Driving forces for the adsorption of a His-tag Chagas antigen. A rational approach to design bio-functional surfaces.

In order to rationally design a bio-functional surface based on the adsorption of a His-tag antigen, three requirements have to be considered: the bio-recognition element, the driving forces for the adsorption process and the detection mode of the bio-recognition event. This work is focused on the study of the adsorption mechanism of the His-tag H49 Chagas antigen on Ni(II) modified substrates. In order to construct the bio-functional surface, the gen of the H49 Chagas antigen was modified to incorporate His6 moiety at the N-terminal (His6-H49). Then, its physical adsorption and bio-affinity interaction with the solid substrate was studied by reflectometry. Besides His-Ni(II) bio-affinity interactions, His6-H49 was also physically adsorbed on Ni(II) modified substrates, leading to randomly oriented antigens. These loosely attached bio-molecules were partially removed using conditions of electrostatic repulsion. On the other hand, bio-affinity interactions, resulting in site-oriented molecules on the substrate, were only removable by specific competitors for Ni(II) surface sites. Finally, the surface bio-activity was determined from the peak separations of voltammetry waves due to the change of the electron transfer kinetics of a redox probe through the bio-functional surface (working electrode).

The role of Fe(III) modified montmorillonite on fluoride mobility: adsorption experiments and competition with phosphate.

Fluoride adsorption onto Fe(III) modified montmorillonite was investigated using batch experiments. The effect of reaction time, pH, ionic strength and phosphate, as a competitive anion, was evaluated. Kinetics indicated that adsorption obeys a pseudo-first-order rate law which involves two steps. The fast one (bulk transport/surface reaction) occurs instantaneously. The slower (diffusion in pores) takes hours to complete. The adsorption rate increases by increasing the fluoride concentration and by decreasing pH. The presence of phosphate reduces fluoride adsorption and reveals that both ions are in competition for surface sites. The reduction in fluoride adsorption when phosphate is present depends on the order of adsorbate addition. The higher fluoride adsorption occurs when both anions are added simultaneously, whereas when either fluoride or phosphate is added first, the fluoride adsorption is lower. The presence of fluoride does not have a measurable effect on phosphate adsorption. The results obtained contribute to our understanding of the mobility of fluoride in surface water which has naturally high levels of fluoride, in both the presence and absence of phosphate.

The effect of interlayer anion on the reactivity of Mg-Al layered double hydroxides: improving and extending the customization capacity of anionic clays.

Layered double hydroxides (LDHs) reactivity and interfacial behavior are closely interconnected and control particle properties relevant to the wide range of these solids' applications. Despite their importance, their relationship has been hardly described. In this work, chloride and dodecylsulfate (DDS(-)) intercalated LDHs are studied combining experimental data (electrophoretic mobility and contact angle measurements, hydroxyl and organic compounds uptake) and a simple mathematical model that includes anion-binding and acid-base reactions. This approach evidences the anion effect on LDHs interfacial behavior, reflected in the opposite particle charge and the different surface hydrophobic/hydrophilic character. LDHs reactivity are also determined by the interlayer composition, as demonstrated by the cation uptake capability of the DDS(-) intercalated sample. Consequently, the interlayer anion modifies the LDHs interfacial properties and reactivity, which in turn extends the customization capacity of these solids.

Infrared study of trifluoroacetic acid unpurified synthetic peptides in aqueous solution: trifluoroacetic acid removal and band assignment.

Synthetic peptide or protein samples are mostly unpurified with trifluoroacetic acid (TFA) used during the synthesis procedure, which strongly interferes with structure determination by infrared (IR) spectroscopy. The aim of this work was to propose a simple strategy to remove TFA contribution from attenuated total reflection (ATR)-IR spectra of the hexahistidine peptide (His6) in aqueous solution to study the conformation of this synthetic peptide without previous purification. Such a strategy is based on the subtraction mode widely employed to remove water contribution, and it is tested with TFA unpurified histidine as a model system. The subtraction is based on eliminating the strong TFA bands at 1147 and 1200cm(-1) by applying a scaling factor (as in buffer correction). The proposed modes represent excellent strategies that do not modify spectral features, and they provide reliable routines to obtain the synthetic peptide spectrum without TFA contribution. The conformational information from the corrected spectra at different pH values is deduced from semiempirical calculated IR spectra of different His6 conformers. The spectral features and the band positions of the corrected spectrum suggest that the peptide molecules mainly adopt an intermolecular ß-sheet structure.

Caracterización de sedimentos provenientes del embalse San Roque y Los Molinos, Córdoba, Argentina. Propiedades superficiales y su relación con las velocidades de liberación de fosfato

El trabajo tiene como objetivo investigar las propiedades superficiales de los sedimentos de los embalses San Roque y los Molinos, Córdoba, Argentina. Para ello, se analiza el efecto del pH en los valores de carga superficial de los sedimentos, se evaluan velocidades de liberación en función del pH y temperatura y se estudia la relación entre velocidad de liberación, área superficial y carga superficial

Caracterización de sedimentos provenientes del embalse San Roque y Los Molinos, Córdoba, Argentina. Propiedades superficiales y su relación con las velocidades de liberación de fosfato

El trabajo tiene como objetivo investigar las propiedades superficiales de los sedimentos de los embalses San Roque y los Molinos, Córdoba, Argentina. Para ello, se analiza el efecto del pH en los valores de carga superficial de los sedimentos, se evaluan velocidades de liberación en función del pH y temperatura y se estudia la relación entre velocidad de liberación, área superficial y carga superficial

The binding of Ni(II) ions to hexahistidine as a model system of the interaction between nickel and His-tagged proteins.

The aim of this work is to study the binding of nickel ions to hexahistidine (His(6)) combining potentiometric titrations and spectroscopic (UV-Vis and circular dichroism) determinations in order to establish the species distribution as a function of the pH, their stoichiometry, stability and geometry. For comparative purposes, the same procedure was applied to the Ni-histidine (His) system. His behaves as a tridentate ligand, coordinating the carboxyl group, the imidazole and the amino nitrogen atoms to Ni(II) ions in an octahedral coordination and a bis(histidine) complex is formed at pH higher than 5. For the Ni-His(6) system, the complex formation starts at pH 4 and five different species (Ni(His(6))H, Ni(His(6)), Ni(n)(His(6))(n), Ni(n)(His(6))(n)H(-n/2), Ni(n)(His(6))(n)H(-n)) are formed as a function of the pH. Ni(His(6))H involves the coordination of the imidazole nitrogen and a deprotonated amide nitrogen (N(Im), N(-)) resulting in an octahedral geometry. In Ni(His(6)), an imidazole nitrogen is deprotonated and coordinated (2N(Im), N(-)) to the metal ion with a square planar geometry. The aggregated forms result from the extra Ni-N(Im) coordination, resulting in a 4N square planar geometry that is stabilized by inter/intramolecular hydrogen bonds. This coordination mode is not altered during the deprotonation steps from Ni(n)(His(6))(n).

Adsorption of human serum albumin (HSA) onto colloidal TiO2 particles, Part I.

The adsorption of human serum albumin (HSA) onto colloidal TiO2 (P25 Degussa) particles was studied in NaCl electrolyte at different solution pH and ionic strength. The HSA-TiO2 interactions were studied using adsorption isotherms and the electrokinetic properties of HSA-covered TiO2 particles were monitored by electrophoretic mobility measurements. The adsorption behavior shows a remarkable dependence of the maximum coverage degree on pH and was almost independent of the ionic strength. Other characteristic features such as maximum adsorption values at the protein isoelectric point (IEP approximately 4.7) and low-affinity isotherms that showed surface saturation even under unfavorable electrostatic conditions (at pH values far away from the HSA IEP and TiO2 PZC) were observed. Structural and electrostatic effects can explain the diminution of HSA adsorption under these conditions, assuming that protein molecules behave as soft particles. Adsorption reactions are discussed, taking into account acid-base functional groups of the protein and the surface oxide in different pH ranges, considering various types of interactions.