Soldier defense secretions of malaysian free-ranging termite of the genusLacessititermes (Isoptera,Nasutitermitinae)

Soldiers of free-ranging termites of the genusLacessititermes (Isoptera, Nasutitermitinae) secrete from their frontal glands a mixture of monoterpenes, sesquiterpenes, and diterpenes.Lacessititermes ransoneti, L. laborator, andL. species A produce species-specific secretions, the composition being most complex forL. laborator. Apart from known mono- and dihydroxytrinervitadienes, the following new diterpenes were isolated and tentatively assigned as trinervita-1(15),8(19)-dien-2,3,9,14-tetraol 2,3,14-O-triacetate, trinervita-1(15),8(19)-dien-2,3,9,14-tetraol 2,3,14-O-triacetate, 2,3,9, 14-tetraacetoxy-1 (15), 8(19)-trinervitadiene, and 2,3,11,13-tetraacetoxy-1(15),8(19)-trinervitadiene. Data on intragenus chemical variations were subjected to canonical discriminant analysis and genetic distances among the species were calculated to depict intragenus identities and affinities.     

Cure monitoring via different techniques: Isothermal cure of an epoxy-novolac molding compound

The isothermal cure of an epoxy-novolac molding compound was studied by means of Fourier-transform infrared spectroscopy (FTIR) and dielectrometry (DE). Results obtained were compared with previous differential scanning calorimetric (DSC) observations. The behavior of epoxide conversion (_FTIR) measured via FTIR was found similar to (but not exactly coinciding with) the extent of cure (_DSC) determined previously by means of DSC. As for the DE analysis, directly measurable properties such as permittivity () and loss factor () varied in a complicated manner during the course of cure, showing strong dependence on both temperature and frequency. Other dielectric parameters (such as ionic conductivity, relaxed permittivity, and characteristic relaxation time) previously suggested in the literature as suitable for cure monitoring purposes were found difficult to determine within the limited frequency range (10⁰ to 10⁴ Hz) here. With some arbitrariness, the relative drop in log (at 100 Hz) was taken as an index (_DE) for the extent of cure. It was observed that _DE behaves in a manner similar to _FTIR and _DSC Comments on the application of these three techniques in the characterization of thermosetting systems were given.     

The effect of carbon black filling and cross-linking in stretched SBR networks: a 2H-NMR study

Summary The line splitting v in ²H-NMR spectra of deuterated benzene in stretched crosslinked SBR depended linearly on the classical stretch term ² – 1/ for samples with and without carbon black filling. The ratio LS = v/(² – 1/) was measured in dependence on the solvent fraction . The extrapolated value L of this ratio at =0 gave a linear dependence on the inverse molecular mass 1/M_c of inter-crosslink chains. This was expected according to a simple model of chain dynamics and offers a further NMR-method for M_c-determination even in filled networks. However, the slope of the L(1/M_c)-line increases with an addition of carbon black which indicates a higher molecular order. Three reasons for this could be discussed. However, one of them is preferable.     

Differential metabolism of 1,8-cineole in insects

In order to compare the metabolism of 1,8-cineole in the pyrgo beetle, Paropsisterna tigrina, three other herbivorous insect species, Faex nigroconspersa, Chrysophtharta bimaculata, and Oxyops vitiosa, were fed 1,8-cineole leaf diets. F. nigroconspersa adults excreted predominantly 9-hydroxy-1,8-cineole (36.2% of the volatile constituents) with some 2-hydroxy-1,8-cineole (11.4%). In contrast, larvae excreted predominantly 2-hydroxy-1,8-cineole (27.4%) and smaller proportions of 9-hydroxy-1,8-cineole (5.2%) and 3-hydroxy-1,8-cineole (4.3%). C. bimaculata adults excreted predominantly 3-hydroxy-1,8-cineole (16.5%). Oxyops vitiosa adults, on a lower 1,8-cineole diet, excreted predominantly 2,9-dihydroxy-1,8-cineole (4.2%) and 2-hydroxy-1,8-cineole (3.5%), with smaller proportions of 3-hydroxy-1,8-cineole (1.1%) and 9-hydroxy-1,8-cineole (0.5%). This is the first reported occurrence of a dihydroxycineole as an insect metabolite. Gas chromatographic and mass spectral data for hydroxycineoles are recorded and interspecific metabolite variation discussed.     

Synergistic Effect of Ethanol to α-Pinene in Primary Attraction of the Larger Pine Shoot Beetle, Tomicus piniperda

-Pinene and ethanol were released in the approximate proportions 1:0.1, 1:0.9 and 1:9 (at 21°C). Ethanol, released in the range of 3–279 mg/day, generally synergized the attraction of T. piniperda to -pinene (30 mg/day at 21°C), although attraction to the mixtures varied within and between years. The low release rate of ethanol together with -pinene attracted a significantly higher number of beetles than -pinene alone in 1995, April of 1996, and in 1997. Lures with the medium release rate of ethanol were the most attractive only in March of 1996. The high dose of ethanol significantly synergized attraction to -pinene in 1995 and 1997. The variable attraction of T. pinipeda to ethanol and -pinene at various release rates and proportions may be due to the temperature dependent nature of beetle antennal sensitivity. At ambient temperatures of 10–13°C. T. piniperda was most attracted to the lures with -pinene and high release rates of ethanol, at 14–17°C it was most attracted to those with medium release rates of ethanol, and at 18°C and higher it was most attraacted to those with low release rates of ethanol.     

Copolymerization of 2-phenoxy-1,3,2-dioxaphosphorinanes with α-keto acids involving deoxygenation of the keto oxygen atom: deoxy-copolymerization

Summary The copolymerization of 2-phenoxy-1,3,2-dioxaphosphorinanes (4) with -keto acids (2) took place at room temperature without added catalyst to produce copolymers (5). The copolymer 5 is composed of phosphoric acid triester unit (5 ) and of -hydroxy-carboxylic acid ester unit (5 ). Unit 5 is an alternating unit of monomers 4 and 2 whereas unit 5 is formed by deoxygenating 2 by 4. 5 can be taken as copolymers of units 5 and 5 , the formation of the latter involving a deoxygenation process (Deoxy-Copolymerization). The ratio of 5 /5 (m-value in 5) increased in the order of unsubstituted (4a)-, 5,5-dimethyl (4b)-, and 5-t-butyl (4c)-phosphorinane systems. The reaction mechanism is also discussed.Dedicated to the 65th birthday of Professor G. Manecke     

Syntheses and optical properties of <Emphasis Type="Italic">α</Emphasis>- and <Emphasis Type="Italic">β</Emphasis>-cyano-poly(<Emphasis Type="Italic">p</Emphasis>-phenylene vinylene) derivatives

Two light emitting molecules with the cyano group at different positions on the vinylene i.e., 2,5-bis(2-thienyl-1-cyanovinyl)-1-(2_-ethylhexyloxy)-4-methoxybenzene (-TPT) and 2,5-bis(2-thienyl-2-cyanovinyl)-1-(2-ethylhexyloxy)-4-methoxybenzene (-TPT), and corresponding polymers, i.e., poly[2,5-bis(2-thienyl-1-cyanovinyl)-1-(2-ethylhexyloxy)-4-methoxybenzene] (denoted as P1) and poly[2,5-bis(2-ethienyl-2-cyanovinyl)-1-(2-ethylhexyloxy)-4-methoxybenzene] (denoted as P2) were synthesized. -TPT and -TPT, respectively, were blended into two host polymers, poly(methyl methacrylate (PMMA) and poly(9-vinylcarbazole) (PVK), to study the optical properties of the dopants in different host polymer matrices. Although -TPT and -TPT have the same backbone structure, their optical properties are much different. The PL emission maximum ( _max) of -TPT was found blue-shifted, compared with that of -TPT, while the PL intensity of -TPT was stronger than that of -TPT. Concentration effect in the optical properties was found, 1 wt% of -TPT in PVK had the maximum fluorescent emission.The PL maximum peak wavelengths for polymer films (P1 and P2) were found red-shifted; while their PL intensities were weaker when compared with those of blends.     

Mass transfer in an annular electrodialysis cell in pulsating flow

The effect of pulsating flow on the mass transfer in an annular electrodialysis cell has been studied in terms of the limiting current. The results indicate that the limiting current is influenced by the fluid velocity, the pulsation amplitude and the pulsation frequency, giving an increase of 400% with respect to the steady state. For a given amplitude, the dimensionless velocity, 0 (0 = a/v), can be taken as a representative parameter of the pulsation effect on the mass transfer. The fractional increase in the Sherwood number in pulsating flow with respect to the steady state has been correlated in terms of the dimensionless velocity, 0, and the Stokes number, 1 (1 = Deq (/)1/2), giving the correlation:     

Synthesis of HFC-134a over CrF3/AlF3 catalysts

The effect of the structure of AlF₃ supports in CrF₃/AlF₃ catalysts and their activity were studied, and a selection of suitable reaction conditions for fluorination of trichloroethylene and HCFC-133a was made. We found that neither AlF₃ (- and -modifications) nor CrF₃/-AlF₃ exhibits significant activity for the reaction of HF with CCl₂=CHC1 or CF₃CH₂Cl. However, CrF₃/-AlF₃ exhibits high activity, which increases with increasing surface area and decreasing crystallite size of the -AlF₃ support, and that dramatically affects the fiuorination of CF₃CH₂Cl. Investigation of a series of CrF₃/-AlF₃ catalysts shows that the turnover rates per unit of the total surface area and of the free CrF₃ surface area significantly increase with increasing content of Cr³⁺ loading. Optimum temperature for the reaction of HF with CCl₂=CHCl is 260°C, while with CF₃CH₂Cl it is 350°C, with flow ratios HFTCE = 61 andHFHCFC-133a = 101.     

Musk deer (Moschus moschiferus): Reinvestigation of main lipid components from preputial gland secretion

The qualitative and quantitative composition of the principal lipid constituents of Siberian musk deer (Moschus moschiferus) preputial gland secretion, main odor carriers and potential precursors of odorous substances, was investigated by means of high-performance liquid chromatography. Free fatty acids and phenols (10%), waxes (38%), and steroids (38%) were found to be the main groups of the secretion lipids. Cholestanol (I), cholesterol (II), androsterone (III), ⁴-3-hydroxy-17-ketoandrostene (IV), 5, 3-hydroxy-17-ketoandrostane (V), 5, 3, 17-dihydroxyandrostane (VI), 5, 3, 17-dihydroxyandrostane (VII), and 5, 3, 17-dihydroxyandrostane (VIII) were isolated from the steroid fraction and their structures confirmed by IR, PMR, and mass spectra. 3-Methylpentadecanone (muscone) was not identified among the secretion lipids. Preputial gland secretion stimulated sex behavior of musk deer females.     

Enhancement of βα-recrystallization in β-form isotactic polypropylene during heating after roll deformation

Summary -form isotactic polypropylene shows -recrystallization behavior (recrystallization from - to -form) during slow heating. This is enhanced by deformation. -form specimen with uniaxially oriented lamellae was deformed by rolling, and -recrystallization was studied by DSC and x-ray diffraction. The result showed that (1) — recrystallization is promoted with the degree of deformation. (2) Deformed specimen shows -recrystallization from considerably low temperature compared with the undeformed one. (3) The recrystallized -form is c-axis-oriented along the roll direction. From these results the -recrystallization mechanism was discussed in view of -nucleus formation by deformation.     

Response ofScolytus multistriatus (Coleoptera: Scolytidae) to α- and δ-multistriatin in Switzerland

Laboratory bioassays and field tests demonstrated that a Swiss population ofS. multistriatus responded much more strongly to - than to -miltistriatin in combination with 4-methyl-3-heptanol and -cubebene. High concentrations of brevicomin appeared to replace -multistriatin in evoking a response byScolytus species, but this effect can be explained by the fact that the brevicomin was contiminated with small amounts of -multistriatin. Frontalin, another bicyclic ketal, showed no biological activity. Field tests indicated thatS. pygmaeus aggregates to the same attractant mixture asS. multistriatus. S. scolytus also responded preferentially to this mixture, but the relative amounts of -multistriatin to 4-methyl-3-heptanol do not appear to be as important as forS. multistriatus.     

Silphinene Sesquiterpenes as Model Insect Antifeedants

Silphinene sesquiterpenes are established chrysomelid antifeedants. In this work, nine silphinene analogs, 11-acetoxy-5-angeloyloxysilphinen-3-one (1), 11-acetoxy-5-tigloyloxysilphinen-3-one (2), 11-acetoxy-5-iso- butyryloxysilphinen-3-one (3), 11-hydroxy-5-angeloyloxysilphinen-3-one (4), 11,5-dihydroxysilphinen-3-one (5), 11,5-diacetoxysilphinen-3-one (6), 5,11-diisobutyryloxysilphinen-3-one (7), silphinen-3,5,11-trione (8), and O-methyl-5-epicantabrenolic acid methyl ester (10), and a presilphiperfolane sesquiterpene (9) were tested against several divergent insect species, including the lepidopteran Spodoptera littoralis, the chrysomelid Leptinotarsa decemlineata, and five aphid species, and their antifeedant effects were compared with those of picrotoxinin, a GABA-antagonist, and thymol, an allosteric modulator for insect GABA receptors. All insects tested responded to at least one silphinene analog and/or GABA antagonist. Compound 3 and thymol were effective antifeedants against all species tested except S. littoralis, with varying potencies according to their feeding ecologies. The toxicity of these compounds was species-dependent and did not correlate with their antifeedant effect.     

Physical Properties of R-PET/CD-PET Polyblended Hollow Filaments and Their Kinetics of Alkaline Hydrolysis

Cationic dyeable poly(ethylene terephthalate) (CD-PET) was formed by copolymerizing dimethylterephthalate (DMT),5-sodium sulfonate dimethyl isophthalate (SIPM) with a molar ratio of 2% and ethylene glycol (EG). Blends of regular poly(ethylene terephthalate) (R-PET) and CD-PET were spun into hollow filaments. The filaments were then treated with aqueous NaOH. This study investigated the physical properties of R-PET/CD-PET polyblended hollow filaments and their kinetic behavior of alkaline hydrolysis using differential scanning calorimetry (DSC), wide angle x-ray diffraction (WAXD), the density gradient method, gel permeation chromatography (GPC), rheometer measurement and statistical analysis using the regression method. Experimental results indicate that the rate constant of alkaline hydrolysis was CD-PET hollow filaments >R-PET/CD-PET polyblended hollow filaments > R-PET hollow filaments. For the alkaline hydrolysis kinetics equation of R-PET, CD-PET/R-PET polyblended and CD-PET hollow filaments: –dW/dt=KC A , is equal to 1. Moreover, R ² of the kinetics equation for from 1.061.29 was better than that of =1.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

The aqueous thermal polycondensation of asparagine and isoasparagine and the structure of polyaspartic acid

Summary Both asparagine and isoasparagine were converted into polyaspartic acids by refluxing the corresponding aqueous solutions at neutral pH in the presence of a salt. The properties of the resulting polyaspartic acids were studied. The dissociation behavior of the carboxyl groups in the polypeptides were studied by the potentiometric titration. The analysis of the titrational data was performed by a modified Speakman's method. The analysis show that both polyaspartic acids prepared from asparagine and isoasparagine have - and -aspartyl residues and the ratio of - and -aspartyl residues is 75 2585 15. A possible mechanism for the formation of - and -aspartyl residues in the polymer was discussed.     

Behavioral and neurosensory responses of the boll weevil,Anthonomus grandis Boh. (Coleoptera: Curculionidae), to fluorinated analogs of aldehyde components of its pheromone

Competitive field tests with -fluorinated analogs of compounds III and IV (III--F and IV--F, respectively) of the boll weevil,Anthonomus grandis Boh., aggregation pheromone showed these compounds, when combined with the other pheromone components [(±)-I and II], to be as attractive as grandlure [(+)-I, II, and III+IV]. Dose-response curves constructed from electroantennograms of male boll weevils to serial stimulus loads of III, IV, III--F, IV--F, and the corresponding acyl fluorinated analogs (III-acyl-F and IV-acyl-F) showed the -fiuorinated analogs to be as active as the pheromone components (threshold=0.1 g), while the acyl fluorinated analogs had a 10-100 x higher threshold (=1-10 g). Single-neuron recordings showed that IV neurons and II neurons (Dickens, 1990) responded to IV--F and III--F, respectively, while IV-acyl-F and III-acyl-F were inactive. Since a previous study showed compounds I, II, and IV to be essential for behavioral responses in the field, it seems likely that the activity of the -fluorinated analogs observed here is due to the stimulation of IV neurons by IV--F as indicated in single neuron recordings.     

Synthesis of novel telechelic monodispersed nonconjugated dienes

Summary The synthesis of novel telechelic monodispersed nonconjugated dienes from commercially available , -dithiols and dienes is presented. The batch reaction produced a polydispersed. mixture separable with difficulty whereas a dropwise addition of dithiol onto an excess of , -diene in the presence of peroxide led selectively and quantitatively to the addition product: diene-dithiol-diene.     

Cationic modifications of polychloroprene

Summary The synthesis of the novel graft-block copolymer poly[chloroprene-g-(isobutylene-b--methylstyrene)], i.e., a polychloroprene backbone carrying isobutylene/-methylstyrene block copolymer branches, is described. The synthesis was accomplished by exploiting detailed insight into the mechanisms of initiation of isobutylene and -methylstyrene polymerization, and termination of isobutylene polymerization.     

Synthesis of α,α′-dipotassio-m-xylene and its use as a dianionic initiator

Summary ,-Dipotassio-m-xylene was prepared by di-metalation of m-xylene with a butyllithium/potassium t-butoxide mixed base system. Its functionality was determined by combining the dianion with chlorotrimethylsilane which resulted in the di-substituted carbosilane. GC and ¹H NMR analysis confirmed that the di-substituted carbosilane was synthesized in>90% yield. The effectiveness of this dianion as an initiator for living anionic polymerization was demonstrated by the polymerization of isoprene and the synthesis of the triblock copolymer of dimethylacrylamide-isoprene-dimethylacrylamide.