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Biomedical subjects

W Boland

Publications and source records attributed to W Boland.

31 records · Page 2Linked to original sources
PubMed1994

Herbivore-induced volatiles: the emission of acyclic homoterpenes from leaves of Phaseolus lunatus and Zea mays can be triggered by a beta-glucosidase and jasmonic acid.

The treatment of healthy, undamaged plants of the Lima bean Phaseolus lunatus with solutions of a beta-glucosidase from bitter almonds (at 5 U.ml-1) through the petiole results in an enhanced emission of volatiles to the environment. The compounds are identical with those emitted in response to infestation with the red spotted spider mite Tetranychus urticae. Dominant products are the two acyclic homoterpenes 4,8-dimethyl-1,3E,7- dimethylnonatriene (homoterpene I) and 4,8,12-trimethyl-1,3E,7E,11-tridecatetraene (homoterpene II) which are of sesquiterpenoid and diterpenoid origin. Therefore, a beta-glucosidase of the herbivore may be considered as the true elicitor for the odor induction. Homoterpene I and most other of the herbivore-induced volatiles can also be triggered by treatment of the plant with solutions of jasmonic acid (JA) at 100 nmol.ml-1 to 10 mumol.ml-1. The C16 homoterpene II is not significantly induced by JA. The time-course of the enzymatic- and the JA-triggered induction of the volatiles is identical. The dose-response to JA parallels previous reports on alkaloid induction in cell cultures. In corn plants (Zea mays) JA triggers the emission of all volatiles which are known to be emitted in response to the damage by the beet army worm Spodoptora exigua. In summary, the emission of volatiles after damage by a herbivore resembles the production of phytoalexins in response to an attacking microorganism and uses similar elicitors and internal transduction pathways.

Animals↗
PubMed1992

5'-Azido-[3,6-3H2]-1-napthylphthalamic acid, a photoactivatable probe for naphthylphthalamic acid receptor proteins from higher plants: identification of a 23-kDa protein from maize coleoptile plasma membranes.

1-Naphthylphthalamic acid (NPA) is a specific inhibitor of polar auxin transport that blocks carrier-mediated auxin efflux from plant cells. To allow identification of the NPA receptor thought to be part of the auxin efflux carrier, we have synthesized a tritiated, photolabile NPA analogue, 5'-azido-[3,6-3H2]NPA ([3H2]N3NPA). This analogue was used to identify NPA-binding proteins in fractions highly enriched for plasma membrane vesicles isolated from maize coleoptiles (Zea mays L.). Competition studies showed that binding of [3H2]N3NPA to maize plasma membrane vesicles was blocked by nonradioactive NPA but not by benzoic acid. After incubation of plasma membrane vesicles with [3H2]N3NPA and exposure to UV light, we observed specific photoaffinity labeling of a protein with an apparent molecular mass of 23 kDa. Pretreatment of the plasma membrane vesicles with indole-3-acetic acid or with the auxin-transport inhibitors NPA and 2,3,5-triiodobenzoic acid strongly reduced specific labeling of this protein. This 23-kDa protein was also labeled by addition of 5-azido-[7-3H]indole-3-acetic acid to plasma membranes prior to exposure to UV light. The 23-kDa protein was solubilized from plasma membranes by 1% Triton X-100. The possibility that this 23-kDa polypeptide is part of the auxin efflux carrier system is discussed.

Journal Article↗
PubMed1992

Some effects of acidic growing conditions on three emergent macrophytes: Zizania aquatica, Leersia oryzoides and Peltandra virginica.

Transplants of Zizania aquatica L., Leersia oryzoides (L.) Shwartz, and Peltandra virginica (L.) Schott and Endl. were grown for ten weeks in simulated marsh conditions under acidic (pH 3.0, pH 4.0) treatment regimes and compared with controls (pH 5.6). Mortality was low in all treatments and nearly all plants of Z. aquatica and L. oryzoides flowered. Under acidic conditions, transplant height and root biomass of Z. aquatica were significantly reduced, with greater culm numbers and total lengths of inflorescences per flowering plant compared to controls. Shoot biomass of L. oryzoides transplants was significantly greater in the most acidic treatment (pH 3.0). Transplants of P. virginica grew slowly and did not flower during the experiment; heights and shoot biomass of P. virginica were significantly reduced with increased leaf chlorosis in acidic conditions.

Journal Article↗
PubMed1990

Stereochemical studies on algal pheromone biosynthesis. A model study with the flowering plant Senecio isatideus (Asteraceae).

Unsaturated C8 and C11 hydrocarbons act as chemical signals (chemotaxis) during sexual reproduction of many marine brown algae. One of these compounds, namely (+)-(6S)-6-(1Z-butenyl)cyclohepta-1,4-diene (= ectocarpene) is also formed as a major hydrocarbon by the flowering plant Senecio isatideus (Asteraceae). On administration of enantiospecifically labelled (8R)- or (8S)-[7,8-2H2]trideca-3,6,9-trienoic acid instead of the natural precursor dodeca-3,6,9-trienoic acid to this plant, the artificial C12 analogue of ectocarpene is formed. Mass spectroscopic analysis of the metabolites revealed this process to be enantiospecific for the C(8)-HRe atom of the precursor acid. The stereochemical course of the overall reaction is in agreement with a precise, U-shaped embedding of the trienoic acid into the active center of the enzyme(s) and Re-attack onto a hydrogen at the C(8) methylene group of this precursor. The reactive intermediate cyclizes by pi-orbital interaction between C(4) and C(6) of the acid and is accompanied by decarboxylation. The first product is a thermally unstable (1S,2R)-cis-1-(1E,3Z-hexadienyl)-2-vinylcyclopropane, which immediately rearranges to (+)-(6S)-ectocarpene (homo-Cope rearrangement). The present work provides first experimental evidence for a homo-Cope rearrangement as a naturally occurring electrocyclic reaction.

Cyclization↗
PubMed1989

Biosynthesis of 1-alkenes in higher plants: stereochemical implications. A model study with Carthamus tinctorius (Asteraceae).

Odd numbered 1-alkenes, such as 1-pentadecene or 1,8,11,14-heptadecatetraene are formed from palmitic or linolenic acid by fragmentative decarboxylation. Incubation studies with germinating safflower (Carthamus tinctorius) and (2R,3R)-12-phenyl[2,3-2H2]dodecanoic acid, (2S,3S)-12-phenyl[2,3-2H2]dodecanoic acid, (2R)-12-phenyl[2-2H]dodecanoic acid and (2S)-12-phenyl[2-2H]dodecanoic acid instead of the natural alpha-linolenic acid precursor revealed the fragmentation to be an overall anti elimination of the 3-pro(S) hydrogen and the carboxyl group (anti-periplanar transition state geometry). Externally offered 3-hydroxy acids are not fragmented to 1-alkenes. The most probable mechanistic alternatives are in agreement with abstraction of the 3-pro(S) hydrogen as a radical followed by electron transfer and fragmentation, or transient insertion of oxygen into the 3-pro(S) C-H bond and subsequent fragmentation into an 1-alkene and CO2 after appropriate activation. The mechanism seems to be of general importance for the biosynthesis of vinylic substructures of natural products from oxygenated precursors.

Alkenes↗
PubMed1988

Biosynthesis of monoterpene hydrocarbons by isolated chromoplasts from daffodil flowers.

Incubation studies using [1-14C]isopentenyl diphosphate and [1-2H2]isopentenyl diphosphate as substrates revealed that isolated chromoplasts from flowers of Narcissus pseudonarcissus L. are able to synthesize monoterpene hydrocarbons and linalool in high yields. The enzymes involved are soluble in the chromoplast stroma. It is hypothesized that in the plant cell plastids are the site of monoterpene biosynthesis, whereas the formation of sesquiterpenes may be restricted to the cytoplasm/endoplasmic reticulum.

Carbon Radioisotopes↗
PubMed1987

Biosynthesis of 1-alkenes in higher plants. A model study with the composite Carthamus tinctorius L.

Uneven numbered 1-alkenes, such as 1-pentadecene, 1-heptadecene, 1,8-heptadecadiene, 1,8,11-heptadecatriene and 1,8,11,14-heptadecatetraene are the predominant hydrocarbons in germinating safflower (Carthamus tinctorius L.). According to their chain length and positions of double bonds they are derived from palmitic, stearic, oleic, linoleic or linolenic acid, respectively. This has been proved by administration of synthetic alpha-, beta-, or gamma-deuterated 12-phenyldodecanoic acids to germinating safflower. Mass spectrometric analysis of the resulting deuterium-labelled 11-phenyl-1-undecenes shows that only a single hydrogen from C-3 and carbon dioxide from C-1 of the precursor fatty acid is lost during vinyl group formation. A strong isotope effect (kH/kD greater than or equal to 10) during the conversion of racemic 12-phenyl[3-2h]dodecanoic acid to 11-phenyl-1-[2-2H]undecene is consistent with an initial enzymatic attack on a non-activated hydrogen at C-3 accompanied by simultaneous fragmentation into the respective 1-alkene and carbon dioxide. Mechanisms, based on ionic or radical abstraction of a hydrogen from C-3 of the fatty acid, followed by decarboxylation are discussed. The results are applicable to the formation of various vinylic substituents in natural products such as porphyrins, acetylenic hydrocarbons, pheromones from marine brown algae and terpenoids.

Alkenes↗
PubMed1985

Biosynthesis of algal pheromones. A model study with the composite Senecio isatideus.

Several cyclic and alicyclic C11 hydrocarbons have been shown to act as gamete releasing and/or attracting pheromones during sexual reproduction of brown algae (Phaeophyceae). The same compounds are also found in the essential oils of various plants, of which the occurrence of the cycloheptadiene-pheromone ectocarpene in Senecio isatideus (Compositae) is noteworthy. Administration of [3H]dodeca-3,6,9-trienoic acid to cuttings of this plant leads to incorporation of radioactivity into ectocarpene. Double-bond-deuterated nona-3,6-dienoic acid is converted to fucoserratene, the pheromone of several Fucales, which is certainly not present among the hydrocarbons of Senecio. This proves that the pool of medium-chain, multiply unsaturated fatty acids includes precursors of all types of highly unsaturated hydrocarbons. Appropriately labelled (deuterium markers) fatty acid homologues were synthesized and applied to Senecio plantlets to unravel the mechanistic aspects. The results strongly suggest radical initiation of the pheromone biosynthesis by abstraction of a single hydrogen from a 1,4-pentadienyl segment of the fatty acid followed by oxidation to the corresponding cation. This causes fragmentation of the reactive intermediate into an olefine and carbon dioxide by neighbouring-group participation of the flanking double bonds. A tentative biosynthetic scheme is deduced from the experimental results which also sets the stereochemistry of the algal pheromones into a uniform mechanistic concept.

Animals↗
PubMed1984

Differentiation of algal chemoreceptors. A comparative receptor study with two seaweed pairs: Cutleria multifida/Syringoderma phinneyi and Desmarestia aculeata/Ectocarpus siliculosus (Phacophyceae).

Gamete encounter in the reproduction of brown algae is supported by lures produced by the female cells. These signals are low-molecular-mass, volatile, olefinic hydrocarbons. Specific receptors on the motile male gametes recognize the pheromones at threshold concentrations as low as 6.5 pmol/l. The pheromones are possibly bound by dispersion and dipolar interactions. Tight fitting has to compensate for these weak contact forces. This causes strong chiral discrimination (relative affinities to enantiomeric lures 1:100). Structurally related messengers with identical substitution patterns and overall space filling are mutually distinguished in several species by means of altered topologies in their receptor mould. Responses to systematically varied synthetic bis-alkenyl-cyclopentene pheromones showed that the sensors of Syringoderma and Cutleria androgametes consist of a mosaic of attachment sites individually adapted to specific structural elements in the messenger molecule. They may be permutated to afford optimal binding. An alternative strategy: distinct reading of electron density combined with variation of sensitivity, brings about 'fidelity' in signal transmission by the alkylated cycloheptadiene pheromones in two species of Desmarestia and Ectocarpus. Inhibition of chemotaxis by ectocarpene is observed in Ectocarpus males in the presence of desmarestene, the lure of Desmarestia, and related parapheromones. This indicates complex interactions between different species of algae sharing a common habitat, in their defense of living space.

Animals↗
PubMed1983

Comparative receptor study in gamete chemotaxis of the seaweeds Ectocarpus siliculosus and Cutleria multifida. An approach to interspecific communication of algal gametes.

Gamete fusion in phaeophytes is initiated by olefinic hydrocarbons as messenger substances. They are secreted by the female gametes and act on male gametes or gametangia. The sensitivity thresholds of the androgametes of Ectocarpus siliculosus and Cutleria multifida, two brown algae of different evolutionary stages, for ectocarpene, which is produced by either species, were found to be 0.89 nmol/l and 8.9 nmol/l sea water, respectively. The molecular recognition mechanism is shown to be identical for these two species and probably also for most other phaeophytes. The pheromones involved are structurally related and sometimes resemble each other in their overall pi-electron distribution (e.g. ectocarpene and multifidene). Knowing the specific messenger, the typical response behaviour of each receptor involved, the pheromone productivity of the considered species as well as other biological parameters (phytogeographic distribution, the natural benthic habitat and times of fertilization), a method is presented to uncover possible interspecific cross-reactions of such algal communication systems as a 'chemical warfare' device in their fight for living space.

Animals↗
PubMed1982

Binding-mechanism and sensitivity in gamete chemotaxis of the phaeophyte Cutleria multifida.

Female gametes of the marine brown alga Cutleria multifida discharge multifidene into the water to attract the swimming males. The physicochemical principle of interaction between semiochemical and membrane receptor site is seen in mutual but complementary induced dipoles. Halogenated derivatives of multifidene with intact overall structure and stereochemistry but altered electronic properties were synthesized and assayed as lures. A direct correlation was observed between increasing polarizability and biological activity, thus proving the proposed mechanism. The low threshold concentration of this communication system (4 X 10(9) molecules/ml), together with a detailed knowledge of the gamete's architecture, swimming velocity and stimulus response time, indicates that very few, may be even single, molecules are able to trigger the sensomotoric chain. The rigidity of the natural signal molecule was recognized as an important element in inducing conformational fitting in the ligand/receptor complex.

Binding Sites↗
PubMedDate not supplied

Enantiospecificity of immobilized horse liver alcohol dehydrogenase.

Horse liver alcohol dehydrogenase (EC 1.1.1.1) accepts a wide structural range of substrates but exhibits a well-defined and predictable stereospecificity. The enzyme was immobilized on CNBr-activated Sepharose 4B. The immobilized preparation was used to oxidize the enantiomeric pair of cis-1,2-bis(hydroxymethyl)-3-cyclopentene enantioselectively to a mixture of two diastereoisomeric chiral lactones. The two diastereoisomeric products are readily separated and each was isolated with an optical yield of greater than 99%.

Alcohol Dehydrogenase↗