Covalently coupling toluidine blue O-tiopronin to a gold nanoparticle forms an enhanced, exceptionally potent antimicrobial agent when activated by white light or 632 nm laser light. Aqueous solutions of tiopronin-gold nanoparticles had no antimicrobial effect and, when added to solutions of toluidine blue O, did not enhance the antimicrobial effect of the latter. The minimum bactericidal concentration of the covalently coupled toluidine blue O-tiopronin gold conjugate for Staphylococcus aureus was at least four times lower than that of free toluidine blue O.
The interactions of charge stabilised gold nanoparticles with cationic and anionic dyes are reported. The nanoparticles were synthesised by the Turkevich citrate reduction method. It was found that when a solution of thiazine dye is titrated against gold citrate hydrosol, at a critical concentration of dye there is an enhanced maximum absorption in the dye. The extinction coefficient is increased up to ten-fold. This enhancement was observed for a number of cationic thiazine dyes, of which methylene blue and toluidine blue are established light-activated antimicrobial agents. The same enhancement was not observed for anionic, acidic dyes such as rose bengal which showed no communication with the gold nanoparticles and showed UV-visible titration experiments with well formed isosbestic points. By studying the interaction of the dye and gold nanoparticles under conditions of different ionic strength and by using a zetasizer and TEM to measure the gold nanoparticle size it was demonstrated that the cause of enhancement was not due to nanoparticle aggregation. It is proposed that thiazine cationic dyes coordinate around a gold nanoparticle and give significantly enhanced UV-visible absorptions.
The electronic states of CeCp(3)(+) have been studied experimentally by variable photon energy photoelectron spectroscopy, and computationally using multi-configurational ab initio methods. Relative partial photoionisation cross section and branching ratio data are presented to confirm our previous conclusion that bands A and D in the valence photoelectron spectrum, despite their 3.2 eV separation, are produced by ionization of the single 4f electron of CeCp(3) [M. Coreno, M. de Simone, J. C. Green, N. Kaltsoyannis, N. Narband and A. Sella, Chem. Phys. Lett., 432, 2006, 17]. The origin of this effect is probed using the CASSCF/CASPT2 approach. While configurations based on the canonical CASSCF orbitals are found to be an unreliable description of the ground and excited states of CeCp(3)(+), the state-specific natural orbitals and their occupations yield greater insight, allowing us to characterize ion states in terms of the presence or otherwise of a Ce 4f-localised electron. Neither the CeCp(3)(+) ground state (assigned to band A), and two excited states ((1)A' and (1)A'', associated with band D), possess such a metal-based electron, as expected of f ionization. The (1)A' and (1)A'' states differ from the ground state in having a significant Ce 5d population, arising from Cp --> Ce charge transfer, which accompanies f ionization, and which is responsible for the energetic separation of bands A and D in the valence photoelectron spectrum.
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