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Fatty Acids Are Hydrocarbon Derivatives

Fatty Acids Are Hydrocarbon Derivatives. Fatty acids are carboxylic acids with hydrocarbon chains ranging from 4 to 36 carbons long (C4 to C36).- some branched and some are unbranced (saturated) The most commonly occurring fatty acids have even numbers of carbon atoms - synthesis (2C)

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Fatty Acids Are Hydrocarbon Derivatives

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  1. Fatty Acids Are Hydrocarbon Derivatives • Fatty acids are carboxylic acids with hydrocarbon chains ranging from 4 to 36 carbons long (C4 to C36).- some branched and some are unbranced (saturated) • The most commonly occurring fatty acids have even numbers of carbon atoms - synthesis (2C) • most monounsaturated fatty acids the double bond is between C-9 and C-10 (9), and the other double bonds of polyunsaturated fatty acids are generally 12 and 15. • Fully saturated fatty acids in the extended form pack into nearly crystalline arrays, stabilized by many hydrophobic interactions. • The presence of one or more cis double bonds interferes with this tight packing and results in less stable aggregates.

  2. Properties of Fatty Acids x methylene • The double bonds of polyunsaturated fatty acids are almost never conjugated alternating single and double bonds are separated by a methylene group. • In nearly all naturally occurring unsaturated fatty acids, the double bonds are in the cis configuration. Trans fatty acids are produced by fermentation in the rumen of dairy animals and are obtained from dairy products and meat or hydrogenation of fish or vegetable oils – French fries, doughnuts and cookies - [LDL]↑. • The nonpolar hydrocarbon chain accounts for the poor solubility of fatty acids in water. • At room temperature (25oC), the saturated fatty acids from 12:0 to 24:0 have a waxy consistency, whereas unsaturated fatty acids of these lengths are oily liquids.- degrees of packing – pack in nearly crystalline arrays by van der Waals contact. • In vertebrates, free fatty acids (unesterified fatty acids, with a free carboxylate group) circulate in the blood bound noncovalently to a protein carrier, serum albumin (血清白蛋白 ). • fatty acids are present in blood plasma mostly as carboxylic acid derivatives such as esters or amides. Lacking the charged carboxylate group - less soluble in water than are the free fatty acids.

  3. Triacylglycerols Are Fatty Acid Esters of Glycerol • The simplest lipids constructed from fatty acids are the triacylglycerols- triglycerides, fats,or neutral fats. Three fatty acids each in ester linkage with a single glycerol. • simple triacylglycerols: same kind of fatty acid in all three positions- ex. Tristearin (16:0); tripalmitin (18:0); triolein (18:1) • Most are mixed

  4. Triacylglycerols Provide Stored Energy and Insulation • Adipocytes (fat cells), store large amounts of triacylglycerols as fat droplets that nearly fill the cell. • Adipocytes and germinating seeds contain lipases hydrolysis of stored triacylglycerols, releasing fatty acids for export to sites where they are required as fuel. • Advantages of using triacylglycerols as stored fuels: (1) the carbon atoms of fatty acids are more reduced than those of sugars, oxidation of triacylglycerols yields more than twice as much energy; (2) triacylglycerols are hydrophobic - unhydrated, the organism that carries fat as fuel does not have to carry the extra weight of water of hydration that is associated with stored polysaccharides (2 g per gram of polysaccharide). • Insulation: ex. temperatures. Seals, walruses, penguins. And hibernation animals - insulation and energy storage. • In sperm whales, a store of triacylglycerols and waxes allows the animals to match the buoyancy of their bodies to that of their surroundings during deep dives in cold water

  5. Many Foods Contain Triacylglycerols • Vegetable oils such as corn (maize) and olive oil are composed largely of triacylglycerols with unsaturated fatty acids and thus are liquids at room temperature. • Become hard when hydrogenation- reduces some of their double bonds to single bonds and converts others to trans double bonds. • beef fat - Triacylglycerols with only saturated fatty acids, such as tristearin, - white, greasy solids at room temperature. • exposed too long to the oxygen in air, they may spoil and become rancid (臭油脂味).

  6. Waxes Serve as Energy Stores and Water Repellents • Biological waxes are esters of long-chain (C14 to C36) saturated and unsaturated fatty acids with long-chain (C16 to C30) alcohols: melting points (60 to 100oC) are generally higher than those of triacylglycerols.- the chief storage form of metabolic fuel of plankton浮游生物 • Bird – secretion of wax – waterproof; • Plants - prevents excessive evaporation of water and protects against parasites. long-chain alcohols long-chain fatty acid

  7. Sperm Whales: Fatheads of the Deep • The sperm whale’s head is very large, accounting for over one-third of its total body weight. About 90% of the weight of the head is made up of the spermaceti organ, a blubbery mass that contains up to 3,600 kg (about 4 tons) of spermaceti oil, a mixture of triacylglycerols and waxes containing an abundance of unsaturated fatty acids. • This mixture is liquid at the normal resting body temperature of the whale, about 37 C, but it begins to crystallize at about 31 C and becomes solid when the temperature drops several more degrees. • The sperm whale undergoes changes in buoyancy to match the density of its surroundings—from the tropical ocean surface to great depths where the water is much colder and thus denser. The key is the freezing point of spermaceti oil. When the temperature of the oil is lowered several degrees during a deep dive, it congeals or crystallizes and becomes denser. Thus the buoyancy of the whale changes to match the density of seawater.

  8. Some common storage and membrane lipids • In triacylglycerols, glycerophospholipids, galactolipids, and sulfolipids, the alkyl groups are fatty acids in esterlinkage. • Sphingolipids contain a single fatty acid, in amide linkage to the sphingosine backbone. • In phospholipids the polar head group is joined through a phosphodiester, whereas glycolipids have a direct glycosidic linkage between the head-group sugar and the backbone glycerol. • The membrane lipids of archaebacteria are variable; that shown here has two very long, branched alkyl chains, each end in ether linkage with a glycerol moiety.

  9. Glycerophospholipids Are Derivatives ofPhosphatidic Acid • phosphoglycerides, are membrane lipids - two fatty acids are attached in ester linkage to the first (C16 or C18 saturated fatty acid) and second carbons (C18 to C20 unsaturated fatty acid)  highly polar or charged (-, 0, +) group is attached through a phosphodiester linkage to the third carbon. • are named as derivatives of the parent compound, phosphatidic acid i.e. Phosphatidylcholine (PC)- choline and phosphatidylethanolamine (PE)- ethanolamine

  10. Ether lipids- Phospholipids with Ether-Linked FAs • The ether-linked chain may be saturated, as in the alkyl ether lipids, or may contain a double bond between C-1 and C-2, as in plasmalogens • Vertebrate heart tissue is uniquely enriched in ether lipids (1/2). and halophilic bacteria, ciliated protists, and certain invertebrate- resistance to the phospholipases (cleave ester-linked FAs). • platelet-activating factor - from basophils and stimulates platelet aggregation and the release of serotonin (a vasoconstrictor) from platelets. It also exerts a variety of effects on liver, smooth muscle, heart, uterine, and lung tissues and plays an important role in inflammation and the allergic response.

  11. Phospholipid and Plasmalogen (體液素原) [ • Plasmalogen: One hydrocarbon chain is attached to glycerol by an ether linkage and the other by an ester linkage (animal and some anaerobic microorganism). • is synthesized on mm of peroxisome in animal. – reservoir of arachidonate (poly unsaturated, long chain FAs)- precursors of signal molecule eicosanoids (prostaglandin-前列腺素, thromboxanes-前列凝素, and leukotrienes 白三烯素 ). Arachidoate from mm glycreophospholipids by phospholipase A2. • Derived of platelet-activating factor (PFA) • May influence the movement of cholesterol within mammalian cells.

  12. Chloroplasts Contain Galactolipids and Sulfolipids • galactolipids (thylakoid membranes) - one or two galactose residues are connected by a glycosidiclinkage to C-3 of a 1,2-diacylglycerol. • Phosphate is often the limiting plant nutrient in soil => evolutionary pressure to conserve phosphate for more critical roles favored plants that made phosphate free lipids. • sulfolipids - a sulfonated glucose residue (- charged) is joined to a diacylglycerol in glycosidic linkage.

  13. Archaebacteria Contain Unique Membrane Lipids • The archaebacteria, most of which live in ecological niches with extreme conditions—high temperatures (boiling water), low pH, high ionic strength, • membrane lipids containing long-chain (32 carbons) branched hydrocarbons linked at each end to glycerol - much more stable to hydrolysis at low pH and high temperature than are the ester bonds • the diphytanyl moieties (yellow) are long hydrocarbons composed of eight five-carbon isoprene groups condensed end-to-end (on the condensation of isoprene units)  twice the length of phospholipids and sphingolipids and span the width of the surface membrane • The glycerol moieties in the archaebacterial lipids are in the R configuration, in contrast to those of eubacteria and eukaryotes, which have the S configuration.

  14. Sphingolipids Are Derivatives of Sphingosine • Sphingolipids (no glycerol)are composed of one molecule of the long-chain amino alcohol sphingosine sphingosine 神經經醯胺醇 (also called 4-sphingenine) or one of its derivatives, one molecule of a long-chain fatty acid, and a polar head group that is joined by a glycosidic linkage in some cases and by a phosphodiester in others • When a fatty acid is attached in amide linkage to the ONH2 on C-2, the resulting compound is a ceramide, which is structurally similar to a diacylglycerol. • three subclasses of sphingolipids, all derivatives of ceramide but differing in their head groups: (1) sphingomyelins, (2). neutral (uncharged) glycolipids, and (3). gangliosides. • Sphingomyelins contain phosphocholine or phosphoethanolamine as their polar head group present in the plasma membranes of animal cells and are especially prominent in myelin, a membranous sheath that surrounds and insulates the axons of some neurons—thus the name “sphingomyelins.” N-acetylneuraminic acid-sialic acid

  15. Structural similarities of phosphatidylcholine and sphingomyelin • Glycosphingolipids (outer face of plasma membranes), have head groups with one or more sugars connected directly to the OOH at C-1 of the ceramide moiety; they do not contain phosphate. • Cerebrosides have a single sugar linked to ceramide; those with galactose are characteristically found in the plasma membranes of neuronal cells , and those with glucose in the plasma membranes of cells in nonneural tissues. • Globosides are neutral (uncharged) glycosphingolipids with two or more sugars, usually D-glucose, D-galactose, or N-acetyl-D-galactosamine. Cerebrosides and globosides are sometimes called neutral glycolipids, as they have no charge at pH 7. • Gangliosides, the most complex sphingolipids, have oligosaccharides as their polar head groups and one or more residues of N-acetylneuraminic acid (Neu5Ac), a sialic acid (often simply called “sialic acid”)- negatively charged • GM: Gangliosides with mono-sialic acid; GD: Gangliosides with two sialic acids; GT: with three sialic acids

  16. Glycosphingolipids as determinants of blood groups • The human blood groups (O, A, B) are determined in part by the oligosaccharide head groups (blue) of these glycosphingolipids. The same three oligosaccharides are also found attached to certain blood proteins of individuals of blood types O, A, and B • at least 60 different sphingolipids have been identified in cellular membranes (prominent in neurons) => present points of recognition for extracellular molecules or surfaces of neighboring cells. • Tumor formation induces the synthesis of a new complement of gangliosides => (induce differentiation of cultured neuronal tumor cells).

  17. Phospholipids and Sphingolipids Are Degraded in Lysosomes • Most cells continually degrade and replace their membrane lipids. For each hydrolyzable bond in a glycerophospholipid, there is a specific hydrolytic enzyme in the lysosome. • Phospholipases of the A type remove one of the two fatty acids, producing a lysophospholipid. (These esterases do not attack the ether link of plasmalogens.) Lysophospholipases remove the remaining fatty acid. • Gangliosides are degraded by a set of lysosomal enzymes that catalyze the stepwise removal of sugar units, finally yielding a ceramide. A genetic defect in any of these hydrolytic enzymes leads to the accumulation of gangliosides in the cell, with severe medical consequences

  18. When sphingolipid degradation is impaired by a defect in one of these enzymes partial breakdown products accumulate in the tissues, causing serious disease. For example, Niemann-Pick disease is caused by a rare genetic defect in the enzyme sphingomyelinase, which cleaves phosphocholine from sphingomyelin. Sphingomyelin accumulates in the brain, spleen, and liver. The disease becomes evident in infants, and causes mental retardation and early death. More common is Tay-Sachs disease, in which ganglioside GM2 accumulates in the brain and spleen owing to lack of the enzyme hexosaminidase A brain cell from an infant with Tay-Sachs disease, showing abnormal ganglioside deposits in the lysosomes.

  19. Cholesterol • The steroid nucleus is almost planar and is relatively rigid; the fused rings (3 X 6C + 1 X 5C rings) do not allow rotation about C-C bonds. • Cholesterol, the major sterol in animal tissues, is amphipathic, with a polar head group (the hydroxyl group at C-3) and a nonpolar hydrocarbon body (the steroid nucleus and the hydrocarbon side chain at C-17), about as long as a 16- carbon fatty acid in its extended form. • stigmasterol in plants and ergosterol in fungi, bacteria can not synthesis of steroid (uptake exogenously). • Affect membrane fluidity and acts as signaling molecule (Steroid hormones). • Bile acids are polar derivatives of cholesterol that act as detergents in the intestine, emulsifying dietary fats to make them more readily accessible to digestive lipases.

  20. Lipid Extraction Requires Organic Solvents • Neutral lipids (triacylglycerols, waxes, pigments) are readily extracted from tissues with ethyl ether, chloroform, or benzene - solvents that do not permit lipid clustering driven by hydrophobic interactions. • Membrane lipids are more effectively extracted by more polar organic solvents, - ethanol or methanol reduce the hydrophobic interactions also weakening the hydrogen bonds and electrostatic interactions • A commonly used extractant is a mixture of chloroform, methanol, and water (1:2:0.8), - then add water - separates into two phases, methanol/water (top phase - proteins and sugars ) and chloroform (bottom phase - lipids)

  21. Adsorption Chromatography Separates Lipids of Different Polarity • adsorption chromatography an insoluble, polar material- silica gel (a form of silicic acid, Si(OH)4) is packed into a glass column - The polar lipids bind tightly to the polar silicic acid, but the neutral lipids pass directly through the column and emerge in the first chloroform wash. • The polar lipids are then eluted, in order of increasing polarity, by washing the column with solvents of progressively higher polarity. Uncharged but polar lipids (cerebrosides) are eluted with acetone, and very polar or charged lipids (glycerophospholipids) are eluted with methanol. • In TLC: a dye (rhodamine) – fluoresces or by exposing the plate to iodine fumes - reacts reversibly with the double bonds in fatty acids, such that lipids containing unsaturated fatty acids develop a yellow or brown color.

  22. Gas-Liquid Chromatography Resolves Mixtures of Volatile Lipid Derivatives • Gas-liquid chromatography (GC) separates volatile components according to their relative tendencies to dissolve in the inert material packed in the chromatography column and to volatilize and move through the column, carried by a current of an inert gas such as helium. • Lipids first heated in a methanol/HCl or methanol/NaOH mixture,- methyl esters - the column is heated to volatilize the compounds. most soluble in the column material partition into (dissolve in) that material; the less soluble lipids are carried by the stream of inert gas and emerge first from the column. The order of elution depends on the nature of the solid adsorbant in the column and on the boiling point of the components of the lipid mixture.

  23. Specific Hydrolysis Aids in Determination of Lipid Structure • all ester-linked fatty acids in triacylglycerols, phospholipids, and sterol esters are released by mild acid or alkaline treatment,and somewhat harsher hydrolysis conditions release amide-bound fatty acids from sphingolipids. • Phospholipase C - releases a water-soluble phosphoryl alcohol and a chloroform-soluble diacylglycerol.

  24. Mass Spectrometry Reveals Complete Lipid Structure

  25. Common procedures in the extraction, separation, and identification of cellular lipids • (a) Tissue is homogenized in a chloroform/methanol/water mixture, which on addition of water and removal of unextractable sediment by centrifugation yields two phases. • (b) Different types of extracted lipids in the chloroform phase may be separated by adsorption chromatography on a column of silica gel, through which solvents of increasing polarity are passed, • (c) thin layer chromatography (TLC), in which lipids are carried up a silica gelcoated plate by a rising solvent front, less polar lipids traveling farther than more polar or charged lipids. TLC with appropriate solvents can also be used to separate closely related lipid species; for example, the charged lipids phosphatidylserine, phosphatidylglycerol, and phosphatidylinositol are easily separated by TLC. • (d) For the determination of fatty acid composition, a lipid fraction containing ester-linked fatty acids is transesterified in a warm aqueous solution of NaOH and methanol producing a mixture of fatty acyl methyl esters. These methyl esters are then separated on the basis of chain length and degree of saturation by • (e) gas-liquid chromatography (GLC) • (f ) high-performance liquid chromatography (HPLC). Precise determination of molecular mass by mass spectrometry allows unambiguous identification of individual lipids.

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