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E. T. Contis et al. (Editors)Food Flavors: Formation, Analysis and Packaging Influences© 1998 Elsevier Science B.V. All rights reserved 647
Effect of crystallization time on composition of butter oil in acetone
F.
M. Fouad\ O. A. Mamer\ F. SaurioP and
F.
ShahidP.^The Biomedical
Mass
Spectrometry
Unit,
McGill
University,
1130 Pine Avenue
West,
Montreal,Quebec, H3A 1A3, Canada^Department of Chemistry, McGill University, Montreal, Quebec, H3A 2K6, Canada^Department of Biochemistry, Memorial University of Newfoundland, St. Johns, Newfoundland,AlB 3X9, CanadaAbstractKinetics of hermal modification ofbutter oil in acetone
at
a constant temperature
was
studied.Anhydrous butter oil was stirred
in
50%
acetone by weight at room temperature
in
order to removeinsoluble residues
(SQ),
mainly high molecular weight-saturated lipids. The resultant lipids in acetonewere further subjected to cooling at 0°C for 10,20 and
50 min
and
the
corresponding solid fractions
(Sj,
S2
and
S3,
respectively) were collected. The remaining liquid lipid (L) together with solidfractions
Sj,
S2
and
S3
were characterized for their fatty acids and triacylglycerol (TAG) profiles.Results indicated that crystallization ofbutter
oil in
acetone at
low
temperatures
may
produce lesssaturated products, similar to those obtained via supercritical fluid extraction usingCO2.The Land S
 fractions
 were found to contain the same TAGs, but in different proportions. Profiles oftriacylglycerols and fatty acids of these lipid fractions were compared with corresponding resultsfor butter lipid
 fractionated
 by supercritical carbon dioxide (SC-CO2) or a dual process involvingSC-CO2 of temperature controlled partial crystallization (TCPC) harvested liquid fraction of neatbutter oil at
17°C(L.
17).
1. mXRODUCTIONHigh contents of cholesterol and saturated long
chain
fatty
acids in
animal fat and butter havebeen associated with coronary heart
disease
(CHD). Accordingly, partially hydrogenated vegetableoils (margarine) were introduced as a nutritional substitute [1]. Economics of changing theconsumption pattern ofbutter
and
margarine
was
costly in general to dairy industry
and
particularlyto dairy farmers. Consequently, as early as the 1940's several investigators tried to developprocedures to improve
the
acceptability ofbutter
via
temperature controlled partial crystallization(TCPC) ofbutteroil.TCPC ofbutter oil was carried out to produce fractions having a fatty aciddistribution that would yield lipids with physical characteristics
more
suitable for food
and
industrialapplications
[2-8].
In view of earlier results pertaining to synthetic or natural manipulation ofbutter oil to yieldfractions with different spectra of triacylglycerols, fatty acids and accordingly physical properties.
 
648we were prompted to examine TCPC of butter oil solutions in acetone at various time intervalsat low temperatures.A simple one-step TCPC of anhydrous butter oil failed to yield lipid fractions that werecharacteristically different in their chemical composition and physical properties [2, 5]. Thedifferences in triacylglycerol and fatty acid analyses between solid (S) and liquid (L) fractions ofbutter oil resembled those brought about by seasonal variations
[2].
Crystallization of anhydrousbutter oil is rather complex
[3,
4] because of the problem
oi crystal packing
associated with the
large number
of triacylglycerols resulting from
in-vivo
substitution of
at
least 37 different fattyacids on the glycerol backbone [9]. Furthermore, it is possible that the unsaturated andpolyunsaturated chains pack within the same layer and
that
saturated chains pack within unsaturatedlayers. The phase diagram of simple triacylglycerol binary systems, tristearin (SSS) and a mixedchain triacylglycerol, stearodipalmitin
(PS? or
SPP), best illustrates the intricacy of he crystallizationpattern of butter oil and reflects the complexity of the interaction between triacylglycerols withsimilar structures. The SSS-PSP system has an eutectic mixture melting at 63.9°C at about 65mole % PSP. On the other hand, the mole fraction of
SPP
in SSS at the eutectic temperature isabout
27% [10,11],
even though
it
differs
only
in
the
position of he stearic acid
moiety.
Therefore,temperature dependent co-nucleation of various triacylglycerols of butter lipids yields solid andliquid fractions with
the same
spectrum of riacylglycerols
and
fatty acids,
but in
different proportions
[2]
rather than fractions
having
different triacylglycerol and fatty
acid
compositions [5
].
As
a result,laboratory scale TCPC of butter oil failed to yield fractions with significantly different chemicaland physical properties, namely melting range. Accordingly, co-nucleation occuring at varioustemperatures,
rate
of cooling, agitation and filtration is expected to minimize the spectral differencesof chemical distribution of triacylglycerols and fatty acids and accordingly the physical propertiesof isolated lipid
 fractions
 [2, 7, 12, 13]. This contrasts with earlier conclusions that butter oil canbe
 fractionally
 crystallized in a one-step process to yield products, which were markedly differentin their physical and chemical properties [5] to warrant their commercialization as a healthyalternative to hydrogenated vegetable oils. Thus one-step TCPC
may not be
suitable for industrialfood applications [5].Therefore, it is the intent of this paper to examine TCPC of butter oil in acetone at various
time
intervals at low temperatures
in
order to produce lipid fractions with different characteristics.As previously reported
[3],
acetone was used
to induce
perturbation of he crystalline packingof various triacylglycerols of butter oil, which is expected to influence crystallization behavior ofbutter oil. However other solvents such as ethanol or petroleum ether could also be used. Theharvested lipid fractions at various time intervals are expected to have a distinctly differenttriacylglycerol and fatty acid profiles which would reflect on their physical properties comparedto TCPC of neat butter oil or butter oil solutions in organic solvents.
2.
EXPERIMENTAL
The effects of continuous lipid depletion at
0°C
according to soLibiii^y aiid molecular weighton the profiles of triacylglycerols and fatty acids of isolated lipid solids at various time intervalsfrom a solution of butter oil in acetone was examined. In general, butter was melted and kept at
60°C
until complete separation of
oily
butter
lipid and
v^ater
layers. Separated butter
oil
was driedover anhydrous sodium sulfate and then manipulated as described
below.
For efiicient separationof crystallized
lipid
 fractions,
 Kenag milk
 filters
 (KenagInc.,
Ashland,
OH) were used which allowedcomplete separation of lipid crystals from mother liquor within 5 to 15 min. For fatty acid and
 
649traicylglycerol analyses, fused silica capillary columns coated with SP-2340 or DB-5 stationaryphase were used, respectively. Anhydrous butter oil was mixed
with acetone
(1:1,
w/w)
and
stirredat room temperature to
remove
an insoluble residue,
SQ.
Filtrate was kept
at
0°C where precipitatedsolid lipid fractions, Sj, Sj and
S3
at 10, 20 and 50 min respectively were separated by filtration.A liquid lipid L was obtained from the final mother liquor by acetone evaporation.For the purpose of comparison with earlier results
[2-9],
butter oil was mehed
at
60°C, treatedwith anhydrous sodium sulfate
and
fihered under vacuum (Whatman #
1
filter paper). The resultingfiltrate was stored under nitrogen at -20°C until use. Molten neat butter oil, warmed to 60°C andseparated into liquid and solid fractions at temperatures 29, 25, 21 and 17°C, without agitation
[2].
The crystallized triacylglycerols
were
harvested using Kenag
milk
filters (Kenag Inc. AshlandOH) which allowed complete separation of crystals from the mother liquor within 5 to 15 min.The solid or liquid fractions obtained were used both as a reference material to compare butterlipids fractionated by supercritical carbon dioxide (SC-CO2) or crystallization at various timeintervals from acetone solution at low temperature and as starting material, e.g., L.17 fraction,for further SC-CO2 fractionation. All samples were kept at -20°C until analyzed. Solid (S) andliquid (L)
 fractions
 were designated according
to the
temperature
at which they were
isolated,
e.g.S.17orL.17.
SC-CO2 Extraction of Anhydrous Butter Oil
In all experiments, research grade
CO2
(99.995% pure, Medigas, St. Laurent, Quebec) was usedin a Newport SC-CO2 apparatus (Newport Scientific Inc., Jessup, MD) with an extraction vesselof 0.85 L capacity maintained at 35°C. The separation vessel was kept at 61.2 atm (900 psi) and30°C throughout each experiment. The pressure
in the
extraction
vessel was
set at 136 atm (2000psi) and maintained constant while extraction of anhydrous butter oil samples was carried out fora period of 14hr. At 2hr intervals, the solubilized fraction
was
removed from
the
separation vesselwithout interruption of
the
run. The mass remaining in the extraction vessel at the end of theexperiment
was
collected and analyzed. In
a
second set of experiments,
the
thermally fractionatedL.17
lipids were
subjected
to SC-CO2
and isolated fractions
were
analyzed for their triacylglyceroland fatty acid profiles.
3.
RESULTS
AND DISCUSSION
Upon stirring butter oil at room temperature in acetone
(1:1,
w/w) the remaining insoluble
lipid
residue, S^ was collected and found to be mostly composed of high-molecular-weight saturatedlipids. Perturbation of the crystalline
packing
of butter
oil
triacylglycerols
by the
combined effectsof removing high molecular weight lipids and addition of acetone forced precipitation of lipidsaccording to their molecular weights and solubilities (Table
1).
Fraction
SQ
contained 40% less ofC24-C36 and
50%
more C44-C54
triacylglycerols than butter oil. Unsaturated and low-molecular-weight triacylglycerols are expected to be more readily soluble in polar organic solvents. Suchdifferences will
be
a function of he proportions oflow melting triacylglycerols extracted
by
acetonetreatment, the amount of acetone used, and number of extractions employed.
This
effect decreased with progression of cry stallization time
as
similar changes in
the
C3 4-C3 6and C44-C54 triacylglycerol content ofSi,
S2
and
S3
(collected at 10,20 and 50 mins respectivelyat OT) were found to be
11%
and
-6%;
+12% and
-9%;
and +14% and
-11%,
respectively. Mostinteresting is the increase (+27%), (+24%) and (+17%) in C36-C38 triacylglycerols in fractionsSi,
S2
and
S3
with respect to butter oil, respectively while the C40-C42 lipids remained almost

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