Fullerene C60-silver nanoparticles hybrid structures: optical and photoelectric characterization.

A detailed optical and photoelectric characterization of pristine fullerene C60 films deposited onto n-silicon substrates (C60/Si), C60 films crosslinked by means of the solvent-free chemical functionalization with 1,8-diaminooctane (C60-DA/Si), and the pristine and crosslinked films decorated with silver nanoparticles (C60-Ag/Si and C60-DA-Ag/Si), was carried out. The reflectance spectra obtained allowed to calculate the absorption coefficient (alpha = 4pik/lamda) spectral dependencies and the spectra of light transmittance in layered barrier structures metal(Au)/fullerene/Si. Photoelectric properties of the films were investigated as well. The experimentally measured values of band gap were in a good agreement with mobility gap values (2.3 +/- 0.1 eV). The decoration of fullerene films (both pristine and chemically crosslinked) with silver nanoparticles did not change the photocurrent spectra as compared to those for undecorated fullerene films, but lowered the values of internal quantum efficiency Qint. The photocurrent generated in fullerene/Si heterostructure, showed a maximum value at lamda to appromimately 450 nm (Qint max approximately = 0.25 for decorated and undecorated C60-DA/Si films), and it was higher for the samples based on pristine C60 films, in accordance with their higher absorption coefficient. Diminishing of Qint for C60-DA/Si and C60-DA-Ag/Si films was observed for the spectral range of photocurrent generated in Si layer. The analysis of dark current-voltage characteristics showed that the barrier properties differ insignificantly, though a certain increase of series resistance was observed for the C60-DA/Si samples.

Phototransformation of C60 thin films by UV pulsed laser irradiation: comparative photoacoustic, AFM, and Raman studies.

Fullerene C60 films deposited by sublimation were irradiated with Kr-F laser in a wide fluence interval from 15 to 40 mJ/cm2. In situ photoacoustic analysis was applied to study the phase transformation during the irradiation. The results obtained were discussed in conjunction with atomic force microscopy (AFM) and Raman spectroscopy data. It was found that for a irradiation fluence interval from 22 to 30 mJ/cm2, 80% of C60 undergoes photopolymerization (presumably through 2 + 2 cycloaddition). For a laser energy higher than 30 mJ/cm2, a new amorphous carbon phase forms, having a large content of diamond-like, tetra-amorphous carbon (ta-C).

Cross-linking of C60 films with 1,8-diaminooctane and further decoration with silver nanoparticles.

We applied the direct solvent-free functionalization of fullerene C60 with aliphatic bifunctional amine, 1,8-diaminooctane, to prepare chemically cross-linked C60 thin films capable of binding silver nanoparticles. The gas-phase diamine treatment of C60 reduced dramatically the fullerene solubility in toluene, indicating the transformation of pristine C60 into a different solid phase with cross-linked fullerene molecules. Compared to the spectra of pristine C60 film and powder samples, Fourier-transform infrared, UV-Visible, Raman, and 13C nucleic magnetic resonance spectra of the functionalization products exhibited new features, which point to a breaking of C60 ideal structure during the formation of new covalent bonds and to the appearance of sp3 hibridization. The covalent functionalization with 1,8-diaminooctane allowed for a stable and homogeneous deposition of silver nanoparticles of ca. 5-nm diameter onto the functionalized films through the coordination bonding between metal atoms and nitrogen donor atoms of the fullerene derivatives. The proposed mechanism of Ag nanoparticle binding was supported by density functional theory calculations using the hybrid BLYP functional in conjunction with the double numerical basis set DND.

(C-rac-5,5,7,12,12,14-Hexamethyl-1,4,8,11-tetraazacyclotetradecane-kappa4N)(nicotinato-O,O')nickel(II) perchlorate.

In the title compound, [Ni(C(6)H(4)NO(2))(C(16)H(36)N(4))]ClO(4), the macrocyclic unit adopts a folded conformation, allowing the two carboxyl O atoms to occupy two neighbouring coordination sites and thus form an additional four-membered chelate ring. The less crowded side of the macrocycle (that with the two asymmetric C-H groups) is directed towards the nicotinate anion and the asymmetric C-CH(3) groups are directed away from it. The macrocyclic NH groups neighbouring the C-CH(3) groups are also directed away from the nicotinate anion, while those NH groups which are near to the geminal methyl groups are directed towards the nicotinate anion. Although the complex does not include water molecules, three types of hydrogen bond were found, involving NH groups of the macrocyclic ligand, pyridine N atoms and O atoms of the perchlorate anions.

Behavior of amino acids when volatilized in the presence of silica gel and pulverized basaltic lava.

To evaluate the types of amino acid thermal transformations caused by silicate materials, we studied the volatilization products of Aib, L-Ala, L-Val and L-Leu under temperatures of up to 270 degrees C in the presence of silica gel as a model catalyst and pulverized basaltic lava samples. It was found that silica gel catalyzes nearly quantitative condensation of amino acids, where piperazinediones are the major products, whereas lava samples have much lower catalytic efficiency. In addition bicyclic and tricyclic amidines and several products of their subsequent thermal decomposition have been identified using the coupled technique of GC-FTIR-MS and HPLC-PB-MS, with auxiliary computer simulation of IR spectra and NMR spectroscopy. The decomposition is due to dehydrogenation, elimination of the alkyl substituents and dehydration as well as cleavage of the bicyclic ring system. The imidazole ring appears to be more resistant to thermal decomposition as compared to the pyperazine moiety, giving rise to the formation of different substituted imidazolones. The amidines were found to hydrolyze under treatment with concentrated HCl, releasing the starting amino acids and thus behaving as amino acid anhydrides. The thermal transformations cause significant racemization of amino acid residues. Based on our observations, the formation of amidine-type products is suggested to be rather common in the high-temperature experiments on amino acid condensation.