lipids biochemistry notes, Study notes of Medical Biochemistry

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2016/2017

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Learning Objectives
Food Quality
-Flavor, aroma, texture, mouth feel
- Safety
Nutritional
-energy source
- cell structures
- essential fatty acids
Biological
-vitamins A, D, E, & K (fat soluble)
- cell membrane characteristics
- cholesterol for Vit. D3, corticosteroids, bile acids
- signaling molecules, e.g. eicosanoids
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Learning Objectives

  • Food Quality
    • Flavor, aroma, texture, mouth feel
    • Safety
  • Nutritional
    • energy source
    • cell structures
    • essential fatty acids
  • Biological
    • vitamins A, D, E, & K (fat soluble)
    • cell membrane characteristics
    • cholesterol for Vit. D3, corticosteroids, bile acids
    • signaling molecules, e.g. eicosanoids

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Background

n Lipids (fats) include a diverse range of compounds that have nonpolar groups that make them relatively insoluble in water (hydrophobic)

n Three major classes:

n Simple lipids – FA, TG, Waxes n Compound lipids – Phospholipids, glycolipids, lipoproteins n Derived lipids - Sterols

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18.1 Lipids

18.2 Fatty Acids

Chapter 18 Lipids

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Diversity in structure leads to a diversity in biological function

n Non-polar lipids (fats) are the principal molecules for energy storage n Polar lipids (nitrogen and phosphorus containing) are components of biological membranes n The steroid class of lipids (cholesterol) is found in biological membranes and used as a precursor for many hormones n Miscellaneous lipids present only in minor quantities in the cell are involved as light-absorbing pigments (â-carotene, retinal), enzyme cofactors (vitamin K), signal molecules (prostaglandins), and electron carries (ubiquinone)

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Classes of Lipids

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Fatty acids are:

  • Long carbon chains that contain a methyl group (CH3) at one end and a carboxyl group (COOH) at the other (usually 12-18) of carbon atoms.

n Insoluble in water. n Saturated or unsaturated.

  • Location and orientation of these bonds (non-conjugated, conjugated; cis , trans )

Fatty Acids

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Fatty Acid Formulas

n The formulas for fatty acids are written as condensed and line-bond formulas. For example caprylic acid with 8 carbon atoms can be written as: CH 3 —(CH 2 ) 6 —COOH CH 3 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —COOH O || CH 3 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —CH 2 —C—OH

OH

O

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General nomenclature

n The carbon atoms of an acid are numbered (or lettered with Greek lettering system, such as á, â, ã) either from the carboxyl group or from the carbon farthest removed from the carboxyl group (n or omega numbering system) n CH 3 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -COOH n 10 9 8 7 6 5 4 3 2 1 n 1 2 3 4 5 6 7 8 9 10 n ù ä ã â á

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Saturated – single bonds

Nomenclature and Structure

Unsaturated – double bonds

R1 C C C C C R

R1 C C C C C R

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Cis-fatty Acids

n A cis configuration means that adjacent

hydrogen atoms are on the same side of the

double bond. The rigidity of the double

bond freezes its conformation.

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Trans-fatty Acids

n A trans configuration, by contrast, means that the next two hydrogen atoms are bound to opposite sides of the double bond. n Animal fats and foods with partially hydrogenated vegetable oils can contain trans-fatty acids

n Increased consumption of partially hydrogenated vegetable oils is associated with increased risk of heart disease

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Saturated Fatty Acids

Saturated fatty acids have single C–C bonds.

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Systematic names

Components Common name Systematic name 1 formic methanoic 2:0 acetic ethanoic 3:0 propionic propanoic 4:0 butyric butanoic 5:0 valeric pentanoic 6:0 caproic hexanoic 8:0 caprylic octanoic 10:0 capric decanoic 12:0 lauric dodecanoic 14:0 mystiric tetradecanoic

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Systematic names (continue)

Components Common name Systematic name 16:0 palmitic hexadecanoic 16:1 (9) palmitoleic cis-9-hexadecenoic 18:0 stearic octadecanoic 18:1 (9) oleic cis-9-octadecenoic 18:1 (11) vaccenic cis-1-octadecenoic 18:2 (9,12) linoleic all cis-9,12- octadecadienoic 18:3 (9,12,15) linolenic all cis-9,12,15- octadecatrienoic 20:0 arachidic eicosanoic 20:4 (5,8,11,14) arachidonic all cis-5,8,11,14- eicosatetraenoic

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Saturated fatty acids have: n Molecules that fit closely together in a regular pattern. n Strong attractions between fatty acid chains. n High melting points that makes them solids at room temperature.

Saturated Fatty Acids

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Unsaturated fatty acids: n Have nonlinear chains that do not allow molecules to pack closely. n Have low melting points. n Are liquids at room temperature.

Unsaturated Fatty Acids

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linoleic acid cis -9, trans -11 CLA trans -11 18:

Double bonds: cis vs. trans

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linoleic acid cis -9, trans -11 CLA trans -11 18:

Double bond pairs: non-conjugated vs. conjugated

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Hydrogenation of Oils

The hydrogenation of oils

  • adds hydrogen (H 2 ) to the carbon atoms of double bonds.
  • converts double bonds to single bonds.
  • increases the melting point.
  • produces solids such as margarine and shortening.

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Essential FA

n Humans are unable to synthesize fatty acids that have double bonds in the omega-3 or omega-6 positions

n Omega-3 EFAs n Eicosapentaenoic acid (EPA): coldwater fish n Docosahexaenoic acid (DHA): coldwater fish n Alpha-linolenic acid (ALA): flax, walnut, soybean oils

n Omega-6 EFAs n Linolenic acid (LA): animal fats, sunflower oil n Gamma-linolenic acid (GLA): sunflower oil

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Omega-6 and Omega-

Fatty Acids

The first double bond: n In vegetable oils is at carbon 6 (omega-6). n In fish oils is at carbon 3 (omega-3).

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Essential fatty acids

n Mammals cannot synthesize the two main types of polyunsaturated fatty acids: the linoleic (omega-6) and linolenic (omega-3) n Essential fatty acid deficiency is characterized by dermatitis and poor wound healing n Most prostaglandins are synthesized from arachidonic acid (a linoleic acid derivative) n Lack of these prostaglandins causes some aspects of the essential fatty acid deficiency syndrome n A small daily intake of linolenic acid is recommended (this may be especially important when the nervous system is developing) n Docosahexaenoic acid (22:6n-3) – omega-3 fatty acid is needed for maximum development of the visual and central nervous systems during the neonatal period (it is present in large amounts in the retina and parts of the brain; it enhances the visual response and the function of certain domains in neural membranes)

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Prostaglandins

Prostaglandins have: n 20 carbon atoms in their fatty acid chains. n An OH on carbon 11 and 15. n A trans double bond at carbon 13.

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LDL

  • Too much LDL can circulate in the blood
  • Build up in arteries; lead to heart attack

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HDL

  • Another lipoprotein that converts cholesterol into a lipoprotein that returns to the liver ; Removes cholesterol out of the bloodstream;
  • believed to prevent heart attacks

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Ratio of LDL to HDL

  • LDL cholesterol of less than 100 mg/dL is the optimal level. Less than 130 mg/dL is near optimal for most people.
  • A high LDL level (more than 160 mg/dL or 130 mg/dL or above if you have two or more risk factors for cardiovascular disease) reflects an increased risk of heart disease
  • Low HDL cholesterol levels [less than 40 mg/dL] is thought to increase the risk for heart disease.

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Other eicosanoids

n When a cell responds to a stimulus, bioactive mediators (prostaglandins, thromboxanes, leukotrienes, and others) often are formed from the lipids contained in its membranes. n Thromboxanes regulate blood coagulation. n Leukotrienes play a role in allergic and inflammation responses. They were isolated from leukocytes (white blood cells).

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