Which fatty acid has the lower melting temperature?
Which fatty acid has the lower melting temperature?
Lipid Question No. 12
Which of the following statements concerning dietary lipids is correct?
a) Corn oil and soybean oil are examples of fats rich in saturated fatty acids
b) Triacylglycerols obtained from plants generally contain less unsaturated fatty acids than those from animals
c) Olive oil is rich in saturated fats
d) Unsaturated fatty acids in our body are usually trans.
e) Fish triacylglycerols are richer in unsaturated fatty acids than triacylglycerols from other animals.
(In this topic you can find the answer to Question L-02)
Lipids are a diverse group of compounds that can be extracted from biological material using non-polar solvents. They are not soluble in water and other polar solvents. (Some lipids are amphipatic, though, since a part of the molecule is hydrophobic, while the other part is hydrophilic).
As you can see, the definition of lipids is not a structural concept, but a functional one. It explains that lipids are very different from the structural point of view.
All of them are carboxylic acids with a hydrocarbon chain usually lineal. Natural fatty acids generally have an even number of carbon. They can be saturated or unsaturated, essentials or no essential, cis or trans (you can find the different criteria for the classification of fatty acids in this post)
Acyl glicerols or Neutral Fats
They are esters of fatty acids with glycerol. Depending on the number of fatty acids that are esterified to the glycerol, they can be sub classified as monoacylglycerols, diacylglycerols and triacylglycerols.
From the structural point of view, they are esters of fatty acids with an alcohol different from glycerol. From the biomedical point of view, the only important waxes are the cholesterol esters (but nobody called them “waxes”!).
The structural backbone of this group of lipids is the phosphatidate: esters of diacylglycerols with phosphoric acid. This group includes lecithins, cephalines, phosphatidyl inositols and other important compounds. (In this link you can find a description of the different sub classes of phosphoglycerides and their functions)
Lipids belonging to this group have in common the alcohol sphingosin in their structure. Some sphingolipids, like sphingomyelin, are linked to phosphatated groups (sphingomyelin and phosphoglycerides are called phospholipids). Other sphingolipids do not have phosphate, but they are linked to carbohydrates, forming the glycosphingolipids. The intracellular accumulation of sphingolipids because of genetic deficit of enzymes related to their metabolism, produce diseases called sphingolipidoses. These conditions include Tay-Sachs disease, Niemann- Pick disease, Fabry’s Disease, Gaucher’s disease, etc. depending on the missing enzyme and/or the kind of sphingolipid that is accumulated.
These lipids have in common that they are formed by isoprene units (methyl butadiene). In some cases, the presence of isoprene is obvious in the structure, like in the terpens (Vitamin A, Vitamin E, Coenzyme Q). In other cases, the isoprene units are evident in the process of synthesis, like in the biosynthesis of steroids, the other important group of isoprenoid lipids.
These lipids are derivative of Arachidonic acid, an unsaturated fatty acid with 20 carbons (Eico is the Greek prefix for twenty, in the same way that deca means ten and penta indicates five). This group includes prostaglandins, leukotriens and thromboxans.
Answer to Question L-04 about Lipids.
Answer (e): Phosphoglycerides.
General structure of Phosphoglycerides
The two acyl groups appear in the orange area, linked to the glycerol (in the white area) by ester (carboxylic ester) linkages. The hydrocarbon chain of the acyl groups represents the hydrophobic or apolar part of these molecules. In the green area, appears the Phosphate linked through a phosphoric ester linkage to the glycerol, but also to X, the hydroxylated compound whose OH group has formed an ester linkage with the Phosphoric acid (Phosphate, at physiological pH). This is the polar part of the molecule.
Depending on the identity of X, the phosphoglyceride can be:
• Phosphatidate (if X is an Hydrogen)
• Phosphatidyl choline aka lecithin (if X is choline)
• Phosphatidyl ethanolamine (if X is ethanolamine)
• Phosphatidyl serine (if X is serine)
• Phosphatidyl glycerol (if X is another glycerol)
• Phosphatidyl inositol (if X is inositol)
• Cardiolipin (if X is a glycerophosphatidate)
In the group of Phosphoglycerides are also included other compounds that do not have the Phosphatidyl structure, since these compounds have linked to the C1 of glycerol an alkyl side chain bound through an ether linkage, instead of the acyl side chain linked through an ester linkage, characteristic of the phosphatidyl group. These compounds are known as Ether lipids. The most important representatives of this kind of phosphoglycerols are Plamalogens and Platelet Activating Factor.
Platelet activating factor
The functions of phosphoglycerides include:
• Structure of cell membranes
• Reservoir for intracellular messengers
• Anchors of some proteins for cell membranes
• Stabilization of protein structure
• Cofactors of enzymes
• Biological detergents
– Surfactants in lungs
– Solubilization of non polar lipids in lipoproteins.
The individual role of the main phosphoglycerides is described below:
Phosphatidic acid: Metabolic intermediary and precursor in the synthesis of other phospholipids and triacylglycerol. It has been implicated in signaling process, when released from other phospholipids by the action of phospholipase D (Phosphatidic acid and related lipids)
Phosphatidyl glycerol: It is a component of membranes, and the main phospholipid component in certain bacteria. In human tissues it is found mainly in mitochondria. It is also the second most abundant phospholipid in lung surfactant and is a precursor of cardiolipin.
Phosphatidyl ethanolamine (cephaline) is the second most abundant phospholipid in animals. It has a key role in the structure of membranes, with a specific role in stabilizing the structure of some proteins, allowing them a transporting or enzymatic function in or at the membrane. (Phosphatidyl ethanolamine and related lipids.)
Phosphatidyl Choline is the most abundant phospholipid in animals and is the key building block of membranes. It is also the main phospholipid of plasmatic lipoproteins. The role of phosphatidyl choline as lung surfactant and its medical implications have been discussed in other post. Phosphatidyl choline may have a role in the signaling system especially in the nucleus, by generating diacylglcycerol under the action of phospholipases C and/or D. (Phosphatidyl Choline and related lipids)
Phosphatidyl Serine is located mainly in the inner surface of the plasma membrane. It is a required cofactor of protein Kinases C and other enzymes and consequently has an important role in the intracellular signaling system, and participates in coagulation, apoptosis and mineral deposition in bones. (Phosphatidyl serine: structure, occurrence, biochemistry and analysis)
Phosphatidyl inositol and phosphorylated derivatives are important phospholipids with roles in the cellular signaling system, in the synthesis of eicosanoids, as a component of membranes and as membrane anchors for protein. The most important phosphorylated derivatives are phosphoinositol 4 (P) and Phosphoinositol 4, 5 diphosphate.
The key role of phosphatidyl inositol 4,5 diphosphate in the Phospholipase C system, yielding different second messengers, has been described elsewhere in this site. Phosphatidyl inositol is the main source of arachidonate in peripheral tissues. (Arachidonate is the precursor of the eicosanoid lipids prostaglandins, leukotrienes and thromboxanes).
Cardiolipin is a very important phospholipid in mitochondrial membrane. It is particularly abundant in heart tissue, where it was discovered. Most of the cardiolipin in humans have four linoleyl groups in its structure. Cardiolipin appears almost exclusively in the inner membrane of the mitochondria, where it interacts with various proteins. It has been demonstrated that cardiolipin is necessary for the activity of different enzymes, including enzymes of the respiratory chain. Cardiolipin apparently participates also in steroidogenesis, apoptosis, regulation of gene expression and the minor quantities found in plasmatic lipoproteins have anticoagulant functions.
Barth Syndrome, a cardiomyopathie in children, is associated to the deficit of tafazzin, a phospholipid acyltransferase that participates in the remodeling of cardiolipin (e.g. in the introduction of specific fatty acids during the synthesis). Children with this X-linked disease have decreased quantities of tetralinoleyl cardiolipin and apparently, it is translated as a reduction in the efficiency of the respiratory chain in the heart muscle.(Cardiolipin: Structure, occurrence, biology and analysis.pdf)
Plasmalogens: Structure of membranes, where they act as reservoirs of polyunsaturated fatty acids that may act as intracellular signaling compounds.
Platelet Activation Factor: This lipid is not stored in a preformed state, but synthesized when necessary as a response to inflammatory process. It is one of the most potent bioactive molecules known, causing effects at concentrations as low as 10 -12 mol/L. It participates in the signaling process activating cytoplasmatic Phospholipases A and C. Phospholipase C produces a release of Ca++ and activation of Protein Kinase C (see related post). It has proinflammatory properties and has been implicated in the pathogenesis of different diseases, from allergic to thrombotic conditions. (Platelet Activating Factor, Chemistry and Biology.)
For more information about Glycerophospholipids, check:
Complex glycerolipids in http://www.lipidlibrary.co.uk/Lipids/complex.html
Phosphoglycerides in Cyberlipid center: http://www.cyberlipid.org/phlip/pgly02.htm#1
CH3-CH2 -CH2– CH2– CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-COOH
Another notation: CH3-(CH2 )14 – COOH
Another notation: C16:0 (It means, 16 carbons, no double bonds)
Palmitic acid or hexadecanoic acid is a 16 carbon fatty acid, It is the most common fatty saturated acid found in plants and animals (no the most abundant, though). It was purified from Palm oil, and it was named after it. Humans can synthetize it, so it is non essential.
FATTY ACIDS CLASSIFICATION
Fatty acids are carboxylic acids derived or contained in lipids. They show the general formula
R-COOH (R-COO- for free fatty acids at physiological pH)
Where R is usually a lineal (unbranched) carbon chain with an even number of carbons.(Funny mistake found in different textbooks…when you think about it, R has an odd number of carbons, so the fatty acid (R + COOH) has an even number of Carbons)
Natural fatty acids usually contain 4 to 28 carbons (Most of the fatty acids in complex lipids contain 14 to 22 carbons, though).
The function of fatty acids are:
Components of more complex lipids
There are multiple classifications of fatty acids. The most used, from the biomedical point of view are:
CHEMICAL: According to the presence of double bonds in the carbon chain:
• Saturated (no double bonds)
CH3-CH2– CH2– CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-COOH
• Unsaturated (one or more double bonds)
CH3– CH2– CH=CH-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-COOH
According to the numbers of double bonds
– monounsaturated (just one double bond)
CH3– CH2– CH=CH-CH2-CH2-CH2-CH2-CH2-CH2-CH2-COOH
– polyunsaturated. (more than one double bond)
CH3– CH2– CH=CH-CH2-CH=CH-CH2-CH2-CH2-CH2-COOH
According to the position of the double bond relative to the last carbon of the chain (sometimes called Metabolic classification)
– Omega 3 (the double bond nearest the last carbon of the chain (Cw) is 3 carbons apart from the end of the chain)
CH3– CH2– CH=CH-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-COOH
– Omega 6 (the doble bond nearest to the last carbon of the chain is 6 carbon apart)
CH3– CH2– CH2-CH2-CH2– CH=CH-CH2-CH2-CH2-CH2-CH2-CH2-COOH
According to the geometric configuration
– Cis fatty acids (both part of the chain adjacent to the double bond are at the same side of the double bond)
– Trans fatty acids (the two parts or the chain adjacent to the double bond are in opposite side or the double bond)
BIOLOGICAL (also called Nutritional classification)
• Essential: Non synthesized by animals. Should be obtained from the diet. Linoleic and Linolenic.
• Non essential: Synthesized by animals. All the others.
ACCORDING TO THE NUMBER OF CARBONS:
There are different classifications based on the number of carbons
Short chain fatty acids: 2 to 6 carbons
Medium Chain: 8 to 14 carbons
Long Chain fatty acids: 16 carbons and up.
Another classification based on the number of carbons:
Short chain 2-4 carbons
Medium chain 6-12 carbons
Long chain 14-22 carbons
Very long chain 24 -26 carbons
Some texts differ in relation to exactly how many carbons a fatty acid should have for belonging to one of these groups. For example, some texts consider a Fatty acid with more than 20 C as a VLCFA,
Only when we know these classifications we are able to understand plently expressions like:
“Saturated fatty acids and trans fatty acids increase cholesterol concentration in blood, while unsaturated fatty acids decrease it.”
“Oils are rich in unsaturated fatty acids”
“Medium Chain Acyl Co A Dehydrogenase Deficiency, the most common inborn error of faty acid oxidation, has been related to Sudden Infant Death Syndrome”
“Defects in the oxidation of Very Long Chain Fatty Acids, is the main metabolic defect found in Zellweger Syndrome and X-linked adrenoleukodistrophy.”
“When following a Fat free diet, it is important to supplement with Liposolubles vitamins and essential fatty acids”
“Vegetable oils are rich in Omega6 fatty acids, while fish oils are rich in Omega3”
Some examples of biological interest:
Alphalinolenic acid (from the biological point of view, it is also essential)
Oleic acid (non essential)
Three-dimensional representation of Fatty acids of different groups:
More information about Fatty acids:
Very good review in Wikipedia
Choose the best answer:
Lipid Question L-02
The following compounds are phospholipids:
a) lecithins and sphingomyelin
b) diacylglycerols and cephalins
c) plasmalogens and cerebrosides
d) glycerol and gangliosides
e) cholesterol and prostaglandins
Lipid Question L-03
According to the chemical and biological classifications of fatty acids, we can classify palmitic acid as:
a) monounsaturated and essential
b) monounsaturated and non essential
c) polyunsaturated and essential
d) polyunsaturated and non essential
e) saturated and essential
f) saturated and non essential
Lipid Question L-04
Different compounds included in this classificatory group of lipids, can act as pulmonary surfactant, component of membranes and precursors of second messengers. This is the group of:
d) fatty acids
Lipid Question L-05
For historical reasons, it is yet called a vitamin, but it is really a steroid hormone that is synthesized in our body from cholesterol:
a) Vitamin A
b) Vitamin D
c) Vitamin E
d) Vitamin F
e) Vitamin K