This work reports kinetic and equilibrium studies of cadmium(II) and lead(II) adsorption by the brown seaweed Cystoseira baccata. Kinetic experiments demonstrated rapid metal uptake. Kinetic data were satisfactorily described by a pseudo-second order chemical sorption process. Temperature change from 15 to 45 degrees C showed small variation on kinetic parameters. Langmuir-Freundlich equation was selected to describe the metal isotherms and the proton binding in acid-base titrations. The maximum metal uptake values were around 0.9 mmol g(-1) (101 and 186 mg g(-1) for cadmium(II) and lead(II), respectively) at pH 4.5 (raw biomass), while the number of weak acid groups were 2.2 mmol g(-1) and their proton binding constant, K(H), 10(3.67) (protonated biomass). FTIR analysis confirmed the participation of carboxyl groups in metal uptake. The metal sorption was found to increase with the solution pH reaching a plateau above pH 4. Calcium and sodium nitrate salts in solution were found to affect considerably the metal biosorption.

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Five different brown seaweeds, Bifurcaria bifurcata, Saccorhiza polyschides, Ascophyllum nodosum, Laminaria ochroleuca and Pelvetia caniculata were studied for their ability to remove cadmium from aqueous solution. Kinetics of cadmium adsorption by all the algae were relatively fast, with 90% of total adsorption occurring in less than 1h. These experiments could be accurately described by a pseudo-second-order rate equation, obtaining values between 1.66x10(-3) and 9.92x10(-3) g/mgmin for the sorption rate constant k. Several equilibrium adsorption isotherms were obtained for the quantitative description of cadmium uptake. The use of the Langmuir isotherm led to values between 64 and 95 mg/g for qmax and between 0.036 and 0.094 L/mg for b. The effect of pH on biosorption was also studied. Acid-base properties of algae were studied by potentiometry to determine pK values (from 3.54 to 3.98) and the total number of acid groups.

We report the Mn(II) complexes with two pyclen-based ligands (pyclen = 3,6,9,15tetraazabicyclo[9.3.1]pentadeca-1(15),11,13-triene) functionalized with acetate pendant arms either at positions 3,6 (3,6-PC2A) or 3,9 (3,9-PC2A) of the macrocyclic fragment. The 3,6-PC2A ligand was synthesized in five steps from pyclenoxalate by protecting one of the secondary amine groups of pyclen using Alloc protecting chemistry. The complex with 3,9-PC2A is characterized by a higher thermodynamic stability (logKMnL = 17.09(2) than the 3,6-PC2A analogue (logKMnL = 15.53(1), 0.15 M NaCl). Both complexes contain a water molecule coordinated to the metal ion, which results in relatively high 1 H relaxivities (r1p = 2.72 and 2.91 mM -1 s -1 for the complexes with 3,6-and 3,9-PC2A, respectively, 25 ºC, 0.49 T). The coordinated water molecule displays fast exchange kinetics with the bulk in both cases; the rates (kex 298 ) are 14010 6 and 12610 6 s -1 for [Mn(3,6-PC2A)(H2O)] and [Mn(3,9-PC2A)(H2O)], respectively. The two complexes were found to be remarkably inert with respect to their dissociation, with half-lives of 63 and 21 h, respectively, at pH 7.4 in the presence of excess Cu(II). The r1p values recorded in blood serum remain constant at least over a period of 120 h. Cyclic voltammetry experiments show irreversible oxidation features shifted to higher potentials with respect to [Mn(EDTA)(H2O)] 2and [Mn(PhDTA)(H2O)] 2-, indicating that the PC2A complexes reported here have a lower tendency to stabilize Mn(III). The superoxide dismutase activity of the Mn(II) complexes was tested using the xanthine/xanthine oxidase/NBT assay at pH 7.8. The Mn(II) complexes of 3,6-PC2A and 3,9-PC2A are capable to assist the decomposition of superoxide anion radical. The kinetic rate constant of the complex of 3,9-PC2A is smaller by one order of magnitude than that of 3,6-PC2A.

Equilibrium, dissociation kinetics, relaxometric and electrochemical properties of the [Mn(PhDTA)]2− complex were investigated and the structure of the [Mn(PhDTA)]2− complex was studied by using DFT calculations.