Formation and structure of copper(II) oxalate layers on carboxy-terminated self-assembled monolayers.

Copper(II) oxalate was grown on carboxy-terminated self-assembled monolayers using a step-by-step approach by dipping the surfaces alternately in ethanolic solutions of copper(II) acetate and oxalic acid with intermediate thorough rinsing steps. The deposition was monitored by reflection absorption infrared spectroscopy (RAIRS), a quartz microbalance with dissipation measurement (QCM-D), scanning electron microscopy (SEM), and helium ion microscopy (HIM). Amounts of material corresponding to a coverage of 75% of a monolayer are deposited in each dipping step in copper(II) acetate solution while deposition of oxalic acid produces a viscoelastic layer that is partially removed by rinsing. This points toward initial aggregation but acid not bound to Cu(2+) ions as oxalate ions is removed by the rinsing steps. RAIRS further indicates that the material grows as copper(II) oxalate ribbons similar to the crystal structure but with ribbons oriented roughly parallel to the surface. SEM and HIM give evidence of the formation of needle-shaped structures which are a possible explanation for the viscoelastic behavior of the layer.

Functionalization of a self-assembled monolayer driven by low-energy electron exposure.

Self-assembled monolayers (SAMs) of 10-undecene-1-thiol on Au were functionalized with nitrogen-containing groups using an approach in which multilayer ammonia (NH(3)) films were deposited at low temperature onto the SAMs and subsequently exposed to 15 eV electrons. The result of this process was investigated after removal of the remaining NH(3) by annealing to room temperature using high-resolution electron energy loss spectroscopy (HREELS) and X-ray photoelectron spectroscopy (XPS). HREELS shows that the CC double bonds disappear during electron exposure, while XPS gives evidence that about 25% of the terminal double bonds of the SAM were functionalized. Also, XPS shows that a sufficiently thick NH(3) layer protects the underlying SAM from electron-induced damage. The process suggested here thus represents a particularly gentle approach to the functionalization of ultrathin molecular layers. Thermal desorption spectrometry (TDS) and electron-stimulated desorption (ESD) experiments on condensed layers of NH(3) reveal production of N(2) but show that significant amounts of the initial NH(3) as well as N(2) produced during electron exposure desorb. Hydrogen released upon formation of N(2) is held responsible for the reduction of double bonds and protection of the SAMs from damage.

Dissociative electron attachment to gas-phase formamide.

Dissociative electron attachment (DEA) to gaseous formamide, HCONH(2), has been investigated in the energy range between 0 eV and 18 eV using a crossed electron/molecule beam technique. The negative ion fragments have been comprehensively monitored and assigned to molecular structures by comparison with the results for two differently deuterated derivatives, namely 1D-formamide, DCONH(2), and N,N,D-formamide, HCOND(2). The following products were observed: HCONH(-), CONH(2)(-), HCON(-), OCN(-), HCNH(-), CN(-), NH(2)(-)/O(-), NH(-), and H(-). NH(2)(-) was also separated from O(-) by using high-resolution negative ion mass spectrometry. Four resonant dissociation channels can be resolved, the strongest ones being located between 2.0 and 2.7 eV and between 6.0 and 7.0 eV. CN(-) as the most abundant fragment and HCONH(-) are the dominant products of the first of these two resonances. The most important products of the latter resonance are NH(2)(-), CN(-), H(-), CONH(2)(-), and OCN(-). It is thus found that the loss of neutral H is a site-selective process, dissociation from the N site taking place between 2.0 and 2.7 eV while dissociation from the C site occurs between 6.0 and 7.0 eV. The suitability of these reactions and thus of formamide as an agent for electron-induced surface functionalisation is discussed.

Electron induced dissociation in the condensed-phase nitromethane: II. Desorption of neutral fragments.

Low energy electron induced dissociation in multilayer films of nitromethane (CD3NO2) was investigated by high resolution electron energy loss spectroscopy (HREELS) and by the electron stimulated desorption (ESD) of neutral species. HREELS measurements show that the lowest electronic states of the condensed molecule are very similar to those seen in the gas phase. Desorbed neutrals were detected using combined non-resonant multi-photon ionization at 355 nm and time of flight mass spectrometry. The most intense signals detected were those of CD3 (+) and NO (+) and are attributed primarily to the desorption of CD3 and NO2 fragments following molecular dissociation via low-lying electronic excited states of nitromethane (the detected NO (+) being the result of the dissociative ionization of NO2). By varying the time delay between the incident electron pulse and the ionizing laser pulse, it is possible to measure the kinetic energy distributions of desorbing fragments. The kinetic energy distributions above ∼ 5 eV appear invariant with incident electron energy, indicating that the same desorption process (dissociation via low-lying electronic states) operates at all the studied incident energies. Nevertheless, measurements of neutral yields as functions of incident electron energy demonstrate that excitation of the dissociative electronic states also proceeds via previously identified transient negative ions. At energies less than ∼ 5 eV, contributions from dissociative electron attachment are also observed in the yield of CD3 and other neutral fragments.

Analysis of band broadening in vibrational high-resolution electron-energy-loss spectra of condensed methane.

High-resolution vibrational electron-energy-loss spectra of multilayer condensed films of methane recorded at 20 K show a strong tailing of the vibrational bands that clearly exceeds the instrumental resolution. At low incident electron energy, this tailing is remarkably less important for the dipole-allowed bending vibration (nu(4)) than for other bands. Also, the tailing becomes less pronounced with increasing size of the molecule as demonstrated by spectra of ethane and heptane recorded under the same conditions. Dipole coupling, rotational broadening, and multiple inelastic scattering have been considered as origins of this band broadening. While the first two effects can be excluded, multiple scattering involving a low-frequency phonon band provides a reasonable explanation as demonstrated by simulations of the spectrum of methane using a classical two-stream model. A lower phonon frequency in the cases of the larger molecules is held responsible for the better resolved vibrational signals in the spectra of ethane and heptane.

Damage induced by low-energy electrons in solid films of tetrahydrofuran.

We report on the low-energy electron-induced production of aldehydes within thin solid films of tetrahydrofuran (THF) condensed on a solid Kr substrate. The aldehyde fragments, which remain trapped within the bulk of the THF film, are detected in situ via their 3,1(n-->pi*) and 3(pi-->pi*) electronic transitions and vibrational excitations in the ground state using high-resolution electron-energy-loss spectroscopy. The production of aldehyde is studied as a function of the electron exposure, film thickness, and incident electron energy between 1 and 18.5 eV. The aldehyde production is calibrated in terms of an electron scattering cross section, which is found to be typically 6-7 x 10(-17) cm(2) between 11 and 19 eV. Its energy dependence is characterized by a small feature around 3 eV, a strong rise from 6 eV up to a maximum at 12.5 eV, followed by two structures centered around 15 and 18 eV. The aldehyde production is discussed in terms of the formation of electron resonances or transient anion states, which may lead to the fragmentation of the molecule and explain the structures seen in the energy dependence of the measured cross section.

Survey of selected diseases in wild swine in Texas.

Tissue, fecal, and serum specimens and swabs of nasal turbinates and tracheas were collected from 100 wild swine (Sus scrofa) from 10 populations in Texas and, along with 24 additional serum specimens, were evaluated for selected swine diseases. Swine positive for pseudorabies were detected in 7 populations. Brucella suis biovar 1 was isolated from 4 swine from 2 populations, but positive serologic results may indicate a more widespread distribution of the organism. All populations contained swine that were positive for leptospirosis. Trichinella spiralis was not found in the swine evaluated.