Production of long-chain alcohols by yeasts

Fourteen yeast strains from six genera were analysed for the presence of long-chain alcohols. Six strains from three genera contained long-chain alcohols, highest levels being found in Candida albicans. The alcohols were identified and determined by TLC, GLC and GLC-MS. The major long-chain alcohols synthesized by these organisms were saturated, primary alcohols with C14, C16 or C18 chain length. Unsaturated long-chain alcohols were not detected. In all strains that produced long-chain alcohols, the relative proportions were C16 greater than C18 greater than C14. Long-chain alcohol contents were higher in organisms from anaerobically, as compared with aerobically, grown cultures reaching about 650 micrograms (g dry wt organisms)-1 in stationary-phase cultures of C. albicans. In cultures of C. albicans, synthesis of long-chain alcohols occurred only after the end of exponential growth. The alcohols were predominantly present as free alcohols. The fatty-acyl chain-length profile of the triacylglycerol and to a lesser extent the sterol/wax ester fractions from C. albicans reflected that of the long-chain alcohols produced by this yeast.     

Utility of ionic liquid for Geotrichum candidum-catalyzed synthesis of optically active alcohols

Ionic liquids have recognized as a solvent for Geotrichum candidum-catalyzed optical resolution and/or deracemization of racemic secondary alcohols, giving optically active alcohols. The immobilized Geotrichum candidum proceeded the enantioselective oxidation of alcohols, producing chiral alcohols in an ionic liquid. Further, deracemization of racemic alcohols was proceeded to give the corresponding chiral alcohols in high yield with excellent stereoselectivity by the Geotrichum candidum–NaBH₄ system in the mixture of MES buffer solution and ionic liquid.     

脂肪醇制备研究进展

脂肪醇是合成表面活性剂、洗涤剂、增塑剂及其他多种精细化学用品的基础化工原料,广泛应用于纺织、日化、造纸、食品、医药、皮革等领域。本文介绍了脂肪醇的市场现状,综述了工业制备脂肪醇的传统方法,阐述了以可再生非粮生物质为原料,利用生物法制备生物基脂肪醇的方法,并对生物基脂肪醇的新合成路线的发展方向进行展望。     

Effect of alcohols on the functional organization of the inner mitochondrial membrane

Monohydric alcohols extract phospholipids from beef heart mitochondria with an efficacy which depends on the chain length of the alcohol. Succinoxidase and ATPase activities are affected by alcohols in a similar way; alcohols make ATPase oligomycin-insensitive at concentrations decreasing with the chain length of the alcohol. Oxidative phosphorylation is inhibited at much lower concentrations of alcohols. Hydrophobic boods must play a role in the organization of all of the activities considered.     

Transesterification/acetylation of long chain alcohols with alkyl acetate

Gas chromatographic characterizations of fatty alcohols are generally carried out as the free alcohols, trimethyl silyl or acetyl derivatives. In this study, transesterification/acetylation of long chain fatty alcohols is simply carried out by dissolving the alcohol in ethyl/methyl acetate and passing through a micro-column packed with solid NaOH. Reaction times are slightly different for alcohols of different chain length. Rice bran alcohols of 24–34 carbon atom are successfully acetylated. Also, castor oil methyl ester can be interesterified but with longer reaction time.     

Effect of the composition of polysaccharides in gelatinized cornstarch on alcohol absorption

Sorption of alcohols in aqueous suspensions of gelatinized cornstarches with various contents of amylose was studied by capillary gas chromatography. Alcohol sorption depended primarily on the structure of alcohols, but not on the composition of polysaccharides. No correlation was found between the efficiency of sorption and amylose content in starch. The amount of substances sorbed by starches depended linearly on their initial concentration in the gel. Normal and highly amylose starches sorbed alcohols to a similar degree. However, increasing the length of alkyl substituents improved sorption of alcohols. Amylopectin starch differed in high affinity for small molecules and low sensitivity to the structure and hydrophobicity of alcohols.     

Secondary fatty alcohols of Mycobacterium xenopi.

Secondary alcohols of Mycobacterium xenopi were studied by gas chromatography and gas chromatography-mass spectrometry. Mycobacterial cells were hydrolysed and the liberated alcohols separated by extraction and analysed both underivatized and as trimethylsilyl, methyl ether- and pentafluorobenzoyl derivatives. Seven straight-chain secondary alcohols containing from 18 to 24 carbon atoms and two branched-chain secondary alcohols with 21 and 23 carbon atoms were present in all of the studied strains.     

Effect of aliphatic alcohols on growth and degree of saturation of membrane lipids in Acinetobacter calcoaceticus

The adaptive responses of the bacterium Acinetobacter calcoaceticus to different aliphatic alcohols on the level of the membrane fatty acids were studied in detail. The toxicity of the aliphatic alcohols increased with an increasing hydrophobicity. As alcohols are known to increase the fluidity of the membrane they consequently should cause the same adaptive effect on membrane level. Yet, cells of A. calcoaceticus react completely different to the alcohols: in the presence of long-chained alcohols they increase their degree of saturation, while in the presence of short-chained alcohols they decrease the degree of saturation. So, there are no observable differences in the adaptive responses of bacteria with the so-called anaerobic pathway, like Escherichia coli and Pseudomonas putida, and the bacterium carrying the so-called aerobic pathway like A. calcoaceticus. These results strongly indicate a physico-chemical difference in the membrane effect of both the partitioning and localisation of the different alcohols into the membrane and the membrane adaptive responses of the bacteria to these effects.     

Effect of the Composition of Polysaccharides in Gelatinized Cornstarch on Alcohol Absorption

Sorption of alcohols in aqueous suspensions of gelatinized cornstarches with various contents of amylose was studied by capillary gas chromatography. Alcohol sorption depended primarily on the structure of alcohols, rather than on the composition of polysaccharides. No correlation was found between the efficiency of sorption and amylose content in starch. The amount of substances sorbed by starches depended linearly on their initial concentration in the gel. Normal and high-amylose starches sorbed alcohols to a similar degree. However, increasing the length of alkyl substituents improved sorption of alcohols. Amylopectin starch differed in high affinity for small molecules and low sensitivity to the structure and hydrophobicity of alcohols.     

Interaction of aliphatid alcohols with cytochrome P-450 from rat liver microsomes]

The interaction of alyphatic alcohols and cyclohexanol with cytochrome P-450 in microsomes has been investigated. All alchohols induced the modified 11 type spectral changes by mixing with microsomes. These changes are characterized by lambdamax = 412 and lambdamin = 380-382 nm in difference spectra. The dissociation constants of the alcohol cytochrome P-450 complexes are determined. On this dissociation constants influence pH and Triton X-100 presence. The interaction of the alcohols with cytochrome P-450 in phosphate buffer pH = 6,0 in the detergents absence is characterized by one dissociation constant for MeOH, EtOH, n-BuOH and cyclohexanol and by two dissociation constants for i-PrOH, i-BuOH and tert.-BuOH. The interaction of the alcohols with cytochrome P-450 in Tris-HCL-buffer (pH 7.5) in the Triton X-100 presence is characterized for all above alcohols by the dissociations constants, which are described by Taft equation with coefficient rho =-1.55. This fact confirms the interaction of alcohols HO-groups with heme iron of cytochrome P-450. The scheme of interaction of alcohols with cytochrome P-450 is discussed.     

Thermodynamic interpretation of effects of alcohols on membrane lipid fluidity

The effect of a series of amphiphilic compounds, the first eight n-aliphatic alcohols, on the fluidity of rat enterocyte brush border was determined by ESR using 5-doxyl stearic acid as a lipid spin probe. Packing order variations are compared to the relative hydrophobic effect of the alcohols. The concentrations, [Ci]5 of each alcohol that decrease the membrane 2T' value by 5%, vary by a factor of 1500 from methanol to octanol. From [Ci]5, the membrane concentrations Cm and the variation of free energy delta F degree due to the incorporation of the alcohols in the lipids, were calculated. These calculations were performed taking into account the respective volumes of the aqueous phase and the membrane lipids. Cm is of the order of 0.18 mol/kg for the odd chain length alcohols and of 0.27 mol/kg for the even alcohols. The value of delta F degree in cal/mol -CH2- is -687 cal on average for the eight alcohols. This work shows that for all the alcohols, the concentrations at equilibrium in the membrane and in the aqueous phase are respectively in agreement with Meyer and Overton's theory and with the gradient of free energy which constitutes the most general index of interaction of lipophilic substances with membranes.     

Phosphatidyl alcohols: Effect of head group size on domain forming properties and interactions with sterols

In this study, we have examined the membrane properties and sterol interactions of phosphatidyl alcohols varying in the size of the alcohol head group coupled to the sn-3-linked phosphate. Phosphatidyl alcohols of interest were dipalmitoyl derivatives with methanol (DPPMe), ethanol (DPPEt), propanol (DPPPr), or butanol (DPPBu) head groups. The Phosphatidyl alcohols are biologically relevant, because they can be formed in membranes by the phospholipase D reaction in the presence of alcohol. The melting behavior of pure phosphatidyl alcohols and mixtures with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) or cholesterol was assessed using high sensitivity differential scanning calorimetry (DSC). DPPMe had the highest melting temperature (∼ 49 °C), whereas the other phosphatidyl alcohols had similar melting temperatures as DPPC (∼ 40-41 °C). All phosphatidyl alcohols, except DPPMe, also showed good miscibility with DPPC. The effects of cholesterol on the melting behavior and membrane order in multilamellar bilayer vesicles were assessed using steady-state anisotropy of 1,6-diphenyl-1,3,5-hexatriene (DPH) and DSC. The ordering effect of cholesterol in the fluid phase was lower for all phosphatidyl alcohols as compared to DPPC and decreased with increasing head group size. The formation of ordered domains containing the phosphatidyl alcohols in complex bilayer membranes was determined using fluorescence quenching of DPH or the sterol analogue cholesta-5,7,(11)-trien-3-beta-ol (CTL). The phosphatidyl alcohols did not appear to form sterol-enriched ordered domains, whereas DPPMe, DPPEt appeared to form ordered domains in the temperature window examined (10-50 °C). The partitioning of CTL into bilayer membranes containing phosphatidyl alcohols was to a small extent increased for DPPMe and DPPEt, but in general, sterol interactions were weak or unfavorable for the phosphatidyl alcohols. Our results show that the biophysical and sterol interacting properties of phosphatidyl alcohols, having identical acyl chain structures, are markedly dependent on the size of the head group.     

Effect of alcohols on the structure and function of D-amino-acid oxidase.

The absorption spectrum of D-amino-acid oxidase (D-amino-acid:oxygen oxidoreductase (deaminating), EC 1.4.3.3) was significantly perturbed by various alcohols; typical fine structures were observed in the visible absorption bands, accompanied by blue shifts of the peaks. Both fluorescence intensity and fluorescence polarization were increased upon the addition of alcohols, indicating that the coenzyme is not liberated from the apoenzyme but the hydrophobicity of the environment of the enzyme-bound flavin is increased. Upon the addition of alcohols, the circular dichroism of the enzyme was markedly modified in the visible and near-ultraviolet regions, while that of the apoenzyme in the near- and far-ultraviolet regions was scarcely modified, indicating a change in the interaction between the flavin coenzyme and protein. Both the apparent maximal velocity and the apparent Michaelis constant of the enzyme were increased by the addition of alcohols. The presence of alcohols tends to dissociate the dimer of this enzyme into the monomer, but the dissociation does not fully explain the increase in the maximal velocity of the enzyme by alcohols, because the increase in the maximal velocity caused by alcohols is larger than that expected from the dissociation. Since the rate of formation of the purple intermediate was decreased by alcohols in both the dimer and the monomer, the increase in the maximal velocity could be ascribed to an increase in the rate of dissociation of the enzyme-product complex. This increase could be ascribed to the protein conformational change, which is probably provoked by combination of alcohols with the enzyme at a locus other than that for substrate binding.     

Comparative study of the effect of aliphatic alcohols on energy-dependent accumulation of Ca2+ in intracellular membranes of smooth muscle cells

The effects of ethanol and other aliphatic alcohols on energy-dependent Ca2+ transport in endoplasmic reticulum and mitochondria were studied in digitonin-treated myometrium cells. The Ca2+ uptake in mitochondria increased (on 15-20%) with increasing methanol, ethanol and propanol concentrations in medium, whereas further rise of concentration inhibited this process. Treatments of myometrial cells with short-chain alcohols caused an inhibition of calcium uptake in endoplasmic reticulum. Butanol inhibited both calcium uptake in mitochondria and endoplasmic reticulum. Ca2+ accumulation in intracellular pools is inhibited by aliphatic alcohols in the following order of potency: butanol > propanol > ethanol > methanol. It is concluded that modifying effect of aliphatic alcohols on energy dependent calcium accumulation in intracellular membrane structures is defined as on origin of Ca(2+)-transporting system and (or) properties of these membrane structures so on properties of alcohols.     

Capillary gas-liquid chromatographic separation of bile alcohols.

Gas-liquid chromatographic separation of C23, C24, C25, C26, and C27 bile alcohols with either 3 alpha, 7 alpha-dihydroxylated or 3 alpha, 7 alpha, 12 alpha-trihydroxylated ring system on two capillary columns, CP-Sil-19 CB and CP-Sil-5 CB, is described. Bile alcohols with two ring hydroxyl groups at 3 alpha- and 7 alpha-positions consistently showed larger retention times on CP-Sil-19 CB columns and smaller retention times on CP-Sil-5 CB columns than the corresponding bile alcohols with three ring hydroxyl groups at 3 alpha-, 7 alpha-, and 12 alpha-positions. Resolutions of all bile alcohols were better on CP-Sil-19 CB columns; however, we hope that the gas-liquid chromatographic characteristics on the two columns will be useful for better identification of bile alcohols in biological fluids.     

A systematic study of chiral homoprolinols and their derivatives in the catalysis of enantioselective addition of diethylzinc to aldehydes

Homoprolinol analogs, a class of optically active γ‐amino alcohols, were examined systematically in the enantioselective addition reactions of diethylzinc to aldehydes. By comparison of the results catalyzed by these γ‐amino alcohols with those by the β‐amino alcohols based on pyrrolidine architecture reported in the literature references, we have observed that the γ‐amino alcohols are superior to the corresponding β‐amino alcohols when the nitrogen and the oxygen are unsubstituted. Among the homoprolinols we tested, 2b gave the best results (45–88% yields, 44–81% ee) in the addition reactions. To the best of our knowledge, 2b has been noticed as one of the most efficient γ‐amino alcohol catalysts based on pyrrolidine framework. Chirality, 2011. © 2011 Wiley‐Liss, Inc.     

The Effect of Alcohols on Growth and Lipase Formation by Staphylococcus aureus

S ummary . The growth of Staphylococcus aureus 111 was inhibited by aliphatic alcohols. The extent of inhibition by primary n -alcohols increased with the elongation of the chain. Secondary alcohols were less inhibitory than the corresponding primary alcohols. The inhibitory effect was influenced by the distance of the hydroxyl group from the end of the carbon chain. When the alcohols were added to the medium in sub-inhibitory amount, enzyme synthesis by the bacteria was decreased, but there was no demonstrable inhibition of enzyme already formed.     

A gas chromatographic-mass spectrometric analysis of the esterifying alcohols of pumpkin seed protochlorophylls

The esterifying alcohols of protochlorophyll a and 4-vinyl-(4-desethyl)-protochlorophyll a (purified as the respective pheophytins) from pumpkin seeds were examined by gas chromatography-mass spectrometry. The results of the analysis suggested that pumpkin seed protochlorophyll a is esterified with all possible C₂₀ isoprenoid alcohols between and including geranylgeraniol and phytol, phytol comprising 90% or more of the mixture of esterifying alcohols, and that the 4-vinyl-(4-desethyl)-protochlorophyll a is esterified with farnesol and all possible C₂₀ isoprenoid alcohols between and including geranylgeranoid and phytanol, phytol comprising 50% or more of the mixture of esterifying alcohols. The 4-vinyl-(4-desethyl)-protochlorophyll a from a sample of older mature pumpkin seeds was found to be richer in esterifying alcohols corresponding to isoprenoid precursors of phytol then was the 4-vinyl-(4-desethyl)-protochlorophyll a from a sample of younger mature seeds. Other isoprenoid alcohols may have been present in very minor quantities in the mixtures of esterifying alcohols from the pumpkin seed protochlorophylls but were not looked for in this study. These results are discussed in terms of a biosynthetic accumulation of 4-vinyl-(4-desethyl)-protochlorophyll a in pumpkin inner seed-coat tissue.     

Long-chain fatty alcohols from pomace olive oil modulate the release of proinflammatory mediators

Pomace olive oil is a by-product of olive oil extraction that is traditionally produced and consumed in Spain. The nonglyceride matter of this oil is a good source of interesting minor compounds, like long-chain fatty alcohols, which are present free or as part of waxes. In the present study, long-chain fatty alcohols were isolated from the nonglyceride fraction of pomace olive oil, and the composition was identified and quantified. The major components of long-chain fatty alcohols were tetracosanol, hexacosanol and octacosanol. We investigated the ability of long-chain fatty alcohols from pomace olive oil to inhibit the release of different proinflammatory mediators in vitro by cells involved in inflammatory processes. Long-chain fatty alcohols significantly and dose-dependently decreased nitric oxide production by RAW 264.7 murine macrophages stimulated with lipopolysaccharide. Western blot analysis showed that nitric oxide reduction was a consequence of the inhibition of inducible nitric oxide synthetase expression. Long-chain fatty alcohols also reduced tumor necrosis factor-alpha and prostaglandin E(2) production, although the potency of inhibition for the latter was lower. On the other hand, long-chain fatty alcohols significantly reduced thromboxane A(2) production in rat peritoneal neutrophils stimulated with the calcium ionophore A-23187. The reduction of eicosanoid release was related to the inhibition of phospholipase A(2) enzyme activity by long-chain fatty alcohols, reaching an inhibitory concentration 50% value of 6.2 microg/ml. These results showed that long-chain fatty alcohols may have a protective effect on some mediators involved in the inflammatory damage development, suggesting its potential value as a putative functional component of pomace olive oil.     

Perturbation of lipid metabolism in L-M cultured cells by elaidic acid supplementation: formation of fatty alcohols

Supplementation of culture medium with elaidic acid (400 μg/flask) in L-M cells results in the formation of an otherwise undetected lipid component. We have identified this lipid component to be a mixture of free fatty alcohols containing primarily elaidyl alcohol with cetyl, stearoyl, and oleoyl alcohols as minor constituents. Formation of fatty alcohols by fatty acid supplementation seems to be specific with $\text{trans}$ fatty acids (i.e., elaidate, $\text{trans}$ vaccenate, and linolelaidate); addition of stearate and oleate to the L-M cells does not produce fatty alcohols. The fatty alcohols accumulated by the $\text{trans}$ fatty acid supplementation are associated with both the particulate and supernatant fractions of the cells.