Microbial Resolution of (±)-Acyclic Alcohols

By selected microorganisms the acetates of the racemic sec-alcohols were asymmetrically hydrolyzed to optically active sec-alcohols and the acetates of their antipodes. Microbial hydrolysis of the acetates of the racemic prim-alcohols having an asymmetrical carbon atom at the β-position gave lower optically active alcohols and the acetates of their antipodes, but the acetates having an asymmetrical carbon atom at the γ-position were hydrolyzed only to give racemic alcohols.     

The role of alcohols in pheromone biosynthesis by two noctuid moths that use acetate pheromone components

Primary alcohols varying in chain length from C₁₃ to C₁₆, and in number, position, and geometric configuration of double bonds, were applied in dimethyl sulfoxide to the surface of the female sex pheromone glands of Heliothis subflexa (Gn.) and Hydraecia micacea (Esper). Capillary gas chromatographic analysis of extracts of the treated glands indicated that the alcohols were converted to the corresponding aldehydes by H. subflexa females and to the acetates by H. micacea females. Conversions of the alcohols showed no preferences for molecular weight, number, position, or geometry of the double bonds in either species. Application of the acetates of the primary alcohols to the gland surface of H. subflexa females resulted in the production of both the corresponding alcohols and aldehydes, while neither alcohols nor aldheydes were produced when acetates were applied to the glands of H. micacea. In addition, application of the acetates to the gland surface of Heliothis virescens (F.) resulted in the production of both the corresponding alcohols and aldehydes. However, no evidence was found to indicate that acetates are ever produced by the pheromone gland of females of H. virescens.     

Optical Rotatory Dispersion of Rotundifolone

Microbial (enzymatic) hydrolysis of (±)-O-acetyl allethrolone gave (?)-(R)-allethrolone with (+)-(S)-O-acetyl allethrolone. And microbial hydrolysis of (±)-cis and trans-2-allylcyclopentyl acetates gave the low optically active cis and trans-2-allylcyclopentanols with the acetates of their antipodes. Also, the acetates of (±)-primary alcohols with cyclopropane and cyclohexene rings: (±)-chrysanthemyl alcohol, α-cyclogeraniol, were hydrolyzed by microorganisms to give the optically active alcohols in low optical purities Further, synthesis and microbial resolution of racemic hydroxy-trimethylcyclohexanones, useful intermediate for synthesis of compounds related to carotenoids, were tried.     

Electroantennographic and field responses of the pea moth, Cydia nigricana, to sex attractants and related compounds

Electroantennographic (EAG) responses of the male pea moth, Cydia nigricana, to a range of saturated and unsaturated straight chain alcohols and acetates were examined. Responses to saturated compounds of different chain lengths (C₁₀ to c₁₆) showed that acetates are much more active than alcohols, the shorter chain compounds (particularly C₁₂ acetates) being the most active. With mono-unsaturated compounds, C₁₂ acetates with the double bond at C-8, C-9 or C-10 elicited the largest responses and (El-10-dodecenyl acetate produced a greater response than any other compound tested. By analogy with results obtained with C.pomonella, (E, E)-8,lO-dodecadienyl acetate was tested and gave an EAG response larger than that for (E)-10-dodecenyl acetate. (E)-10-dodecenyl acetate and (E, E)-8,lO-dodecadienyl acetate were found to be strong attractants for male C.nigricana in the field.     

Comparison of Sex Pheromonal Activity on the American Cockroach between Acetates and Propionates of Verbenyl Type Alcohols

Sex pheromonal activity was evaluated for propionates of 4 alcohols having a 6,6-dimethyl-bicyclo[3.1.1]heptane skeleton by behavioral assay with the male American cockroach. Their activities were compared with the corresponding acetates. The propionates were active at 20 μg or 500 μg, demonstrating stronger activities than the corresponding acetates. The male to female response ratio (M/F ratio) in EAG was also evaluated for the acetates and propionates, as well as for germacrene-D and camphor. The order of the behavioral activity was represented by that of the ratio. Sex pheromonal activity of (+)-verbanyl propionate (7) and germacrene-D were compared. Stronger activity was consequently observed in 7 at 5 μg dose, supporting the M/F ratio result.     

Fern constituents: Cycloartane triterpenoids and allied compounds from Polypodium formosanum and P. niponicum

From the rhizomes of Polypodium formosanum, new triterpenoids of the cycloartane group, (24R)-cyclolaudenol and (24R)-cyclomargenol, were isolated as the corresponding acetates, alcohols and ketones, and their structures were established. Also, from the rhizomes of P. niponicum eight acetates of cycloartane derivatives and two acetates of new methyl sterols were isolated and characterized.     

Behavioral and electroantennogram analysis of olfactory stimulation inlozenge: ADrosophila mutant lacking antennal basiconic sensilla (Diptera: Drosophilidae)

Two alleles of the mutant lozengeof Drosophila melanogaster, lzand lz³,lack basiconic sensilla on the antennal funiculus. To elucidate the role of these sensilla for the perception of food odors, we studied the locomotor behavior and the electroantennogram (EAG) activity of lozenge flies in response to olfactory stimuli. The significance of basiconic sensilla on the maxillary palps was assessed by testing the locomotion of flies surgically deprived of their palps. The behavioral data suggest that antennal and maxillary basiconic sensilla may be important receptors for short chain alcohols and organic acids but less crucial receptors for acetates, aldehydes, and ketones. In agreement with this interpretation, EAG responses to alcohols (but not to esters) were found to be markedly lower in lozengethan in the wild type.     

Enzymatic Resolutions of Heterocyclic Alcohols

The butyrates and acetates of heterocyclic alcohols like 3 - hydroxy tetrahydrofuran and - pyran, 3- and 4 - chromanol as well as the corresponding sulfur heterocycles were hydrolyzed using lipase from Candida rugosa (CRL) and from Pseudomonas cepacia, (PCL). Poor to excellent enantioselectivities were obtained depending on the structure of the substrates. An electrostatic amendment to the steric substrate model for PGL is proposed.     

Electrophysiological and behavioural responses of Melolontha melolontha to saturated and unsaturated aliphatic alcohols

Male Melolontha cockchafers are known to use green leaf volatiles induced by female feeding on host plants for their mate location. Earlier studies of the response of the European cockchafer, Melolontha melolontha L. (Coleoptera: Scarabaeidae), to different green leaf aldehydes, alcohols, and acetates revealed that only green leaf alcohols were attractive to males in the field. Females were not attracted at all by these volatiles. Here, we present a study that aimed to elucidate the structure–activity relationships of aliphatic alcohols. Both behavioural and physiological responses were studied in male and female M. melolontha by field tests and electroantennography. The compounds tested were saturated aliphatic alcohols with chain lengths between five and eight carbon atoms. Furthermore, the cockchafer's response to six‐carbon alcohols with (E)‐2‐, (E)‐3‐, (Z)‐2‐, (Z)‐3‐, and (Z)‐4‐configurated double bonds was tested. All compounds elicited dose‐dependent responses on the antennae of both sexes. In general, males showed a stronger normalized EAG response to the stimuli than females. However, only the naturally occurring six‐carbon alcohols, i.e., 1‐hexanol (E)‐2‐, (Z)‐3, and (E)‐3‐hexen‐1‐ol were attractive to M. melolontha males in the field. Females were not attracted to any of the tested compounds, confirming previous results on the olfactory orientation of Melolontha cockchafers.     

Enantioselective hydrolysis of bromo- and methoxy-substituted 1-phenylethanol acetates using carrot and celeriac enzymatic systems

Enantioselective hydrolysis of bromo- and methoxy-substituted 1-phenylethanol acetates was conducted using comminuted carrot (Daucus carota L.) and celeriac (Apium graveolens L. var. rapaceum) roots. Hydrolysis of the acetates led to alcohols, preferentially to R-(+)-enantiomers. Efficiencies of both reactions - hydrolysis of the acetates with an electron-donating methoxy group and oxidation of the resulting alcohols - increased in the following order: ortho < meta < para. The presence of an electron-withdrawing bromine atom in the aromatic ring had the opposite effect. Oxidation of alcohols with both types of substituents in the aromatic ring showed that location of a substituent had stronger impact on the oxidation rate than its electronic properties.     

Availability of Energy in Esters of Aliphatic Acids and Alcohols by Growing Chicks

Biological availability of 106 esters of alcohols and aliphatic mono-, di- and tri-carboxylic acids and diethylene glycol succinate was compared by the mini-test with chicks. Chicks can utilize methyl esters of saturated fatty acids of carbon chain from 10 to 14, ethyl esters of those from 9 to 12, propyl caprate, n-butyl esters of those from 8 to 12, n-amyl esters of those from 6 to 12, n-hexyl n-butyrate and i-vaterate, and n-octyl and n-decyl acetates. Only 3 dicarboxylates, i.e. di-octyl and di-lauryl succinates and di-methyl cis-cyclopropane-l,2-dicarboxylate, were available among the dicarboxylates tested. Availability of ethyl esters of succinic, fumaric and citric, acid was unexpectedly low.     

Transformations of acetates of citronellol,geraniol, and linalool by Aspergillus niger: regiospecific hydroxylation of citronellol by a cell-free system

Summary Incubation of acetates of geraniol, citronellol and linalool with Aspergillus niger resulted in their hydrolysis to corresponding alcohols which were further hydroxylated to their respective 8-hydroxy derivatives. In the case of linalyl acetate, besides linalool and 8-hydroxylinalool, small amounts of geraniol and -terpineol were also formed. Microsomes (105 000xg sediment) prepared from induced cells of A. niger were found to convert (1-³H)citronellol to 8-hydroxy citronellol in the presence of NADPH and O₂. The pH optimum for the hydroxylase was found to be 7.6.     

Contribution by Saccharomyces cerevisiae yeast to fermentative flavour compounds in wines from cv. Albariño

A comparative study was made of the fermentation products of Spanish Albariño wines produced with spontaneous yeast flora and an indigenous selected Saccharomyces cerevisiae strain (Alb16). The content of fermentative volatile compounds was determined by gas-chromatography-FID. Fifteen compounds (5 alcohols, 7 esters and 3 acetates) were identified in the two Albariño wines studied. Higher alcohols, ethyl esters (except ethyl hexanoate and ethyl octanoate) and acetates were in greater concentration in the spontaneous fermentation wine than in that with selected Alb16 strain. Principal components analysis showed good separation between the different wines.     

Geometric isomers of sex pheromone components do not affect attractancy of Conopomorpha cramerella in cocoa plantations

The cocoa pod borer (CPB), Conopomorpha cramerella (Snellen), sex pheromone was previously identified as a blend of (E,Z,Z)‐ and (E,E,Z)‐4,6,10‐hexadecatrienyl acetates and corresponding alcohols. These pheromone components were synthesized by modification of an existing method and the relative attractiveness of synthetic blends that included different levels of non‐target pheromone components and chemical purities was tested in a cocoa field using Delta traps. Male captures were not significantly different among traps baited with pheromone blends containing 5% to 47% (based on four identified pheromone components) of other geometric acetates [(E,Z,E)‐, (Z,Z,Z)‐, (Z,E,Z)‐ and (Z,E,E)‐4,6,10‐hexadecatrienyl acetates], indicating that C. cramerella males did not discriminate among the pheromone components and other geometric isomers in the blends. Therefore, neither antagonistic nor synergistic effects from other pheromone geometric isomers were observed. The modified synthetic pathway offers the prospect of more economical production of CPB sex pheromone. During 17 weeks when C. cramerella monitoring coincided with the main cocoa pod harvest period in 2013–2014, CPB trap catch data from some blends showed a good correlation with the number of pods with C. cramerella infestation symptoms.     

The human carbonic anhydrase isoenzymes I and II inhibitory effects of some hydroperoxides,alcohols, and acetates

The carbonic anhydrases (CAs, EC 4.2.1.1) represent a superfamily of widespread enzymes, which catalyze a crucial biochemical reaction, the reversible hydration of carbon dioxide to bicarbonate and protons. Human CA isoenzymes I and II (hCA I and hCA II) are ubiquitous cytosolic isoforms. In this study, a series of hydroperoxides, alcohols, and acetates were tested for the inhibition of the cytosolic hCA I and II isoenzymes. These compounds inhibited both hCA isozymes in the low nanomolar ranges. These compounds were good hCA I inhibitors (K_is in the range of 24.93–97.99?nM) and hCA II inhibitors (K_is in the range of 26.04–68.56?nM) compared to acetazolamide as CA inhibitor (K_i: 34.50?nM for hCA I and K_i: 28.93?nM for hCA II).     

Epicuticular wax of Cirsium arvense

Epicuticular wax of Cirsium arvense contains hydrocarbons (12%), esters (35%), free acids (3%), free alcohols (10%), triterpene acetates (8%) and 1,3-ditetradecanoyl-2-hexanoylglycerol (8%) as major components. Minor components are triterpene alcohols (3%) and nonacosan-10-ol (2%). The esters contain triterpene alcohol esters (19%) as well as esters of alkanols.     

Foliar terpenoids in Tsuga species and the fecundity of scale insects

Summary The relationship between the reproductive success of two Japanese scale insects, Fiorinia externa Ferris and Nuculaspis tsugae (Marlatt) (Homoptera: Diaspididae) and the concentrations of 15 terpenoids in needles of Tsuga sieboldii, the Japanese host, and T. canadensis, the North American host, was investigated during 1981 and 1982 in a field plot of 8-year-old trees in New Haven, CT, USA. Both scales produced significantly more eggs per female on T. sieboldii than on T. canadensis. Stepwise multiple regression analyses indicated that the variation in fecundity within both scales was strongly associated with variation in the terpenoid profile between tree species.General patterns of phytochemical variation between the two Tsuga species based on differences in the concentration of terpenoids having similar chemical structures were revealed by the multivariate statistical technique, principal components analysis. The volatile leaf oil profile of T. sieboldii was relatively richer in terpene alcohols, while that of T. canadensis was relatively richer in terpene hydrocarbons and terpene acetates. The individual terpenoids were then assigned to one of five groups based on chemical structure and regression analyses were repeated; fecundity of both scales increased with increasing concentration of terpenoid alcohols. Fecundity of F. externa was negatively associated with the relative concentration of acyclic terpenes but the opposite was true for N. tsugae. Analysis of foliar terpenoids may provide a basis for predicting the relative susceptibility of Tsuga species to attack by F. externa and N. tsugae.     

Enzymatic resolution of homoallyllic alcohols using various Rhizopus species

The asymmetric resolution of various 1-aryl-3-buten-1-ols via microbial hydrolysis of the corresponding acetates has been investigated using different Rhizopus species. The chosen species, R. arrhizus (wild type), efficiently hydrolyzed 1-phenyl- and 1-para-substituted phenyl-3-buten-1-ol acetates, producing the enantiomerically pure (R)-alcohols with 53–65% yields. Although the antipode acetates were obtained with 9–52% enantiomeric excess, the (S)-alcohols were amenable in > 99% enantiomeric excess via a R. arrhizus mediated asymmetric reduction of the corresponding ketones.     

Distribution of l-Leucine-pyruvate Transaminase in Bacteria

Dodecadien-1-ols, tetradecadien-1-ols and hexadecadien-1-ols with a conjugated (E,E)- or (E)-diene system between the ωl,ω3- and ω5, ω7-positions, their acetates, and aldeh?de derivatives (lepidopterous sex pheromones and candidates) were analyzed by electron impact mass spectrometry, which was operated at 70 eV ionization voltage. Three functional derivatives with a same diene system presented a similar spectral pattern, except for the molecular ions (M⁺), [M ? H₂O]⁺ of the alcohols and [M ? CH₃CO₂H]⁺ of the acetates. Each isomer showed a characteristic fragment ion series of C_nH_2n?2⁺ ~C_nH_2n?5⁺ (C₄~C₉), which reflected the double-bond position in the molecule, indicating a method for determining the position of a natural diene pheromone by comparing its mass spectrum with those of the synthetic dienes. By this method, the natural pheromone of Hellula undalis was confirmed to be a ω3, ω5-diene. Furthermore, the fitness indexes proposed by Kuwahara et al. were calculated for some pheromone components, using the mass spectra of synthetic dienes, in order to examine the possibility and limitation for applications of those mass spectra to natural pheromone studies.     

Metabolic engineering in strawberry fruit uncovers a dormant biosynthetic pathway

Wild strawberry (Fragaria vesca) fruit contains several important phenylpropene aroma compounds such as eugenol, but cultivated varieties are mostly devoid of them. We have redirected the carbon flux in cultivated strawberry (Fragaria×ananassa) fruit from anthocyanin pigment biosynthesis to the production of acetates of hydroxycinnamyl alcohols, which serve as the precursors of the phenylpropenes, by downregulating the strawberry chalcone synthase (CHS) via RNAi-mediated gene silencing and, alternatively, by an antisense CHS construct. Simultaneous heterologous overexpression of a eugenol (EGS) and isoeugenol synthase (IGS) gene in the same cultivated strawberry fruits boosted the formation of eugenol, isoeugenol, and the related phenylpropenes chavicol and anol to concentrations orders of magnitude greater than their odor thresholds. The results show that Fragaria×ananassa still bears a phenylpropene biosynthetic pathway but the carbon flux is primarily directed to the formation of pigments. Thus, partial restoration of wild strawberry flavor in cultivated varieties is feasible by diverting the flavonoid pathway to phenylpropene synthesis through metabolic engineering.