Gil Markovich

PHOTOELECTRON SPECTROSCOPY OF CL-, BR-, AND I- SOLVATED IN WATER CLUSTERS

We present the photoelectron‐spectra of Cl−, Br−, and I−, solvated in water clusters‐(H2O)n, where n is 1–7, 1–16, and 1–60, respectively, taken with 7.1 eV photon energy. The vertical binding energies of the solvated anions are used to extract the solvent electrostatic stabilization energies of the anion. The photoelectron spectra of the solvated I− indicate the formation of the first solvation layer with a coordination number of six. Ab initio calculations support solvation shell closure at n=6. This conclusion is not born‐out by current molecular dynamics calculations. These calculations favor structures with a surface solvated anion (coordination number of 3–4) and reproduce (within 0.2 eV) our vertical binding energies. The fitting of the experimental binding energies of large I−(H2O)n to the models of classical electrostatic solvation is consistent with surface solvation. In the size range n=34–40 we have detected special cluster structures, with very low electrostatic stabilization.

Silver nanoparticle-E. coli colloidal interaction in water and effect on E. coli survival.

Silver nanoparticles exhibit antibacterial properties via bacterial inactivation and growth inhibition. The mechanism is not yet completely understood. This work was aimed at elucidating the effect of silver nanoparticles on inactivation of Escherichia coli, by studying particle-particle interactions in aqueous suspensions. Stable, molecularly capped, positively or negatively charged silver nanoparticles were mixed at 1 to 60microgmL(-1) with suspended E. coli cells to examine their effect on inactivation of the bacteria. Gold nanoparticles with the same surfactant were used as a control, being of similar size but made up of a presumably inert metal. Log reduction of 5log(10) and complete inactivation were obtained with the silver nanoparticles while the gold nanoparticles did not show any inactivation ability. The effect of molecularly capped nanoparticles on E. coli survival was dependent on particle number. Log reduction of E. coli was associated with the ratio between the number of nanoparticles and the initial bacterial cell count. Electrostatic attraction or repulsion mechanisms in silver nanoparticle-E. coli cell interactions did not contribute to the inactivation process.

Transparent metal nanowire thin films prepared in mesostructured templates.

The preparation of conductive and transparent gold/silver nanowire mesh films is reported. The nanowires formed after the reduction of the metal ions was triggered and a thin growth solution film was spread on a substrate. Metal reduction progressed within a template of a highly concentrated surfactant liquid crystalline mesostructure formed on the substrate during film drying to form ordered bundles of ultrathin nanowires. The films exhibited metallic conductivity over large areas, high transparency, and flexibility.

Plasmon-Resonance-Enhanced Absorption and Circular Dichroism†

Transmission electron microscopy of the silver nanoparticles formed in the presence of the l-GSH with an Ag/ ligand concentration ratio of 50:1 showed a broad particlesize distribution in the range of 2–50 nm, with no apparent change in size distribution on addition of the bimane to the

Photoelectron spectroscopy of iodine anion solvated in water clusters

We have measured the photoelectron spectra of clusters of I‐ solvated in water up to fifteen water molecules. The vertical binding energy of the electron increases with cluster size and levels off in clusters containing more than six water molecules. These results strongly indicate that the first solvation layer around the ion consists of six water molecules. This picture is quantitatively consistent with the photoelectron spectroscopy result of I‐ solvated in bulk water.

Amplification of Chiroptical Activity of Chiral Biomolecules by Surface Plasmons

Chiral molecules are shown to induce circular dichroism (CD) at surface plasmon resonances of gold nanostructures when in proximity to the metal surface without direct bonding to the metal. By changing the molecule-Au separation, we were able to learn about the mechanism of plasmonic CD induction for such nanostructures. It was found that even two monolayers of chiral molecules can induce observable plasmonic CD, while without the presence of the plasmonic nanostructures their own CD signal is unmeasurable. Hence, plasmonic arrays could offer a route to enhanced sensitivity for chirality detection.

Broad Band Enhancement of Light Absorption in Photosystem I by Metal Nanoparticle Antennas

The photosystem I (PS I) protein is one of natures most efficient light harvesting complexes and exhibits outstanding optoelectronic properties. Here we demonstrate how metal nanoparticles which act as artificial antennas can enhance the light absorption of the protein. This hybrid system shows an increase in light absorption and of circular dichroism over the entire absorption band of the protein rather than at the specific plasmon resonance wavelength of spherical metal nanoparticles (NPs). This is explained by broad-resonant and nonresonant field enhancements caused by metal NP aggregates, by the high dielectric constant of the metal, and by NP-PS I-NP antenna junctions which effectively enhance light absorption in the PS I.

Plasmonic Chiroptical Response of Silver Nanoparticles Interacting with Chiral Supramolecular Assemblies

Silver nanoparticles were prepared in aqueous solutions of chiral supramolecular structures made of chiral molecular building blocks. While these chiral molecules display negligible circular dichroism (CD) as isolated molecules, their stacking produced a significant CD response at room temperature, which could be eliminated by heating to 80 °C due to disordering of the stacks. The chiral stack-plasmon coupling has induced CD at the surface plasmon resonance absorption band of the silver nanoparticles. Switching between two plasmonic CD induction mechanisms was observed: (1) Small Ag nanoparticles coated with large molecular stacks, where the induced plasmonic CD decayed together with the UV molecular CD bands on heating the solution, indicating some type of electromagnetic or dipole coupling mechanism. (2) Larger Ag nanoparticles coated with about a monolayer of molecules exhibited induced plasmonic CD that was temperature-independent. In this case it is estimated that the low chiroptical response of a molecular monolayer is incapable of inducing such a large chiroptical effect, and a model calculation shows that the plasmonic CD response may be the result of a slight chiral shape distortion of the silver nanoparticles.

The solvation of Cl−, Br−, and I− in acetonitrile clusters: Photoelectron spectroscopy and molecular dynamics simulations

We present the photoelectron spectra of Cl−, Br−, and I− solvated in acetonitrile clusters (CH3CN)n with n=1–33, 1–40, and 1–55, respectively, taken with 7.9 eV photon energy. Anion–solvent electrostatic stabilization energies are extracted from the measured vertical electron binding energies. The leveling of stabilization energies beyond n=10–12 for the three halides signifies the completion of the first solvation layer. This is different from the behavior of anion–water clusters which probably do not fill the first solvation layer, but rather form surface solvation states. Classical molecular dynamics simulations of halide–acetonitrile clusters reproduce the measured stabilization energies and generate full solvation shells of 11–12, 12, and 12–13 solvent molecules for Cl−, Br−, and I−, respectively. Ordered shell structures with high stability were found for the clusters of Cl−, Br−, and I− with n=9, 9, and 12. This special stability is reflected in the intensity distribution of the clusters in the mas...

Size Dependence of Chiroptical Activity in Colloidal Quantum Dots

The synthesis of chiral penicillamine-capped CdS and CdSe quantum dots (QDs) was adjusted to control the size of the nanoparticles. This, together with size separation, allowed for simultaneous tuning of absorption, circular dichroism (CD), and fluorescence on a wide wavelength range. Band edge transitions were accompanied by circular dichroism peaks which red-shifted together with the increase in particle size. The clear correlation between absorption and CD bands as well as between absorption bands and size in semiconductor QDs was used to derive an experimental scaling law for optical activity. The decrease in the intensity of circular dichroism-to-absorption ratio (dissymmetry) with the increase in particle size was stronger than linear, probably exponential. In addition, strong material type dependence was observed. The CD line shape appeared to be sensitive to the nature of the transition and may thus serve as a tool for sorting out the electronic states of the QDs. Fluorescence-detected circular dichroism (FDCD) was introduced as a new probe of optically active fluorescent nanoparticles. The analysis of the size and material dependence of the chiroptical induction effect leads to the conclusion that it is primarily an electronic interaction effect between the adsorbed chiral molecules and the electron-hole states.