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POLYMORPHISM

POLYMORPHISM

Polymorphism
Polymorphism

The occurrence of several different crystal forms

for a same compound.

Packing Types of Fatty Acids and Position
Packing Types of Fatty Acids and Position
Fatty Acid Crystal Structure
Fatty Acid Crystal Structure
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta

Cross-Sectional Structures of Triglycerides

Freedom of molecular motion

Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta

Alpha

Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta
Cross-Sectional Structures of Triglycerides Freedom of molecular motion Alpha Beta Prime Beta

Beta Prime

Beta

Crystal forms
Crystal forms
c a b b a g
c
a
b
b
a
g

Triclinic

c b a Orthorhombic
c
b
a
Orthorhombic
c b a 120º
c
b
a
120º

Hexagonal

Space Arrangements of Triglyceride Crystals 1 2 3 1 3 2 Tuning fork form Chair form

Space Arrangements of Triglyceride Crystals

1

 

2

3

1

 

3

2

Tuning fork form

Chair form

Double Chain Length Structures of Triglycerides D D D Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning

Double Chain Length Structures of Triglycerides

D D D Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning fork) Beta (Stacked chair)
D
D
D
Alpha
(Vertical tuning fork)
Beta-Prime
(Tilted tuning fork)
Beta
(Stacked chair)
Transformation of Crystal Structures
Transformation of Crystal Structures
Transformation of Crystal Structures Simple Collapse Cataclysmic Chain shift

Simple

Transformation of Crystal Structures Simple Collapse Cataclysmic Chain shift

Collapse

Transformation of Crystal Structures Simple Collapse Cataclysmic Chain shift
Transformation of Crystal Structures Simple Collapse Cataclysmic Chain shift

Cataclysmic

Transformation of Crystal Structures Simple Collapse Cataclysmic Chain shift

Chain shift

Transformation of Crystal Structures Simple Collapse Cataclysmic Chain shift
Types of Fatty Acids and Positions for Double Chain Length
Types of Fatty Acids and Positions for
Double Chain Length
Types of Fatty Acids and Positions for Double Chain Length
Molecular Arrangement in Trilaurin Lattice

Molecular Arrangement in Trilaurin Lattice

D D D Triple Chain Length Structures of Triglycerides Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning
D D D Triple Chain Length Structures of Triglycerides Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning
D D D Triple Chain Length Structures of Triglycerides Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning

D

D D D Triple Chain Length Structures of Triglycerides Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning
D D D Triple Chain Length Structures of Triglycerides Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning

D

D D D Triple Chain Length Structures of Triglycerides Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning

D

D D D Triple Chain Length Structures of Triglycerides Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning
D D D Triple Chain Length Structures of Triglycerides Alpha (Vertical tuning fork) Beta-Prime (Tilted tuning

Triple Chain Length Structures of Triglycerides

Alpha (Vertical tuning fork)

Beta-Prime (Tilted tuning fork)

Beta (Stacked chair)

Types of Fatty Acids and Positions for Triple Chain Length

Types of Fatty Acids and Positions for Triple Chain Length
Types of Fatty Acids and Positions for Triple Chain Length
Types of Fatty Acids and Positions for Triple Chain Length
Unit Cell of Stearic Acid
Unit Cell of Stearic Acid

63º38’

Unit Cell of Stearic Acid 63º38’ = CH = 48.84 Å c = COOH 63º38’ sin
  • = CH 3

= 48.84 Å

c

  • = COOH

63º38’ sin = 43.76 Å
63º38’
sin = 43.76 Å

a = 5.54 Å

b =

7.38 Å

Crystal Structure of Oleic Acid
Crystal Structure of Oleic Acid
Crystal Structure of Oleic Acid
Analytical Methods for Polymorphism Study 1. X-ray diffraction analyses 2. Microscopic analyses 3. IR spectroscopic analyses

Analytical Methods for Polymorphism Study

1. X-ray diffraction analyses

  • 2. Microscopic analyses

  • 3. IR spectroscopic analyses

  • 4. Thermal analyses

Characteristics of Triglygeride Polymorphs

________________________________________________________________________ Alpha Beta-Prime Beta ________________________________________________________________________
________________________________________________________________________
Alpha
Beta-Prime
Beta
________________________________________________________________________

X-ray Diffraction Analyses

Hexagonal

Orthorhombic Triclinic

Tuning fork

Tuning fork

Chair form

Acyl groups oriented at 90 to the plane of the glyceryl group

Acyl groups are tilted 68-70 from plane of the glyceryl group

Acyl groups are tilted about 59 from the plane of the glyceryl groups

Vertical chain

Tilted chain

Tilted chain

orientation

orientation

orientation

Longest long

Intermediate

Shortest long

spacing

long spacing

spacing

Randomly ordered

In-between

Highly ordered

Most loosely packed

More closely packed

Most closely packed

________________________________________________________________________

Characteristics of Triglyceride Polymorphs Alpha Beta-Prime Beta
Characteristics of Triglyceride Polymorphs
Alpha
Beta-Prime
Beta

Microscopic Analyses

Platelet

Fine needle

Long needle

5 m

1 m

25-50 m

Infrared Spectroscopic Analyses

A singlet at 720 cm -1

A doublet at

719 and 727 cm -1

A singlet at 717 cm

-1

Characteristics of Triglyceride Polymorphs Alpha Beta-Prime Beta
Characteristics of Triglyceride Polymorphs
Alpha
Beta-Prime
Beta

Thermal Analyses

Thermodynamically

most unstable

Lowest melting point

Color Analyses

Translucent

Thermodynamically

unstable

Intermediate melting point

In-between

Most stable form

Highest melting point

Opaque

___________________________________________________________________

Dilatometric Curve of Tristearin Polymorphic Form 1.10 1.08 1.06 1.04 1.02 Alpha 1.00 0.98 Beta 0.96
Dilatometric Curve of Tristearin Polymorphic Form
1.10
1.08
1.06
1.04
1.02
Alpha
1.00
0.98
Beta
0.96
0.94
30
50
70
Specific volume

Temperature C

Formation of Triglyceride Polymorphs Alpha Beta-Prime Beta
Formation of Triglyceride Polymorphs
Alpha
Beta-Prime
Beta

________________________________________________________________________

Rapid cooling

of liquid fat

_ _ _ _ _ _ _

_

Slow cooling

of liquid fat

Polymorphic

transformation of

the alpha form

Very slow cooling

of liquid fat

Polymorphic

transformation of

beta-prime

Activation Energy of Crystal Nucleation
Activation Energy of Crystal Nucleation
Activation Energy of Crystal Nucleation
Factors for Different Crystals Formation
Factors for Different Crystals Formation

Tristearin

Heat

Melt

Drop into dry ice pieces

Solid Heat Heat Heat
Solid
Heat
Heat
Heat

Melts at 55 C and Resolidification

Melts at 64 C

and Resolidification

Melt at 73 C Room temperature for 2 weeks

Heat
Heat

Melt at 73 C

APPLICATION OF POLYMORPHISM IN FOODS

APPLICATION OF POLYMORPHISM

IN FOODS

Crystal Form Preference of Oils
Crystal Form Preference of Oils

Beta- type

Beta- Prime Type

Coconut oil Corn oil

Olive oil Lard Palm kernel oil

Cottonseed oil Herring oil

Menhaden oil Milk fat Palm oil

Application of Polymorphism in Foods
Application of Polymorphism in Foods

The incorporation of air, plasticity and consistency, and solid-liquid ratio are important characteristics of shortenings.

These physical characteristics in turn depend upon the polymorphic forms of the fats used and the methods of preparation.

Plasticity and consistency, as well as solid-liquid ratio, depends on the melting range, proper tempering is required to form the mixed crystals required for a broad melting range.

Shortening

Shortening

1. Incorporated Air
1. Incorporated Air

Beta-prime crystals large amount of small air bubbles Beta-crystals small amount of large air bubbles

Beta-Prime Crystal Shortening

Small crystals Whiter, creamier, more tender, smoother texture Uniform and glossy texture

Beta-Crystal Shortening Large clustered crystals A waxy or grainy texture

Beta-prime crystal shortening helps the incorporation of an abunda quantity of small air bubbles in batters

Beta-prime crystal shortening helps the incorporation of an abunda quantity of small air bubbles in batters for good volume, texture and tenderness of baked goods.

Natural lard (palmitic acid at 2 position is 64%) b-crystal (OPS)

Rearranged lard (palmitic acid at 2 position is 24%) b-crystal (PO

Lard conversion methods from beta to beta-prime
Lard conversion methods from beta
to beta-prime
  • Interesterification

  • Interesterification and hydrogenation

  • Winterization (destearinization)

  • Addition of cottonseed oil and/or tallow flakes (beta- prime)

2. Plasticity and Consistency
2. Plasticity and Consistency

Plasticity is the changes in consistency as a function of

temperature.

Consistency is the apparent hardness at a temperature

2. Plasticity and Consistency Plasticity is the changes in consistency as a function of temperature. Consistency
Margarine
Margarine

Spreadability

Plasticity

Water -in-Oil Emulsion:

Scraped surface heat exchanger

Margarine Spreadability Plasticity Water -in-Oil Emulsion: Scraped surface heat exchanger Partial solidification Crystallizer Crystallization to have

Partial solidification

Crystallizer

Margarine Spreadability Plasticity Water -in-Oil Emulsion: Scraped surface heat exchanger Partial solidification Crystallizer Crystallization to have

Crystallization to have desired plastic

properties

Blend of soybean oil (b) and hydrogenated cottonseed oil (b prime) for margarine

Confectionary Fat (Enrobing Fat)
Confectionary Fat (Enrobing Fat)

Cocoa Butter Short melting range at mouth temperature

Melting range of confectionary fat:

Fatty acid composition

Proper crystallization

Cocoa Butter: 80% of cocoa butter is disaturated triglyceride.

SOS

  • 20%

POS

  • 55%

POP

  • 5%

POS determines characteristic cocoa butter texture
POS determines characteristic cocoa butter texture

POS:

Alpha form

17.0C

Beta-prime form

27.0C

Beta form

35.5C

Beta-prime

POS determines characteristic cocoa butter texture POS: Alpha form 17.0  C Beta-prime form 27.0 

beta form

Chocolate “bloom” – white

spots and dull surface appearance

Beta

POS determines characteristic cocoa butter texture POS: Alpha form 17.0  C Beta-prime form 27.0 

Small crystal structure a good glossy texture

Large clustered crystal structure

Tempering
Tempering

A process which permits transformation to the proper polymorphic form.

During crystallization, the heat of transformation

must be removed to avoid melting and a later conversion into large beta crystal.

Melting Points of Triglycerides vs. Chain Length

Melting Points of Triglycerides vs. Chain Length Fatty Acid Chain Length

Fatty Acid Chain Length