Chemistry, Functionality, & Applications Pectin Chemistry, Functionality, & Applications Developed by, and in fond memory of-- Andrew C. Hoefler

Types of Pectin High Methoxyl (HM) or High Ester Low Methoxyl Conventional (LMC) or Low Ester Conventional Low Methoxyl Amidated (LMA) or Low Ester Amidated

~500 repeating units /molecule Alpha (1- 4) linked D-polygalacturonic acid H OH COOH COOH o o o o OH H OH H o OH H o o H COOCH3 OH H OH (-OCOCH3) ~500 repeating units /molecule

High Ester (HM) Pectin With a D.E. of 60% HO HO O OH HOOC OH H COOC OH 3 OH OH H COOC 3 3 H COOC OH HOOC HO HO HO

Pectin Functional Groups  - D - GALACTURONIC ACID COOH OH HO O  - D - GALACTURONIC ACID - METHYL ESTER OH HO O COOCH3  - D - GALACTURON - AMIDE OH O HO CONH2

Gelation of Pectin: 2 ways Ability to Gel with Ca++ Ability to Gel at low pH and high Solids % DE of Pectin

HM Pectin - Conditions for Gelation pH = 3.5 or Lower (Range = 1.0 to 3.5) Soluble Solids = 55% or Higher (Range = 55% to 85%) Calcium is not normally a factor

HM Pectin Gelation Mechanism H-bonding sites

LM Pectin - Conditions for Gelation pH = 1.0 to 7.0 or Higher (pH affects Texture) Soluble Solids = 0% to 85% (S.S. affects Ca++ required) Calcium = REQUIRED!!!

LM Pectin Gelation Mechanism

Calcium Alginate Gel Structure

Gel Strength Versus PPM Calcium (The Calcium Response Curve)

LMC Pectin - Calcium Reactivity D.E. D.F.A. Ca++ Reactivity Ca++ required at 30% S.S. 31  4 69  4 High 25 mg/gm 40  4 60  4 Medium 50 mg/gm 49  4 51  4 Low 100 mg/gm

LMA Pectin Calcium Reactivity

Gel Strength vs: Ca+ Reactivity As Ca++ Reactivity goes up, Ca++ Curve Shifts towards the origin. (the pectin requires less calcium to get the job done) GOOD NEWS As Ca++ Reactivity goes up, Ca++ Bandwidth decreases you must be more accurate about amount of calcium is in your product - BAD NEWS

Soluble Solids Versus Ca++ Required (40 DE)

Soluble Solids Versus Ca++ Required 300 100 500 700

Gel Strength versus Soluble Solids Is a Trade-Off As Brix goes up, Ca++ Curve Shifts towards the origin. IE, the pectin needs less calcium = GOOD NEWS As Brix goes up, Ca++ Bandwidth decreases = BAD NEWS

Factors Which Shift the Calcium Response Curve and Affect the Calcium Bandwidth Ca++ React. of the Pectin Brix (Sol. Solids) Ionic Strength Shifts towards origin Shifts away from origin

Suggested Pectin Types at Various Soluble Solids Solids Range LMC Type LMA Type 0 to 45% DE ~ 30% DE/DA ~ 30%/20% 45 to 70% DE ~ 40% DE/DA ~ 32%/17% 55 to 85% DE ~ 50% DE/DA ~ 37%/13%

Making Pectin Solutions The idea is to slightly separate the particles from each other JUST BEFORE they hit the water. Method Maximum % Pectin in Water High Shear 10% Hercules Eductor 7% 5/1 Sugar/Pectin Dry Blend 5% Non-Solvent 5%

Making Pectin Solutions The idea is to slightly separate the particles from each other JUST BEFORE they hit the water. Polymer Disperser Separates particles with AIR 5 / 1 with Sugar Separates particles with SUGAR Non Solvents Separates particles with INERT media High Shear Separates particles with Fast Moving WATER

OK NOT OK IN / OUT / GELLED Three Possible States for Gelling Hydrocolloids IN SOLUTION (Dissolved, Hydrated) OK NOT OK GELLED (Half in & Half out of Solution) OUT OF SOLUTION (precipitated, dried)

LM Pectin "Pregel" Too FAST a reaction between the LM pectin and Calcium ions, resulting in a non-homogeneous, “Applesauce-like” gel MOST PROBABLE CAUSES: 1. Calcium containing ingredients added incorrectly to pectin (too fast or too conc’d) 2. Wrong pectin (too calcium sensitive) 3. Ionic Strength of System Too Low

The Ideal Order of Addition For LM Pectin Based Products

Comparison of Functional Properties PROPERTY HM LMC LMA Response to Gel is broken Generally shear Shear reversible at mechanical does not re-knit reversible at pH > 3.5, not shear syneresis occurs all pH's reversible < 3.5 Setting Temp. Can be varied usually usually of Gel from 35 to 90oC 40 to 100+oC 30 to 70oC Thermal Generally No Yes Remelt temps Yes Remelt temps reversibility can be up to 150oC usually below 75oC of Gel

Comparison of Functional Properties PROPERTY HM LMC LMA Texture of Gel Jello-like, rigid Preserve-like, Jello-like or at pH values of gel (will hold a spreadable, some HM-like, but 3.5 or lower cut surface ) degree of gel more rubbery structure (will hold a cut surface ) Texture of Gel Will not gel Preserve-like, Preserve-like, at pH values of Will provide spreadable, spreadable, 3.5 or higher some viscosity thixotropic, thixotropic, (will not hold (will not hold a cut surface) a cut surface)

PECTIN FOOD APPLICATIONS

Three varieties of fruit preserves: strawberry, quince, and red plum Traditional Jams, Jellies, & Preserves (65% S.S.) 0.2 - 0.5% HM Pectin Rapid Set (72 DE) Slow Set (64 DE) Extra Slow Set (60 DE) Three varieties of fruit preserves: strawberry, quince, and red plum

Jams, Jellies, Preserves, & Conserves Low / Reduced Calorie Jams, Jellies, Preserves, & Conserves 0.4 - 1.1% LMA and / or LMC Match the calcium reactivity to the soluble solids

Bakery Jellies (55% - 78% S.S.) Must be Pumpable & Resist Melting 0.7 - 1.3% LMC (popular in Europe) 0.7 - 1.3% HM Medium Rapid Set (traditional for USA)

Confectionery Products (80% S.S.) FRUIT FLAVORED: 1.0 - 2.0% HM Extra Slow Set NEUTRAL FLAVORED: 1.4 - 2.8% Buffered LMA Pectin

Tomato Based Products (10 - 46%S.S.) BBQ Sauce, Salsa, Pesto Sauce, et al 0.3 - 1.0% LMC pectin, DE ~ 30%

Beverages (3 - 15% S.S.) Carbonated and Still Low Calorie, Citrus, and Punch 0.05 - 0.30% HM Pectin, sugar beet pectin

Low pH Milk Applications (Cultured & Directly Acidified) Milk Based Foods with pH below 4.6 (The Isoelectric pH of Casein) Requires a calcium reactive pectin

Casein Particles in Milk: pH 6.8 Net Negative Charge - - + - - - - - - + - - - - - + - - - + - - - - - - + - - - - - - + - - + - - - - - - - - - -

Casein Particles in Milk: pH 4.6 Net Zero Charge - Hydrophobic Surface - - + + + + + + - - - - - - - - + + - - + + + + + + + + - - - - + + + + + + + + - - - - - - - - + + + + Clumps of Casein!!! - - - -

Casein Particles in Milk: pH 4.0 With Pectin

Pectin pKa Influences

Casein Particles in Milk: pH 4.0 - With Pectin - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

Low pH Milk Applications (Cultured & Directly Acidified) Yogurt Beverages HM Yogurt / Juice Beverages HM Milk / Juice Beverages HM Yogurt LM Buttermilk LM Sour Cream LM Milk Based Foods with pH below 4.6

Yogurt Fruit, Fruit Toppings, & Ice Cream Ripple (0 - 65% S.S.) 0.3 - 1.2% LM Pectin Calcium reactivity as required by the Soluble Solids of the Product

Yogurt Fruit Preparation (0 - 65%S.S.) The Function of the Pectin is: Prevent Fruit Floatation (Yield Point, Gel) The Gel must be "Pumpable" ( Shear Reversible) Swiss style Yogurt

FOB Yogurt Fruit Ca++ H2O Osmotic Difference = H2O & Ca++ Migrate !! Yogurt Layer soluble solids = 15% Ca++ H2O Fruit Layer Soluble solids = 55% Osmotic Difference = H2O & Ca++ Migrate !!

Gel Strength Versus PPM Calcium (The Calcium Response Curve)

Fat Replacement (Many Applications) All three types of pectin can be utilized