Prof. Dr. Jocelyn Millerjocelyn.millar@ucr.edu

A BRIEF SCIENTIFIC ACCOUNT of

Presented By:

Jawwad Hassan MirzaStudent ID# 435108485Ph. D. Scholar (2nd Semester)College of Food and Agriculture SciencesKing Saud University, Riyadh, KSA

INTRODUCTION• Organic Chemist

– Insect semiochemistry– Chemical ecology

• Study of natural chemicals that mediate interactions between organisms

• Sex or aggregation pheromones (chemical signals) and cues from hosts or habitats– locate and recognize their preferred feeding and egg-laying sites.

• Synthesize newly discovered pheromone and kairomone structures• Biological control of exotic pests of eucalyptus, vibrational signaling in

true bugs and other insects

OBJECTIVES To gain insight into the role of chemical and other types of signals as

mediators of insect behavior To develop practical applications for pheromones, kairomones, and other

behavior-modifying chemicals

• Degrees– BSc Chemistry 1978 Simon Fraser University, B.C. Canada– PhD Organic Chemistry 1983 Simon Fraser University, B.C. Canada

• Awards– 2008 - Entomological Society of America, National Award for Excellence in Integrated Pest

Management.– 2008 - Entomological Society of America, Pacific Branch, Award for Excellence in Integrated Pest

Management– 2006 - Entomological Society of America Team IPM Award– 2006 - C.W. Woodworth Award, Pacific Branch of the Entomological Society of America– 2005-6 - President, International Society of Chemical Ecology– 2005 - Entomological Society of America, Pacific Branch, ESA Foundation Team Award in IPM– 2003 - Fellow, American Association for the Advancement of Science– 2001 - Entomological Society of America, Pacific Branch, Recognition Award in Entomology– 2001 - Entomological Society of America, Syngenta Crop Protection Recognition Award– 1996 - Japanese Government Research Award For Foreign Specialist

• Publications– About 240 mostly on identification, synthesis of Pheromones and their use in IPM Program

• Edited Books– K. Nakamuta and J.G. Millar (eds.) Chemical Ecology of Wood-boring Insects. Forestry and Forest

Products Research Institute, Tsukuba, Japan. 98 pp.– Cardé, R.T. and J.G. Millar. 2004. Advances in Insect Chemical Ecology. Cambridge University Press.– Haynes, K.F. and J.G. Millar. 1998. Methods in Chemical Ecology. Volume 2: Bioassay Methods.

Kluwer, NY.– Millar, J.G. and K.F. Haynes. 1998. Methods in Chemical Ecology. Volume 1: Chemical Methods.

Kluwer, NY.

RESEARCH INTERESTS

AGGREGATION & SEX PHEROMONES

1. IDENTIFICATION OF PHEROMONES

2. SYNTHESIS OF PHEROMONES

3. USE IN IPM PROGRAM

TARGET INSECT FAMILILES:

• HEMIPTERA• LEPIDOPTERA• COLEOPTERA• DIPTERA

1.1: IDENTIFICATION OF THE SEX PHEROMONE OF A PROTECTED SPECIES, THE SPANISH MOON MOTH GRAELLSIA ISABELLAE (LEPIDOPTERA: SATURNIIDAE).

• Sex attractant pheromones are highly sensitive and selective tools

• Only one reported case of pheromones

being used to monitor protected species

• Analyses of SPME wipe samples and

solvent extracts of dissected pheromone glands by GC-EAD

• Identification as the single component

(4E,6E,11Z)-hexadecatrienal.

• Lures loaded with this compound attracted male moths from populations of this species at a number of widely separated field sites

• The utility of pheromones in sampling for potentially endangered insect species.

Jocelyn G. Millar1,*, J. Steven McElfresh1, Carmen Romero1, Marta Vila2, Neus Mari-Mena2, and Carlos Lopez-Vaamonde. 2010. Identification of the Sex Pheromone of a Protected Species, the Spanish Moon Moth Graellsia isabellae (Lepidoptera: Saturniidae). J. Chem. Ecology 36, 923-932.

1.2: SEX PHEROMONE OF THE MIRID BUG PHYTOCORIS RELATIVUS

• Adult females 2:1 blend of hexyl acetate with (E)-2-octenyl butyrate

– Hexyl acetate from both sexes

– (E)-2-octenyl butyrate only by females.

• Adults anesthetized, cut in pieces and extract were analyzed

• Attraction of males increased with dose, with doses of 0.1 to 33 mg loaded on grey rubber septa.

• Attractiveness of rubber septum lures decreased quickly

with age due to the volatility of the two pheromone components.

Millar, J.G., R.E. Rice, and Q. Wang. 1997. Sex Pheromone of the Mirid Bug Phytocoris relativus Knight. J. Chem. Ecology 23:1743-1754.

by GC and GC-MS

1.3: IDENTIFICATION OF OVIPOSITION ATTRACTANTS FOR CULEX QUINQUEFASCIATUS FROM FERMENTED BERMUDA GRASS INFUSIONS

• Compounds isolated and identified from a fermented Bermuda glass infusion

• Fractionation by liquid chromatography (Phenol) (4-methylphenol) (4-ethylphenol) (Indole) (3-methylindole)

• A blend of the 5 compounds strongly stimulated oviposition, as did blends of any 4 of them.

• Only 3-methylindole consistently induced oviposition, in concentrations spanning 5 orders of magnitude

Millar, J. G., J. D. Chaney, and M. S. Mulla. 1992. Identification of Oviposition Attractants for Culex quinquefasciatus from Fermented Bermuda Grass Infusions. J. Amer. Mosq. Control Assoc. 8: 11-17.

1.4: SEX PHEROMONE COMPONENTS OF THE GEOMETRID MOTHS LOBOPHORA NIVIGERATAa AND EPIRRHOE SPERRYIb.

• b3Z,6Z,9Z-Nonadecatriene (3Z,6Z,9Z-19 : H) female sex pheromone component

• 3Z,6Z,9Z-18:H and 6Z,9Z-19:H no apparent

biological activity.

• Extracts of sex pheromone glands from female moths prepared by a 20-min pentane extraction of the terminal three or four abdominal segments.

• GC-EAD

• a3Z,6Z,9Z-21:H female sex pheromone component

• Attraction of male moths synergized by the addition of small amounts of 6Z,9Z-21:H to lures.

Millar, J. G., M. Giblin, D. Barton and E. W. Underhill. 1992. Sex Pheromone Components of the Geometrid Moths Lobophoranivigerata and Epirrhoe sperryi. J. Chem. Ecol. 18: 1057-1068.

2.1: STEREOSPECIFIC SYNTHESIS OF THE SEX PHEROMONE OF THE PASSIONVINE MEALYBUG, PLANOCOCCUS MINOR

• A short and completely stereospecific synthesis of (E)-2-isopropyl-5-methyl-2,4-hexadienyl acetate, the very recently identified sex pheromone of the passionvine mealybug Planococcus minor, is described.

• In the key step, CuI-catalyzed anti-addition of a Grignard reagent to a propargyllic alcohol intermediate gave the required trisubstituted alkene with 100% regio- and stereospecificity.

• The stereochemical purity of the pheromone is critically important because the (Z)-isomer is a powerful behavioral antagonist.

Jocelyn G. Millar. 2008. Stereospecific synthesis of the sex pheromone of the passionvine mealybug, Planococcus minor. Tetrahedron Letters 49:315-317.

2.2: SYNTHESIS OF THE SEX PHEROMONE OF THE OBSCURE MEALYBUG, THE FIRST EXAMPLE OF A NEW CLASS OF MONOTERPENOIDS

• A diastereoselective synthesis of (1R*,2R*,3S*)-1-acetoxymethyl-2,3,4,4-tetramethylcyclopentane, the sex pheromone

• of the obscure mealybug Pseudococcus viburni, is described. Key steps included the polyphosphoricacid-catalyzed cyclization of

• isobutyl methacrylate to form the core five-membered ring, and diastereoselective quenching of an enolate intermediate to give

• the thermodynamically less favored cis orientation of vicinal methyl groups in a cyclopentanoneintermediate.

Jocelyn G. Millar and Sharon L. Midland. Synthesis of the sex pheromone of the obscure mealybug, the first example of a new class of monoterpenoids. Tetrahedron Letters 48:6377-6379. Published online Aug 11-07, http://dx.doi.org/10.1016/j.tetlet.2007.06.169

2.3: (9Z)-9,13-TETRADECADIEN-11-YNAL, THE SEX PHEROMONE OF THE AVOCADO SEED MOTH,STENOMA CATENIFER

• The highly unsaturated aldehyde (9Z)-9,13-tetradecadien-11-ynal and the corresponding alcohol were

• identified as possible sex pheromone components of the avocado seed moth, Stenoma catenifer. The aldehyde

• as a single component attracted more male moths than caged virgin female moths, and addition of

• the analogous alcohol and/or acetate decreased attraction. A stereospecific synthesis of the pheromone is

• described.Jocelyn G. Millar, Mark Hoddle, J. Steven McElfresh, Yunfan Zou, and Christina Hoddle. 2008. (9Z)-9,13-Tetradecadien-11-ynal, the sex

pheromone of the avocado seed moth,Stenoma catenifer. Tetrahedron Lett. 49: 4820-4823. Published online June 13-08 http://dx.doi.org/10.1016/j.tetlet.2008.06.019

2.4: METHYL (2E,4Z,6Z)-DECA-2,4,6-TRIENOATE, A THERMALLY UNSTABLE, SEX-SPECIFIC COMPOUND FROM THE STINK BUG THYANTA PALLIDOVIRENS

• Sexuallymaturernaletinkbuga, Thyuntupallidovirwrs,rekasea rnsle-specificblendof

• volatiks, includingseveralseaquiterpenehydrowbo33s,andthe highlyconjugatedestermethyl

• (2E,4Z,6Z)4eca-2,4,6-trienoate 1. Thelattereompormdwassynthesize andfoundtorearrange

• underGCconditionsvia a 1,7aigmatropicrearrangemen

Millar, J.G. 1997. Methyl (2E,4Z,6Z)-deca-2,4,6-trienoate, a Thermally Unstable, Sex-Specific Compound from the Stink Bug Thyanta pallidovirens. Tetrahedron Letters 38:7971-7972.

3.1: FIELD TRIALS OF AGGREGATION PHEROMONES FOR THE STINK BUGS CHLOROCHROA UHLERI AND CHLOROCHROA SAYI(HETEROPTERA: PENTATOMIDAE).

• Cylindrical Screen Traps baited male-produced pheromone,

methyl (E)-6-2,3-dihydrofarnesoate

• Host Plant odor volatiles + pheromones = no significant

• Combining the pheromone of two sympatric stink bug species decreased trap captures– Chlorochroa sayi, Euschistus conspersus

• With C. sayi, all three of the male-specific pheromone compounds required for optimal attraction.

• With C. uhleri, adults of both sexes attracted to pheromone lures in approximately equal numbers.

• Lures loaded with high amount of methyl (E)-6-2,3-dihydrofarnesoate to obtain the best trap catch

• The pheromone components of C. uhleri or E. conspersus not interfered with the attractiveness of the C. sayi pheromone in lures containing a blend of all three pheromones.

Jocelyn G. Millar, Heather M. McBrien, and J. Steven McElfresh. 2010. Field Trials of Aggregation Pheromones for the Stink Bugs Chlorochroauhleri and Chlorochroa sayi(Heteroptera: Pentatomidae). Journal of Economic Entomology 103:1603-1612.

3.2: PENTATOMID BUG PHEROMONES IN IPM: POSSIBLE APPLICATIONS AND LIMITATIONS• Male-produced pheromone components have been identified from several

species of

• agriculturally important stink bugs

• T. pallidovirens = thermally unstable ester, methyl (2E,4Z,6Z)-decatrienoate– Pheromone attracted only females, as well as a specialist predator, the sphecid wasp Astata

occidentalis.

• A. hilare = two isomers, (4S)-cis- and (4S)-trans-(Z)-bisabolene epoxides(19:1)– Both compounds were required for attraction of females.

• Male C. sayi = methyl geranate (methyl citronellate and methyl dihydrofarnesoate)– Only methyl geranate appeared to be required for attraction.

• Males of C. uhleri and C. ligata = methyl dihydrofarnesoateas (other minors)– Only methyl dihydrofarnesoate appeared to be required for attraction of females.

• Relatively low numbers of bugs caught = inefficient trap designs.

• Phytophagous stink bugs communicate over shorter distances– Substrate-borne vibrational signals, critically important in attracting bugs right up to pheromone

sources.

Millar, J.G., H. L. McBrien, H.-Y. Ho, R. E. Rice, E. Cullen, F. G. Zalom, and A. Cokl. Pentatomid Bug Pheromones in IPM: Possible Applications and Limitations. 2002. Bulletin of the International Organization of Biological Control, Pheromone Working Group. Vol. 25:1-11. Published on the

Web at http://phero.net/iobc/samos/bulletin/millar.pdf .

3.3: DEVELOPMENT AND OPTIMIZATION OF METHODS FOR USING SEX PHEROMONE FOR MONITORING VINE MEALYBUG IN CALIFORNIA VINEYARDS

• Lavandulyl senecioate (synthetic)– As attractive to male mealybugs as the insect-produced (S)-

enantiomer

• Lavandulol, found in extracts from virgin females– antagonized attraction of males at higher doses.

• Rubber septum lures (10-1,000 gm doses) – Were equally attractive

• Lures remained attractive for at least 12 wks under field conditions.

• Delta traps were more effective than double-sided sticky cards– minimized captures of nontarget insects.

• Pheromone-baited traps had an effective range of at least 50 m. • Comparison of visual sampling methods and sampling of males

with pheromone-baited traps– significantly correlated

Millar, J.G., K. M. Daane, J. S. McElfresh, J. Moreira, R. Malakar-Kuenen, M. Guillen, and W. J. Bentley. 2002. Development and Optimization of Methods for Using Sex Pheromone for Monitoring Vine Mealybug in California Vineyards. J. Economic Entomol. 95: 706-714.

3.4: TECHNOLOGICAL PROBLEMS ASSOCIATED WITH USE OF INSECT PHEROMONES IN INSECT MANAGEMENT

• Sex pheromone components were identified for many of the major lepidopteran pests of concern to agriculture a number of years ago. However, despite intensive efforts, implementation of large-scale, effective, and reliable insect control strategies based on pheromones remains elusive for many pest species. For example, pheromone-based mating disruption of codling moth still suffers from problems which have prevented the widespread adoption of mating disruption for control of this world-wide pest, in spite of continuous research efforts spanning 20 years. During this time, our knowledge and understanding of possible causes of unsatisfactory performance of pheromones in insect pest management has increased substantially. It is now commonly acknowledged that site characteristics such as the slope of a site and edge effects associated with adjacent cropping systems can contribute to the failure of mating disruption. However, field researchers have focused less attention on technological factors such as pheromone dispenser performance, pheromone purity, and pheromone degradation under field conditions. Both field researchers and growers are usually dependent on commercial outlets for supplies of both pheromone and dispensers, but the pressure on commercial suppliers to market product may result in products being released before adequate efficacy tests under field conditions have been conducted. In this paper, we will summarize results from several studies which examined pheromone dispenser characteristics, pheromone purity, and pheromone degradation under field conditions. The results will be discussed in terms of the performance of several pheromone products in different agricultural systems.

Jocelyn G. Millar, J. Steven McElfresh, and Richard E. Rice. 1997. Technological problems associated with use of insect pheromones in insect management. IOBC wprs Bulletin 20: 19-25.

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