Thermal and photolytic degradation of plates of poly(methyl methacrylate) containing monomer

Specimens of 1.5 mm thick absorber-free poly(methyl methacrylate) (PMMA) containing ～0.6% monomer but no absorber have been photolytically degraded in air at 50°, 85° and 115°C and thermally degraded in air at 115° and 125°C. Specimens were exposed to a simulated solar spectral range. Degradation was followed by gel permeation chromatographic determinations of molecular weight as a function of depth in the specimens. The results show increased photodegradation at the plate faces (back and front) over that occurring in the centres, and a rapidly attained constant amount of degradation for thermal degradation. Degradation mechanisms are proposed. The thermal degradation is ascribed to weak links and unspent initiator. Photolytic initiation is ascribed, at least in part, to degradation of the ester group by wavelengths in the range 300 to 330 nm. The effect of oxygen is to convert alkyl radicals into peroxyl radicals, some of which form alkoxyl radicals which tne undergo β-scission to give in-chain ruptures. Where the oxygen concentration is low, monomer changes non-tertiary alkyl radical sinto tertiary radicals by addition to the monomer double bond. After their peroxidation by molecular oxygen, tertiary radicals react with one another to give alkoxyl radicals and subsequent chain scission rather than undergoing the Russell termination reaction with no chain scission characteristic of non-tertiary peroxyl radicals. The effect of temperature is mostly to decrease the importance of the cage effect and to allow the initial radicals formed to diffuse away from one another. The products of photo-oxidation absorb the shorter (300 to 330 nm) radiation significantly and progressively shield the remainder of the plate as degradation proceeds.     

Southern pine beetle: Olfactory receptor and behavior discrimination of enantiomers of the attractant pheromone frontalin

In laboratory and field bioassays, the response ofDendroctonus frontalis was significantly greater to the mixture of (1S, 5R)-(–)-frontalin andalpha-pinene than to (1R,5S)-(+)-frontalin andalpfa-pinene. Electro-physiological studies revealed that antennal olfactory receptor cells were significantly more responsive to (1S, 5R)-(–)-frontalin than to (1R, 5S)-(+)-frontalin. Both enantiomers stimulated the same olfactory cells which suggests that each cell possesses at least two types of enantiomer-specific acceptors.Texas Agricultural Experiment Station paper no. 14496. The work was funded in part by McIntire-Stennis project 1525 (TAES) and the USDA program entitled The Expanded Southern Pine Beetle Research and Applications Program through TAES-CSRS grant 680-15-10. The findings, opinions, and recommendations reported herein are those of the authors and not necessarily those of the United States Department of Agriculture.     

Differential recognition of geometric isomers by the boll weevil,Anthonomus grandis Boh. (Coleoptera: Curculionidae): Evidence for only three essential components in aggregation pheromone

For two decades, the aggregation pheromone of the boll weevil,Anthonomus grandis Boh. (Coleoptera: Curculionidae), was thought to consist of four compounds: I [(+)-(Z)-2-isopropenyl-1-methylcyclobutane ethanol]; II [(Z)-3,3-dimethyl-^I,-cyclohexane ethanol]; III [(Z)-3,3-dimethyl-^1,-cyclohexane acetaldehyde); and IV [(E)-3,3-dimethyl-^1,-cyclohexane acetaldehyde). Evidence is presented from behavioral and electrophysiological studies to show that only three of these components, I, II, and IV, are essential for attraction. Competitive field tests, in which each possible three-component blend was tested against the four-component mixture, demonstrated that omission of I, II. or IV resulted in decreased trap captures (P < 0.01). Trap captures by these blends lacking I, II, or IV resembled those by the hexane solvent alone in a similar experiment. However, omission of III did not significantly alter field attractiveness of the blend. Dosage-response curves constructed from electroantennogram responses of both males and females to serial dilutions of III, IV, and a 5050 mixture of the geometric isomers III and IV showed both sexes to be 10- to 100-fold more sensitive to IV than III. Data from the electrophysiological studies were consistent with a single acceptor type for the (E)-cyclohexylidene aldehyde, IV, for males, and possibly one or two acceptor types for III and IV for females. Possible roles for the (Z)-cyclohexylidene aldehyde, III, and implications for the pheromonal attractant currently used in boll weevil eradication/suppression programs are discussed.     

Electroantennogram responses of mediterranean fruit fly,Ceratitis capitata (Diptera: Tephritidae) to trimedlure and itstrans isomers

Electroantennograms (EAGs) of unmated laboratory-reared male and femaleCeratitis capitata (Wiedemann) were recorded in response to the attractant trimedlure [tert-butyl 4(and 5)-chloro-trans-2-methylcyclohexane-1-carboxylate] and its fourtrans isomers. For both sexes, the magnitude of the EAG response was relatively low as compared to other previously tested compounds (i.e., plant volatiles). Dosage-response curves generated for all TML isomers revealed that flies responded to increasing dosages over a relatively narrow range (two to three log steps). Responses for both sexes peaked at ca. 10 μg dose for all isomers. Antennal response in males was greatest to the C isomer followed by the B₁, A, and B₂ isomers, while responses of females were greatest for the A isomer followed by B₁, C, and B₂. Both sexes exhibited a long recovery period for the response potential to return to baseline at doses above 1 μg for all of the isomers tested, except for B₂. The low EAG sensitivity to trimedlure and the apparent EAG selectivity to the C isomer in males are discussed in relation to the known field attractancy of males to the C, A, B₁, and B₂ isomers.     

Antennal olfactory responsiveness of Douglas-fir beetle,Dendroctonus pseudotsugae Hopkins (Coleoptera: Scolytidae) to pheromones and host odors

Electroantennograms were obtained fromD. pseudotsugae in response to the pheromones 3-methylcyclohex-2-en-1-one (3,2-MCHone), 3-methylcyclohex-2-en-1-ol (3,2-MCHol), frontalin,trans-verbenol, verbenone, and the host terpene hydrocarbons limonene and camphene. Male and female beetles were 10 and 100 times more sensitive to 3,2-MCH-one and 3,2-MCHol than to the other compounds. Of the other compounds, males were most sensitive totrans-verbenol, verbenone, and camphene, while females were most sensitive to frontalin, limonene, and camphene. The results parallel and help explain behavior of individual males and females during host tree selection, aggregation, and colonization.