The use of de novo designed peptides is a powerful strategy to elucidate Hg(II)-protein interactions and to gain insight into the chemistry of Hg(II) in biological systems. Cysteine derivatives of the designed alpha-helical peptides of the TRI family [Ac-G-(L(a)K(b)A(c)L(d)E(e)E(f)K(g))(4)-G-NH(2)] bind Hg(II) at high pH values and at peptide/Hg(II) ratios of 3:1 with an unusual trigonal thiolate coordination mode. The resulting Hg(II) complexes are good water-soluble models for Hg(II) binding to the protein MerR. We have carried out a parallel study using (199)Hg NMR and (199m)Hg perturbed angular correlation (PAC) spectroscopy to characterize the distinct species that are generated under different pH conditions and peptide TRI L9C/Hg(II) ratios. These studies prove for the first time the formation of [Hg{(TRI L9C)(2)-(TRI L9C-H)}], a dithiolate-Hg(II) complex in the hydrophobic interior of the three-stranded coiled coil (TRI L9C)(3). (199)Hg NMR and (199m)Hg PAC data demonstrate that this dithiolate-Hg(II) complex is different from the dithiolate [Hg(TRI L9C)(2)], and that the presence of third alpha-helix, containing a protonated cysteine, breaks the symmetry of the coordination environment present in the complex [Hg(TRI L9C)(2)]. As the pH is raised, the deprotonation of this third cysteine generates the trigonal thiolate-Hg(II) complex Hg(TRI L9C)(3)(-) on a timescale that is slower than the NMR timescale (0.01-10 ms). The formation of the species [Hg{(TRI L9C)(2)(TRI L9C-H)}] is the result of a compromise between the high affinity of Hg(II) to form dithiolate complexes and the preference of the peptide to form a three-stranded coiled coil.

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Abstract. TiO 2 nanoparticles (anatase) with diameters between 2 and 4 nm were synthesized by controlled hydrolysis of a solution of titanium (IV)isopropoxide to which 44 Ti in 4M HCl was added. Inactive nanoparticles were analyzed by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM), the active ones were analyzed by measuring the nuclear quadrupole interaction (NQI) of the I = 1 state in 44 Sc using time differential perturbed angular correlation (TDPAC). Rather broad distributions were obtained. We also synthesized nanowires with typical diameters of 2 nm and 100 nm length using shape controllers. They were analyzed by HRTEM and XRD. The material turned out to be TiO 2 (B). The 44 Ti was added by impregnation and diffusion at 180°C for two hours. Two well-defined NQI signals were observed which we tentatively assigned to the "volume" fraction and the "surface" fraction, i.e. 44 Ti-probes with OH-termination. In addition, we studied AMT-100 (anatase, uncoated, 6 nm), Eusolex T-2000 (rutile, Al 2 O 3 -coated, 20×20×100 nm 3 , simethicone additive) and P25 (mainly anatase, uncoated, 20 nm diameter) using the impregnation and diffusion method. P25 and the isolated rutile fraction from P25 yield spectra which correspond to anatase and rutile volume signals plus their surface signals, respectively. TDPAC thus proved very useful in characterizing the nanomaterials, especially their disorder, by measuring the NQI. In addition, information on surface properties is obtained. The relatively narrow surface signals indicate a lower degree of disorder and are possibly also a result of partial motional averaging of Ti-signals with OH-bonds due to mobile H-atoms.