POLYMORPHISM

Polymorphism

The occurrence of several different crystal forms for a same compound.

Packing Types of Fatty Acids and Position

Fatty Acid Crystal Structure

Cross-Sectional Structures of Triglycerides

Freedom of molecular motion

Alpha

Beta Prime

Beta

Crystal forms
c a g c c b b a b a 120

b
a

Triclinic

Orthorhombic

Hexagonal

Space Arrangements of Triglyceride Crystals

1 1 3

2 2

Tuning fork form

Chair form

Double Chain Length Structures of Triglycerides

Alpha (Vertical tuning fork)

Beta-Prime (Tilted tuning fork)

Beta (Stacked chair)

Transformation of Crystal Structures

Simple Collapse

Cataclysmic
Chain shift

Types of Fatty Acids and Positions for Double Chain Length

Molecular Arrangement in Trilaurin Lattice

Triple Chain Length Structures of Triglycerides

D D D

Alpha (Vertical tuning fork)

Beta-Prime (Tilted tuning fork)

Beta (Stacked chair)

Types of Fatty Acids and Positions for Triple Chain Length

Unit Cell of Stearic Acid

= COOH = CH3

c = 48.84

6338

6338
a = 5.54 b = 7.38

sin = 43.76

Crystal Structure of Oleic Acid

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 ________________________________________________________________________ X-ray Diffraction Analyses

Hexagonal

Orthorhombic

Triclinic

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

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

Chair form
Acyl groups are tilted about 59 from the plane of the glyceryl groups Tilted chain orientation Shortest long spacing

Vertical chain orientation Longest long spacing

Tilted chain orientation Intermediate long spacing

Randomly ordered

In-between

Highly ordered

Most loosely packed More closely packed Most closely packed ________________________________________________________________________

Characteristics of Triglyceride Polymorphs

Alpha Beta-Prime Beta

Microscopic Analyses

Platelet 5m

Fine needle 1m

Long needle 25-50 m

Infrared Spectroscopic Analyses A singlet at 720 cm -1 A singlet at 717 cm -1

A doublet at

719 and 727 cm-1

Characteristics of Triglyceride Polymorphs

Alpha Beta-Prime Beta

Thermal Analyses

Thermodynamically most unstable

Lowest melting point

Thermodynamically unstable
Intermediate melting point

Most stable form

Highest melting point

Color Analyses Translucent In-between Opaque ___________________________________________________________________

Dilatometric Curve of Tristearin Polymorphic Form

1.10

1.08

Specific volume

1.06 1.04 1.02 1.00

Alpha

0.98

Beta
0.96 0.94 30 50 70

Temperature C

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

Factors for Different Crystals Formation

Tristearin Heat

Melt
Drop into dry ice pieces

Solid

Heat
Heat

Melts at 55 C and Resolidification

Melts at 64 C and Resolidification Melt at 73 C

Heat

Room temperature for 2 weeks Heat Melt at 73 C

APPLICATION OF POLYMORPHISM IN FOODS

Crystal Form Preference of Oils

Beta -type Coconut oil Corn oil Olive oil Lard Palm kernel oil Beta -Prime Type Cottonseed oil Herring oil Menhaden oil Milk fat Palm oil

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

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 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 (POS

Lard conversion methods from beta to beta-prime

Interesterification Interesterification and hydrogenation Winterization (destearinization) Addition of cottonseed oil and/or tallow flakes (betaprime)

2. Plasticity and Consistency

Plasticity is the changes in consistency as a function of temperature.
Consistency is the apparent hardness at a temperature

Margarine
Spreadability
Plasticity Water-in-Oil Emulsion: Scraped surface heat exchanger Partial solidification Crystallizer Crystallization to have desired plastic properties Blend of soybean oil (b) and hydrogenated cottonseed oil (b prime) for margarine

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 POS POP

20% 55% 5%

POS determines characteristic cocoa butter texture

POS: Alpha form Beta-prime form Beta form 17.0C 27.0C 35.5C

Beta-prime beta form Chocolate bloom white spots and dull surface appearance
Small crystal structure a good glossy texture

Beta
Large clustered crystal structure

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

Fatty Acid Chain Length