Oxidation of isobutane catalyzed by vanadyl, copper and cesium substituted H3PMo12O40

Effects of Cs⁺, H⁺ and Cu²⁺ counterions in the vanadium containing heteropoly compounds Cs_xH_1-xVO[PMo₁₂O₄₀] and Cs_yH_0.5-yCu_0.25VO[PMo₁₂O₄₀] on the catalytic oxidation of isobutane and characterization by TGA, IR and ESR spectroscopies are reported. A high selectivity of 76% for methacrylic acid and methacrolein together has been obtained with Cs_0.75H_0.25VO[PMo₁₂O₄₀] catalysts at a reactivity of 5.3x10^-1 mmol/h cm³.     

Etude des copolymeres (ethylene-hexene-1) par resonance magnetique nucleaire du proton et du carbone 13

Ethylene 1-hexene copolymers obtained by catalytic polymerization have been examined by ¹H and ¹³C NMR. Copolymer compositions have been determined by ¹H NMR and i.r. and the sequence distributions for 1-hexene by ¹³C NMR. Variations of the copolymer microstructure have been related to the experimental conditions for copolymerization.     

Palladium(II) and platinum(II) complexes of Schiff bases derived from 2,6-diacetylpyridine and S-methyldithiocarbazate and the X-ray crystal structure of the [Pd(mdapsme)Cl] complex

Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H₂dapsme) which reacts with K₂MCl₄ (M = Pd^II, Pt^II) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me₂CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H₂dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K₂PdCl₄ in an EtOH–H₂O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination.     

Reverse zymography using fluorogenic substrates for protease inhibitor detection

A novel, sensitive method for detecting protease inhibitors by using fluorescent protease substrates in gels is described. The protease inhibitors were separated on sodium dodecyl sulfate (SDS)-polyacrylamide gels containing a copolymerized peptide substrate, namely 4-methyl-coumaryl-7-amide (MCA). As the incorporated substrates in the gel, Boc-Phe Ser-Arg-MCA was used for trypsin, Suc-Ala-Ala-Pro-Phe-MCA for alpha-chymotrypsin, and Z-Phe-Arg-MCA for papain. After electrophoresis, washing and incubating the gel with the target protease solutions allowed the substrate to be cleaved by the protease, and the release of the fluorescent 7 amino-4 methyl-coumarin (AMC), which was detected under a UV transilluminator. The uncleaved peptide-MCA substrate remained where the inhibitors were present, and was visualized as dark blue bands on the light-green fluorescent background gel. This new method offers several advantages over other previous methods including: (i) greatly increased sensitivity can be achieved in a shorter period of time, which may be useful for discovering new protease inhibitors in small amounts of crude material; (ii) the procedure is quite simple and quick since the incubation period is very short and no time is needed for staining and destaining steps; (iii) since these probes using substrate specificity/target proteases, they are excellent tools for detection and discrimination of unknown protease inhibitors for various target proteases.     

The molecular structure and conformation of dichlorotetramethyldisiloxane as determined by gas phase electron diffraction

Dichlorotetramethyldisiloxane is studied by gas-phase electron diffraction at room temperature. The least-squares values of the bond distances (r_g) and bond angles () are: r(C---H)=1.084(5) Å, r(Si---O) = 1.624(2) Å, r(Si---C) = 1.852(2) Å, r(Si---Cl) = 2.067(2) Å, SiOSi = 154.0° (1.5), ClSiO = 110.2° (0.8), ClSiC = 109.6°(0.7), HCSi = 111.7°(1.5), OSiC = 110.0°(0.8), τ₁ (zero corresponds to the Si---Cl bond trans to the Si---O---Si linkage) = 78°(6) and τ₂ = 141°(19). A two-conformer model cannot be ruled out.     

Fermentation of “Quick Fiber” produced from a modified corn-milling process into ethanol and recovery of corn fiber oil

Approximately 9% of the 9.7 billion bushels of corn harvested in the United States was used for fuel ethanol production in 2002, half of which was prepared for fermentation by dry grinding. The University of Illinois has developed a modified dry grind process that allows recovery of the fiber fractions prior to fermentation. We report here on conversion of this fiber (Quick Fiber [QF]) to ethanol. QF was analyzed and found to contain 32%wt glucans and 65%wt total carbohydrates. QF was pretreated with dilute acid and converted into ethanol using either ethanologenic Escherichia coli strain FBR5 or Saccharomyces cerevisiae. For the bacterial fermentation the liquid fraction was fermented, and for the yeast fermentation both liquid and solids were fermented. For the bacterial fermentation, the final ethanol concentration was 30 g/L, a yield of 0.44 g ethanol/g of sugar(s) initially present in the hydrolysate, which is 85% of the theoretical yield. The ethanol yield with yeast was 0.096 gal/bu of processed corn assuming a QF yield of 3.04 lb/bu. The residuals from the fermentations were also evaluated as a source of corn fiber oil, which has value as a nutraceutical. Corn fiber oil yields were 8.28%wt for solids recovered following prtetreatment.     

Microstructure of vinyl acetate–butyl acrylate copolymers studied by 13C-NMR spectroscopy: Influence of emulsion polymerization process

The compositions and sequence distributions of vinyl acetate–butyl acrylate copolymers obtained with batch and semicontinuous emulsion polymerizations have been studied by ¹H and ¹³C NMR. The batch process gives heterogeneous copolymers while with the semicontinuous one the sequence distribution is statistical. These differences in sequence distributions have been related to the physical properties of the copolymers.     

Flash photolysis studies of the reaction of NH2 radicals with NO

The kinetics of the reaction NH₂ + NO → N₂ + H₂O were studied, using a conventional flash photolysis system. A value of k₁ = (1.1 ± 0.2) × 10¹⁰ & mole^?1 s^?1 was obtained at room temperature and in the pressure range 2–700 torr in the presence of nitrogen. A slight negative temperature coefficient was observed between 300 and 500 K, equivalent to a negative activation energy of 1.05 ± 0.2 kcal mole^?1.     

Molecular structure and conformation of 2,3-dichloro-1-propene as determined by gas-phase electron diffraction

The molecular structure and conformation of 2,3-dichloro-1-propene have been determined by gas-phase electron diffraction at nozzle temperatures of 24, 90 and 273°C. The molecules exist as a mixture of two conformers with the chlorine atoms anti (torsion angle ∠φ = 0°) or gauche (∠φ = 109°) to each other and with the anti form the more stable. The composition (mole fraction) of the vapor with uncertainties estimated at 2σ was found to be 0.55 (0.08), 0.49 (0.08) and 0.41 (0.10) at 24, 90 and 273°, respectively. These values correspond to an energy difference with estimated standard deviation ΔE° = E°_g-E°_a = 0.7 ± 0.3 kcal mol^?1 and an entropy difference ΔS° = S°_g-S°_a = 0.6 ± 0.9 cal mol^?1 K^?1. Some of the diffraction results, together with spectroscopic observations, permit the evaluation of an approximate torsional potential function of the form 2V = V₁ (1 - cos φ) + V₂ (1 - cos 2φ) + V₃ (1 - cos 3φ); the results are V₁ = 4.4 ± 0.5, V₂ = ?2.9 ± 0.5 and V₃ = 4.8 ± 0.2, all in kcal mol^?1. The results at 24°C for the distance (r_a) and angle (∠_α) parameters, with estimated uncertainties of 2σ, are: r(C_sp²-H) = 1.098(0.020)Å, r(C_sp³-H) = 1.103(0.020)Å, r(CC) = 1.334(0.009)Å, r(C-C) = 1.504(0.013)Å, r(C_sp²-Cl) = 1.752(0.021)Å, r(C_sp³-Cl) = 1.776(0.020)Å, ∠C-CC = 127.6(1.1)°, ∠C_sp³-C_sp²-Cl = 110.2(1.0), ∠C_sp²-C_sp³-Cl = 113.1(1.2)°, ∠H-C_sp³-H = 109.5° (assumed), ∠CC-H = 120.0° (assumed) and ∠φ = 108.9(3.4)°.