Jerrold Meinwald

Jerrold Meinwald
Cornell University | CU · Department of Chemistry and Chemical Biology

Ph.D.

About

465
Publications
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14,544
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Publications

Publications (465)
Article
Full-text available
Species that sequester toxins from prey for their own defense against predators may exhibit population-level variation in their chemical arsenal that reflects the availability of chemically defended prey in their habitat. Rhabdophis tigrinus is an Asian snake that possesses defensive glands in the skin of its neck ('nuchal glands'), which typically...
Article
Full-text available
Chemical defenses are widespread among animals, and the compounds involved may be either synthesized from nontoxic precursors or sequestered from an environmental source. Defensive sequestration has been studied extensively among invertebrates, but relatively few examples have been documented among vertebrates. Nonetheless, the number of described...
Article
Full-text available
Rhabdophis tigrinus is an Asian natricine snake that possesses unusual defensive glands on the dorsal surface of its neck. These nuchal glands typically contain cardiotonic steroidal toxins known as bufadienolides, which are also abundant in the skin of toads. Feeding experiments demonstrated that toads consumed as prey are the ultimate sources of...
Article
Full-text available
Small molecules of biological origin continue to yield the most promising leads for drug design, but systematic approaches for exploring nature's cache of structural diversity are lacking. Here, we demonstrate the use of 2D NMR spectroscopy to screen a library of biorationally selected insect metabolite samples for partial structures indicating the...
Article
With the passing of Thomas Eisner on 25 March 2011, at the age of 81, the world has lost one of its most original and influential scientists. We owe the development of the contemporary discipline of chemical ecology largely to him. Eisner was fascinated by insects throughout his childhood. Wherever he found himself, he would observe in meticulous d...
Article
Extracts of the red alga Laurenciaintricata, collected in Bermuda, have yielded two new halogenated C-15 enynes, bermudenynol and its acetate. Spectroscopic evidence for the assignment of structures 1a and 1b to these compounds is presented. X-ray analysis verified the proposed structures and established their stereochemistry.
Article
The chemistry of naturally occurring compounds has long been pursued in the search for medicines, dyes, pesticides, flavors, and fragrances. In addition, the deeper aim of understanding life itself as a chemical phenomenon has motivated generations of scientists. One consequence of such studies has been the realization that natural products often s...
Article
The major sex attractant released by Scrobipalpuloides absoluta, a devastating tomato pest, was identified as (3E,8Z,11Z)-3,8,11-tetradecatrienyl acetate by a novel strategy involving the random reduction of double bonds. The technique is applicable to double bond localization of polyunsaturated compounds available even in nanogram quantities. The...
Article
The pupal defensive secretion of the coccinellid beetle Epilachna borealis is composed principally of a combinatorial library of several hundred macrocyclic polyamines. This new family of natural products is characterized by extremely large-ring monocyclic polylactones, which are derived from the oligomerization of three homologous (ω-1)-(2-hydroxy...
Article
(R)- and (S)-Chlorofluoroacetic acid (CFA) esters of several chiral secondary alcohols have been prepared and compared with the corresponding esters of Mosher's acid. CFA itself is a readily accessible and optically stable acid which gives the expected diastereoisomeric products with chiral alcohols without epimerization. The resulting diastereoiso...
Article
The important discoveries made during the last two centuries which are largely responsible for our current understanding of organic chemistry in general, and of natural products chemistry and chemical ecology in particular, are reviewed. A brief personal history follows, including an account of a few examples from our own work which illustrate the...
Article
Full-text available
Rhabdophis tigrinus obtains defensive steroids (bufadienolides) from its diet and sequesters those compounds in specialized structures on its neck known as nuchal glands. Hatchling snakes lacking these steroids must acquire them from toads consumed as prey. Here we show that females provision bufadienolides to their offspring in amounts correlated...
Article
Full-text available
Extensive chemical analyses of spider venoms from many species have revealed complex mixtures of biologically active compounds, of which several have provided important leads for drug development. We have recently shown that NMR spectroscopy can be used advantageously for a direct structural characterization of the small-molecule content of such co...
Article
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Beetles of the family Lycidae have long been known to be chemically protected. We present evidence that North American species of the lycid genera Calopteron and Lycus are rejected by thrushes, wolf spiders, and orb-weaving spiders, and that they contain a systemic compound that could account, at least in part, for this unacceptability. This compou...
Article
Fine fescue grasses displace neighboring plants by depositing large quantities of an aqueous phytotoxic root exudate in the soil rhizosphere. Via activity-guided fractionation, we have isolated and identified the nonprotein amino acid m-tyrosine as the major active component. m-Tyrosine is significantly more phytotoxic than its structural isomers o...
Article
Full-text available
Dufour glands of Paratrechina longicornis were analyzed chemically using GC-MS techniques. The glands contained twelve alkanes between C9 and C20 chain length with undecane and tridecane as the main components, six alkenes (1- and 4-undecene, 1-, 4-, and 6- tridecene, and heptadecadiene), two alkyl formates (C11 and C13), and saturated and polyunsa...
Article
The formicine ant Paratrechina longicornis is known for its extremely opportunistic foraging behaviour. Only a single trail pheromone source, the rectum, was previously described from this ant. Our detailed examination of this ant’s chemical communication system revealed the presence of at least four sources of pheromones. Rectum, poison sac, and D...
Article
Full-text available
The Asian snake Rhabdophis tigrinus possesses specialized defensive glands on its neck that contain steroidal toxins known as bufadienolides. We hypothesized that R. tigrinus does not synthesize these defensive steroids but instead sequesters the toxins from toads it consumes as prey. To test this hypothesis, we conducted chemical analyses on the g...
Article
Full-text available
Pinoresinol, a lignan of wide distribution in plants, is found to occur as a minor component in the defensive secretion produced by glandular hairs of caterpillars of the cabbage butterfly, Pieris rapae. The compound or a derivative is appropriated by the larva from its normal food plant (the cabbage, Brassica oleracea). Pinoresinol was shown to be...
Article
Full-text available
Lucidota atra, a diurnal firefly, shares possession of defensive steroids (lucibufagins or LBGs) with nocturnal fireflies of the genus Photinus. Photinus are protected against predators by their LBGs, but not against fireflies of the genus Photuris, the so-called firefly femmes fatales, which prey upon Photinus, thereby acquiring LBGs for their own...
Article
Capillary NMR spectroscopy (CapNMR) was used to characterize 13 new cardenolides and related steroids from a severely mass-limited natural products sample derived from a rare firefly, Lucidota atra. These analyses were carried out on only partially purified samples, each containing 20-100 mug of up to three steroids. Compared to other NMR spectrosc...
Article
Two random reduction procedures (NH2NH2/H2O2 and NH2NH2/O2) were compared and conditions optimized for the reduction of two synthetic pheromone compounds (9Z,11E)-9,11-tetradecadienyl acetate and (9Z,12E)-9,12-tetradecadienyl acetate on a 300 microg scale at 60 degrees C. The relative amounts of the four products (completely reduced acetate, unreac...
Article
The author reflects on his early experiences as a chemist, and on the subsequent shift in emphasis that his research has undergone from mechanistic and synthetic organic chemistry to natural products chemistry. Finally, the extension of the field of natural products chemistry into the emerging discipline of chemical ecology is noted. This essay con...
Article
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Chlorisondamine (CHL), a neuronal nicotinic ganglionic blocker, when injected in the cerebral ventricle of rats chronically blocks the increase in locomotion and rearing by subcutaneous nicotine injection. The blocking of the ion channel(s) prevents nicotine from exerting its rewarding effects on the CNS. When administered intraperitoneally, a dose...
Article
Lucibufagins. Part III† . 11-Oxo-and 12-oxo-bufalins, defensive steroids from the fireflies Photinus ignitus and P. marginellus (Coleoptera: Lampyridae) Four lucibufagins (4, 8, 9 and 10), defensive bufadienolides from the fireflies Photinus ignitus and P. marginellus (Coleoptera: Lampyrida), have been isolated and are characterized by spectroscopi...
Article
[structure: see text]Derivatization with (+)- and (-)-chloromenthoxydiphenylsilane was used to determine the absolute configuration of the insect defensive agent pinoresinol (1). Although the (1)H NMR chemical shift differences of the resulting two diastereomers are small, (1)H NMR spectroscopy provided for the unambiguous assignment of the natural...
Article
Using a new approach based on the NMR spectroscopic analysis of the entire, unpurified spider venom, we identified a family of unusual sulfated nucleoside derivatives from the venom of the hobo spider, Tegenaria agrestis. These compounds are ribonucleoside mono- and disulfates derived from guanosine and xanthosine, some of which are glycosylated, b...
Article
Full-text available
Analyses of pygidial gland contents of two species of a previously uninvestigated family of beetles (Trachypachidae) by Gas Chromatography-Mass Spectrometry (GC-MS) revealed that their chemistry is similar to that reported from many members of the family Carabidae. Nevertheless, the composition of defensive gland fluids of the two species Trachypac...
Article
Small molecules often carry vital information. Compounds as simple as nitric oxide, carbon dioxide, and ethylene play essential roles as hormones or pheromones in plants and animals. Extensive research during the past century has revealed that chemical signaling is not only the primary means whereby organisms coordinate and regulate their internal...
Article
Natural products chemistry, a field greatly invigorated nowadays by its partnership with chemical ecology, is currently being de-emphasized. We argue that such curtailment will restrain an exploratory process of immense scientific promise.
Article
Six new labdane-type, non-glycosidic diterpenes, sterebins I-N (1-6), were isolated from the leaves of Stevia rebaudiana. Their structures, analogous to those of the previously described sterebins A-H, were elucidated on the basis of spectroscopic and chemical studies.
Chapter
This chapter highlights certain insects in which foreplay is a sexually selective process involving assessment by the female of certain male traits that are a measure of an eventual benefit to the offspring. The foreplay is in the nature of a pheromone-mediated dialog and the insects are certain butterflies and moths. The female's mating preference...
Article
The crystal and molecular structure of the iron π complex obtained from the reaction of methyllithium with tricarbonyl-8,8-dibromobicyclo[5.1.0]octa-2,4-dieneiron has been determined by a single-crystal three-dimensional X-ray diffraction study. The complex crystallizes in the monoclinic space group P21/c with lattice parameters a = 10.740 ± 0.003,...
Article
[reaction: see text] Herein we report a new set of silyl ether reagents for determining the enantiomeric purity and absolute stereochemistry of secondary alcohols. These derivatives are easily synthesized, provide straightforward spectroscopic results, and allow for facile recovery of the original chiral alcohol.
Article
A tandem Wittig approach has been employed for the synthesis of both (11S,9Z,12Z,15Z)- and (11R,9Z,12Z,15Z)-hydroxyoctadeca-9,12,15-trienoic acid (11-hydroxylinolenic acid, 11-HLA) from (R)-glyceraldehyde acetonide. From (11R)-HLA we have prepared the corresponding palmitic acid and stearic acid esters, mayolene-16 (1) and mayolene-18 (2), insect d...
Article
Full-text available
The moth Utetheisa galapagensis (Lepidoptera, Arctiidae) is an endemic of the Galápagos Islands. Unlike other species of Utetheisa, which are gaudily aposematic, it is uniformly grayish in appearance. Our initial presumption that U. galapagensis lacks the plant-derived systemic pyrrolizidine alkaloids that account for the aposematism of its congene...
Article
Larvae of the European cabbage butterfly, Pieris rapae (Pieridae), are beset with glandular hairs, bearing droplets of a clear oily secretion at their tip. The fluid consists primarily of a series of chemically labile, unsaturated lipids, the mayolenes, which are derived from 11-hydroxylinolenic acid. In bioassays with the ant Crematogaster lineola...
Article
Full-text available
The secretion of the paracloacal glands of the American crocodile (Crocodylus acutus) contains over 80 lipophilic compounds, including saturated and unsaturated long-chain alcohols along with their formic, acetic, and butyric acid esters, and several isoprenoids. Most of these compounds were identified on the basis of mass spectra, obtained by GC-M...
Article
Full-text available
The flower of Hypericum calycinum, which appears uniformly yellow to humans, bears a UV pattern, presumably visible to insects. Two categories of pigments, flavonoids and dearomatized isoprenylated phloroglucinols (DIPs), are responsible for the UV demarcations of this flower. Flavonoids had been shown previously to function as floral UV pigments,...
Article
To offer an alternative to the survey and foundation frameworks, the authors designed The Language of Chemistry course to use only three to four case studies over the entire semester. In direct contrast to both the traditional concept exposition of foundation courses and the fleeting, often superficial, treatment of survey courses, these case studi...
Article
Full-text available
The thyridid caterpillar, Calindoea trifascialis, when disturbed, emits a defensive secretion from two sac-like glands that open dorsolaterally on the first abdominal segment. The larva has two arm-like protuberances that project outward from the body just in front of the gland openings. These "arms", which are wetted by secretion when the larva ac...
Article
In wind-tunnel bioassays, dispensers loaded with 1 microg of the synthetic major component (3E,8Z, 11Z)-3,8,11-tetradecatrienyl acetate (TDTA) of the sex pheromone emitted by Tuta absoluta (Meyrick) females were found to be highly attractive to conspecific males. Field experiments were conducted to evaluate the efficacy of five trap designs. The be...
Article
Alliarinoside, a feeding inhibitor against early instar larvae of Pieris napi oleracea, was isolated from the foliage of Alliaria petiolata and characterized as (2Z)-4-(beta-D-glucopyranosyloxy)-2-butenenitrile (1) by spectroscopic methods. The structural assignment was confirmed by synthesis of peracetylated alliarinoside (2) and its 2E isomer (3)...
Article
Full-text available
The collisionally-induced dissociation mass spectra of a variety of organic sulfate ester anions are described and mechanistically rationalized. A cyclic syn-elimination pathway, analogous to that of the Cope elimination, is postulated for the commonly observed formation of bisulfate anion (HSO4−, m/z 97). Deuterium labeling experiments confirm tha...
Article
The pupal defensive secretion of the ladybird beetle Subcoccinella vigintiquatuorpunctata consists of a mixture of macrocyclic polyamines (polyazamacrolides, PAMLs) dominated by three dimeric, 30-membered bislactones (1, 2, and 3), which represent the three possible head-to-tail combinations of the two building blocks (S)-(Z)-11-(2-hydroxyethylamin...
Article
The synthesis of three analogues of the single most abundant component of a ladybird beetle (Epilachna borealis) defensive secretion, the trimeric 42-membered polyazamacrolide PAML 681, is described. Construction of the nonnatural macrocyclic trimers began with the preparation of the corresponding monomeric segments, followed by their oligomerizati...
Article
Full-text available
Males of the moth Cosmosoma myrodora (Arctiidae) acquire pyrrolizidine alkaloid by feeding on the excrescent fluids of certain plants (for instance, Eupatorium capillifolium). They incorporate the alkaloid systemically and as a result are protected against spiders. The males have a pair of abdominal pouches, densely packed with fine cuticular filam...