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Pectin

Pectin
Occurs in plant middle lamella Gel former, e.g., fruit jelly From the Greek word meaning to congeal Pectin was discovered in 1790 by Vauquelin and later (1825) crudely characterized by Braconnot

Pectic Substance Nomenclature

Protopectin-high methyl ester content Pectinic acid-intermediate methyl ester content, soluble

Salts are pectinates

Pectin-intermediate methyl ester content, colloidal Pectic Acid-little methyl ester content

Salts are pectates

Pectin--Chemical structure

Some other sugars, mainly L-rhamnose, are also present

Pectin structure

Other monosaccharides (L-rhamnose, Larabinose, D-xylose) in the structure may limit the size of junctions zones that can be formed and, thus, at least partially determine ultimate gel strength

Carboxyl Substitution in Pectin

Degree of Methoxylation (DM)

Protopectin 16% Normal pectin 8% Low Methoxyl Pectin 2-4% Protopectin Normal Pectin Low Methoxyl Pectin 100% 50% 12.5-25%

Degree of Esterification

High and low methoxyl pectins

If DE is greater than 50%, it is a high methoxyl pectin (HM pectin) If the DE is less than 50%, it is a low methoxyl pectin (LM pectin)

Degree of amidation (DA)

The DA value indicates the percentage of carboxyl groups that nave been converted to the amide form by ammonia processing Amidated LM pectins may have a DA of 15-25% Amidated pectins are especially sensitive to Ca+2 (see W&B, Figure 13.5)

Types of pectins
HM -COOCH3 (> 50%) -COOH + -COO Na LM -COOCH3 (< 50%) -COOH + -COO Na Amidated LM -COOCH3 (< 50%) -COOH + -COO Na -CONH2 (15-25%)

Pectic Substances and Gelation

Normal Pectin

Gels in the presence of acid and sugar Doesnt need sugar, but does need calcium ion Forms insoluble calcium pectate. This reaction is responsible for the firming effect seen in certain plant tissues, e.g., canned tomatoes

Low Methoxyl Pectin

Pectic Acid

Pectin gels

Chemistry of pectic substances

Me O H O O O O O O H H dilute acid or base H O O O H O O O H O

dilute acid high temperature

depolymerization

Commercial (Normal) Pectin

Liquid or powdered Source -- mostly lemon and lime peel (20-30% pectin). This is the highest quality. Some from apple pomace (10-15% pectin) Pectin grade = number of pounds of sugar that one pound of pectin can carry in a jelly

Pectin production
Citrus peel is extracted at pH 1.5-3.0 and 60-100oC Extract is filtered Pectin is precipitated by addition of isopropanol

Commercial (Normal) Pectin

Grade is influenced by DE and molecular weight Gel strength -- measured by ridgelimeter (measures % sag), penetrometer, Instron, or texture analyzer.

Low methoxyl pectin

Available commercially Requires no sugar to gel Requires calcium ion to gel Preparation

Enzyme, acid, alkali Pectin LM Pectin Acid preparation is best, produces firmer gels Enzyme preparation is inferior as demethylation is not random

Low methoxyl pectin

Range of pH for gel formation = 2.5-6.5

Pectin uses

Principally used in jellies and jam However, some is used in

Confections Beverages Acidified drinks

See W&B, Table 13.2 for other uses of pectins

Jelly making
Need -- pectin + acid + sugar Pectin

0.5-1.0% If juice is low in pectin, may concentrate by boiling or add more as commercial pectin Peach -- poor gel, pectin contains acetyl groups Citrus -- forms a good gel

Jelly making

Acid

Contributes flavor pH optimum is 3.2 If juice is low in acid, add lemon juice

Jelly making

Sugar

Preservative Micororganisms cannot grow due to the jellys high osmotic pressure Optimum sugar concentration is about 65% soluble solids

Jelly making

Sugar

This is reflected in the final cooking temperature (colligative properties) of 104.5o C During this cooking some of the sucrose is hydrolyzed to invert sugar which will discourage sugar crystallization in the jelly

Gel strength in normal pectin jellies

Jelly strength Continuity of structure [Pectin] Optimum is about 1% Acidity Rigidity of structure [Sugar]

Optimum is 3.2 Low-hard gel High-no gel

Optimum 65% Low-weak gel High-crystals form

Setting times HM pectins

Rapid set Medium set Slow set DE 72-75% 68-71% 62-68% Setting time 20-70 sec -180-250 sec

Setting times
Rapid set pectins are used in jams where quick gelling is desired to prevent flotation of the fruit Slow set pectins are used in jellies to provide time for bubbles to escape

Theory of normal pectin gel formation

A pectin junction zone Hydrogen bonds

Pectin junction zones

O HO H H O H OH OH H O H OH H O H OH CH3 H H OH O H OH O H OH H O O O CH3 H OH H OH H H OH OH OH OH H OH

H H H HO OH H H OH O CH3 H O O

O H OH H

CH3 OH O

H H OH H O

OH O H OH CH3

HO H OH H H

O OH H OH OH

H OH

Theory of low methoxyl pectin gel formation

Calcium ion Ionic bonds

LMP junction zones

H H H HO OH H O
2+

O O H OH O
-

O H OH H H

OH O H H O OH O H

CH3 H OH H OH O H O H O
-

O H OH H H

O O H H OH OH

Ca

Ca O
-

2+

O HO H H

H H OH O H H O O H H OH H O

OH O H O H CH3

H H OH H H OH O O H H O H OH H

OH OH H O H O CH3

Theory of low methoxyl pectin gel formation

pH needs to be higher (3.2-4.0) because only carboxylate (COO-) groups can participate in these types of ionic bonds These gels can not usually be melted and reformed

Methyl ester content and gelling ability

Ability to gel with Ca+2

Ability to gel with acid and high solids

20

40 60 DE

80

100

Characteristics and uses of low methoxyl pectin gels

These gels can be melted and reformed repeatedly No sugar is needed to form the gel, hence these types of pectins are used in dietetic products. In practice, a small amount of sugar is left in the dietetic products as a tenderizer/texturizer. When included in these preparations, the resulting jellies are not as brittle as they would be in the absence of the sugar.

Uses of low methoxyl pectin gels

Fat mimetic

From Hercules, this is a LM pectin gelled with Ca+2 and microparticulated (particle size < 1 m) Trade name is Slendid

Labeling

Both HM and LM pectin may be labeled pectin