[18F]PRIMATX,a New Positron Emission Tomography Tracer for Imaging of Autotaxin in Lung Tissue and Tumor-Bearing Mice

Autotaxin (ATX) is a secreted enzyme with tissue levels associated with tissue injury, which increase during wound healing and chronic fibrotic diseases. We selected [¹⁸F](R,E)-3-(4-chloro-2-((5-methyl-2H-tetrazol-2-yl)methyl)phenyl)-1-(4-((5-(2-fluoroethoxy)pyridin-2-yl)methyl)-2-methylpiperazin-1-yl)prop-2-en-1-one ([¹⁸F]PRIMATX, [¹⁸F] 2 ), a tracer for positron emission tomography, to image ATX expression in vivo. It successfully differentiates expression levels in lung tissue samples from idiopathic pulmonary fibrosis patients, and allows the detection of ATX-expressing tumors in living mice, confirming its potential for development as a clinical imaging agent.     

Preparation and characterization of novel grafted polyethylene based azo-polymers bearing oligo(ethylene glycol) spacers

Novel grafted azo-polymers were prepared from commercial low density polyethylene plates (PE). First, precursor polymers were synthesized by reacting PE in the presence of acryloyl chloride using gamma radiation. Further esterification of the resulting grafted polymers with four new amino-nitro substituted azobenzene derivatives bearing oligo(ethylene glycol) segments: N-methyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}-N-(5-hydroxy-3-oxapentas-1-yl)amine (RED-PEG-2), N-methyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}-N-(8-hydroxy-3,6-dioxaoctas-1-yl)amine (RED-PEG-3), N-methyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}-N-(11-hydroxy-3,6,9-trioxaundecas-1-yl)amine (RED-PEG-4) and N-methyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}-N-(17-hydroxy-3,6,9,12,15-pentaoxaheptadecas-1-yl)amine (RED-PEG-6) led to the formation of branched azo-polymers. These polymers were characterized and their thermal and optical properties were studied. Besides, the influence of the irradiation dose, irradiation time and the structure of the dyes on the properties of the obtained polymers are discussed.     

Coupling of cyclohexene oxide (CHO) and carbon disulfide (CS2) catalyzed by the asymmetric bis-Schiff-base Zn(II) complex

Based on the self-assembly of the asymmetric bis-Schiff-base ligand H₂L (H₂L = 4-((E)-(2-((E)-3,5-dibromo-2-hydroxybenzylideneamino)phenylimino)(phenyl)methyl-1-(4-chlorophenyl)-3-methyl-1H-pyrazol-5-ol) and Zn(OAc)₂·2H₂O, a new [Zn(L)] (1) was obtained and shown to efficiently catalyze the coupling of CHO (cyclohexene oxide) and CS₂ (carbon disulfide) in activation with [PPN]Cl (PPN⁺ = bis(triphenylphosphoranyidene)-ammonium), n-Bu₄NBr or n-Bu₄NI, where both poly[thio]carbonates and cyclic [thio]carbonates were produced, and the strong O/S exchange afforded the limited formation of trithiocarbonate in the cyclic [thio]carbonate byproducts.     

Preparation and characterization of a novel host (zeolite NaY)/guest (copper(II) complex of a new bidentate Schiff base ligand) nanocomposite material (HGNM): a comparison between catalytic reactivity of free and encapsulated complexes in oxidation of benzyl alcohol and aldol condensation

A copper(II) complex of 4-((E)-(4-(1H-benzo[d]imidazol-2-yl)phenyl)diazenyl)-2-((E)-(4-hydroxyphenylimino) methyl)phenol (HL) was encapsulated in zeolite NaY by flexible ligand method. The structure of encapsulated complex was characterized by spectroscopic (electronic and FT-IR), XRD, TGA, BET and elemental analysis data. Furthermore, catalytic activity of the neat and encapsulated complexes was studied in oxidation of benzyl alcohol and aldol condensation. The encapsulated complex was more reactive and stable than the corresponding free complex. Nanocomposite material was enough stable to be reused for several times. Finally, the reaction parameters were optimized for oxidation of benzyl alcohol and aldol condensation.     

Attraction of pea mothCydia nigricana F. (Lepidoptera: Tortricidae) to female sex pheromone (E,E)-8,10-dodecadien-1-YL acetate,is inhibited by geometric isomersE,Z, Z,E, andZ,Z

Field attraction ofCydia nigricana males to synthetic female sex pheromone (E,E)-8,10-dodecadien-1-yl acetate, formulated on red rubber septa, declined continuously during two weeks. This was due to isomerization of (E,E)-8,10-dodecadien-1-yl acetate: eight days after application of purifiedE,E isomer, the proportion ofE,Z;Z,E; andZ,Z isomers in rubber septa aged in the laboratory was 4%; a 5% addition of any one of these isomers to fresh lures of (E,E)-8,10-dodecadien-1-yl acetate significantly reduced male attraction. Stereospecific syntheses of (E,Z)-, (Z,E)-, and (Z,Z)-8,10-dodecadien-1-yl acetate are described. The pheromone gland ofCydia nigricana contains 0.8 ng/female of (E,E)-8,10-dodecadien-1-yl acetate, accompanied by three monounsaturated acetates, (E)-9-dodecen-1-yl acetate, (Z)-5-tetradecen-1-yl acetate, and (Z)-7-tetradecen-1-yl acetate (0.1 ng/female each). These compounds did not augment male trap catch when added to (E,E)-8,10-dodecadien-1-yl acetate.     

Sex Pheromone of the Saturniid Moth, <Emphasis Type="Italic">Hemileuca burnsi</Emphasis>, from the Western Mojave Desert of California

The sex pheromone blend of Hemileuca burnsi (Lepidoptera: Saturniidae) from the western Mojave Desert was determined to be a combination of (10E,12Z)-hexadecadien-1-yl acetate (E10,Z12-16:Ac), (10E,12Z)-hexadecadien-1-ol (E10,Z12-16:OH), (10E,12E)-hexadecadien-1-yl acetate (E10,E12-16:Ac), and hexadecyl acetate (16:Ac). (10E,12Z)-Hexadecadienal (E10,Z12-16:Ald) was tentatively identified in pheromone gland extracts based on electroantennographic responses and, when added to the above blend, it enhanced trap captures at low doses. The mean ratio of the compounds in extracts of pheromone glands was 100:23:232:14:0.4 (E10,Z12-16:Ac: E10,E12-16:Ac: 16:Ac: E10,Z12-16:OH: E10,Z12-16:Ald). Field trials indicated that although E10,Z12-16:Ac and E10,Z12-16:OH were essential for attraction, the two-component blend was not attractive by itself. Addition of the three other compounds was necessary for maximum attraction, rendering this the most complicated pheromone blend described for a Hemileuca species to date. Similarities between the sex pheromone of H. burnsi and that of the allopatric Hemileuca electra electra and differences between the blends of H. burnsi and that of the sympatric H. electra mojavensis support a case for reproductive character displacement in the pheromone communication channel of H. electra.     

Optical properties and aggregation of novel azo-dyes bearing an end-capped oligo(ethylene glycol) side chain in solution,solid state and Langmuir–Blodgett films

Optical properties and aggregation of two novel azo-dyes N-methyl-N-{4-[(E)-(4-nitrophenyl)diazenyl]phenyl}-N-(3,6,9-trioxadecas-1-yl)amine (RED-PEGM-3) and N-methyl-N-{4-[(E)-(4-nitrophenyl)diazenyl] phenyl}-N-(3,6,9,12,15,18,21,24-octaoxapentaeicos-1-yl)amine (RED-PEGM-8) were studied by UV–vis spectroscopy in solution, solid state and Langmuir–Blodgett films. The results were compared to those obtained for their precursor 1-amino-4′-nitroazobenzene (Disperse Orange 3, DO3) and 1-N-methylamino-4′-nitroazobenzene (RED-H). Increasing the polarity of methanol:water mixtures gave rise to the formation of H-aggregates for all dyes. Similar aggregates were also detected in cast films. NOESY, 2D ¹H NMR experiments carried out in aqueous solutions of RED-PEGM-8 revealed the formation of atypical antiparallel H-aggregates. Only RED-PEGM-3 gave traces of J-aggregates in the solid state. RED-PEGM-3 and RED-PEGM-8 readily form J-aggregates in Y-type Langmuir–Blodgett films.     

Sex pheromone of tomato pestScrobipalpuloides absoluta (Lepidoptera: Gelechiidae)

The sex attractant ofScrobipalpuloides absoluta females is a 90:10 mixture of (3E,8Z,11Z)-3,8,11-tetradecatrien-1-yl acetate and (3E,8Z)-3,8-tetradecadien-1-yl acetate. Tetradecadienyl acetates bearing 8Z,11Z; 3E,8Z; and 3E,11Z double bonds were synthesized by stereospecific procedures; the mass spectral and gas chromatographic properties of the 3E,8Z isomer were found to be congruent with those of the tetradecadienyl acetate fromS. absoluta. In wind tunnel bioassays, a 10:1 mixture of synthetic (3E,8Z,11Z)-3,8,11-tetradecatrien-1-yl acetate and (3E,8Z)-3,8-tetradecadien-1-yl acetate was highly attractive toS. absoluta males. Interestingly, the presence of (8Z,11Z)-8,11-tetradecadien-1-yl acetate (10%) inhibited the response to (3E,8Z,11Z)-3,8,11-tetradecatrien-1-yl acetate completely.     

Synthesis,Characterization and Anti-Breast Cancer Activity of New 4-Aminoantipyrine-Based Heterocycles

4-Aminoantipyrine was utilized as key intermediate for the synthesis of pyrazolone derivatives bearing biologically active moieties. The newly synthesized compounds were characterized by IR, ¹H- and ¹³C-NMR spectral and microanalytical studies. The compounds were screened as anticancer agents against a human tumor breast cancer cell line MCF7, and the results showed that (Z)-4-((3-amino-5-imino-1-phenyl-1H-pyrazol-4(5H)-ylidene)methylamino)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 5, 3-(4-bromophenyl) -1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 13, 1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1-Hpyrazol- 4-yl)-3-(4-iodophenyl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 14, 3,3′-(4,4′-sulfonylbis(4,1-phenylene))bis(1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol- 4-yl)-4-oxo-2-thioxo-1,2,3,4-tetrahydropyrimidine-5-carbonitrile) 16, (Z)-1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-hydrazono-4-oxo-3-phenyl-1,2,3,4-tetrahydropyrimidine-5-carbonitrile 17, (Z)-1-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-4-oxo-3-phenyl-2-(2-phenylhydrazono)-1,2,3,4-tetrahydro pyrimidine-5-carbonitrile 18, and (Z)-4-(3-amino-6-hydrazono-7-phenyl-6,7-dihydro pyrazolo[3,4-d]pyrimidin-5-yl)-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 19 were the most active compounds with IC₅₀ values ranging from 30.68 to 60.72 μM compared with Doxorubicin as positive control with the IC₅₀ value 71.8 μM.     

Ring-opening copolymerization of CHO and MA catalyzed by the asymmetrical Cr(III)-bis-Schiff-base complex

Using an asymmetrical Cr(III)-bis-Schiff-base complex [Cr(L)Cl] (1; H₂L obtained from condensation of 5-bromo-salicylaldehyde and HL⁰ ((Z)-4-((2-aminophenylimino)(phenyl)methyl)-3-methyl-1H-pyrazol-5(4H)-one) as the catalyst, bulk solvent-free ring-opening copolymerization of CHO (cyclohexene oxide) and MA (maleic anhydride) in the presence of cocatalyst DMAP (4-(dimethylamino)-pyridine) was effectively realized, in which, on the condition of low 1/DMAP concentration for a controllable polymerization, perfectly alternating polyester while not poly(ester-co-ether) could be obtained.     

Synthesis, Spectroscopic Characterization and Structures of Tributyltin(IV) 4-[((E)-1-{2-hydroxy-5-[(E)-2-(aryl)-1-diazenyl]phenyl}methylidene)amino]benzoates. Toxicity Studies on the Second Larval Instar of the Anopheles stephensi Mosquito Larvae

A series of tributyltin(IV) complexes of 4-[((E)-1-{2-hydroxy-5-[(E)-2-(aryl)-1-diazenyl]phenyl}methylidene)amino]benzoates have been investigated by ¹H, ¹³C, ¹¹⁹Sn NMR, IR and ¹¹⁹Sn M?ssbauer spectroscopic techniques in combination with elemental analyses. Single crystal X-ray crystallography of Bu₃Sn[O₂CC₆H₄{N=C(H)C₆H₃-2-OH(N=NC₆H₄CH₃-4)}-p] reveals a distorted tetrahedral structure which is further supported by ¹¹⁹Sn M?ssbauer data. Toxicity studies of the tributyltin(IV) complexes along with their ligands 4-[((E)-1-{2-hydroxy-5-[(E)-2-(aryl)-1-diazenyl]phenyl}methylidene)amino]benzoic acids on the second larval instar of the Anopheles stephensi mosquito larvae are also reported.     

Sex pheromone components of the oblique-banded leafroller,Choristoneura rosaceana in the Okanagan Valley of British Columbia

(Z)-11-Tetradecen-1-yl acetate, (E)-11-tetradecen-1-yl acetate, and (Z)-11-tetradecen-1-ol were previously reported as the sex pheromone in New York strains of the oblique-banded leafroller,Choristoneura rosaceana (Harris), and (E)-11-tetradecen-1-ol was tentatively identified in female tip extracts. For Okanagan Valley strains ofC. rosaceana, an additional component, (Z)-11-tetradecenal, was identified from female tip extracts by split-less capillary gas-liquid chromatography and mass spectroscopy and was strongly stimulatory in electroantennogram studies. In field tests, 3 mg of 96.521.5 (Z)-11-tetradecen-1-yl acetate, (E)-11-tetradecen-1-yl acetate, and (Z)-11-tetradecen-1-ol (containing approx. 1%E isomer) was not as attractive as female-baited traps, and significant numbers of European leafrollerArchips rosanus L. were attracted. The above blend with 1% (Z)-11-tetradecenal added was significantly more attractive than traps baited with femaleC. rosaceana, butA. rosanus males were still attracted. Increased percentages of (Z)-11-tetradecenal up to 4% caused increased catches ofC. rosaceana and decreased catches ofA. rosanus. Low amounts of (E)-11-tetradecen-1-ol and (E)-11-tetradecenal male also contribute to increased specificity of the synthetic pheromone blend toC. rosaceana.Lepidoptera: Tortricidae.Contribution No. 638, Agriculture Canada, Research Station, Summerland, British Columbia, Canada.     

Amino Alcohol Acrylonitriles as Activators of the Aryl Hydrocarbon Receptor Pathway: An Unexpected MTT Phenotypic Screening Outcome

Lead (Z)-N-(4-(2-cyano-2-(3,4-dichlorophenyl)vinyl)phenyl)acetamide, 1 showed MCF-7 GI₅₀=30 nM and 400-fold selective c.f. MCF10A (normal breast tissue). Acetamide moiety modification ( 13 a - g ) to introduce additional hydrophobicity was favoured with MCF-7 breast cancer cell activity enhanced at 1.3 nM. Other analogues were potent against the HT29 colon cancer cell line at 23 nM. Textbook SAR data was observed in the MCF-7 cell line, in an MTT assay, via the ortho ( 17 a ), meta ( 17 b ) and para ( 13 f ). The amino alcohol -OH moiety was pivotal, but no stereochemical preference noted. But, these data did not fit our homology modelling expectations. Aberrant MTT ((3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl-tetrazolium bromide) screening results and metabolic interference confirmed by sulforhodamine B (SRB) screening. Interfering analogues resulted in 120 and 80-fold CYP1A1 and CYP1A2 amplification, with no upregulation of SULT1A1. This is consistent with activation of the AhR pathway. Piperidine per-deuteration reduced metabolic inactivation. 3-OH / 4-OH piperidine analogues showed differential MTT and SRB activity supporting MTT assay metabolic inactivation. Data supports piperidine 3-OH, but not the 4-OH, as a CYP substrate. This family of β-amino alcohol substituted 3,4-dichlorophenylacetonitriles show broad activity modulated via the AhR pathway. By SRB analysis the most potent analogue was 23 b , (Z)-3-(4-(3-(4-phenylpiperidin-1-yl)-2-hydroxypropoxy)phenyl)-2-(3,4-dichlorophenyl)-acrylonitrile.     

Synthesis of Bitopic Ligands as Potent Dopamine D2 Receptor Agonists

In this study, we designed and synthesized twelve bitopic ligands as dopamine D₂ receptor (D₂R) agonists. The forskolin-induced cAMP accumulation assay revealed that all the finial compounds are able to activate D₂R. Furthermore, bitopic ligand N-((trans)-4-(((2,3-dihydro-1H-inden-2-yl)(propyl)amino)methyl)cyclo-hexyl)-1H-pyrrolo[2,3-b]pyridine-2-carboxamide ( 11 b ) showed 21-fold higher potency than lead compound propyl aminoindane ( 2 ) and 17-fold higher subtype selectivity for D₂R over D₄R, indicating that the optimal length of spacer affects the D₂R functionality. Molecular modeling study exhibited that 11 b formed an electrostatic interaction and two H-bonds with amino acid Asp114, which contributes significantly to the D₂R functional activity. Taken together, we discovered a bitopic ligand 11 b as potent D₂R agonist, which may be used as a tool compound for further study.     

Enantiomerically Pure Quinoline-Based κ-Opioid Receptor Agonists: Chemoenzymatic Synthesis and Pharmacological Evaluation

Racemic _K-opioid receptor (KOR) agonist 2-(3,4-dichlorophenyl)-1-[(4aRS,8SR,8aSR)-8-(pyrrolidin-1-yl)-3,4,4a,5,6,7,8,8a-octahydroquinolin-1(2H)-yl]ethan-1-one ((±)- 4 ) was prepared in a diastereoselective synthesis. The first key step of the synthesis was the diastereoselective hydrogenation of the silyl ether of 1,2,3,4-tetrahydroquinoin-8-ol ((±)- 9 ) to afford cis,cis-configured perhydroquinoline derivative (±)- 10 . Removal of the TBDMS protecting group led to a β-aminoalcohol that reacted with SO₂Cl₂ to form an oxathiazolidine. Nucleophilic substitution with pyrrolidine resulted in the desired cis,trans-configured perhydroquinoline upon inversion of the configuration. In order to obtain enantiomerically pure KOR agonists 4 (99.8 % ee) and ent- 4 (99.0 % ee), 1,2,3,4-tetrahydroquinolin-8-ols (R)- 8 (99.1 % ee) and (S)- 8 (98.4 % ee) were resolved by an enantioselective acetylation catalyzed by Amano lipase PS-IM. The absolute configuration was determined by CD spectroscopy. The 4aR,8S,8aS-configured enantiomer 4 showed sub-nanomolar KOR affinity (K_i=0.81 nM), which is more than 200 times higher than the KOR affinity of its enantiomer ent- 4 . In the cAMP assay and the Tango β-arrestin-2 recruitment assay, 4 behaved as a KOR agonist. Upon incubation of human macrophages, human dendritic cells, and mouse myeloid immune cells with 4 , the number of cells expressing co-stimulatory receptor CD86 and proinflammatory cytokines interleukin 6 and tumor necrosis factor α was significantly reduced; this indicates the strong anti-inflammatory activity of 4 . The anti-inflammatory effects correlated well with the KOR affinity: (4aR,8S,8aS)- 4 was slightly more potent than the racemic mixture (±)- 4 , and the distomer ent- 4 was almost inactive.     

A Multi-step Virtual Screening Protocol for the Identification of Novel Non-acidic Microsomal Prostaglandin E2 Synthase-1 (mPGES-1) Inhibitors

Microsomal prostaglandin E₂ synthase-1 (mPGES-1) is a potential therapeutic target for the treatment of inflammatory diseases and certain types of cancer. To identify novel scaffolds for mPGES-1 inhibition, we applied a virtual screening (VS) protocol that comprises molecular docking, fingerprints-based clustering with diversity-based selection, protein–ligand interactions fingerprints, and molecular dynamics (MD) simulations with molecular mechanics Poisson–Boltzmann surface area (MM-PBSA) calculations. The hits identified were carefully analyzed to ensure the selection of novel scaffolds that establish stable interactions with key residues in the mPGES-1 binding pocket and inhibit the catalytic activity of the enzyme. As a result, we discovered two promising chemotypes, 4-(2-chlorophenyl)-N-[(2-{[(propan-2-yl)sulfamoyl]methyl}phenyl)methyl]piperazine-1-carboxamide ( 6 ) and N-(4-methoxy-3-{[4-(6-methyl-1,3-benzothiazol-2-yl)phenyl]sulfamoyl}phenyl)acetamide ( 8 ), as non-acidic mPGES-1 inhibitors with IC₅₀ values of 1.2 and 1.3 μm , respectively. Minimal structural optimization of 8 resulted in three more compounds with promising improvements in inhibitory activity (IC₅₀: 0.3–0.6 μm ). The unprecedented chemical structures of 6 and 8 , which are amenable to further derivatization, reveal a new and attractive approach for the development of mPGES-1 inhibitors with potential anti-inflammatory and anticancer properties.     

The Phenoxyalkyltriazine Antagonists for 5-HT6 Receptor with Promising Procognitive and Pharmacokinetic Properties In Vivo in Search for a Novel Therapeutic Approach to Dementia Diseases

Among the serotonin receptors, one of the most recently discovered 5-HT₆ subtype is an important protein target and its ligands may play a key role in the innovative treatment of cognitive disorders. However, none of its selective ligands have reached the pharmaceutical market yet. Recently, a new chemical class of potent 5-HT₆ receptor agents, the 1,3,5-triazine-piperazine derivatives, has been synthesized. Three members, the ortho and meta dichloro- (1,2) and the unsubstituted phenyl (3) derivatives, proved to be of special interest due to their high affinities (1,2) and selectivity (3) toward 5-HT₆ receptor. Thus, a broader pharmacological profile for 1–3, including comprehensive screening of the receptor selectivity and drug-like parameters in vitro as well as both, pharmacokinetic and pharmacodynamic properties in vivo, have been investigated within this study. A comprehensive analysis of the obtained results indicated significant procognitive-like activity together with beneficial drug-likeness in vitro and pharmacokinetics in vivo profiles for both, (RS)-4-[1-(2,3-dichlorophenoxy)propyl]-6-(4-methylpiperazin-1-yl)-1,3,5-triazin-2-amine (2) and (RS)-4-(4-methylpiperazin-1-yl)-6-(1-phenoxypropyl)-1,3,5-triazin-2-amine (3), but insensibly predominant for compound 2. Nevertheless, both compounds (2 and 3) seem to be good Central Nervous System drug candidates in search for novel therapeutic approach to dementia diseases, based on the 5-HT₆ receptor target.     

Field Trapping of Tomato Moth, Tuta absoluta with Pheromone Traps

Field evaluations demonstrate that the addition of the minor pheromone component (3E,8Z)-tetradecadien-1-yl acetate to the major component (3E,8Z,11Z)-tetradecatrien-1-yl acetate does not significantly increase the trap catches of Tuta absoluta males in the field. The triene acetate itself is highly attractive, catching about 869 ± 255 males per trap in three consecutive nights. The addition of two isomers of the minor component (3E,8Z)-tetradecadien-1-yl acetate, (3E,11Z)-tetradecadienyl-yl acetate and (8Z,11Z)-tetradecadien-1-yl acetate, to the major component (3E,8Z,11Z)-tetradecatrien-1-yl acetate also did not significantly alter the number of the males caught in the traps.     

Sex pheromone components of the obliquebanded leafroller moth,Choristoneura rosaceana

Previously, (Z)-11-tetradecen-1-yl acetate was reported as the sex pheromone of the obliquebanded leafroller,Choristoneura rosaceana (Harris). A mixture of 92% (Z)-11-tetradecen-1-yl acetate and 8% (E)-tetradecen-1-yl acetate has been reported as an attractant for this insect. (E)-11-tetradecen-1-yl acetate and (Z)-11-tetradecen-1-ol have now been isolated and identified from female tip extracts and shown to be behaviorally active; in addition, there is some evidence for the presence of (E)-11-tetradecen-1-ol in these extracts. TheZE ratio for both the acetates and the alcohols in these tip extracts was about 982; the proportion of alcohols was rather variable, but the acetates always predominated. Maximum trap catches fn the field during the course of this study were obtained with 5 mg of 955 (Z)(E)-11-tetradecen-1-yl acetates containing 0.5–10% (Z)-11-tetradecen-1-ol (approx. 1%Eisomer) in polyethylene caps. No evidence was found for the presence of (Z)-11-tetradecenal in female tip extracts, and this compound was found to be ineffective in increasing trap catches.Lepidoptera: Tortricidae: Tortricinae.This research was supported in part by the Rockefeller Foundation, and by NSF Grant No. GB-38020.     

Female sex pheromone of the Yunnan pine caterpillar moth Dendrolimus houi: first (E,Z)-isomers in pheromone components of Dendrolimus spp

The Yunnan pine caterpillar Dendrolimus houi Lajonquière is a serious defoliator of coniferous forests in southwestern China. Gas chromatography–electroantennography (GC–EAG) analyses of extracts of female sex pheromone glands of D. houi moths revealed the presence of three compounds eliciting antennal responses. These were identified as (5E,7Z)-5,7-dodecadien-1-ol (E5,Z7-12:OH), (5E,7Z)-5,7-dodecadien-1-yl acetate (E5,Z7-12:OAc), and (5E,7Z)-5,7-dodecadienal (E5,Z7-12:Ald) by comparison of their GC retention indices, mass spectra, and EAG activities with those of synthetic standards. Average amounts of E5,Z7-12:OH, E5,Z7-12:OAc, and E5,Z7-12:Ald per calling virgin D. houi female were 14.7 ± 12.9 ng (± SD), 5.8 ± 5.4 ng, and 0.8 ± 1.4 ng, respectively, in a ratio of 100:39.7:5.6. These three components were also collected from the headspace of calling virgin female moths by solid-phase microextraction (SPME). In addition, trace quantities of (Z)-5-dodecen-1-ol (Z5-12:OH), (5Z,7E)-5,7-dodecadien-1-ol (Z5,E7-12:OH), (5E,7E)-5,7-dodecadien-1-ol (E5,E7-12:OH), (5Z,7E)-5,7-dodecadien-1-yl acetate (Z5,E7-12:OAc), (5Z,7Z)-5,7-dodecadien-1-yl acetate (Z5,Z7-12:OAc), and (5E,7E)-5,7-dodecadien-1-yl acetate (E5,E7-12:OAc) were tentatively identified in female pheromone gland extracts by selected ion monitoring GC-MS. Field trapping experiments showed that E5,Z7-12:OH, E5,Z7-12:OAc, and E5,Z7-12:Ald were essential for attraction of male D. houi moths. Traps baited with a 20:1:1 blend (alcohol/acetate/aldehyde) loaded on gray rubber septa were as effective as traps baited with virgin female moths. The optimum ratio of acetate to aldehyde was 1:1, and this ratio was more critical than the ratio of either compound to the alcohol. This represents the first example of (E,Z)-isomers in pheromone blends of Dendrolimus species.