Valorisation of waste fractions from autohydrolysis of selected lignocellulosic materials

Non‐isothermal processing of lignocellulosic materials in aqueous media (autohydrolysis reaction) under mild conditions leads to solutions containing valuable chemicals (oligosaccharides, sugars and acetic acid) and other, undesired, compounds (belonging to the extractive and acid‐soluble lignin fractions) which have to be removed in further purification treatments. Liquors obtained by non‐isothermal autohydrolysis of Eucalyptus globulus wood and corncobs under a variety of operational conditions were extracted with ethyl acetate in order to remove non‐saccharide components, and the suitability of the fraction dissolved in the organic phase was assayed for possible utilisation as an antioxidant. The yield and antioxidant activity of ethyl acetate extracts (measured by the α,α‐diphenyl‐β‐picrylhydrazyl (DPPH) radical scavenging capacity) showed a strong dependence on the autohydrolysis conditions. The antioxidant activity of extracts obtained under selected operational conditions compared well with synthetic antioxidants. © 2003 Society of Chemical Industry     

An attempt to compare the performance of bioscrubbers and biotrickling filters for degradation of ethyl acetate in gas streams

This study presents a comparison of the efficiency of a bioscrubber and a biotrickling filter (BTF) for the removal of ethyl acetate (EA) vapour from a waste gas stream, under the same operating conditions. The maximum EA elimination capacity achieved in the bioscrubber was 550 g m^?3 h^?1 with removal efficiency higher than 96%. For higher EA loadings the bioscrubber was oxygen limited, which caused incomplete EA biodegradation. When pure oxygen was fed to the bioscrubber at a rate of 0.02 L min^?1, the bioscrubber recovered and could treat higher EA loadings without any oxygen limitation. The BTF achieved EA elimination capacity of 600 g m^?3 h^?1 with removal efficiency higher than 97% and the dissolved oxygen concentration remained substantially higher than in the bioscrubber. However, severe channelling and blockage of the spray nozzle occurred due to the excessive biomass growth. Overall, the bioscrubber system was easier to operate and control than the BTF, while an enhancement of the oxygen mass transfer in the bioscrubber could potentially increase its performance by up to three times. Copyright © 2005 Society of Chemical Industry     

Vinyl acetate monomer—a pilot plant study

The kinetics of the reaction of acetic acid and acetylene over zinc acetate-activated carbon catalyst was investigated over a wide range of process variables in a pilot reactor. Although various catalytic reaction mechanisms were postulated, the rate of reaction was most satisfactorily correlated by a mechanism of surface reaction between charged adsorbed acetic acid and acetylene, which assumes that the rate controlling step was the irreversible charged adsorption of acetylene and acetic acid.     

γ 射线引发 VAc 乳液聚合以制备白乳胶的动力学及工艺条件研究

研究了ＶＡｃ的辐射乳液聚合动力学，并对其聚合工艺条件作了初步探索。得出ＶＡｃ乳液在进行辐射聚合时，成核期结束较早（转化率在１０％以下），有相当长的恒速期存在。乳胶粒子直径在０．５～３μｍ之间，比一般的乳液聚合乳胶粒子要大。同时从动力学数据还可以看出几种成核机理（胶束成核，水相成核和液滴成核）同时存在，由此对试验条件提出了相应的要求。     

Intraspecific variation and interspecific differences in sex pheromones of sibling species inCtenopseustis obliquana complex

The specific status ofCtenopseustis obliquana pheromone-types I, II, and III has been more fully examined. Females of types I and III produce a mixture of (Z)-8- and (Z)-5-tetradecenyl acetates (Z8-14:Ac, Z5-14: Ac). The previously reported different ratios of these two components in females of the two types (type I=8020, III=9010) have been reinvestigated. The median ratios of each type differed significantly, although there was some overlap in the ranges of these ratios. A field cage trial showed that males of type III are attracted to females of type I, so the observed differences may be ascribed to intraspecific variation. In contrast to females of types I or III, females of type II produce Z5-14Ac but no Z8-14Ac. The electroantennogram (EAG) profile of antennae of type II males shows a maximum response to Z5-14Ac, while the EAG profiles of types I and III show a strong response to Z8-14Ac. In wind tunnel tests using mixtures of these two compounds, type II males prefer blends consisting of all or mostly Z5-14: Ac, while type I males showed a preference to a mix of 70% Z8-14Ac plus 30% Z5-14Ac. We found that type I males are attracted to type I females when offered a choice between type I and type II females in a field cage test and that type II males similarly prefer type II females. Males of types I and II have specialist cells for Z8-14Ac and Z5-14Ac but differ with respect to relative densities of these cells and to further cell types responsive to other alkenyl acetates. Type IIC. obliquana is considered therefore a sibling species of types I and III. In addition, the amount of Z5-14Ac produced by type II females varied geographically. Females from the North Island produced significantly less (median=1.2 ng) Z5-14Ac than females from the South Island (median=2.2 ng). Type II populations in the North Island morphologically resembled sympatric type I, rather than type II from the South Island and are designated as type II (North Island). Type II (North Island) populations have so far been found only at Rukuhia (near Hamilton) and from Kerikeri. In contrast, type II populations are sympatric with type III populations over much of the South Island. In a field cage trial, males of types II and II (North Island) were attracted to females of both II and II (North Island). We tentatively ascribe the differences between type II and type II (North Island) to intraspecific variation.     

Structural significance of the alkyl substituent at the C-4 of (+)-trans-verbenyl acetate in sex pheromonal activity of the American cockroach

The significance of the alkyl group at the C-4 of (+)-trans-verbenyl acetate, which is the sex pheromone mimic of the American cockroach, was investigated. Seven alcohols possessing an ethyl, propyl, or dimethyl group at this position of the 6,6-dimethylbicyclo[3.1.1]heptane skeleton were synthesized and evaluated by behavioral assay. All of the alcohols were inactive, while three of four acetates of the 2-alcohols induced sexual behavior in male cockroaches at the 0.02 or 0.5 mg dosage level, either of which is many orders of magnitude higher than the threshold level of the natural sex pheromones (10^–8 mg). Among the acetates, the compounds with a methyl group or an -oriented ethyl group at C-4 showed the highest activity. The results are discussed in terms of spatial requirements of the molecules for interactions with the receptor.Studies on the sex pheromone mimic of the American cockroach, (+)-trans-verbenyl acetate. Part VIII. For Part VII, seeComp. Biochem. Physiol.,70A: 229–234 (1981).     

Specificity of the pheromone system ofAdoxophyes orana andClepsis spectrana

The pheromone system of the summer fruit tortrix mothAdoxophyes orana (Fischer von Röslerstamm) consists of a mixture ofcis-9- andcis-11-tetradecen-1-ol acetate (cis-9- andcis-11-TDA, respectively) in a ratio of 9:1. Substitution of one or both of these compounds by related unsaturated acetates reduced the attractancy. Onlycis-11-TDA could be replaced bycis-11-tridecen-1-ol acetate (cis-11-TriDA), although the 9:1 mixture ofcis-9-TDA andcis-11-TriDA was less attractive in the field than the pheromone system itself. The major component of the pheromone system of the leaf rollerClepsis spectrana (Treitschke)(cis-9-TDA:cis-11-TDA=1:9) could also be replaced bycis-11-TriDA, again with some reduction in attractancy.     

Field trapping of threeEpinotia species with (Z,Z)-7,9-dodecadienyl acetate (Lepidoptera: Tortricidae)

Field survey of the geometrical isomers of 7,9-dodecadienyl alcohol, acetate, and aldehyde has resulted in attractants and inhibitors for three species of tortricid moths.Epinotia silvertoniensis and an undescribedEpinotia sp. were all attracted to (Z,Z)-7,9-dodecadienyl acetate. AnotherEpinotia sp. was attracted to (Z,Z)-7,9-dodecadienyl acetate and (Z,Z)-7,9-dodecadien-1-ol. Electroantennogram data and inhibition patterns for one of theEpinotia sp. are also reported. In addition,E. criddleana was attracted to lures containing (E)-9-dodecenyl acetate.     

An economical synthesis of the major sex attractant of the oak leaf roller—cis-10-tetradecenyl acetate

The major sex attractant of the oak leaf roller (Archips semiferanus Walker),cis-10-tetradecenyl acetate (I), was synthesized in 55–62% overall yield by a highly economical route from inexpensive azelaic acid (II).Authorized as Paper No. 4779 in the Journal Series of the Pennsylvania Agricultural Experiment Station.     

Sex pheromone specificity as a reproductive isolating mechanism among the sibling speciesArchips argyrospilus andA. mortuanus and other sympatric tortricine moths (Lepidoptera: Tortricidae)

MaleArchips argyrospilus (Walker) were maximally attracted to a 60404200 admixture of (Z)-11-tetradecenyl, (E)-11-tetradecenyl, (Z)-9-tetradecenyl and dodecyl acetates. The identification of (Z)-9-tetradecenyl acetate, in addition to the other 3 components reported previously, is the first report of a 4-component pheromone system in moths.Archips mortuanus Kearfoot, a sibling species, was maximally attracted to a blend of the same components, but in a 90101 mix of the tetradecenyl acetates. Among a number of tortricine moths that co-occur on apples and other hosts in New York, British Columbia, and elsewhere, differences in diel rhythms of attraction and seasonal distribution are insufficient to maintain reproductive isolation. Although the attractant systems of these species often possess components in common, males are maximally attracted to a speciesspecific blend. In tortricine moths attraction specificity appears to be a paramount mechanism for species partitioning.