Dihydroxyphenylalanine (DOPA) and similar molecules are of considerable interest in studies of bioadhesion to minerals, solar cells involving titanium dioxide, and biomedical imaging. However, the extent and mechanisms of DOPA adsorption on oxides in salt solutions are unknown. We report measurements of DOPA adsorption on well-characterized rutile (α-TiO₂) particles over a range of pH, ionic strength, and surface coverage as well as a surface complexation model analysis establishing the stoichiometry, model surface speciation, and thermodynamic equilibrium constants, which permits predictions in more complex systems.
View Article and Find Full Text PDFWe studied the adsorption of short single-stranded deoxyribonucleic acid (ssDNA) oligomers, of approximately 30 nucleotides (nt) in length, of varying sequence, adenine+guanine+cytosine (AGC) content, and propensity to form secondary structure, to equal surface area samples of olivine, pyrite, calcite, hematite, and rutile in 0.1M NaCl, 0.05M pH 8.
View Article and Find Full Text PDFAttenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy and quantum chemical calculations were used to elucidate the influence of solution chemistry (pH, amino acid concentration) on the binding mechanisms of glutamic and aspartic acid to rutile (α-TiO(2)). The amino acids, glutamate and aspartate, contain carboxyl and amine groups whose dissociation over a pH range results in changes of molecular charge and reactivity, including reactions with mineral surfaces. At pH 3, a decrease of IR bands corresponding to protonated carboxyl groups is observed upon reaction with TiO(2) and indicates involvement of distal carboxyl groups during sorption.
View Article and Find Full Text PDFNucleic acids, the storage molecules of genetic information, are composed of repeating polymers of ribonucleotides (in RNA) or deoxyribonucleotides (in DNA), which are themselves composed of a phosphate moiety, a sugar moiety, and a nitrogenous base. The interactions between these components and mineral surfaces are important because there is a tremendous flux of nucleic acids in the environment due to cell death and horizontal gene transfer. The adsorption of mono-, oligo-, and polynucleotides and their components on mineral surfaces may have been important for the origin of life.
View Article and Find Full Text PDFInteractions between aqueous amino acids and mineral surfaces influence the bioavailability of amino acids in the environment, the viability of Ti implants in humans, and the role of mineral surfaces in the origin of life on Earth. We studied the adsorption of l-glutamate on the surface of rutile (alpha-TiO(2), pH(PPZC) = 5.4) in NaCl solutions using potentiometric titrations and batch adsorption experiments over a wide range of pH values, ligand-to-solid ratios, and ionic strengths.
View Article and Find Full Text PDFHydrous ferric oxide (HFO) and titanium dioxide exhibit similar strong attachment of many adsorbates including biomolecules. Using surface complexation modeling, we have integrated published adsorption data for glutamate on HFO over a range of pH and surface coverage with published in situ ATR-FTIR studies of glutamate speciation on amorphous titanium dioxide. The results indicate that glutamate adsorbs on HFO as a deprotonated divalent anion at pH 3-5 and 0.
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