The absorption of pulsed CO2-laser radiation by ethylene at total pressures from 25 to 3000 Torr

The absorption of pulsed CO₂-laser radiation by ethylene has been measured at total pressures from 25 to 3000 Torr, using the P(12) and P(14) lines in the 10.6 m band, with incident fluences from 0.1 to 0.7 J/cm². Marked deviations from the Beer-Lambert absorption law were observed, with the effective absorption coefficient varying with pressure, fluence, absorption path-length and the addition of non-absorbing gas. Pressure broadening of the rotational lines of the ethylene absorption spectrum was shown to be the major cause of these deviations, together with lesser effects which can be attributed to the rise in temperature of the absorbing gas during the laser pulse.     

Kinetic studies of nickel speciation in model solutions of a well-characterized humic acid using the competing ligand exchange method

Publications on the binding characteristics of metals with humic acid (HA) are sparse. Here we investigated the release of nickel from Ni(II)-HA complexes using model solutions of three different [Ni(II)]/[HA] mole ratios at three different pH values; we also compared the results with those of [Ni(II)]/[FA] complexes from previous work in this laboratory. Ligand exchange kinetics using the competing ligand exchange method (CLEM) were studied using two different techniques: graphite furnace atomic absorption spectrometry (GFAAS) with Chelex 100 resin as the competing ligand, and adsorptive cathodic stripping voltammetry (AdCSV) with dimethylglyoxime as the competing ligand to measure the rate of dissociation of Ni(II)-HA complexes. The results of the kinetic studies showed that as the [Ni(II)]/[HA] mole ratio was decreased, the rate of dissociation of Ni(II)-HA complexes decreased, and the proportion of free Ni²⁺ ions plus very labile nickel complexes decreased while the proportion of the less labile kinetically distinguishable components increased. Generally, the rate of dissociation of Ni(II)-HA complexes was slower than that of Ni(II)-FA complexes. Studies on the validity of the kinetic model showed that the concentrations of chemical species varied in a reasonable way with pH and the [Ni(II)]/[HA] mole ratios, indicating that the kinetically distinguishable components have chemical significance and the kinetic model is valid.     

Stereospecific rearrangements during the synthesis of pyrrolidines and related heterocycles from cyclizations of amino alcohols with vinyl Sulfones

Conjugate additions of amino alcohols derived from alpha-amino acids to vinyl sulfones, followed by N-benzylation, chlorination, and intramolecular alkylation, provide a convenient route to substituted pyrrolidines. The process is accompanied by the stereospecific rearrangement of substituents from the alpha-position of the amine to the beta-position of the product and takes place via the corresponding aziridinium ion intermediates. Another type of rearrangement was observed during the reaction of (2-piperidine)methanol or 2-(2-piperidine)ethanol with phenyl trans-1-propenyl sulfone, in which the methyl group appears to migrate from the beta- to the alpha-position of the sulfone moiety. This process involves the isomerization of phenyl trans-1-propenyl sulfone to phenyl 2-propenyl sulfone by the addition-elimination of catalytic benzenesulfinate anion to the former vinyl sulfone, followed by conjugate addition of the amino group to the latter sulfone. Chlorination and intramolecular alkylation then afford the corresponding rearranged indolizidine and quinolizidine derivatives, respectively.     

Predicting adsorption isotherms of low-volatile compounds by temperature programmed desorption: iodine on carbon

Equilibrium adsorption isotherms for low-volatile compounds are extremely difficult to measure. A simple technique using temperature programmed desorption (TPD) is proposed. It is demonstrated that the two parameters needed for constructing the Langmuir isotherm can be derived with data from the TPD technique alone. Thus, the Langmuir isotherms of iodine on AX-21 super-activated carbon were obtained with this technique. A series of TPD experiments for samples with different initial loadings of iodine were carried out by varying the heating rates which resulted in different peak desorption temperatures. The peak desorption temperature decreased as the initial loading was increased because of the re-adsorption effect. The Langmuir constant was derived from kinetic theory with the activation energy for desorption obtained from the experiment. The activation energy for desorption was 12.3 kcal/mol. The Langmuir constants determined by this technique were in comparable order of magnitude to the reported values for iodine on activated carbon. The saturation capacity of AX-21 for iodine could also be determined from the TPD data obtained from samples with different initial loadings. The estimated saturation capacity from the TPD experiment was 2.96 g I(2)/g AX-21, which was close to the experimentally measured saturation capacity of 3.25 g I(2)/g AX-21 for the same system.     

Studies of tetracene- and pentacene-based organic thin-film transistors fabricated by the neutral cluster beam deposition method

The neutral cluster beam deposition (NCBD) method has been applied to produce and characterize organic thin-film transistors (OTFTs) based upon tetracene and pentacene molecules as active layers. Organic thin films were prepared by the NCBD method on hexamethyldisilazane (HMDS)-untreated and -pretreated silicon dioxide (SiO2) substrates at room temperature. The surface morphology and structures for the tetracene and pentacene thin films were examined by atomic force microscopy (AFM) and X-ray diffraction (XRD). The measurements demonstrate that the weakly bound and highly directional neutral cluster beams are efficient in producing high-quality single-crystalline thin films with uniform, smooth surfaces and that SiO2 surface treatment with HMDS enhances the crystallinity of the pentacene thin-film phase. Tetracene- and pentacene-based OTFTs with the top-contact structure showed typical source-drain current modulation behavior with different gate voltages. Device parameters such as hole carrier mobility, current on/off ratio, threshold voltage, and subthreshold slope have been derived from the current-voltage characteristics together with the effects of surface treatment with HMDS. In particular, the high field-effect room-temperature mobilities for the HMDS-untreated OTFTs are found to be comparable to the most widely reported values for the respective untreated tetracene and pentacene thin-film transistors. The device performance strongly correlates with the surface morphology, and the structural properties of the organic thin films are discussed.     

N-Heterocyclic carbene-palladium complex on polystyrene resin surface as polymer-supported catalyst and its application in Suzuki cross-coupling reaction

A poly(imidazoliummethyl styrene)-surface grafted-polystyrene resin was prepared by suspension polymerization. This was used as the polymer-supported carbene precursor for the palladium complex, which efficiently catalyzed the Suzuki cross-coupling of aryl halides and phenylboronic acid.