The limiting mechanism in tarsal chemoreception

Rejection thresholds of eight primary alcohols applied to the tarsal chemoreceptors of the blowfly Phormia regina Meigen and the ovipositor of Gryllus assimilis Fab. have been determined. Three different solvents for the alcohols have been used: water, ethylene glycol, and mineral oil. The comparative stimulating effectiveness of the alcohols assumes a different aspect with each different solvent. In oil the range of thresholds from methanol to octanol extends over less than one log unit as compared with the corresponding thresholds in water which extend over four log units. In glycol the thresholds extend over two and one half log units only. When water is employed as a solvent, the line which describes the relationship between threshold concentration and chain length of the compound exhibits a sharp break at or near butanol. No such discontinuity is evident when glycol or oil is employed as solvent. This is offered as evidence supporting the hypothesis that the limiting mechanism in tarsal chemoreception involves a two phase system whereby highly water-soluble compounds gain access to the receptor through an aqueous phase and the larger lipoid-soluble molecules chiefly through a lipoid phase. Additional facts which support this idea are gained from data which show that the inflection in the curve occurs at different points with different species of insects and is conspicuously absent in the case of man. When thresholds in aqueous solutions are converted from molar concentrations to activities, it is clear that the relation of equal physiological effect at equal thermodynamic activities does not apply here. The lower members of the series stimulate at progressively increasing activities up to pentanol and then at progressively decreasing activities. Furthermore, the ratio of water threshold to oil threshold exhibits no obvious agreement with the water/oil partition coefficients determined experimentally. These results indicate either that the limiting process of chemoreception in these insects does not depend upon the establishment of an equilibrium or that some kinetic effect is obscuring an underlying relationship which does so depend.     

Microbial Oxidation of Allylic Alcohols

A new method for the oxidation of primary ad secondary allylic alcohols to the corresponding aldehydes/acids and ketones respectively is described utilizing Nocardia corallina B-276. In contrast, Pseudomonas oleovorans TF4-1L oxidized only the primary allylic alcohols but not the secondary allylic alcohols.     

Cascade blue derivatives: water soluble, reactive, blue emission dyes evaluated as fluorescent labels and tracers.

Fluorescent dyes based on the pyrenyloxytrisulfonic acid (Cascade Blue) structure were prepared and evaluated. The dyes contain functional groups that react with amines, thiols, acids, aldehydes, and ketones, forming covalently bonded, fluorescent derivatives of molecules with broad biological interest. Reactive groups in the Cascade Blue dyes include carboxylic acids and activated esters, amines, hydrazides, alcohols, photoaffinity reagents, acrylamides, and haloacetamides. The dyes exhibited absorption maxima at 374-378 nm and 399-403 nm, with extinction coefficients in the range of 1.9 x 10(4)-2.4 x 10(4) M-1cm-1 and 2.3 x 10(4)-3.0 x 10(4) M-1cm-1, respectively. Emission maxima ranged from 422-430 nm. The spectral properties of the fluorescent dyes are sufficiently different from fluorescein to permit simultaneous use of both dyes with minimum spectral interference. The Cascade Blue derivatives have narrower spectral bandwidths and smaller Stokes' shifts than other reactive dyes with similar spectral properties, do not show appreciable sensitivity to pH, have higher solubilities in aqueous solution, and have good to excellent quantum yields. Cascade Blue conjugates of a number of histochemically and biologically useful molecules were prepared, including dextrans, albumins, Fc receptor binding proteins, antibodies, lectins, membrane receptor binding proteins, and biotin binding proteins, as well as biological particles and bacteria. Cascade Blue conjugates of secondary and tertiary labels yielded specific fluorescence localization in the indirect immunofluorescent staining of human epithelial cell (HEp-2) nuclei.     

Lipoprotein lipase releases esterified oxylipins from very low-density lipoproteins

We previously demonstrated that defects in lipoprotein metabolism alter the distribution of oxygenated polyunsaturated fatty acids (PUFAs) in lipoprotein particles. If these oxidation products are released by lipoprotein lipase (LpL), then their delivery to peripheral tissues with bulk lipids could influence cellular function. Using 26-week-old normolipidemic and hyperlipidemic Zucker rats, we measured PUFA alcohols, epoxides, diols, ketones, and triols (i.e. oxylipins) in esterified and non-esterified fractions of whole plasma, VLDL, and LpL-generated VLDL-lipolysates. Whole plasma, VLDL, and lipolysate oxylipin profiles were distinct and altered by hyperlipidemia. While >90% of the whole plasma oxylipins were esterified, the fraction of each oxylipin class in the VLDL varied: 46% of alcohols, 30% of epoxides, 19% of diols, <10% of ketones, and <1% triols. Whole plasma was dominated by arachidonate alcohols, while the linoleate alcohols, epoxides, and ketones showed an increased prevalence in VLDL. LpL-mediated VLDL lipolysis of PUFA alcohols, diols and ketones was detected and the relative abundance of oxygenated linoleates was enhanced in the lipolysates, relative to their corresponding VLDL. In summary esterified oxylipins were seen to be LpL substrates with heterogeneous distributions among lipoprotein classes. Moreover, oxylipin distributions are changes within the context of obesity-associated dyslipidemia. These results support the notion that the VLDL–LpL axis may facilitate the delivery of plasma oxylipins to the periphery. The physiological implications of these findings are yet to be elucidated; however, these molecules are plausible indicators of systemic oxidative stress, and could report this status to the peripheral tissues.     

Green Asymmetric Synthesis: β‐Amino Alcohol‐Catalyzed Direct Asymmetric Aldol Reactions in Aqueous Micelles

The ability of chiral β‐amino alcohols to catalyze the direct asymmetric aldol reaction was evaluated for the first time in aqueous micellar media. A family of cheap and easily accessible β‐amino alcohols, obtained in one step from naturally occurring amino acids, was shown to successfully catalyze the asymmetric aldol reaction between a series of ketones and aromatic aldehydes. These aldol reactions furnished the corresponding β‐hydroxy ketones with up to 93% isolated yield and 89% ee. (S)‐2‐phenylglycinol and Triton X‐100 proved to be the best organocatalyst and surfactant, respectively. Chirality 25:119–125, 2013. © 2012 Wiley Periodicals, Inc.     

Olfactory responses of blowflies to aliphatic aldehydes

The response of the blowfly Phormia regina to stimulation by aldehydes in the vapor phase has been studied by means of a specially designed olfactometer. The median rejection threshold and the maximum acceptance threshold were selected as criteria of response. For both acceptance and rejection the distribution of thresholds in the population is normal with respect to the logarithm of concentration. When thresholds are expressed as molar concentrations, the values decrease progressively as chain length is increased. There is no attraction beyond decanal and no rejection beyond dodecanal. When thresholds are expressed as activities, most members of the aldehyde series are approximately equally stimulating at rejection and equally stimulating at acceptance. The relationship is most exact over the middle range of chain lengths. There is a tendency for the terminal members to stimulate at higher activities. These relationships are in close agreement with those which were found earlier to apply to the normal aliphatic alcohols. The similarity between the relative actions of the members of the two series suggests that the relation of equal olfactory stimulation at equal thermodynamic activities by homologous aliphatic compounds at least for homologues of intermediate chain length may be of rather general application in olfaction.     

An analysis of the volatile flavour compounds in a soft raw goat milk cheese

The major components of the musty cow rind cheeses were identified in a soft raw goat milk cheese as heptan-2-one, nonan-2-one, their corresponding secondary alcohols, some esters and sulfur compounds. Their production was associated with the manufacturing process and its influence on the microbial activity. However a specificity in goat cheese compounds was displayed concerning in particular limonene and some ketones, alcohols and aldehydes.     

The reducing capacities of cyanobacteria for aldehydes and ketones

Summary Several strains of filamentous and unicellular cyanobacteria are capable of converting aldehydes and ketones into their corresponding alcohols during the active growth phase. Efficient conversions have been observed with aliphatic aldehydes, methyl and ethyl ketones. Cyanobacteria proved to be potent reducters of nor-carotenoids, acyclic monoterpene aldehydes and ketopantolactone. Neither bicyclic monoterpene ketones nor aromatic aldehydes have been reduced by any cyanobacterial strain so far tested.     

The kinetics and mechanism of liver alcohol dehydrogenase with primary and secondary alcohols as substrates

1. The activity of liver alcohol dehydrogenase with propan-2-ol and butan-2-ol has been confirmed. The activity with the corresponding ketones is small. Initial-rate parameters are reported for the oxidation of these secondary alcohols, and of propan-1-ol and 2-methylpropan-1-ol, and for the reduction of propionaldehyde and 2-methylpropionaldehyde. Substrate inhibition with primary alcohols is also described. 2. The requirements of the Theorell-Chance mechanism are satisfied by the data for all the primary alcohols and aldehydes, but not by the data for the secondary alcohols. A mechanism that provides for dissociation of either coenzyme or substrate from the reactive ternary complex is described, and shown to account for the initial-rate data for both primary and secondary alcohols, and for isotope-exchange results for the former. With primary alcohols, the rapid rate of reaction of the ternary complex, and its small steady-state concentration, result in conformity of initial-rate data to the requirements of the Theorell-Chance mechanisms. With secondary alcohols, the ternary complex reacts more slowly, its steady-state concentration is greater, and therefore dissociation of coenzyme from it is rate-limiting with non-saturating coenzyme concentrations. 3. Substrate inhibition with large concentrations of primary alcohols is attributed to the formation of an abortive complex of enzyme, NADH and alcohol from which NADH dissociates more slowly than from the enzyme-NADH complex. The initial-rate equation is derived for the complete mechanism, which includes a binary enzyme-alcohol complex and alternative pathways for formation of the reactive ternary complex. This mechanism would also provide, under suitable conditions, for substrate activation or substrate inhibition in a two-substrate reaction, according to the relative rates of reaction through the two pathways.     

Enantioselective phenylacetylene addition to aldehydes and ketones catalyzed by recyclable polymeric Zn(salen) complex

New polymeric Zn(salen) complex was employed in the enantioselective phenylacetylene addition to aldehydes and ketones to produce corresponding chiral secondary propargylic alcohols with yields (up to 96%) and enantioselectivity (up to 72%) and tertiary propargylic alcohols with yields (up to 79%) and enantioselectivity (up to 68%) at room temperature, with added advantage of four times reuse with retention of enantioselectivity.     

Highly Enantioselective Production of Chiral Secondary Alcohols Using Lactobacillus paracasei BD101 as a New Whole Cell Biocatalyst and Evaluation of Their Antimicrobial Effects

Chiral secondary alcohols are valuable intermediates for many important enantiopure pharmaceuticals and biologically active molecules. In this work, we studied asymmetric reduction of aromatic ketones to produce the corresponding chiral secondary alcohols using lactic acid bacteria (LAB) as new biocatalysts. Seven LAB strains were screened for their ability to reduce acetophenones to their corresponding alcohols. Among these strains, Lactobacillus paracasei BD101 was found to be the most successful at reducing the ketones to the corresponding alcohols. The reaction conditions were further systematically optimized for this strain and high enantioselectivity (99%) and very good yields were obtained. These secondary alcohols were further tested for their antimicrobial activities against important pathogens and significant levels of antimicrobial activities were observed although these activities were altered depending on the secondary alcohols as well as their enantiomeric properties. The current methodology demonstrates a promising and alternative green approach for the synthesis of chiral secondary alcohols of biological importance in a cheap, mild, and environmentally useful process.     

Degradation of long chain n-alkanes by mucorales

Summary Extracellular oxidation products isolated from the substrates ofMortierella isabellina (CBS 224. 35) grown on n-dodecane and n-tridecane were primary and secondary isomeric alcohols, isomeric ketones, aldehydes and isomeric esters with the same numbers of carbon atoms presented in the used n-alkanes as detected by combined glass capillary gas chromatography — mass spectrometry. All esters were identified which theoretically could originate in the isomeric ketones by a reaction mechanism resembling a Baeyer-Villinger-type oxidation.     

Availability of Energy in Alcohols,Aldehydes and Ketones by Growing Chicks

Biological availability of 23 alcohols, 16 aldehydes and 2 ketones was compared by the mini-test with chicks. Chicks can utilize methanol and ethanol, but not the alcohols of carbon chain from 3 to 9. Lauryl and myristyl alcohols were well utilized but those of higher carbon chain than 14 were not, mainly due to low digestibility. Glycerol and D-sorbitol were well utilized but not 4 other poly alcohols tested. Aldehydes and ketones with free carbonyl group showed low availability or even toxicity, but their derivatives with masked group showed no detrimental effect. Acetaldehyde, acetal and aldehydes of carbon chain longer than 9 were partially utilized.     

Stimulation of hemoglobin synthesis in murine erythroleukemia cells by low molecular weight ketones,aldehydes, acids,alcohols and ethers

The effects of short chain (C1-C5) aldehydes, ketones, acids, alcohols and ethers on murine erythroleukemia (MEL) cells were examined to determine which particular chemical moieties and some of their combinations stimulated hemoglobin synthesis in these cells. The C4 series of compounds was active at lower concentrations than homologs of shorter chain lengths. Within an homologous series the potency and efficacy of the alcohol was always less than that of the acid and aldehyde compounds. Though heptanoic acid was found to be an inducer of hemoglobin synthesis in MEL cells, the 4,6-dioxoheptanoic acid analog is a potent inhibitor of hemoglobin synthesis. Analysis of porphyrin content of MEL cells incubated with the inducers 2-butanone, 2-methoxyethanol, acetone and methanol, showed that increased hemoglobin synthesis was always accompanied by the accumulation of porphyrins, most of which was protoporphyrin. These studies suggest that low molecular weight ketones, aldehydes, acids, ethers and alcohols can correct the defect in erythroid differentiation exhibited by MEL cells and they further suggest that the physiological trigger for inducing hemoglobin synthesis in these cells is less discriminating than previously recognized.     

Permeability of Red Cell Membranes to Small Hydrophilic and Lipophilic Solutes

The permeability coefficients of a series of amides, ureas, and diols have been measured on red cells of man and dog using the minimum volume method of Sha'afi et al. When the molecules are grouped according to their ether-water partition coefficients, k_ether, the behavior of the hydrophilic molecules, with k_ether less than water, is different from that of the lipophilic molecules, characterized by k_ether greater than water. The rate of permeation of the hydrophilic molecules through an aqueous pathway is determined by the molar volume, a parameter in which the geometrical measure of molecular volume is modified by hydrogen-bonding ability. This indicates the importance of chemical interactions within the aqueous path. The permeation of the lipophilic molecules is determined in the first instance by k_ether, taken as a measure of the ease with which the molecule can escape from its aqueous environment. Within the membrane, lipophilic permeability is modified both by steric factors and by the formation of hydrogen bonds with membrane components. These data allow one to infer that lipid-soluble molecules travel through an organized structure within the lipid membrane and come into contact with polar moieties.     

Alcohol induction of interdigitation in distearoylphosphatidylcholine: fluorescence studies of alcohol chain length requirements.

Although it is now well established that the fully interdigitated phase is induced in saturated like-chain phosphatidylcholines (PCs) by a variety of amphipathic molecules including alcohols, no systematic study of the properties of the inducing molecules has been reported. To elucidate the stereochemical features that lead to the alcohol induction of interdigitation in PCs, we have investigated the induction of interdigitation in distearoylphosphatidylcholine (DSPC) by a series of alcohols. Our previously established DPH (1,6-diphenyl-1,3,5-hexatriene) fluorescence intensity method has been expanded (P. Nambi, E. S. Rowe, and T. M. McIntosh (1988), Biochemistry 27:9175-9182) and used to determine which of the alcohols induce interdigitation and to determine the threshold concentrations for each. We have found that each of the n-alcohols up to heptanol and several branched alcohols are capable of inducing interdigitation in DSPC; octanol and nonanol do not appear to induce interdigitation by these criteria. The threshold concentrations for interdigitation for each of these alcohols up to heptanol were found to be correlated with the membrane: buffer partition coefficients. The mole fraction of bound alcohol at the threshold concentration was similar for each of the alcohols up to pentanol. These results are discussed in terms of a general mechanism of the formation of the interdigitated phase.     

The oxidation of chiral alcohols catalyzed by catalase in organic solvents

The catalytic properties of bovine liver catalase have been investigated in organic solvents. In tetrahydrofuran, dioxane, and acetone (all containing 1% to 3% of water), the enzyme breaks down tert-butyl hydroperoxide several fold faster than in pure water. Furthermore, the rate of catalase-catalyzed production of tert-butanol from tert-butyl hydroperoxide increases more than 400-fold upon transition from aqueous buffer to ethanol as the reaction medium. The mechanistic rationale for this striking effect is that in aqueous buffer the rate-limiting step of the enzymatic process involves the reduction of catalase's compound I by tert-butyl hydroperoxide. In ethanol, and additional step in the reaction scheme becomes available in which ethanol, greatly outcompeting the hydroperoxide, is oxidized by compound I regenerating the free enzyme. In solvents, such as acetonitrile or tetrahydrofuran, which themselves are not oxidizable by compound I, catalase catalyzes the oxidation of numerous primary and secondary alcohols with tert-butyl hydroperoxide to the corresponding aldehydes or ketones. The enzymatic oxidation of some chiral alcohols (2,3-butanediol, citronellol, and menthol) under these conditions occurs enantioselectively. Examination of the enantioselectivity for the oxidation of 2,3-butanediol in a series of organic solvents reveals a considerable solvent dependence. (c) 1995 John Wiley & Sons, Inc.     

Biological origins of normal-chain hydrocarbons: a pathway model based on cuticular wax analyses of maize silks

Long-chain normal hydrocarbons (e.g. alkanes, alkenes and dienes) are rare biological molecules and their biosynthetic origins are obscure. Detailed analyses of the surface lipids that accumulate on maize silks have revealed that these hydrocarbons constitute a large portion (>90%) of the cuticular waxes that coat this organ, which contrasts with the situation on maize seedling leaves, where the cuticular waxes are primary alcohols and aldehydes. The normal hydrocarbons that occur on silks are part of a homologous series of alkanes, alkenes and dienes of odd-number carbon atoms, ranging between 19 and 33 in number. The alkenes and dienes consist of a homologous series, each of which has double bonds situated at defined positions of the alkyl chains: alkenes have double bonds situated at the sixth, ninth or 12th positions, and dienes have double bonds situated at the sixth and ninth, or ninth and twelfth positions. Finding a homologous series of unsaturated aldehydes and fatty acids suggests that these alkenes and dienes are biosynthesized by a series of parallel pathways of fatty-acid elongation and desaturation reactions, which are followed by sequential reduction and decarbonylation. In addition, the silk cuticular waxes contain metabolically related unsaturated long-chain methylketones, which probably arise via a decarboxylation mechanism. Finally, metabolite profiling analyses of the cuticular waxes of two maize inbred lines (B73 and Mo17), and their genetic hybrids, have provided insights into the genetic control network of these biosynthetic pathways, and that the genetic regulation of these pathways display best-parent heterotic effects.     

Kinetic and Mechanistic Studies of a Novel Carbonyl Reductase Isolated from Candida Parapsilosis

The novel carbonyl reductase from Candida parapsilosis (CPCR) exhibits a very broad substrate specificity, accepting primary and secondary alcohols, aldehydes, ketoacetals, aliphatic and aromatic ketones, cyclic ketones, diketones, halogenated ketones, keto esters and halogenated keto esters of variable chain length as substrates. Based on the kinetic constants of a variety of different substrates a hypothetical model of the substrate-binding site is proposed. The small alkyl side chain of the carbonyl compound is bound to a small pocket of the binding site, while the large alkyl group is orientated towards the large hydrophobic pocket. This model and the kinetic data enables the prediction of whether a substrate of interest may be reduced by the CPCR. Product inhibition studies are reported which show that the kinetic mechanism of the CPCR is Ordered Bi-Bi, with the nucleotide adding to free enzyme before the other substrate. Alcohols and/or ketones are adsorbed at sites other than the active site and alter the catalytic properties of the enzyme. The enzyme transfers the pro-R hydride of NADH to the re face of the carbonyl compounds yielding (S) alcohols.     

Identification by gas-liquid chromatography-mass spectrometry of low-molecular-weight products from the aqueous alkaline degradation of cellulose

Low-molecular-weight products from the degradation of pure cellulose in 0.3–0.65M sodium carbonate or hydrogencarbonate at 300° have been identified by g.l.c-m.s. Both the aqueous residual phase and the floating-oil product phase were examined, and contained essentially the same compounds, which were further characterized by the trifluoroacetyl derivatives. They consisted primarily of unsaturated aliphatic and alicyclic hydrocarbons, aldehydes, ketones, alcohols, and furans. Specifically identified were cyclopentanone, cyclohexanone, phenol, cresols, 2-ethyl- cyclopentanone, 2- or 3-methylcyclopentanone, 2,5-dimethyl-2- cyclopentenone, acrolein, 2,5-dimethyl-2,4-hexadiene, and octene. Probably present were 2,4-dimethylfuran, 2,5-diethylfuran, ethylmethylfuran, 4-octyne, and decyne. The formation of these compounds demonstrates not only the degradation of cellulose but the resynthesis of molecules with carbon-chain lengths greater than 6 atoms.