Ecotoxicological effect of insecticides on Ooencyrtus nezarae (Hymenoptera: Encyrtidae) reared from refrigerated and unrefrigerated Riptortus pedestris (Hemiptera: Alydidae) host

Due to increased field occurrence of Riptortus pedestris (Fabricius) (Hemiptera: Alydidae) on various crops including soybean, persimmon and apple in recent years in Korea, demand for insecticide applications to control the stink bug has increased. Acute toxicity of eight pesticides on Ooencyrtus nezarae Ishii (Hymenoptera: Encyrtidae), a major egg parasitoid of R. pedestris, was compared in the laboratory. Fenitrothion, spinosad, cyfluthrin, etofenprox and carbosulfan caused 100% mortality of O. nezarae within 24 hours by topical application or exposure to residue. Fenitrothion was also highly toxic to the parasitoid when ingested orally. In a previous study, release of refrigerated inviable eggs of R. pedestris was found to increase field parasitism; therefore, we evaluated the sublethal effect of fenitrothion when O. nezarae parasitised refrigerated or unrefrigerated host eggs. Although parasitism rates on both kinds of eggs significantly decreased when O. nezarae were provided with host eggs sprayed with fenitrothion, no difference in parasitism rate, adult emergence, sex ratio, development time and longevity of O. nezarae was found between the refrigerated or unrefrigerated host eggs when the insecticide was treated either before or after oviposition. There was no significant sublethal effect when parasitised host eggs were treated with the insecticide. From these results, all the insecticides tested showed high, acute toxicity against O. nezarae with relatively lower sublethal effects. Refrigeration of host eggs did not affect the susceptibility of O. nezarae to insecticides.     

Biological attributes of Ooencyrtus nezarae Ishii (Hymenoptera: Encyrtidae) reared on refrigerated eggs of Riptortus pedestris (= clavatus) Fabricius (Hemiptera: Alydidae)

Storing host eggs at low temperatures has been used to mass rear parasitoids of stink bugs, including Riptortus pedestris Fabricius (Hemiptera: Alydidae), a major soybean pest in Korea and Japan. However, no information on the effect of cold storage on parasitization by Ooencyrtus nezarae Ishii (Hymenoptera: Encyrtidae), one of the major parasitoids of R. pedestris, has been published. In this study, we examined biological attributes, including parasitism rate, development time, sex ratio, adult size, and longevity, of O. nezarae when the adult parasitoids were provided with host eggs refrigerated for 0, 15, 30, 60, and 120 days at 2.0 °C. None of the attributes of the first or second generation of O. nezarae was negatively affected by host egg refrigeration up to 30 days. In addition, O. nezarae could parasitize refrigerated host eggs successfully for the first four days of post-refrigeration period when they were kept at 26.3 °C and 78.7% RH conditions. Therefore, refrigeration of R. pedestris eggs can be a good method to mass rear O. nezarae.     

Kinetic study of the photochemical changes of (ZZ)-bilirubin IX alpha bound to human serum albumin. Demonstration of (EZ)-bilirubin IX alpha as an intermediate in photochemical changes from (ZZ)-bilirubin IX alpha to (EZ)-cyclobilirubin IX alpha.

The present study was performed to elucidate why the photochemical reaction of (ZZ)-bilirubin bound to human serum albumin is singularly selective, and only one of the two (EZ)- and (ZE)-bilirubins, the (ZE)-isomer, is produced. In a kinetic study of the photochemical reaction in vitro, the sum of the relative rate constants of photochemical transformation of (EZ)-bilirubin into both (EZ)-cyclobilirubin and (ZZ)-bilirubin, with a significant preference for the former, was proved to be considerably larger than that of the transformation of (ZZ)-bilirubin into (EZ)-bilirubin. Therefore only one of the geometrical isomers, namely (ZE)-bilirubin, is apparently formed. It was concluded that (EZ)-bilirubin photochemically undergoes (EZ)-cyclization, i.e. structural photoisomerization, while bound to its high-affinity site on human serum albumin, and is an intermediate in the transformation of (ZZ)-bilirubin into (EZ)-cyclobilirubin.     

Differential response of male and female emerald ash borers (Col., Buprestidae) to (Z)‐3‐hexenol and manuka oil

We conducted two trapping experiments in green ash plantations in Ontario, Canada to compare the response of the emerald ash borer (EAB), Agrilus planipennis, to (Z)‐3‐hexenol (Z3‐6:OH) and manuka oil. In the first experiment, Z3‐6:OH (7.6 mg/day) in purple prism traps hung 1.5 m above ground caught significantly more EAB than the unbaited controls, with male catches significantly greater than female catches at two locations. Manuka oil (50 mg/day) attracted equal numbers of males and females but they were significantly greater than the controls at only one location. Adding (Z)‐3‐hexenal or (Z)‐3‐hexenyl acetate in binary or ternary combinations with Z3‐6:OH did not enhance trap catch. In the second experiment, Z3‐6:OH released at two rates (7.6 or 80 mg/day) in light green prism traps placed in the ash canopy also caught significantly more males than females and more males than the unbaited controls or manuka oil‐baited traps. Manuka oil had no significant effect on catches relative to the controls. Combining Z3‐6:OH with manuka oil did not enhance catches of EAB. We conclude that there was a strong male‐biased EAB response to Z3‐6:OH lures, whereas manuka oil, when effective, attracted both sexes equally. Z3‐6:OH in light green prism traps in the canopy is an effective lure for EAB, particularly for males.     

Development and optimisation of a sex pheromone lure for monitoring populations of saddle gall midge,Haplodiplosis marginata

Saddle gall midge, Haplodiplosis marginata (von Roser) (Diptera: Cecidomyiidae), is a sporadic pest of cereals in Northern and Central Europe and is of increasing importance in the UK. Recently, the major component of the sex pheromone produced by adult female H. marginata was reported to be 2‐nonyl butyrate. The importance of absolute configuration on attractiveness, the effects on trap catches of the addition of minor pheromone components, dispenser type, and pheromone loading are described in the development of an optimised pheromone lure with which to trap H. marginata males. In analyses of volatiles collected from virgin female H. marginata by gas chromatography (GC) coupled with electroantennographic recording (EAG) from the antenna of a male H. marginata, two EAG responses were observed. Analyses by coupled GC‐mass spectrometry (MS) indicated these were due to 2‐nonyl butyrate and a trace amount (1%) of 2‐heptyl butyrate. A similar trace amount of 2‐nonanol was detected in GC‐MS analyses but this compound did not elicit an EAG response when the synthetic compound was tested, whereas the other two compounds did. These three compounds were not observed in collections of volatiles made from male H. marginata. The 2‐nonyl butyrate was shown to be the (R)‐enantiomer. In field trapping tests (R)‐2‐nonyl butyrate was at least 10× more attractive to male H. marginata than the racemic compound, and the (S)‐enantiomer was unattractive. Addition of the potential minor components individually or together at the naturally occurring ratios did not increase or reduce the attractiveness of the lure. Polyethylene vials and rubber septa were equally effective as pheromone dispensers, lasting for at least 5 weeks in the field in the UK, although laboratory tests indicated release from the former was more uniform and more likely to last longer in the field. Increasing loading of pheromone in the dispenser increased attractiveness. Traps baited with polyethylene vials containing 0.5 mg of (R)‐2‐nonyl butyrate are recommended for monitoring H. marginata and these are far more sensitive than water or sticky traps currently used for monitoring this pest.     

Development of 2‐phenylethanol plus acetic acid lures to monitor obliquebanded leafroller (Lepidoptera: Tortricidae) under mating disruption

We evaluated the effectiveness of 2‐phenylethanol (PET) in combination with acetic acid (AA) as a binary lure for monitoring male and female obliquebanded leafroller, Choristoneura rosaceana (Harris). Studies were conducted in apple, Malus domestica Borkhausen, orchards treated with or without sex pheromone dispensers for mating disruption (MD). Open polypropylene vials, closed membrane cups, and rubber septa loaded with AA and/or PET in varying amounts were first evaluated in a series of trapping experiments. Membrane cups loaded with 800 mg of PET were as effective as 10‐mg septa, but longer lasting, and were comparable to the open vials. A membrane cup AA lure was effective in tests, but further work is needed to increase its release rate and extend its activity. Catches of codling moth, Cydia pomonella (L.), and C. rosaceana were unaffected by combining PET with (E,E)‐8,10‐dodecadien‐1‐ol, the sex pheromone of codling moth, pear ester, (E,Z)‐2,4‐ethyl‐decadienoate and AA lures. Adding (E)‐4,8‐dimethyl‐1,3,7‐nonatriene to this blend to enhance codling moth catch significantly reduced catches of C. rosaceana. PET + AA was a more attractive binary lure than AA plus phenylacetonitrile (PAN) for C. rosaceana. The addition of PET or PAN to traps already baited with the sex pheromone of C. rosaceana significantly reduced male catches. Traps baited with PET + AA placed in blocks not treated with MD caught significantly fewer C. rosaceana than traps baited with sex pheromone. In comparison, sex pheromone‐baited traps in MD blocks caught ≤1 male moth per season which was significantly lower than total moth (>10) or female moth (≥3) catch in these blocks with PET + AA. A high proportion (>70%) of trapped females were mated in both untreated and MD‐treated orchards. Further refinement of this binary, bisexual lure using membrane cup technology may allow the establishment of action thresholds and improve management timings for C. rosaceana.     

Population parameters and growth of Riptortus pedestris (Fabricius) (Hemiptera: Alydidae) under elevated CO2 concentrations

We evaluated the direct effects of three different CO₂ concentrations (400, 600 and 1,000 ppm) on the population parameters and growth of the bean bug, Riptortus pedestris, while being fed on soybean. The raw life history data from R. pedestris was analyzed using an age‐stage, two‐sex life table to take the viable development rate among individuals into account. Based on the age‐stage, two‐sex life table analysis, the population projections of R. pedestris provide the stage structure and variability of the population growth under different CO₂ treatments. Our results showed significantly shorter immature durations and higher pre‐adult survival rate under elevated CO₂ (1,000 ppm) than those under ambient CO₂ (400 ppm). The population of R. pedestris reared under elevated CO₂ conditions showed higher intrinsic and finite rates of increase but a lower mean generation time than R. pedestris reared under ambient CO₂ conditions. Our results show the population parameters and growth of R. pedestris are influenced by increased CO₂ relative to ambient CO₂ treatment. Further studies on the long‐term direct effects of different CO₂ levels on R. pedestris are essential to understand their population dynamics and to establish appropriate management strategies.     

Identification and field evaluation of (E)‐11,13‐tetradecadienal as sex pheromone of the strawberry tortrix (Acleris comariana)

The strawberry tortrix (Acleris comariana Lienig and Zeller) (Lepidoptera: Tortricidae), is a major pest of strawberry in Denmark and southern Sweden. Chemical and electrophysiological analyses revealed a single compound, (E)‐11,13‐tetradecadienal (E11,13‐14:Ald), in gland extracts of females eliciting a strong antennal response in conspecific males. Also (Z)‐11,13‐tetradecadienal (Z11,13‐14:Ald) was found to be antennally active, but not detected in gland extracts. The corresponding alcohol and acetate of E11,13‐14:Ald, which are biologically active in other Acleris species, were not produced by females and did not trigger electrophysiological response in males. Trapping experiments at a commercial strawberry farm in southern Sweden showed that E11,13‐14:Ald and Z11,13‐14:Ald, alone or in combination, attracted large numbers of males. Trap catches increased with increasing dose of E11,13‐14:Ald, with traps baited with 100 µg and 1,000 µg being most attractive. Our results confirm the widespread use of E11,13‐14:Ald as a key sex pheromone component in the genus Acleris. The identification of a highly attractive sex pheromone is a first step in developing pheromone‐based methods for monitoring and control of A. comariana in European strawberry production.     

Purification of glutathione S‐transferase enzyme from quail liver tissue and inhibition effects of (3aR,4S,7R,7aS)‐2‐(4‐((E)‐3‐(aryl)acryloyl)phenyl)‐3a,4,7,7a‐tetrahydro‐1H‐4,7‐methanoisoindole‐1,3(2H)‐dione derivatives on the enzyme activity

The use of quail meat and eggs has made this animal important in recent years, with its low cost and high yields. Glutathione S‐transferases (GST, E.C.2.5.1.18) are an important enzyme family, which play a critical role in detoxification system. In our study, GST was purified from quail liver tissue with 47.88‐fold purification and 12.33% recovery by glutathione agarose affinity chromatography. The purity of enzyme was checked by SDS‐PAGE method and showed a single band. In addition, inhibition effects of (3aR,4S,7R,7aS)‐2‐(4‐((E)‐3‐(aryl)acryloyl)phenyl)‐3a,4,7,7a‐tetrahydro‐1H‐4,7methanoisoindole‐1,3(2H)‐dion derivatives ( 1a–g ) were investigated on the enzyme activity. The inhibition parameters (IC₅₀ and K_i values) were calculated for these compounds. IC₅₀ values of these derivatives ( 1a–e ) were found as 23.00, 15.75, 115.50, 10.00, and 28.75 μM, respectively. K_i values of these derivatives ( 1a–e ) were calculated in the range of 3.04 ± 0.50 to 131.50 ± 32.50 μM. However, for f and g compounds, the inhibition effects on the enzyme were not found.     

In vitro rearing of Ooencyrtus nezarae (Hymenoptera: Encyrtidae), an egg parasitoid of Riptortus pedestris (Hemiptera: Alydidae)

Ooencyrtus nezarae Ishii (Hymenoptera: Encyrtidae) is a polyphagous egg parasitoid of various true bugs, including Riptortus pedestris (Fabricius) (Hemiptera: Alydidae), a major pest of soybean and fruit trees in northeastern Asia. This study was conducted to develop artificial host eggs containing insect haemolymph for mass rearing of O. nezarae. The haemolymph of Chinese oak silkworm (Antheraea pernyi Guérin-Méneville) pupae was found to be most suitable for artificial eggs for the complete development of O. nezarae. Among 764 parasitoid eggs laid in artificial eggs, 49.2% successfully developed to adult parasitoids. The developmental time in artificial eggs was delayed by 3–5 days relative to that observed in natural host eggs; however there was no significant difference in the length of hind tibia between adults that emerged from artificial and natural host eggs. Moreover, new generations that emerged from artificial eggs reproduced on all egg types offered (either natural or artificial eggs). We propose that the artificial eggs developed herein can therefore be an effective means for mass rearing O. nezarae.     

Interspecific larval competition between two egg parasitoids in refrigerated host eggs of Riptortus pedestris (Hemiptera: Alydidae)

In a previous study, we found that soybean fields could be supplemented with refrigerated eggs of Riptortus pedestris (Fabricius) (Hemiptera: Alydidae) to enhance parasitism. As a part of a study to evaluate the effect of host egg refrigeration on parasitism, host acceptance behavior and interspecific larval competition between Gryon japonicum (Ashmead) (Hymenoptera: Scelionidae) and Ooencyrtus nezarae Ishii (Hymenoptera: Encyrtidae) were studied in multiparasitized unrefrigerated and refrigerated eggs. O. nezarae showed complete host acceptance behavior when offered refrigerated host eggs that were preparasitized by G. japonicum. Adult emergence rate of O. nezarae was 43 and 74% when the interval between the first and second oviposition was 0 and 4 days, respectively, and was not different between refrigerated and unrefrigerated eggs. Refrigeration did not change host acceptance behavior of G. japonicum, but adult emergence declined from 80% in unrefrigerated eggs to 37% in refrigerated eggs that were pre-parasitized by O. nezarae on the same day. No negative effects of refrigeration on sex ratio, adult longevity, and adult size of the both parasitoids were found. Generally host egg refrigeration did not negatively affect host acceptance behavior of the both parasitoids on preparasitized eggs or larval competition between the two parasitoids in multiparasitized host eggs with exceptions in the development time and emergence rate of G. japonicum. Therefore, host egg refrigeration may not interrupt interactions between the parasitoid populations in the field.     

Efficacy of the pheromone (3Z)‐lactone and the host kairomone (3Z)‐hexenol at detecting early infestation of the emerald ash borer,Agrilus planipennis

The invasive emerald ash borer, Agrilus planipennis Fairmaire (Coleoptera: Buprestidae), is a major pest of ash trees, Fraxinus spp., in its introduced range in North America. Field studies were conducted to quantify the efficacy of traps baited with kairomone and pheromone lures for early detection of A. planipennis infestation. A trapping experiment demonstrated that green traps baited with the kairomone (3Z)‐hexenol detected at least one adult A. planipennis in 55.3% of plots with ‘nil to low’‐density infestations and in 100% of plots with ‘moderate to high’‐density A. planipennis infestations. Mean trap captures increased significantly with increasing infestation density. In terms of the optimal number of traps per plot, when one (3Z)‐hexenol‐baited trap was placed per plot, the trap detected populations in 62% of the plots with ‘low to moderate’‐density infestations through branch sampling. Detectability was increased to 82% when two traps were placed per plot. Finally, addition of female‐produced (3Z)‐lactone pheromone to traps significantly increased detection rates at both the trap and plot level, as compared with traps baited with the host volatile, (3Z)‐hexenol, alone (88 vs. 60%, respectively). Our results are the first to demonstrate the efficacy of baited green sticky traps for detecting low‐density A. planipennis infestations, particularly when the (3Z)‐lactone pheromone is used. This combination is therefore recommended for development of early‐detection protocols against A. planipennis.     

Synthesis by Ring‐Closing Alkyne Metathesis with Selective Hydrogenation,and Olfactory Comparison of (7E)‐ and (7Z)‐Cyclohexadec‐7‐enone (Aurelione®)

Both C?C‐bond isomers of cyclohexadec‐7‐enone ( 6 , Aurelione^®) were selectively synthesized via cyclohexadec‐7‐ynol ( 16 ) by ring‐closing alkyne metathesis of icosa‐2,18‐diyn‐9‐ol ( 15 ), employing an in situ‐formed catalyst from Mo(CO)₆ and 4‐(trifluoromethyl)phenol. Pyridinium chlorochromate (PCC) oxidation and subsequent Lindlar hydrogenation afforded the (7Z)‐configured isomer (7Z)‐ 6 , while hydrosilylation of the intermediate cyclohexadec‐7‐ynone ( 17 ), followed by desilylation, provided the (7E)‐configured cyclohexadec‐7‐enone ((7E)‐ 6 ). The substrate for the alkyne metathesis was prepared from cycloheptanone ( 7 ) by cycloaddition of chloromethylcarbene to its trimethylsilyl enol ether 8 , and subsequent ring enlargement of the adduct 9 under rearrangement to 2‐methylcyclooct‐2‐enone ( 10 ), which was subjected to Weitz? Scheffer epoxidation and Eschenmoser? Ohloff fragmentation to non‐7‐ynal ( 12 ). Its reaction with the Grignard reagent of 11‐bromoundec‐2‐yne ( 14 ), prepared from the corresponding alcohol 13 by Appel? Lee bromination, furnished the icosa‐2,18‐diyn‐9‐ol ( 15 ). While both isomers of cyclohexadec‐7‐enone ( 6 ) possess warm and powdery musk odors with tobacco‐type ambery accents, (7Z)‐ 6 is more animalic and waxy, whereas (7E)‐ 6 was found to be more floral, sweet, and hay‐like in tonality. Interestingly, however, with odor detection thresholds of 2.0 ng/l air and 2.3 ng/l air, respectively, both (7Z)‐ 6 and (7E)‐ 6 were found to be almost identical in their odor strength, with the (7Z)‐ 6 being only very slightly more powerful.     

Microbial production of conjugated γ‐linolenic acid from γ‐linolenic acid by Lactobacillus plantarum AKU 1009a

Aims: Optimal production conditions of conjugated γ‐linolenic acid (CGLA) from γ‐linolenic acid using washed cells of Lactobacillus plantarum AKU 1009a as catalysts were investigated. Methods and Results: Washed cells of Lact. plantarum AKU 1009a exhibiting a high level of CGLA productivity were obtained by cultivation in a nutrient medium supplemented with 0·03% (w/v) α‐linolenic acid as an inducer. Under the optimal reaction conditions with 13 mg ml^?1γ‐linolenic acid as a substrate in 5 ‐ml reaction volume, the washed cells [32% (wet cells, w/v) corresponding to 46 mg ml^?1 dry cells] as the catalysts produced 8·8 mg CGLA per millilitre reaction mixture (68% molar yield) in 27 h. The produced CGLA was a mixture of two isomers, i.e., cis‐6,cis‐9,trans‐11‐octadecatrienoic acid (CGLA1, 40% of total CGLA) and cis‐6,trans‐9,trans‐11‐octadecatrienoic acid (CGLA2, 60% of total CGLA), and accounted for 66% of total fatty acid obtained. The CGLA produced was obtained as free fatty acids adsorbed mostly on the surface of the cells of Lact. plantarum AKU1009a. Conclusion: The practical process of CGLA production from γ‐linolenic acid using washed cells of Lact. plantarum AKU 1009a was successfully established. Significance and Impact of the Study: We presented the first example of microbial production of CGLA. CGLA produced by the process is valuable for evaluating their physiological and nutritional effects, and chemical characteristics.     

Genetic manipulation of the γ‐aminobutyric acid (GABA) shunt in rice: overexpression of truncated glutamate decarboxylase (GAD2) and knockdown of γ‐aminobutyric acid transaminase (GABA‐T) lead to sustained and high levels of GABA accumulation in rice kernels

Gamma‐aminobutyric acid (GABA) is a non‐protein amino acid commonly present in all organisms. Because cellular levels of GABA in plants are mainly regulated by synthesis (glutamate decarboxylase, GAD) and catabolism (GABA‐transaminase, GABA‐T), we attempted seed‐specific manipulation of the GABA shunt to achieve stable GABA accumulation in rice. A truncated GAD2 sequence, one of five GAD genes, controlled by the glutelin (GluB‐1) or rice embryo globulin promoters (REG) and GABA‐T‐based trigger sequences in RNA interference (RNAi) cassettes controlled by one of these promoters as well, was introduced into rice (cv. Koshihikari) to establish stable transgenic lines under herbicide selection using pyriminobac. T₁ and T₂ generations of rice lines displayed high GABA concentrations (2–100 mg/100 g grain). In analyses of two selected lines from the T₃ generation, there was a strong correlation between GABA level and the expression of truncated GAD2, whereas the inhibitory effect of GABA‐T expression was relatively weak. In these two lines both with two T‐DNA copies, their starch, amylose, and protein levels were slightly lower than non‐transformed cv. Koshihikari. Free amino acid analysis of mature kernels of these lines demonstrated elevated levels of GABA (75–350 mg/100 g polished rice) and also high levels of several amino acids, such as Ala, Ser, and Val. Because these lines of seeds could sustain their GABA content after harvest (up to 6 months), the strategy in this study could lead to the accumulation GABA and for these to be sustained in the edible parts.     

Light emitting diode(LED)‐based trapping of the greenhouse whitefly (Trialeurodes vaporariorum)

Visual traps like yellow sticky card traps are used for monitoring and control of the greenhouse whitefly (Trialeurodes vaporariorum). However, reflected intensity (brightness) and hence, attractiveness depend on the ambient light conditions, and the colour (wavelength) might not fit with the sensitivity of whitefly photoreceptors. The use of light emitting diodes (LEDs) is a promising approach to increase the attractiveness, specificity and adaptability of visual traps. We constructed LED‐based visual traps equipped with blue and green high‐power LEDs and ultraviolet (UV) standard LEDs according to the putative spectral sensitivities of the insects' photoreceptors. In a series of small‐scale choice and no‐choice recapture experiments, the factors time of day as well as light intensity and light quality (colour) of LED traps were studied in terms of attractiveness compared to yellow traps without LEDs. Green LED traps (517 nm peak wavelength) were comparably attractive in no‐choice experiments but clearly preferred over yellow traps in all choice experiments. The time of day had a clear effect on the flight activity of the whiteflies and thereby on the trapping success. Blue LEDs (474 nm) suppressed the attractiveness of the light traps when combined with green LEDs suggesting that a yet undetected photoreceptor, sensitive for blue light, and an inhibiting interaction with the green receptor, might exist in T. vaporariorum. In choice experiments between LED traps emitting green light only or in combination with UV (368 nm), the green‐UV combination was preferred. In no‐choice night‐time experiments, UV LEDs considerably increased whitefly flight activity and efficacy of trapping. Most likely, the reason for the modifying effect of UV is the stimulating influence on flight activity. In conclusion, it seems that the use of green LEDs alone or in combination with UV LEDs could be an innovative option for improving attractiveness of visual traps.     

2‐(Undecyloxy)‐ethanol is a major component of the male‐produced aggregation pheromone of Monochamus sutor

The small white‐marmorated longicorn beetle, Monochamus sutor (L.) (Coleoptera: Cerambycidae), is widely distributed throughout Europe and Asia. It is a potential vector of the pine wood nematode, Bursaphelenchus xylophilus (Steiner et Buhrer) Nickle, the causal agent of the devastating pine wilt disease. Volatiles were collected from both male and female beetles after maturation feeding. In analyses of these collections using gas chromatography (GC) coupled to mass spectrometry, a single male‐specific compound was detected and identified as 2‐(undecyloxy)‐ethanol. In analyses by GC coupled to electroantennography the only consistent responses from both female and male antennae were to this compound. Trapping tests were carried out in Spain, Sweden, and China. 2‐(Undecyloxy)‐ethanol was attractive to both male and female M. sutor beetles. A blend of the bark beetle pheromones ipsenol, ipsdienol, and 2‐methyl‐3‐buten‐2‐ol was also attractive to both sexes in Spain and Sweden, and further increased the attractiveness of the 2‐(undecyloxy)‐ethanol. The host plant volatiles α‐pinene, 3‐carene, and ethanol were weakly attractive, if at all, in all three countries and did not significantly increase the attractiveness of the blend of 2‐(undecyloxy)‐ethanol and bark beetle pheromones. 2‐(Undecyloxy)‐ethanol is thus proposed to be the major, if not only, component of the male‐produced aggregation pheromone of M. sutor, and its role is discussed. This compound has been reported as a pheromone of several other Monochamus species and is another example of the parsimony that seems to exist among the pheromones of many of the Cerambycidae. Traps baited with 2‐(undecyloxy)‐ethanol and bark beetle pheromones should be useful for monitoring and control of pine wilt disease, should M. sutor be proven to be a vector of the nematode.     

Synthesis and Anticancer Activity of 3‐(Substituted Aroyl)‐4‐(3,4,5‐trimethoxyphenyl)‐1H‐pyrrole Derivatives

A series of 3‐(substituted aroyl)‐4‐(3,4,5‐trimethoxyphenyl)‐1H‐pyrrole derivatives were synthesized and determined for their anticancer activity against eleven cancer cell lines and two normal tissue cell lines using MTT assay. Among the synthesized compounds, compound 3f was the most potent compound against A375, CT‐26, HeLa, MGC80‐3, NCI‐H460 and SGC‐7901 cells (IC₅₀ = 8.2 – 31.7 μm ); 3g , 3n and 3a were the most potent compounds against CHO (IC₅₀ = 8.2 μm ), HCT‐15 (IC₅₀ = 21 μm ) and MCF‐7 cells (IC₅₀ = 18.7 μm ), respectively. Importantly, all the target compounds showed no cytotoxicity towards the normal tissue cell (IC₅₀ > 100 μm ). Thus, these compounds with the potent anticancer activity and low toxicity have potential for the development of new anticancer chemotherapy agents.     

Chromatographic profiles of tryptophan and kynurenine enantiomers derivatized with (S)‐4‐(3‐isothiocyanatopyrrolidin‐1‐yl)‐7‐(N,N‐dimethylaminosulfonyl)‐2,1,3‐benzoxadiazole using LC–MS/MS on a triazole‐bonded column

d ‐ and l ‐Tryptophan (Trp) and d ‐ and l ‐kynurenine (KYN) were derivatized with a chiral reagent, (S )‐4‐(3‐isothiocyanatopyrrolidin‐1‐yl)‐7‐(N,N‐dimethylaminosulfonyl)‐2,1,3‐benzoxadiazole (DBD‐PyNCS), and were separated enantiomerically by high‐performance liquid chromatography (HPLC) equipped with a triazole‐bonded column (Cosmosil HILIC) using tandem mass spectrometric (MS/MS) detection. Effects of column temperature, salt (HCO₂NH₄) concentration, and pH of the mobile phase in the enantiomeric separation, followed by MS detection of (S )‐DBD‐PyNCS‐d ,l ‐Trp and ‐d ,l ‐KYN, were investigated. The mobile phase consisting of CH₃CN/10 mM ammonium formate in H₂O (pH 5.0) (90/10) with a column temperature of 50–60 °C gave satisfactory resolution (R s) and mass‐spectrometric detection. The enantiomeric separation of d ,l ‐Trp and d ,l ‐KYN produced R s values of 2.22 and 2.13, and separation factors (α) of 1.08 and 1.08, for the Trp and KYN enantiomers, respectively. The proposed LC–MS/MS method provided excellent detection sensitivity of both enantiomers of Trp and KYN (5.1–19 nM).     

Emission analysis of Tb3+‐and Sm3+‐ion‐doped (Li2O/Na2O/K2O) and (Li2O + Na2O/Li2O + K2O/K2O + Na2O)‐modified borosilicate glasses

Four series of borosilicate glasses modified by alkali oxides and doped with Tb³⁺ and Sm³⁺ ions were prepared using the conventional melt quenching technique, with the chemical composition 74.5B₂O₃ + 10SiO₂ + 5MgO + R + 0.5(Tb₂O₃/Sm₂O₃) [where R = 10(Li₂O /Na₂O/K₂O) for series A and C, and R = 5(Li₂O + Na₂O/Li₂O + K₂O/K₂O + Na₂O) for series B and D]. The X‐ray diffraction (XRD) patterns of all the prepared glasses indicate their amorphous nature. The spectroscopic properties of the prepared glasses were studied by optical absorption analysis, photoluminescence excitation (PLE) and photoluminescence (PL) analysis. A green emission corresponding to the ⁵D₄ → ⁷F₅ (543 nm) transition of the Tb³⁺ ions was registered under excitation at 379 nm for series A and B glasses. The emission spectra of the Sm³⁺ ions with the series C and D glasses showed strong reddish‐orange emission at 600 nm (⁴G_5/2 →⁶H_7/2) with an excitation wavelength λ_exci = 404 nm (⁶H_5/2→⁴F_7/2). Furthermore, the change in the luminescence intensity with the addition of an alkali oxide and combinations of these alkali oxides to borosilicate glasses doped with Tb³⁺ and Sm³⁺ ions was studied to optimize the potential alkali‐oxide‐modified borosilicate glass.