Effects of ZnO nanowire length on surface-assisted laser desorption/ionization of small molecules.

The effects of nanowire (NW) length on surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) of small molecules were investigated using ZnO NWs of 50 nm diameter with a broad range of lengths ranging from 25 to 1600 nm. Characterization of the ZnO NWs revealed that the length was the only parameter that varied in this study, while other properties of the NWs remained essentially the same as the bulk properties. Experiments on SALDI efficiency exhibited that the SALDI processes on NWs have a certain length window. In the present case of ZnO NWs, the SALDI efficiency was found to be enhanced on the nanowires of 250 nm length, corresponding to an aspect ratio of 5. The roles of NW length in the SALDI processes were discussed from the viewpoint of efficient energy-transfer media as well as physical obstacles screening laser irradiation and preventing the escape of nascent ions from NW surfaces. The existence of the length window may provide valuable insight for tailoring new nanostructures for efficient SALDI of small molecules.

Ultraviolet photodepletion spectroscopy of dibenzo-18-crown-6-ether complexes with alkali metal cations.

Ultraviolet photodepletion spectra of dibenzo-18-crown-6-ether complexes with alkali metal cations (M(+)-DB18C6, M = Cs, Rb, K, Na, and Li) were obtained in the gas phase using electrospray ionization quadrupole ion-trap reflectron time-of-flight mass spectrometry. The spectra exhibited a few distinct absorption bands in the wavenumber region of 35 450-37 800 cm(-1). The lowest-energy band was tentatively assigned to be the origin of the S(0)-S(1) transition, and the second band to a vibronic transition arising from the "benzene breathing" mode in conjunction with symmetric or asymmetric stretching vibration of the bonds between the metal cation and the oxygen atoms in DB18C6. The red shifts of the origin bands were observed in the spectra as the size of the metal cation in M(+)-DB18C6 increased from Li(+) to Cs(+). We suggested that these red shifts arose mainly from the decrease in the binding energies of larger-sized metal cations to DB18C6 at the electronic ground state. These size effects of the metal cations on the geometric and electronic structures, and the binding properties of the complexes at the S(0) and S(1) states were further elucidated by theoretical calculations using density functional and time-dependent density functional theories.