Collisions and reactions of gaseous propanol with molten NaOH/KOH

Molecular beam scattering experiments are used to investigate collisions of a protic molecule, deuterated 1-propanol (PrOD), with an extremely basic solvent, the 5149 mol % NaOH/KOH eutectic mixture. This powerful deprotonating medium readily absorbs PrOD from the gas phase. Nearly all PrOD molecules that thermalize at the surface of the melt enter the liquid and dissolve for long times, most likely residing as PrO- after deprotonation by OH-. The PrO- solvation time is controlled by dissolved H2O, which reprotonates the anion and liberates D --> H exchanged PrOH. We find no evidence for decomposition of the alcohol; at the 463 K temperature of the experiments, the hydroxide solution appears to store propanol reversibly.     

Cellulase production and regulation byAgaricus bisporus

Cellulose is degraded during the growth of the cultivated mushroomA. bisporus on composted straw. At the time of sporophore enlargement, a marked increase in extracellular endocellulase activity occurs. A high level of enzyme activity is maintained during subsequent cropping cycles. Some of the factors affecting growth and production of extracellular endocellulase activity byA. bisporus cultured in simple defined liquid media have been examined. Endocellulase production by the fungus closely paralleled mycelial growth in cultures containing microcrystalline cellulose. The enzyme was induced by various celluloses and cellobiose. In the presence of a cellulose inducer, glucose and cellobiose repressed enzyme production. Endocellulase activity in culture filtrates was inversely related to cellulose concentration in the culture. Although the activity of free enzyme was low, in high concentrations of cellulose more cellulose was degraded. Evidence was obtained for the existence of two forms of endocellulase activity. One form adsorbed strongly to cellulose and was predominant in cultures low in cellulose. In cultures with a high cellulose content, a nonadsorbable form of the enzyme was more abundant. It is suggested that the pattern of cellulase activities produced whenA. bisporus is grown on different concentrations of cellulose is partly accounted for by its adsorption to the cellulose.     

Logarithmic Capacity and Renormalizability for Landing on the Mandelbrot Set

We study renormalizability of external angles of the Mandelbrotset M. Estimates are made of the logarithmic capacity of setsof angles that are infinitely renormalizable with a specificsequence of periods, using a substitution due to Douady. Theseshow that many of the infinitely renormalizable rays do landon M, which provides further evidence in support of the conjecturethat M is locally connected.     

Reversed-phase liquid chromatography of elastin peptides

Soluble fragments of elastin are frequently present in biological tissue in small amounts. Because of their hydrophobic character, these peptides are not well resolved by a number of conventional techniques. However, their separation should be possible by reversed-phase chromatography. A wide range of columns, gradients and solvents were evaluated. Two systems are described. One was a C18 liganded silica column eluted isocratically by gravity flow. Some degree of size fractionation was achieved with larger peptides being eluted with methanol and smaller ones with isopropanol. The second system uses a pressurized elution from another C18 ligand column. A concave gradient of trifluoroacetic acid-acetonitrile with a decreasing acetonitrile concentration was optimal. Similar resolution of peptides produced by a variety of digestion methods was obtained with the lower-molecular-mass peptides eluting in the middle of the gradient.     

Simultaneous thermal/mass spectral investigations of ammonium exchanged zirconium phosphates and zirconium arsenates

The half- and fully-ammonium ion exchanged forms of α- and γ-zirconium phosphates and of α-zirconium arsenate have been prepared. Their modes of thermal decomposition were studied by thermal methods of analysis, including simultaneous DTA/mass spectrometry. The samples heated to various temperatures were also characterized by X-ray diffraction analysis together with IR spectroscopy. The loss of water and ammonia of the various exchanged samples is compared in terms of the changes taking place in the layer lattice upon heating. The use of DTA/MS for a system involving water and ammonia as volatiles is demonstrated     

Studies on nucleophilic additions at bridging vinyl ligands in triosmium clusters

The bridging vinyl clusters [HOs₃(CHCHR)(CO)₁₀] (R = H, Ph, or n-Bu) react with PMe₂Ph to give the zwitterionic adducts [HOs₃(CHCHRPMe₂Ph)(CO)₁₀] which contain μ₂-alkylidene ligands. The adducts are not formed so readily when R = Ph or n-Bu but most readily when polar solvents are used. All three CHCHR complexes add cyanide ion irreversibly to give the anionic clusters which were isolated as [N(PPh₃)₂][HOs₃(CHCHRCN)(CO)₁₀]. There is infrared evidence for the addition of various other anions. Acid reverses the addition of methoxide but HCl reacts with the cyanide adduct [HOs₃(CHCH₂CN)(CO)₁₀]^? to give [HOs₃Cl(CO)₁₀] and EtCN. No evidence for nucleophilic addition at [HOs₃(PhCCHPh)(CO)₁₀] was obtained.     

[Fe(CO)2P(OPh)32(CS)]. The first stable thiocarbonyl derivative of iron(0) pentacarbonyl

In some circumstances, P-nBu₃ pr P-nBu₃/CC1₄ desulphurises [Fe(CO)₂{P(OPh)₃}₂(CS₂)] to give [Fe(CO)₂{P(OPh)₃}₂(CS)] which has trigonal bipyramidal coordination about the iron atom with the phosphite ligands in axial positions.     

Vanadium(IV) oxide thin films on glass and silicon from the atmospheric pressure chemical vapour deposition reaction of VOCl3 and water

The dual source atmospheric pressure chemical vapour deposition (APCVD) reaction of VOCl₃ and H₂O was used to prepare thin films of vanadium oxides on glass and silicon substrates. The thin films were characterised by X-ray diffraction, Raman spectroscopy X-ray photoelectron spectroscopy and scanning electron microscopy. At reactor temperatures above 600 °C with a gas-phase excess of water over VOCl₃, vanadium(IV) oxide thin films were produced which show a thermochromic transition temperature of 67 °C. The APCVD process is directly compatible with high throughput float-glass production enabling the use of a thin film of VO₂ as an intelligent window coating. With reactor temperatures below 600 °C or with a gas-phase excess of VOCl₃ over water, V₂O₅ thin films were produced. Vanadium(IV) oxide thin films could also be prepared on silicon substrates from the APCVD reaction of VOCl₃ and H₂O, which opens up further technological applications for the APCVD of VO₂ thin films.