Partial purification and characterization of acylester hydrolase from Lupinus mutabilis

An alkaline acylester hydrolase was partially purified from germinated seeds of Lupinus mutabilis. Hydrolytic activity was absent in the crude extract of ungerminated lupine seed, but it increased and peaked at the fourth day in the germinating seedling. The purification scheme involved homogenization, centrifugation, acetone precipitation, anion exchange chromatography, pH precipitation, and hydrophobic interaction chromatography. The acylester hydrolase was purified 126-fold, and the overall activity yield was 10%. The molecular weight estimated by sodium dodecylsulfate-polyacrylamide gel electrophoresis was 60 kDa. The enzyme had an isoelectric point of 6.2 and showed maximal activity at pH 8.0. The enzyme showed good stability between pH 5.0 and 9.0. In the pH range 7.0–7.5, enzyme precipitation was observed. The enzyme was stable from 0 to 25°C for 5 h and at 45°C lost 50% of its activity in the same period of time. At higher temperatures, the enzyme showed low thermal stability. However, the highest initial activity was found to be at 45°C. Nonionic surfactants and cholic acid enhanced the activity of the enzyme. The activity was reduced by the addition of toluene and isooctane and increased by the addition of diethyl ether, acetonitrile, methanol, and pyridine. The activity was reduced by 37% in the presence of 1 mM Cu²⁺ ions. The enzyme-hydrolyzed triolein showing no positional specificity.     

In situ UV‐VIS diffuse reflectance spectroscopy of reduction–reoxidation of heteropoly compounds by methanol and ethanol: a correlation between spectroscopic and catalytic data

The degree of reduction/oxidation of H₄PVMo₁₁O₄₀ (HPA) and Cs₂H₂PVMo₁₁O₄₀ (CsPA) was studied during reduction and reoxidation by methanol, ethanol and mixtures with oxygen, respectively. The peak intensity of the intervalence charge transfer (IVCT) band, the apparent band gap energy (E _g ^* ) and catalytic data were obtained by in situ UV‐VIS diffuse reflectance spectrosccopy (UV‐VIS‐DRS) and on‐line gas chromatography (GC), respectively. The peak intensity of the IVCT band and E _g ^* increase during the reduction of heteropoly compounds by the alcohols. The spectroscopic and catalytic data (conversion, selectivity) correlate in the transient state during the reoxidation process. It is shown that isolated Keggin anions act as precursors for the active states of the catalysts, which molecular structure cannot be deduced from UV‐VIS spectroscopy alone. UV‐VIS spectroscopy, however, can serve as a tool to determine the degree of reduction in future combined in situ UV‐VIS/Raman/XRD studied. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synergism in the wetting properties of ternary surfactant mixtures

It has been shown that ternary surfactant synergism can be predicted on the basis of nonideality parameters of binary subsystems derived from advancing contact angles. Studies with appropriate surfactant mixtures of glucamides, ether sulfates, secondary alkane sulfonates, and alkylamidopropyl betaines were performed on substrates of different polarity.     

Compensatory fertilization of Scots pine stands polluted by heavy metals

The results from four compensatory fertilization experiments located at different distances (0.5, 2, 4 and 8 km) along a heavy metal deposition gradient extending from the Harjavalta Cu-Ni smelter in SW Finland are presented. The experiments were established in middle-age Scots pine stands growing on dryish sites of sorted glaciofluvial sediments. The soil type in all the experiments is ferric podsol. The treatments in the experiments consisted of liming, a powdered slow-release mineral mixture and stand-specific fertilization which comprised at least methylene urea and ammonium nitrate.Monitoring of deposition and soil solution and studies on soil chemical and microbiological properties, on the nutrient status of trees and needle litterfall, on fine root dynamics and on the growth of the tree stands were carried out during a 5-year period.There was a severe shortage of exchangeable Ca and Mg in the organic layer of the most polluted stands. Although the uppermost mineral soil layer had relatively high exchangeable Ca and Mg concentrations, the trees were not able to utilize these nutrient reserves presumably due to the toxic effects of Cu and Ni on the plant roots and mycorrhizas.The treatments that included limestone markedly decreased the Cu and Ni concentrations in the soil solution and soil organic layer, presumably due to immobilisation through precipitation or absorption. The Ca and Mg concentrations correspondingly increased, which certainly contributed to the partial recovery of fine root and stand growth. The powdered mineral mixture and the combination of methylene urea and ammonium nitrate had no short-term effect on the microbial biomass and activity. All the fertilizer treatments increased volume growth in the most polluted stand. The stand-specific fertilization increased needle mass in heavily polluted stands, but the response of the needle mass to fertilizer treatments was low in the less polluted stands. No clear evidence was found to support the role of nutrient status in tree resistance.     

Characterization of Pheromone Blend for Grapevine Moth, Lobesia botrana by Using Flight Track Recording

The behavioral responses of Lobesia botrana males to calling females, pheromone gland extracts, and synthetic sex pheromones were recorded in a wind tunnel. Gland extracts and synthetic pheromones were released from a pheromone evaporator. The numbers of males reaching the source and their flight tracks in response to calling females and pheromone gland extracts were compared to those of synthetic blends. Upwind flights to natural sex pheromone were straighter and faster than to a three-component blend of (E)-7,(Z)-9-dodecadienyl acetate (E7,Z9–12:Ac), (E)-7,(Z)-9-dodecadien-1-ol (E7,Z9–12:OH), and (Z)-9-docecenyl acetate (Z9–12:Ac) (100:20:5). The optimum ratio of E7,Z9–12:OH and Z9–12:Ac to E7,Z9–12:Ac was found to be 5% and 1%, respectively. An additional seven compounds identified in the sex pheromone gland were investigated for their biological activity. Two unsaturated acetates, i.e., (E)-9-dodecenyl acetate (E9–12:Ac) and 11-dodecenyl acetate (11–12:Ac), increased the number of males reaching the source as well as straightness, linear velocity, and decreased the track angle of upwind flight. Optimum response was obtained by releasing 10 pg/min E7,Z9–12:Ac in a mixture with 0.5 pg/min E7,Z9–12:OH, 0.1 pg/min Z9–12:Ac, 0.1 pg/min E9– 12:Ac and 1 pg/min 11-12–Ac. The saturated acetates previously identified in the female glands were biologically inactive.     

Epoxidation of propylene and direct synthesis of hydrogen peroxide by hydrogen and oxygen

The autoreduction of palladium–platinum-containing titanium silicalite leads to an effective catalyst for the epoxidation of propylene to propylene oxide by O₂ in the presence of H₂. The one-pot reaction is favoured compared to the two-step reaction path.     

Leaf Volatiles from Nonhost Deciduous Trees: Variation by Tree Species, Season and Temperature, and Electrophysiological Activity in Ips typographus

The leaf volatiles emitted from four nonhost tree species of Ips typographus, i.e. Betula pendula, B. pubescens, Populus tremula, and Sambucus nigra, were collected outdoors by headspace sampling in situ and analyzed by GC-MS. Three major classes of compounds, aliphatics [mainly green-leaf volatiles (GLVs)], monoterpenes, and sesquiterpenes, existed in all the deciduous tree species investigated. In June, when the bark beetles are searching in flight for host trees, GLVs mainly consisting of (Z)-3-hexenyl acetate and (Z)-3-hexen-1-ol were the dominant constituents in B. pendula and S. nigra. In B. pubescens and P. tremula, sesquiterpenes (and their derivatives) and monoterpenes made up the major part of whole volatile blends, respectively. Surprisingly, sesquiterpene alcohols and other oxides released from B. pubescens in considerable amounts were not found in the closely related species, B. pendula. By August, both the total volatiles and individual compounds significantly decreased, mainly due to the maturation of leaves, since the light intensity and temperatures during sampling were the same as in June. There were almost no volatiles detected from P. tremula and S. nigra leaves in August. The total emissions from these deciduous species were significantly different among the species, with B. pubescens releasing 5–10 times more than other species. Under the conditions of constant light intensity and humidity, emissions of both total volatiles and most individual components of severed B. pendula and S. nigra branches (with fresh leaves) increased according to a saturation curve from 16°C to 40°C. Ips typographus antennae responded strongly to green leaf alcohols: (Z)-3-hexen-1-ol, 1-hexanol, and (E)-2-hexen-1-ol, but not to aldehydes or acetates in GC-EAD analyses of B. pendula and B. pubescens leaf volatiles. No antennal responses to monoterpenes, sesquiterpenes, or sesquiterpene oxides were found. These three antennally active GLVs emitted from nonhost tree leaves might be indicators of a wrong habitat in the host selection of conifer bark beetles.     

Rigid cinchona conformers in enantioselective catalytic reactions: new cinchona‐modified platinum catalysts in the Orito reaction

The use of cinchona alkaloids (cinchonidine, cinchonine, quinine, quinidine, α-isocinchonine, α-isoquinidine, γ-isoquinidine) in the Orito reaction (hydrogenation of ethyl pyruvate and ethyl benzoylformate) strongly supports the structure of the intermediate complex (cinchona alkaloid “anti‐open” conformer–pyruvate 1 : 1 complex); in addition, so far unknown stereochemical conditions have been identified and the utilization of rigid cinchona conformers in the study of asymmetric syntheses have been generalized. This revised version was published online in July 2006 with corrections to the Cover Date.     

Michael addition of ethyl acrylate and acetone over solid bases

The catalytic behaviour of the superbases Na/NaOH/-Al₂O₃ and Cs_xO/-Al₂O₃ as well as of the basic zeolites Na/NaX and Cs_xO/CsX were investigated in the Michael addition of ethyl acrylate and acetone. The reactions were carried out in the liquid phase at catalyst loadings varying from 0.05 to 0.1 mol ester/g catalyst.     

Supported binary oxide monolayers as selective oxidation catalysts: Bi2Mo3O12/TiO2

Monolayers of bismuth molybdates supported on low-area TiO₂ (anatase) catalyse the oxidation/isomerisation of 1-butene to butadiene and 2-butenes with combined selectivities of 80–100% and show significantly lower specific rates of deep oxidation than does -Bi₂Mo₃O₁₂. As loadings are increased above 2 wt% (equivalent to one monolayer), selectivities remain high and, although the butadiene yields are generally only moderate, in some cases they exceed that shown by the unsupported -phase. This revised version was published online in July 2006 with corrections to the Cover Date.