential for differentiating areas under contrasting agricultural management regimes

The aim of this study was to examine interrelationships between functional biochemical and microbial indicators of soil quality, and their suitability to differentiate areas under contrasting agricultural management regimes. The study included five 0.8 ha areas on a sandy-loam soil which had received contrasting fertility and cropping regimes over a 5 year period. These were organically managed vegetable, vegetable -cereal and arable rotations, an organically managed grass clover ley, and a conventional cereal rotation. The organic areas had been converted from conventional cereal production 5 years prior to the start of the study. All of the biochemical analyses, including light fraction organic matter (LFOM) C and N, labile organic N (LON), dissolved organic N and water-soluble carbohydrates showed significant differences between the areas, although the nature of the relationships between the areas varied between the different parameters, and were not related to differences in total soil organic matter content. The clearest differences were seen in LFOM C and N and LON, which were higher in the organic arable area relative to the other areas. In the case of the biological parameters, there were differences between the areas for biomass-N, ATP, chitin content, and the ratios of ATP: biomass and basal respiration: biomass. For these parameters, the precise relationships between the areas varied. However, relative to the conventionally managed area, areas under organic management generally had lower biomass-N and higher ATP contents. Arbuscular mycorrhizal fungus colonization potential was extremely low in the conventional area relative to the organic areas. Further, metabolic diversity and microbial community level physiological profiles, determined by analysis of microbial community metabolism using Biolog GN plates and the activities of eight key nutrient cycling enzymes, grouped the organic areas together, but separated them from the conventional area. We conclude that microbial parameters are more effective and consistent indicators of management induced changes to soil quality than biochemical parameters, and that a variety of biochemical and microbial analyses should be used when considering the impact of management on soil quality. (C) 2004 Elsevier Ltd. All rights reserved.

Phosphorus sorption and availability in soils amended with animal manures and sewage sludge

Soils that receive large applications of animal wastes and sewage sludge are vulnerable to releasing environmentally significant concentrations of dissolved P available to subsurface flow owing to the gradual saturation of the soil's P sorption capacity. This study evaluated P sorption (calculated from Langmuir isotherms) and availability of P (as CaCl2-P and resin P) in soils incubated for 20 d with poultry litter, poultry manure, cattle slurry, municipal sewage sludge, or KH2PO4, added on a P-equivalent basis (100 mg P kg(-1)). All the P sources had a marked negative effect on P sorption and a positive effect on P availability in all soils. In the cattle slurry- and KH2PO4- treated soils, the decreases in P sorption maximum (19-66%) and binding energy (25-89%) were consistently larger than the corresponding decreases (7-41% and 11-30%) in poultry litter-, poultry manure-, and sewage sludge-treated soils. The effects of cattle slurry and KH2PO4 on P availability were, in most cases, larger than those of the other P sources. In the poultry litter, poultry manure, and sewage sludge treatments, the increase in soil solution P was inversely related (R-2 = 0.75) to the input of Ca from these relatively high Ca (13.5-42 g kg(-1)) sources. Correlation analyses implied that the magnitude of the changes in P sorption and availability was not related to the water-extractable P content of the P sources. Future research on the sustainable application of organic wastes to agricultural soils needs to consider the non-P- as well as P-containing components of the waste.