Elucidation of Kinetic and Symmetry Effects on
the Viscosity and Flow Behavior of Stearic and
Oleic Triacylglycerols
Laziz Bouzidia, Mark Bakera, Nissim Gartib and Suresh S. Narinea
a
Trent Centre for Biomaterials Research
Departments of Physics & Astronomy and Chemistry, Trent University
1600 West Bank Drive, Peterborough, Ontario K9J 7B8, Canada
b
Casali Institute of Applied Chemistry, Faculty of Science, Givat Ram, The Hebrew
University of Jerusalem, Jerusalem 91904, Israel

TP
PT
Author to whom correspondence should be addressed:
Professor Suresh S. Narine
Tel: 1-705-748-1011
Fax: 1-705-748-1652
E-mail: sureshnarine@trentu.ca
1
1.1
Synthesis of structured triacylglycerols (TAGs)
Materials
Stearoyl chloride (98%), palmitoyl chloride (98%), linoleic acid (99%), elaidic acid (99%),
linolenic acid (99%), oleoyl chloride (85%), 1, 3-dihydroxyacetone (99%), glycerol (99%),
solketal (99%), pyridine (99%), N, N’-dicyclohexylcarbodiimide
(DCC), 4-dimethyl
aminopyridine (DMAP), and sodium borohydride were purchased from Sigma-Aldrich.
Chloroform was purified by distillation over calcium hydride.
1.2
Synthesis routes of triacylglycerols
The different structures of the TAGs presented here are shown in Scheme S1. Depending
on the fatty acid moiety, TAGs can be classified as Type I where R1≠ R2 ≠ R3, type II where R1≠
R2 = R3, type III, where R1= R3≠ R2, and type IV, where R1= R3= R2.
Scheme S1. Structure of triacylglycerols. Type I: R1≠ R2 ≠ R3; Type II: R1≠ R2 = R3; Type III:
R1= R3≠ R2; Type IV: R1= R3= R2. SSO and SOO are type II TAG and SOS and OSO are type
III TAG. S: stearic acid, O: oleic acid
Type I TAGs were prepared as shown in Scheme S2. One fatty acid (R1COOH) or its
chloride was reacted with 1, 3 -dihydroxyacetone with DMAP as catalyst and DCC as the
condensing agent (or in the presence of pyridine), giving the hydroxyl substituted
glyceroloxypropan-2-one (I-a), which was reacted to another fatty acid (R3COOH) or its chloride
to give 1,3-Di-substituted glyceroloxypropan-2-one (I-b), followed by a reduction reaction with
S2
NaBH4, yielding 1,3- glycerol. The type I TAGs were synthesized from 1, 3 –glycerol and fatty
acids (R2COOH) or their chloride.
Scheme S2. General synthesis of asymmetrical triacylglycerols with R1 ≠ R2 ≠ R3 (Type I
triacylglycerols)
R1,2,3COOH= stearic acid, palmitic acid, linolenic acid, oleic acid, linoleic acid, elaidic acid
Type II TAGs were synthesized from an intermediate (2,3-dihydroxy-1- substituted
propane (II-b)) and fatty acids as shown in Scheme S3. 1,2-Isopropylidene-3-substituted
glycerol (II-a) was synthesized by esterification of solketal and fatty acids (or their chloride)
with DMAP as catalyst and DCC as the condensing agent (or in the presence of pyridine). 2,3dihydroxy-1- substituted propane (II-b) was prepared by removing the protection group with
concentrated HCl in dioxane [1] from II-a.
S3
Scheme S3. General synthesis of asymmetrical triacylglycerols with R1≠ R2 = R3 (Type II
triacylglycerols)
R1,2COOH= stearic acid, palmitic acid, linolenic acid, oleic acid, linoleic acid, elaidic acid
Type III TAGs were prepared as shown in Scheme S4. An intermediate, 1, 3substituted-2-oxopropane (III-a) was prepared from 1, 3-dihydroxylacetone and fatty acids (or
chlorides) with DMAP as catalyst and DCC as the condensing agent (or in the presence of
pyridine). The resultant ketone was reduced by NaBH4 in a solution of THF.
S4
Scheme S4. General synthesis of symmetrical triacylglycerols with R1= R3≠ R2 (Type III
triacylglycerols)
R1,2COOH= stearic acid, palmitic acid, linolenic acid, oleic acid, linoleic acid, elaidic acid
Type IV TAGs were synthesized by the etherification of glycerol and fatty acids (or
chloride), as shown in Scheme S5.
Scheme S5. General synthesis of symmetrical triacylglycerols with R1= R3= R2 (Type IV
triacylglycerols).
R1= stearic acid, palmitic acid, linolenic acid, oleic acid, linoleic acid, elaidic acid
S5