Adsorbed state and vibrational excitation of N2 on Pd(110)

High-resolution vibrational electron energy loss spectroscopy, low-energy electron diffraction and Auger electron spectroscopy have been used to study the interactions of nitrogen with the Pd(110) surface. At 120 K, N₂ is chemisorbed molecularly on the Pd(110) surface, and the (2 × 1)-N₂ structure is formed. Most probably, the N₂ molecules are chemisorbed in the on-top sites of the bulk-like Pd(110) surface in the upright-linear structure. The Pd---N₂ bond energy is estimated to be ˜ 6 kcal/mol. The Pd---N₂ and N---N stretching vibrations of N₂ admolecules on Pd(110) are observed at 30 and 278 meV, respectively. The primary-energy dependence and angle dependence of their excitation cross sections agree reasonably well with the prediction of the dipole theory. The electron beam-induced effects are briefly discussed.     

Inductively-coupled plasma/atomic emission spectrometry of sulfur with a vacuum scanning spectrometer and its application to the analysis of coal liquefaction catalysts

Inductively-coupled plasma/atomic emission spectrometry with a high-resolution vacuum scanning monochromator is described for the determination of sulfur at 180.734 nm. The behavior of the signal-to-background ratio is investigated as functions of RF power, argon gas flow rate and observation height above the load coil. Under the operating conditions selected, the detection limit is 3 μg l^?1. The Se I 196.090-nm line is chosen as internal standard, because the S/Se line pair exhibited the least change with carrier gas flow rate and acid concentration of solution. Sulfur in NiMo and CoMo/ Al₂O₃ catalysts used for coal liquefaction is determined as S(II) and S(VI) species. The total amount of the species agreed well with the sulfur value obtained by the conventinal combustion method.     

Reaction of poly(vinyl alcohol) with tetravalent ceric ion

Poly(vinyl alcohol) (PVAI) was oxidized by ceric ion, Ce(IV), in aqueous HNO₃ medium at different temperatures and found to be degraded as a result of selective cleavage of the 1,2-glycol unit existing in PVAl. The rate of oxidation increased with increasing temperature. The aldehyde groups formed at the ends of the degraded polymer upon oxidation were relatively stable at 0°C. With rise of temperature, the aldehyde groups reacted either with excess of Ce(IV) to carboxylic acids or with hydroxyl groups of PVAl molecules to give acetal linkage. When the acetalization predominated over the oxidation to carboxyl group, gelation of the reaction mixture was observed. Based on these results, a plausible mechanism of oxidation of PVAl with Ce(IV) and the subsequent reactions is discussed.     

Chemo-enzymatic Synthesis of Novel Oligo-N-acetyllactosamine Derivatives having a β(1-4)–β(1-6) Repeating Unit by Using Transition State Analogue Substrate

Chitinase-catalyzed hydrolytic and transglycosylating behavior of 1,2-oxazoline derivative of N-acetyllactosamine (LacNAc-oxa) 1 has been investigated. An extremely rapid hydrolysis (ring-opening of the oxazoline moiety) could be observed, suggesting that 1 behaves as a transition state analogue substrate for chitinase A1 (Bacillus circulans WL-12). This disaccharide monomer 1 was found to polymerize under basic conditions, giving rise to novel oligosaccharides having a β(1-4)–β(1-6) repeating unit in the main chain. The degree of polymerization of the resulting oligosaccharides was up to 5. This is the first example of enzymatic glycosylation reaction forming a β(1-6) bond catalyzed by chitinase.     

New catalytic cycle for couplings of aldehydes with organochromium reagents

[reaction: see text] A new catalytic cycle has been developed to effect all three subgroups of Cr-mediated couplings, i.e., (1) Ni/Cr-mediated alkenylation, alkynylation, and arylation, (2) Co/Cr-mediated 2-haloallylation, alkylation, and propargylation, and (3) Cr-mediated allylation. In the presence of chiral sulfonamide ligands, good asymmetric inductions can be achieved for some of the Ni/Cr-mediated alkenylation, Co/Cr-mediated 2-haloallylation and propargylation, and Cr-mediated allylation.     

Determination of optimal formulation for extrusion granulation by compression test of wet kneaded mass

The purpose of this study is to propose the application of a compression test to the determination of an optimal formulation for extrusion granulation. The electric current during extrusion was measured and the characteristics of the wet kneaded mass in the compression test were analyzed under various operating conditions, with different types of extruders and several formulations of kneaded mass. It was found that addition of a binder (HPC-L) to pharmaceutical powders lowered the load of a high-compressing type extruder, since the binder reduced the friction among the wet mass during extrusion. Also, the support stress was found to be proportional to the compression pressure without a binder, although an inflection point appeared on the support stress curve when a binder was present. This inflection point suggested large water retention of the wet kneaded mass, at which the medium of pressure was changed from a discontinuous solid powder to a continuous liquid, and large water retention contributed to the low friction of the wet mass. The friction of the wet kneaded mass and the aptitude of the formulation for extrusion were understood by using the compression test. The compression test is a very useful procedure at the first stage of a formulation study.     

Surprisingly efficient catalytic Cr-mediated coupling reactions

[reaction: see text] With use of 1 mol % of Cr catalyst 5, surprisingly efficient Cr-mediated couplings of aldehydes with various types of nucleophiles have been realized. The catalyst set of Cr catalyst 5 and Ni catalyst 4 is used for alkenylation, alkynylation, and arylation, whereas the catalyst set of Cr catalyst 5 and CoPc (cobalt phthalocyanine) is used for 2-haloallylation, alkylation, and propargylation. Only the Cr catalyst 5 is required for allylation. The reaction rates in DME and THF have been found significantly faster than that in MeCN.     

Remarkably Selective Ag(+) Extraction and Transport by Thiolariat Ethers

Synthesis and metal binding properties of thiolariat ethers, where a sulfide side chain is introduced into a framework of a crown ether, have been performed. Remarkably high Ag(+) selectivity among heavy metal ions was observed in solvent extraction and transport across a liquid membrane using thiolariat ethers with a 15-crown-5 ring as carriers. Thiolariat ethers with a 12-crown-4 or a 18-crown-6 do not exhibit such a high Ag(+) selectivity. The former binds metal ions weakly, and the latter recognizes Pb(2+) as well as Ag(+). The corresponding oxygen analogs, i.e. lariat ethers, do not show Ag(+) selectivity. The Ag(+) binding strength of the sulfoxide and sulfone analogs is much lower than that of thiolariat ethers. Thiolariat ethers with a benzocrown framework containing a sulfide chain at the 4 position of the benzene nucleus showed very low affinity to Ag(+). Extractability and transport ability using various thiolariat ether derivatives strongly suggested that this high Ag(+) selectivity is a result of the synergistic coordination of the ring oxygen and the sulfur atom of the thiolariat ether. NMR chemical shifts of protons and carbons in the proximity of the sulfur atom of the thiolariat ether were changed significantly in accordance with the synergistic coordination described above. 1:1 Complexation between a thiolariat ether and Ag(+) were supported by a Job plot using the chemical shift of the methylene protons adjacent to the sulfur atom.     

Making the liquid-phase catalytic hydrodechlorination of pce over Pd/C safer

Summary The hydrodechlorination of tetrachloroethylene in methanol (MeOH) over palladium catalysts on activated carbon (Pd/C) at 20°C and atmospheric pressure was rendered safer by using ethanol (EtOH), isopropanol (IPA) or water-alcohol mixtures as solvents. Adding water to MeOH was better than using EtOH or IPA since it resulted in a faster reaction and better stability of Pd/C, which could also be completely reactivated.     

Gas-phase generation of highly reactive hexatriyne-bridged [6n]paracyclophynes

[6n]Paracyclophenediynes 2a-d (n = 3-6) having [4.3.2]propellatriene units were prepared as precursors of the corresponding [6n]paracyclophynes. Laser irradiation of 2a-d produced the negative ions of [6n]paracyclophynes 1a-d (n = 3-6) by extrusion of the indan fragments, which were detected by time-of-flight mass spectrometry.