Omega-3 Acids Fight Cancer

Scientists at the University of Guelph have found that omega-3s from fish are better at preventing cancer than omega-3s from plants.

"Omega-3s" refer to omega-3 fatty acids which are a type of long-chain, polyunsaturated carboxylic  acid. Long-chain carboxylic acids are referred to as "fatty acids".
The three omega-3 fatty acids studied were: 

• α-linolenic acid (ALA) which is found in plant seeds and oils

• eicosapentaenoic acid (EPA) which is found in fish, algae and phytoplankton

• docosahexaenoic acid (DHA) which is found in fish, algae and phytoplankton

 The skeletal structural formula for α-linolenic acid is shown below:

 The IUPAC name of α-linolenic acid is (9Z,12Z,15Z)-9,12,15-octadecatrienoic acid. 
The carbon atom of the carboxyl functional group (COOH) is labelled as 1, the next carbon atom in the chain is 2, then 3, etc, up until we reach the last carbon in the chain, carbon 18. The parent hydrocarbon for this molecule is therefore octadecane, with a suffix added for the carboxyl functional group, so we have octadecanoic acid. 
Along the way we find 3 (tri) double bonds (en) at carbons numbered 9, 12 and 15, so we modify the name of the carboxylic acid in one of two ways:

• 9,12,15-octadecatrienoic acid

• octadeca-9,12,15-trienoic acid

The "Z" indicates the 3-dimensional geometry,  in this case the "Z" geometry equates to a "cis" geometry.
So why would  (9Z,12Z,15Z)-9,12,15-octadecatrienoic acid be called an omega-3 acid?
There is an alternative naming "system" (not IUPAC)  in which the first carbon atom is not labelled 1, but instead it is called "alpha" (α), and, the carbon atom at the end of the long hydrocarbon chain is called "omega" (ω). Then, the last carbon atom in the chain (omega) is labelled 1, and you start counting back towards the carboxyl functional group. If you do this, you will find that carbon 3 has a double on it, hence, (9Z,12Z,15Z)-9,12,15-octadecatrienoic acid is called an omega-3 fatty acid. The 3 indicates the position of the first double bond from the omega carbon atom.

The skeletal structural formula of eicosapentaenoic acid is shown below:

The IUPAC name for this molecule is (5Z,8Z,11Z,14Z,17Z)-5,8,11,14,17-Icosapentaenoic acid. 
There are 20 carbon atoms in the chain so the parent hydrocarbon chain is icosane, which is modified with a suffix because there is a carboxyl functional group, icosanoic acid.
There are 5 (pent) double bonds (en) located on carbons 5, 8, 11, 14 and 17, so the name of this molecule is either:

• 5,8,11,14,17-icosapentenoic acid

• icosa-5,8,11,14,17-pentenoic acid

Once again, the Zs in the name refer to the geometry (same as a "cis" geometry in this case).
Notice that, in the alternative naming "system" in which the last carbon atom in the chain is labelled "omega" and then you count backwards from this, we see that the first double bond encountered is on carbon 3, so this molecule is also referred to as an omega-3 fatty acid.

The skeletal structural formula below is that of docosahexaenoic acid:

This molecule has the IUPAC name (4Z,7Z,10Z,13Z,16Z,19Z)-4,7,10,13,16,19-Docosahexaenoic acid. 22 carbon atoms in the chain (docosa), 6 (hexa) double bonds on carbons 4, 7, 10, 13, 16, 19 and a carboxyl functional group: 4,7,10,13,16,19-docosahexaenoic acid or docosa-4,7,10,13,16,19-hexenoic acid. Zs indicate geometry (same as "cis" in this case).
Using the alternative numbering system, the first double bond occurs of the third carbon atom from the omega carbon atom (last carbon in the chain) so it is also classified as an omega-3 fatty acid.

While all three of these omega-3 fatty acids were shown to be effective in reducing the size of tumours in mice, however, higher doses of the plant-based α-linolenic acid was required to deliver the same impact as the omega-3 fatty acids found in fish (icosapentaenoic acid and docosahexaenoic acid)



Reference:

Jiajie Liu, Salma A. Abdelmagid, Christopher J. Pinelli, Jennifer M. Monk, Danyelle M. Liddle, Lyn M. Hillyer, Barbora Hucik, Anjali Silva, Sanjeena Subedi, Geoffrey A. Wood, Lindsay E. Robinson, William J. Muller, David W.L. Ma. Marine fish oil is more potent than plant based n-3 polyunsaturated fatty acids in the prevention of mammary tumours. The Journal of Nutritional Biochemistry, 2017; DOI: 10.1016/j.jnutbio.2017.12.011

Further Reading:
Introduction to naming organic molecules: http://www.ausetute.com.au/namctut1.html
Introduction to functional groups: http://www.ausetute.com.au/fungroup.html
Fatty acids: http://www.ausetute.com.au/fattyacid.html 
Structure and properties of carboxylic acids: http://www.ausetute.com.au/carboxyl.html
Molecular formula: http://www.ausetute.com.au/molecularformula.html
2-Dimensional structural formula: http://www.ausetute.com.au/structural2D.html
Condensed structural formula: http://www.ausetute.com.au/condensedsf.html
Skeletal structural formula: http://www.ausetute.com.au/skeletal.html
Cis-trans isomers: http://www.ausetute.com.au/cistranso.html 


Suggested Study Questions:

1. What functional group is common to all fatty acids? 
2. Define the following terms as they are used in chemistry:
   • saturated
   • unsaturated
   • monounsaturated
   • polyunsaturated
3.  Give the molecular formula for each of the three omega-3 acids in the article
4. The structural formula given in the article are referred to as "skeletal". What does this mean in chemistry?
5. Draw a 2-dimensional (full display) structural formula for each of the omega-3 acids in the article.
6. On the structural formula of each of the three omega-3 acids circle the:
   
   • carboxyl functional group in red
   • double bonds in blue
7. What features are common to three omega-3 acids in the article?
8.  In what ways do the the three omega-3 acids in the article differ?
9. You have probable heard about omega-6 acids. How do you think an omega-6 acid will be similar to an omega-3 acid?
10. How will an omega-6 acid be different from an omega-3 acid?
11. What is meant by a cis isomer and a trans isomer?
12. All the omega-3 fatty acids in the article are the cis isomers. Build a model, and draw, a trans isomer of one of the fatty acids.

Trans Fats

Some fats, such as polyunsaturated fats, are thought to be good for us.

They lower the "bad" type of cholesterol which has been linked to heart disease.

Other fats, such as saturated fats and trans fats, are considered to be bad for us because they increase this "bad" type of cholesterol.

Since the beginning of the 21st century, health authorities all over the world have been calling for the elimination of trans fats from commercially produced food products.

But what is a trans fat and where does it come from?

Go to the June 2014 issue of AUS-e-NEWS for the chemistry of Trans Fats.

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Azobenzene: cis-trans isomers

A new soluble, light sensitive polymer has been created at the University of Helsinki. The polymer partially dissolves in water or certain alcohols, and, when exposed to light, the polymer switches to its cis isomer and dissolves completely.

This new polymer chain is known to contain azo compounds, and azo compounds are known for this ability to switch between cis and trans isomers using light.

Azo compounds are organic molecules in which two benzene rings (known as phenyl groups) are linked by two nitrogen atoms.
Azobenzene has the IUPAC name diphenyldiazene and is the simplest of the azo compounds.
When the 2 benzene rings (phenyl groups) are on the same side of the N=N bond this is known as the cis isomer. The structural formula for cis-azobenzene is shown below:

When the 2 benzene rings (phenyl groups) are on different sides of the N=N bond this is known as the trans isomer. The structural formula for trans-azobenzene is shown below:

The cis isomer is less stable than the trans isomer. In the presence of light (hν) , the trans isomer will convert to the cis isomer:

hν →

but because the cis isomer is less stable, it will relax back to the trans isomer over time:

→

Cis-azobenzene is more polar than trans-azobenzene so cis-azobenzene is more water soluble than trans-azobenzene.

Reference:
Szymon Wiktorowicz, Heikki Tenhu, Vladimir Aseyev. Using Light To Tune Thermo-Responsive Behavior and Host–Guest Interactions in Tegylated Poly(azocalix[4]arene)s. Macromolecules, 2013; 46 (15): 6209 DOI: 10.1021/ma4011457

Further Reading:
Cis-trans (geometric) Isomers

Suggested Study Questions:

1. Give the molecular formula for cis-azobenzene and trans-azobenzene.
2. Explain why azobenzene displays cis-trans (geometric) isomerism.
3. If the N=N bond in azobenzene was replaced with N-N, would the resulting molecule display cis-trans (geometric) isomerism? Explain your answer.
4.  On a drawing of the structural formula of trans-azobenzene, circle a phenyl group.
5. Diazene (diimine) has the molecular formula (NH)₂ . It contains the same N=N bond as azobenzene or diphenyldiazene. Diazene also displays cis-trans (geometric) isomerism. Draw both cis-diazene and trans-diazene.
6. Hydrazine has the molecular formula N₂H₄. Draw a possible structural formula for hydrazine. 
7. Do you expect hydrazine to display cis-trans (geometric) isomerism? Explain your answer.
8. Draw the molecular formula for the molecule trans-dibutyldiazene.
9. Dibutyldiazene undergoes an addition reaction with hydrogen gas. Draw the structural formula for the product of this reaction.