MODELISATION DES SOLUTIONS AQUEUSES D’ELECTROLYTES DU TYPE 3-1 MODELLING OF AQUEOUS ELECTROLYTES SOLUTIONS OF 3-1 TYPE

Pour modéliser les coefficients d’activité des solutions aqueuses d’électrolytes du type 3-1, nous avons repris la théorie originale de Pitzer concernant l’énergie d’excès de Gibbs pour les solutions aqueusesd’électrolyte. Le modèle a été appliquépour 11 systèmes incluant des électrolytes du type 3-1. La performance de ce modèle a été comparée avec d’autres modèles existant dans la littérature. Les résultats montrent que le modèle de Pitzer peut représenter les coefficients d’activité des électrolytes dans des solutions aqueuses avec une déviation standard comparable aux autres modèles et dans la plupart des cas meilleure que les autres. To model the activity coefficients of aqueous solutions of 3-1 electrolytes, we took again the original theory of Pitzer concerning the excess Gibbs energy for the aqueous solutions ofelectrolytes. The model was applied for 11 systems including 3-1 electrolytes. The performance of this model was compared withother models existing in the literature. The results show that the model of Pitzer can represent the mean ionic activitycoefficients of 3-1 electrolytes in aqueous solutions with a standard deviation comparable with the other models and in the majority of the cases better than the others

Regeneration of Algerian

Stigma/style somatic embryogenesis is one of the efficient methods in plant regeneration of most Citrus ssp., without inducing somaclonal variations. Furthermore, somatic embryogenesis from style/stigma proved to be effective in the elimination of the main citrus virus and virus-like diseases. This technique was applied on Algerian citrus collection. Different Citrus species [Citrus sinensis (L.) Osbeck, C. limon (L.) Burm, C. reticulata Blanco, C. paradisi Macfad, C. reshni Hort. ex Tan., C. jambhiri Lush and C. maxima (Burm.) Merrill] were chosen and tested for the presence of the main virus and virus-like agents. Most of the genotypes showed to be infected, mainly by viroid agents. Closed flowers were collected and in vitro cultured on a Murashige and Skoog (MS) medium supplemented with 6- benzylaminopurine. All explants produced callus about 4 to 9 days after culture initiation, whereas embryogenesis occurred after 38 to 150 days in most of the cultured genotypes. Formed embryos were cultured in a single tube before in vivo acclimatization. After sanitary assays, regenerated plants were shown to be free from the agents detected in the mother trees.Key words: Algeria, citrus germplasm, plant regeneration, sanitation, somatic embryogenesis

N-ftaloil-glicin-hidroksamska kiselina kao kelator željeza u serumu štakora

The aim of this study was to investigate the activity of N-phthaloyl-glycine-hydroxamic acid (Phth-Gly-HA) as a new iron chelator in vivo to be used in iron overload diseases. After intraperitoneal application of Phth-Gly-HA to male rats (1 mg kg1 body mass) once a day for seven days, iron serum level decreased by 21%, whereas the iron value dropped by 32% in female rats (1.5 mg kg1 body mass). The results indicate that the tested substance has the ability to bind serum iron by complexation. Besides transferrin iron release, mobilization of ferritin iron is also possibleU cilju pronalaženja novog efikasnog kelatora koji bi mogao poslužiti u liječenju bolesti izazvanih viškom željeza, u ovom je radu ispitano djelovanje N-ftaloil-glicin-hidroksamske kiseline (Phth-Gly-HA) in vivo. Istraživan je utjecaj kelatora na razinu željeza u serumu štakora nakon intraperitonealne primjene vodene otopine Phth-Gly-HA (0,1 mg mL1) jednom dnevno tijekom 7 dana. Kontrolne su životinje primale fiziološku otopinu. Kod mužjaka injektiranje test supstancije (1 mg kg1) uzrokovalo je pad serumskog željeza za 21%. Kod ženki je nakon tretmana (1,5 mg kg1) izmjereno sniženje razine željeza za 35%. Rezultati pokazuju da ispitivana supstanca ima sposobnost kompleksiranja serumskog željeza, pretežno transferinskog, ali da postoji mogućnost mobilizacije željeza i iz feritinskih zaliha

Adsorption of hydroxamate siderophores and EDTA on goethite in the presence of the surfactant sodium dodecyl sulfate

Siderophore-promoted iron acquisition by microorganisms usually occurs in the presence of other organic molecules, including biosurfactants. We have investigated the influence of the anionic surfactant sodium dodecyl sulfate (SDS) on the adsorption of the siderophores DFOB (cationic) and DFOD (neutral) and the ligand EDTA (anionic) onto goethite (α-FeOOH) at pH 6. We also studied the adsorption of the corresponding 1:1 Fe(III)-ligand complexes, which are products of the dissolution process. Adsorption of the two free siderophores increased in a similar fashion with increasing SDS concentration, despite their difference in molecule charge. In contrast, SDS had little effect on the adsorption of EDTA. Adsorption of the Fe-DFOB and Fe-DFOD complexes also increased with increasing SDS concentrations, while adsorption of Fe-EDTA decreased. Our results suggest that hydrophobic interactions between adsorbed surfactants and siderophores are more important than electrostatic interactions. However, for strongly hydrophilic molecules, such as EDTA and its iron complex, the influence of SDS on their adsorption seems to depend on their tendency to form inner-sphere or outer-sphere surface complexes. Our results demonstrate that surfactants have a strong influence on the adsorption of siderophores to Fe oxides, which has important implications for siderophore-promoted dissolution of iron oxides and biological iron acquisition

Complexes Formed in Solution Between Vanadium(IV)/(V) and the Cyclic Dihydroxamic Acid Putrebactin or Linear Suberodihydroxamic Acid

The ability of microbial siderophores to coordinate metal ions, particularly Fe(III), continues to generate interest in the poten-tial applications of these bioligands in the environment and medicine.13 Siderophores produced by terrestrial and marin

Protonation States of Remote Residues Affect Binding-Release Dynamics of the Ligand but not the Conformation of apo Ferric Binding Protein

We have studied the apo (Fe3+ free) form of periplasmic ferric binding protein (FbpA) under different conditions and we have monitored the changes in the binding and release dynamics of H2PO4- that acts as a synergistic anion in the presence of Fe3+. Our simulations predict a dissociation constant of 2.2$\pm$0.2 mM which is in remarkable agreement with the experimentally measured value of 2.3$\pm$0.3 mM under the same ionization strength and pH conditions. We apply perturbations relevant for changes in environmental conditions as (i) different values of ionic strength (IS), and (ii) protonation of a group of residues to mimic a different pH environment. Local perturbations are also studied by protonation or mutation of a site distal to the binding region that is known to mechanically manipulate the hinge-like motions of FbpA. We find that while the average conformation of the protein is intact in all simulations, the H2PO4- dynamics may be substantially altered by the changing conditions. In particular, the bound fraction which is 20$\%$ for the wild type system is increased to 50$\%$ with a D52A mutation/protonation and further to over 90$\%$ at the protonation conditions mimicking those at pH 5.5. The change in the dynamics is traced to the altered electrostatic distribution on the surface of the protein which in turn affects hydrogen bonding patterns at the active site. The observations are quantified by rigorous free energy calculations. Our results lend clues as to how the environment versus single residue perturbations may be utilized for regulation of binding modes in hFbpA systems in the absence of conformational changes.Comment: 26 pages, 4 figure

Purification and Structural Characterization of Siderophore (Corynebactin) from Corynebacterium diphtheriae

During infection, Corynebacterium diphtheriae must compete with host iron-sequestering mechanisms for iron. C. diphtheriae can acquire iron by a siderophore-dependent iron-uptake pathway, by uptake and degradation of heme, or both. Previous studies showed that production of siderophore (corynebactin) by C. diphtheriae is repressed under high-iron growth conditions by the iron-activated diphtheria toxin repressor (DtxR) and that partially purified corynebactin fails to react in chemical assays for catecholate or hydroxamate compounds. In this study, we purified corynebactin from supernatants of low-iron cultures of the siderophore-overproducing, DtxR-negative mutant strain C. diphtheriae C7(β) ΔdtxR by sequential anion-exchange chromatography on AG1-X2 and Source 15Q resins, followed by reverse-phase high-performance liquid chromatography (RP-HPLC) on Zorbax C8 resin. The Chrome Azurol S (CAS) chemical assay for siderophores was used to detect and measure corynebactin during purification, and the biological activity of purified corynebactin was shown by its ability to promote growth and iron uptake in siderophore-deficient mutant strains of C. diphtheriae under iron-limiting conditions. Mass spectrometry and NMR analysis demonstrated that corynebactin has a novel structure, consisting of a central lysine residue linked through its α- and ε- amino groups by amide bonds to the terminal carboxyl groups of two different citrate residues. Corynebactin from C. diphtheriae is structurally related to staphyloferrin A from Staphylococcus aureus and rhizoferrin from Rhizopus microsporus in which d-ornithine or 1,4-diaminobutane, respectively, replaces the central lysine residue that is present in corynebactin

In Situ NMR Spectroscopy of Supercapacitors: Insight into the Charge Storage Mechanism

Electrochemical capacitors, commonly known as supercapacitors, are important energy storage devices with high power capabilities and long cycle lives. Here we report the development and application of in situ nuclear magnetic resonance(NMR) methodologies to study changes at the electrode−electrolyte interface in working devices as they charge and discharge. For a supercapacitor comprising activated carbon electrodes and an organic electrolyte, NMR experiments carried out at different charge states allow quantification of the number of charge storing species and show that there are at least two distinct charge storage regimes. At cell voltages below 0.75 V, electrolyte anions are increasingly desorbed from the carbon micropores at the negative electrode, while at the positive electrode there is little change in the number of anions that are adsorbed as the voltage is increased. However, above a cell voltage of 0.75 V, dramatic increases in the amount of adsorbed anions in the positive electrode are observed while anions continue to be desorbed at the negative electrode. NMR experiments with simultaneous cyclic voltammetry show that supercapacitor charging causes marked changes to the local environments of charge storing species, with periodic changes of their chemical shift observed. NMR calculations on a model carbon fragment show that the addition and removal of electrons from a delocalized system should lead to considerable increases in the nucleus-independent chemical shift of nearby species, in agreement with our experimental observations