PubMed · 15100763
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Elisabeth Verpoorte. 2003-07-24. Chip vision-optics for microchips.. https://doi.org/10.1039/b307927a
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The influence of the spontaneous surface modification of titanium by exposure to Ringer's solution at open-circuit conditions on the passive behavior was studied. The electrochemical behavior of Ti was compared in a simple NaCl and in Ringer's physiological solution. Potentiodynamic polarization curves show significantly higher passive current densities in Ringer's solution as compared with the simple saline solution. Furthermore, impedance spectra measured at the open-circuit potential as a function of time indicate that in saline solution a long-term exposure over some days leads to a strong increase of the protectiveness of the passive film. This improvement of the passive behavior cannot be observed in Ringer's solution, but a strong modification of the passive film/electrolyte interface can be seen in the impedance spectra. The changes in the impedance spectra can be correlated with the results observed by surface characterization regarding the morphology (scanning electron microscopy) and chemical composition of the surface (X-ray photoelectron spectroscopy). In agreement with previous work by others, a spontaneous modification of the surface of Ti by Ca and P species was observed. The composition of the Ca/P precipitates changes as a function of time, indicating a slow formation of a hydroxyapatite-like deposit layer on the surface. The results of the present work indicate that the formation of the outer Ca-P deposit layer on the passive Ti surface (which is beneficial for the biological performance) hinders the normal aging of the passive TiO(2). Even though the protectiveness of the passive film can be considered as high also in Ringer's solution, significantly higher passive dissolution rates (i.e., higher metal-ion release) for Ti exposed to Ringer's solution can be expected as compared with a simple saline solution.
The photophysical properties of the series of quadruply bonded M(2)(O(2)C-Ar)(4) [M = Mo, Ar = phenyl (ph), 1-naphthalene (1-nap), 2-naphthalene (2-nap), 9-anthracene (9-an), 1-pyrene (1-py), and 2-pyrene (2-py); M = W, Ar = ph, 2-nap] complexes were investigated. The lowest energy absorption of the complexes is attributed to a metal-to-ligand charge transfer (1)MLCT transition from the metal-based delta HOMO to the pi* O(2)C-Ar LUMO. The Mo(2)(O(2)C-Ar)(4) complexes exhibit weak short-lived emission (<10 ns) and a nonemissive, long-lived (40-76 mus) excited state detected by transient absorption spectroscopy. The short- and long-lived species are attributed to the (1)MLCT and (3)MLCT excited states, respectively, based on the large Stokes shift, vibronic progression in the low-temperature emission spectrum, and solvent dependence. Comparisons are made to the W(2)(O(2)C-Ar)(4) complexes, which are easier to oxidize and exhibit greater spin-orbit coupling than the Mo(2) systems. From the excited-state energy of the emissive (1)MLCT state and the electrochemical properties of the complexes, it is predicted that this excited state should be a powerful reducing agent. The crystal and molecular structure of Mo(2)(O(2)C-9-an)(4) is also reported together with electronic structure calculations employing density functional theory. To our knowledge, this is the first observation of MLCT excited states in quadruply bonded complexes. In addition, the photophysical properties of the present systems parallel those of organic aromatic molecules and may be viewed as metal-mediated organics. The introduction of the M(2) delta orbital in the complexes in conjugation with the organic pi-system of the ligands affords the opportunity to tune the excited-state energies and redox potentials.