Fatty acid oxidation in anoxic marine sediments: the importance of hydrogen sensitive reactions

In anoxic marine sediments fatty acids may be oxidized directly by sulfate reducing bacteria, or may be oxidized by pathways which result in hydrogen production. Some of these latter reactions are quite sensitive to hydrogen concentrations ... in other words if hydrogen concentrations become elevated, fatty acid oxidation will cease. Thus sulfate reducers may actually play two important roles in the metabolism of fatty acids in marine sediments. The sulfate reducers both can utilize fatty acids directly, and also can oxidize hydrogen and thus control hydrogen partial pressures in the sediments. Therefore sulfate reducers may act indirectly to facilitate fatty acid oxidation by hydrogen-producing pathways. We carried out a series of incubations of slurried salt marsh sediment under high and low hydrogen partial pressures and in the presence and absence of molybdate to investigate the relative importance of sulfate reducers and other bacteria mediating hydrogen-sensitive reactions. Our results suggest that both classes of bacteria contribute significantly to fatty acid turnover in marine sediments. Studies of low molecular weight fatty acid turnover in sediment must explicitly recognize that manipulation of sediment (including addition of molydbate to inhibit sulfate reducers) may have a large impact on hydrogen partial pressures in sediment, and may thus significantly alter the pathways and/or rates of fatty acid turnover.     

Routes to 4-hydroxynonenal: fundamental issues in the mechanisms of lipid peroxidation

Although investigation of the toxicological and physiological actions of alpha/beta-unsaturated 4-hydroxyalkenals has made great progress over the last 2 decades, understanding of the chemical mechanism of formation of 4-hydroxynonenal and related aldehydes has advanced much less. The aim of this review is to discuss mechanistic evidence for these non-enzymatic routes, especially of the underappreciated intermolecular pathways that involve dimerized and oligomerized fatty acid derivatives as key intermediates. These cross-molecular reactions of fatty acid peroxyls have also important implications for understanding of the basic initiation and propagation steps during lipid peroxidation and the nature of the products that arise.     

Linoleic acid peroxidation and lignin degradation by enzymes produced by Ceriporiopsis subvermispora grown on wood or in submerged liquid cultures

Ceriporiopsis subvermispora is a white-rot fungus used in biopulping processes and seems to use the fatty acid peroxidation reactions initiated by manganese-peroxidase (MnP) to start lignin degradation. The present work shows that C. subvermispora was able to peroxidize unsaturated fatty acids during wood biotreatment under biopulping conditions. In vitro assays showed that the extent of linoleic acid peroxidation was positively correlated with the level of MnP recovered from the biotreated wood chips. Milled wood was treated in vitro by partially purified MnP and linoleic acid. UV spectroscopy and size exclusion chromatography (SEC) showed that soluble compounds similar to lignin were released from the milled wood. SEC data showed a broad elution profile compatible with low molar mass lignin fractions. MnP-treated milled wood was analyzed by thioacidolysis. The yield of thioacidolysis monomers recovered from guaiacyl and syringyl units decreased by 33% and 20% in MnP-treated milled wood, respectively. This has suggested that lignin depolymerization reactions have occurred during the MnP/linoleic acid treatment.     

An overview on the recent advances in the transesterification of vegetable oils for biodiesel production using chemical and biocatalysts

Biodiesel, chemically defined as monoalkyl esters of long chain fatty acids, are derived from renewable feed stocks like vegetable oils and animal fats. It is produced by both batch and continuous transesterification processes in which, oil or fat is reacted with a monohydric alcohol in the presence of a catalyst. The conventional method of producing biodiesel involves acid and base catalysts to form fatty acid alkyl esters. Downstream processing costs and environmental problems associated with biodiesel production and byproducts recovery have led to the search for alternative production methods and alternative substrates. Enzymatic reactions involving lipases can be an excellent alternative to produce biodiesel through a process commonly referred to as alcoholysis, a form of transesterification reaction or through an interesterification reaction. In order to increase the cost effectiveness of the process, the enzymes are immobilized using a suitable matrix. The use of immobilized lipases and whole cells may lower the overall cost, while presenting less downstream processing problems. Main focus of this paper is to discuss the important parameters that affect the biodiesel yield, various immobilization techniques employed, mechanisms and kinetics of transesterification reaction and the recent advances in continuous transesterification processes.     

Serological activity of glycosphingolipids: effect of chain length of the fatty acid residue in cytolipin H

Serological reactions (complement-fixation) of a series of synthetic lactosyl dihydroceramides containing fatty acid residues with 2 to 18 carbon atoms were studied with two antisera reacting well with naturally occurring cytolipin H. The chain length of the fatty acid residue played an important role in activity of the hapten: molecules with 6 carbon atoms or less were unreactive, whereas molecules with 10 or more carbon atoms were maximally reactive.     

Synthesis and antioxidant activity of new lipophilic dihydropyridines

Dihydropyridines (DHPs) obtained from Hantzsch multicomponent reactions are an important pharmaceutical class of compounds marketed as antihypertensive (e.g., nifedipine, nitrendipine, and amlodipine) drugs. This study synthesized new symmetrical and unsymmetrical long-chain fatty DHPs using multicomponent reactions under metal-free conditions with sulfamic acid as a catalyst. The DHPs were tested for antioxidant activity using three different methods. The insertion of a long chain into the DHP core contributed to antioxidant potential, and compounds derived from nitro aldehydes have better antioxidant potential than the antihypertensive drug nifedipine. In addition, fatty analogs to nifedipine derived from palmitic and oleic chains showed similar antioxidant activity to the common standards butylated hydroxytoluene and vitamin E. These results showed that our new synthesized products may find novel applications as antioxidant additives or for tools for use in drug discovery.     

Inactivation and conformational changes of fatty acid synthase from chicken liver during unfolding by sodium dodecyl sulfate

Fatty acid synthase is an important enzyme participating in energy metabolism in vivo. The inactivation and conformational changes of the multifunctional fatty acid synthase from chicken liver in SDS solutions have been studied. The results show that the denaturation of this multifunctional enzyme by SDS occurred in three stages. At low concentrations of SDS (less than 0.15 mM) the enzyme was completely inactivated with regard to the overall reaction. For each component of the enzyme, the loss of activity occurred at higher concentrations of SDS. Significant conformational changes (as indicated by the changes of the intrinsic fluorescence emission and the ultraviolet difference spectra) occurred at higher concentrations of SDS. Increasing the SDS concentration caused only slight changes of the CD spectra, indicating that SDS had no significant effect on the secondary structure of the enzyme. The results suggest that the active sites of the multifunctional fatty acid synthase display more conformational flexibility than the enzyme molecule as a whole.     

Studies on the regulation of lipid biosynthesis in plants: application of control analysis to soybean

Although there is much knowledge of the enzymology (and genes coding the proteins) of lipid biosynthesis in higher plants, relatively little attention has been paid to regulation. We have demonstrated the important role for cholinephosphate cytidylyltransferase in the biosynthesis of the major extra-plastidic membrane lipid, phosphatidylcholine. We followed this work by applying control analysis to light-induced fatty acid synthesis. This was the first such application to lipid synthesis in any organism. The data showed that acetyl-CoA carboxylase was very important, exerting about half of the total control. We then applied metabolic control analysis to lipid accumulation in important oil crops — oilpalm, olive, and rapeseed. Recent data with soybean show that the block of fatty acid biosynthesis reactions exerts somewhat more control (63%) than lipid assembly although both are clearly very important. These results suggest that gene stacks, targeting both parts of the overall lipid synthesis pathway will be needed to increase significantly oil yields in soybean. This article is part of a Special Issue entitled: Membrane Structure and Function: Relevance in the Cell's Physiology, Pathology and Therapy.     

Uptake and metabolic conversion of saturated and unsaturated fatty acids in Hep2 human larynx tumor cells

Research on fatty acid metabolism in cultured human larynx tumor cells Hep2 was carried out.The cells were incubated with either a saturated (palmitic) or a polyunsaturated (linoleic, alpha-linolenic and eicosatrienoic (n-6)) radioactive fatty acid (0.66 pM, 24 h). The best incorporation capacity was observed in the linoleic acid followed by alpha-linolenic, palmitic and eicosatrienoic acids. All fatty acids tested were anabolized to higher derivatives within their own family. Palmitic acid was primarily monodesaturated rather than elongated, proving to have a very active A9 desaturase activity.With respect to polyunsaturated acid metabolism, the conversion of alpha-linolenic acid to higher homologs, although better than linoleic acid, occurred far less efficiently than that observed in other non-highly undifferentiated human tumor cells. This impairment in higher polyunsaturated fatty acid biosynthesis, reflected in the low levels of arachidonic acid in the fatty acid composition, would not reside in the A5 desaturation step since Hep2 cells can readily convert eicosatrienoic acid into arachidonic acid. Considering the potential regulatory role of specific polyunsaturated fatty acids in the cell proliferative control, the knowledge of the metabolism of fatty acids in this human tumor cell would be important for designing future experiments in order to clarify the mechanism involved in balance, proliferation and cell death.     

COMMERCIAL DEVELOPMENTS IN MICROALGAL BIOTECHNOLOGY

A number of important advances have occurred in microalgal biotechnology in recent years that are slowly moving the field into new areas. New products are being developed for use in the mass commercial markets as opposed to the "health food" markets. These include algal-derived long-chained polyunsaturated fatty acids, mainly docosahexaenoic acid, for use as supplements in human nutrition and animals. Large-scale production of algal fatty acids is possible through the use of heterotrophic algae and the adaptation of classical fermentation systems providing consistent biomass under highly controlled conditions that result in a very high quality product. New products have also been developed for use in the development of pharmaceutical and research products. These include stable-isotope biochemicals produced by algae in closed-system photobioreactors and extremely bright fluorescent pigments. Cryopreservation has also had a tremendous impact on the ability of strains to be maintained for long periods of time at low cost and maintenance while preserving genetic stability.     

Abnormal fatty acid profile in chronic hemodialysis patients: possible deficiency of essential fatty acids

Plasma fatty acid profiles from maintenance hemodialysis patients (n = 9) were compared with those from healthy volunteers (n = 9). Hemodialysis patients had significantly higher levels of oleic acid, 15.3 +/- 1.1 vs. 8.9 +/- 0.6% (p less than 0.0001), and lower levels of arachidonic acid (6.0 +/- 0.5 vs. 8.4 +/- 0.3%, p less than 0.0009). Linolenic and linoleic acids, the essential fatty acid and precursors of arachidonic acid, were also significantly lower than normal in the dialysis group. These data show that dialysis patients have fatty acid abnormalities suggesting relative depletion of essential fatty acids. These observations are important because these abnormalities may play an important role in the pathogenesis of some common clinical conditions associated with uremia, such as a constellation of skin problems, fragility of erythrocytes, lipid anomalies and hormonal aberrations.     

Continuous enzymatic esterification of glycerol with (poly)unsaturated fatty acids in a packed-bed reactor

Enzymatic synthesis of mono-, di-, and triacyglycerols from (poly)unsaturated fatty acids (linoleic, oleic, and conjugated linoleic acids) has been studied as a solvent-free reaction in a packed-bed reactor containing an immobilized lipase from Mucor miehei. The extents of the esterification reactions of interest are primarily determined by the molar ratio of glycerol to fatty acid because the presence of excess glycerol as a immiscible phase is responsible for reducing the activity of the water produced by the esterification reactions. For molar ratios of fatty acid to glycerol of less than 1.5, the percentage of the fatty acid esterified decreases quasi-linearly with an increase in this molar ratio. By appropriate manipulation of the fluid-residence time, one can control the relative proportions of the various acylglycerols in the effluent stream. At the outlet of the reactor, one observes excellent spontaneous separation of the glycerol and acylglycerol/fatty acid phases. At 50 degrees C and a fluid residence time of 1 hour, as much as 90% of the fatty acid can be esterified when the molar ratio of fatty acid to glycerol is 0.33 or less.     

Protein fatty acylation: a novel mechanism for association of proteins with membranes and its role in transmembrane regulatory pathways

A wide range of proteins of cellular and viral origin have been shown to be modified covalently by long-chain fatty acids. Recent studies have revealed at least two distinct types of protein fatty acylation which involve different fatty acyltransferases. The abundant fatty acid, palmitate, is incorporated post-translationally through a thiol ester linkage into a variety of cell surface glycoproteins and non-glycosylated intracellular proteins. In contrast, the rare fatty acid, myristate, is incorporated co-translationally through an amide linkage into numerous intracellular proteins. Identification of proteins that contain covalent fatty acids has revealed that this modification is common to a broad array of proteins that play important roles in transmembrane regulatory pathways. For many of these proteins, the fatty acid moiety appears to play an important role in directing the polypeptide to the appropriate membrane and in mediating protein-protein interactions within the membrane. This review will summarize recent studies that define different pathways for protein fatty acylation and will consider the potential functions for this unique covalent modification of proteins.     

Analysis of interspecific variation in relative fatty acid composition: use of flow cytometry to estimate unsaturation index and relative polyunsaturated fatty acid content in microalgae

Relative polyunsaturated fatty acid content and unsaturation index are very important composition variables in the use of microalgae both for animal and human nutrition and biofuel production. A readily available technique to rapidly and inexpensively estimate relative fatty acid composition is very important for mass screening of new strains for the production of different types of oil. This study demonstrates the validity of Nile Red staining and flow cytometry for quick estimation of unsaturation index and relative fatty acid content in microalgae. Nile Red staining allows polar and neutral lipid contents to be estimated, and in this study a significant correlation was observed between polar/neutral ratio and fatty acid content in the species studied, corresponding to higher polyunsaturated fatty acid content in the polar lipid fraction of microalgae. This technique enables quick estimation of relative polyunsaturated fatty acid content and interspecific variation, as well as variations caused by culture conditions. In the species studied, most variability in fatty acid composition was due to variation in monounsaturated and polyunsaturated fatty acids, with less variation observed in saturated fatty acid content.     

细菌脂肪酸合成多样性的研究进展

与哺乳动物、真菌采用I型脂肪酸合成系统不同,细菌采用II型脂肪酸合成系统,每步反应都由独立的酶催化,因此细菌脂肪酸合成酶是研究抗菌药物的优良靶标。研究表明,在不同细菌中参与脂肪酸合成的酶都具有较高的多样性,而脂肪酸种类不同,合成方式也不尽相同,本文对此进行了总结。     

Development and quantification of biodiesel production from chicken feather meal as a cost-effective feedstock by using green technology

Increased urbanization and increase in population has led to an increased demand for fuels. The result is the prices of fuels are reaching new heights every day. Using low-cost feedstocks such as rendered animal fats in biodiesel production will reduce biodiesel expenditures. One of the low-cost feedstocks for biodiesel production from poultry feathers. This paper describes a new and environmentally friendly process for developing biodiesel production technology from feather waste produced in poultry industry. Transesterification is one of the well-known processes by which fats and oils are converted into biodiesel. The reaction often makes use of acid/base catalyst. If the material possesses high free fatty acid then acid catalyst gives better results. The data resulted from gas chromatography (GC) revealed these percentages for fatty acid compositions: myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid and arachidonic acid. The biodiesel function group was analyzed by using FTIR. This study concluded that the rooster feathers have superior potential to process them into biodiesel than broiler chicken feathers fat because of fatty acid composition values and it has important properties of biodiesel.     

Fatty acids covalently bound to erythrocyte proteins undergo a differential turnover in vivo

Recently, covalently bound fatty acids have been identified on a variety of proteins. Many of these acyl proteins are physiologically important, and the lipid modification often appears to be essential for their function. In this investigation mature erythrocytes have been used to study in detail the metabolic behavior of protein-bound fatty acids. Although deficient in protein synthesis, these cells are still able to covalently attach [3H]palmitic acid to proteins located at the plasma membrane and its associated cytoskeleton. Linkage analyses demonstrated that the labeled polypeptides contained ester- or thioester-bound fatty acids. The covalent binding of fatty acid was rapidly reversible. Half-lives of the protein-bound fatty acid molecules ranged from less than 30 min to more than 3 h. The deacylation reaction was not due to a chemically labile linkage of protein and fatty acid but appeared to be physiologically induced. Differences in the fatty acid turnover rates between the acyl proteins suggested an independent regulation of their lipid turnover. A number of proteins underwent dynamic fatty acid acylation, indicating that palmitylated proteins undergoing fatty acid turnover are not a rare exception.     

Versatile synthesis of phenoxydiazirine-based fatty acid analogues and photoreactive galactosylceramide.

A versatile synthesis of diazirine-based photoreactive fatty acid analogues is reported. The key step is phenoxy alkylation of diazirine with halo alkyl acid esters. The conditions described will be acceptable for the synthesis of various alkyl-length derivatives. The fatty acid derivatives are acceptors for reverse reactions of sphingolipid ceramide N-deacylase (SCDase), which catalyzes the condensation of psychosine and fatty acids to form photoreactive galactosylceramide. The photoreactive galactosylceramide can also be prepared with chemical synthesis, condensation of psychosine and fatty acid succinimidyl ester, and is recognized with anti-GarCer antibody both before and after irradiation.     

Effect of simvastatin on the uptake and metabolic conversion of palmitic, dihomo-gamma-linoleic and alpha-linolenic acids in A549 cells

It is well known that simvastatin affects cholesterol synthesis. Furthermore it inhibits growth and proliferation and perturbs fatty acid metabolism in some cell lines. We have studied the effects of simvastatin on the uptake and metabolism of exogenous fatty acid in the human lung adenocarcinoma A549 cells. Simvastatin inhibited the proliferation of A549, and caused an increment in phospholipid/cholesterol ratio due to an increment in phospholipid content without affecting cholesterol content. All the fatty acids were uptaken and metabolized in both control and treated cells. The conversion of palmitic, linoleic and dihomo-gamma-linoleic acids to their metabolites and products/precursor ratios for the desaturation and elongation reactions showed that simvastatin enhanced the Delta5 desaturation step and altered some elongating steps. The machinery for unsaturated fatty acid synthesis in A549 is quite sensitive to simvastatin and its effects could have important implication taking into account that highly unsaturated fatty acids are involved in the regulation of diverse cellular functions by themselves or through their metabolites.