Pectin

Overview
Pectin, a white to light brown powder, is a heteropolysaccharide derived from the cell wall of higher terrestrial plants. It was first isolated and described in 1825 by Henri Braconnot.

It is mainly used in food as a gelling agent in jams and jellies. Today it is also used in fillings, sweets, as a stabilizer in fruit juices and milk drinks and as a source of dietary fiber in foods.

Biology
Naturally, pectin in the form of complex, insoluble protopectin is part of the non-woody parts of terrestrial plants. In the middle lamella between plant cells, pectin helps to bind cells together and regulates water in the plant.

The amount and structure of the pectin differs between plants and also within a plant over time and in different parts of a plant. Tough parts contain more pectin than soft parts of a plant. During ripening, pectin is broken down; in this process the fruit gets softer as the cell walls break down.

Pectin is a natural part of human diet, but does not contribute significantly to nutrition. The daily intake of pectin from fruit and vegetables can be estimated to be around 5 g (assuming consumption of approximately 500 g fruit and vegetable per day).

In human digestion, pectin is not used as nutrient, but passes through the small intestine more or less intact. In the large intestine and colon, microorganisms degrade pectin and liberate short-chain fatty acids that have positive influence on health (prebiotic effect). Pectin is thus a soluble dietary fiber.

Consumption of pectin has been shown to reduce blood cholesterol levels. The mechanism appears to be a decrease of viscosity in the intestinal tract, leading to a reduced absorption of cholesterol from bile or food.

Chemistry
The characteristic structure of pectin is a linear chain of α-(1-4)-linked D-galacturonic acid that forms the pectin-backbone, a homogalacturonan.

Into this backbone, there are regions where galacturonic acid is replaced by (1-2)-linked L-rhamnose. From rhamnose, sidechains of various neutral sugars branch off. This type of pectin is called rhamnogalacturonan I. Over all, up to every 25th galacturonic acid in the main chain is exchanged with rhamnose. Some stretches consisting of alternating galacturonic acid and rhamnose – “hairy regions”, others with lower density of rhamnose – “smooth regions”. The neutral sugars are mainly D-galactose, L-arabinose and D-xylose; the types and proportions of neutral sugars vary with the origin of pectin.

A third structural type of pectin is Rhamnogalacturonan II, which is a less frequent complex, highly branched polysaccharide. Isolated pectin has a molecular weight of typically 60 - 130 000 g/mol, varying with origin and extraction conditions.

In nature, around 80% of carboxyl groups of galacturonic acid are esterified with methanol. This proportion is decreased more or less during pectin extraction. The ratio of esterified to non-esterified galacturonic acid determines the behavior of pectin in food applications. This is why pectins are classified as high- vs. low-ester pectins – or in short HM vs. LM-pectins, with more or less than half of all the galacturonic acid esterified.

The non-esterified galacturonic acid units can be either free acid or salts with sodium, potassium or calcium. The salt of partially esterified pectins are called pectinates, if the degree of esterification is below 5% the salts are called pectates, the insoluble acid form, pectic acid.

Some plants like sugar-beet, potatoes and pears contain pectins with acetylated galacturonic acid in addition to methyl esters. Acetylation prevents gel-formation but increases the stabilisating and emulsifying effects of pectin.

Amidated pectin is a modified form of pectin. Here, some of the galacturonic acid is converted with ammonia to carboxylic acid amide. These pectins are more tolerant of varying calcium concentrations that occur in use.

To prepare a pectin-gel, the ingredients are heated, dissolving the pectin. Upon cooling below gelling temperature, a gel starts to form. If gel formation is too strong, syneresis or a granular texture are the result, whilst weak gelling leads to excessively soft gels. In high-ester pectins at soluble solids content above 60% and a pH-value between 2.8 and 3.6, hydrogen-bonds and hydrophobic interactions bind the individual pectin chains together. These bonds form as water is bound by sugar and forces pectin strands to stick together. These form a 3-dimensional molecular net that creates the macromolecular gel. The gelling-mechanism is called a low-water-activity gel or sugar-acid-pectin gel.

In low-ester pectins, ionic bridges are formed between calcium and carboxylic acid of the galacturonic acid. This is idealised in the so-called “egg box-model”. Low-ester pectins need calcium to form a gel, but can do so at lower soluble solids and higher pH-values than high-ester pectins.

Amidated pectins behave like low-ester pectins but need less calcium and are more tolerant of excess calcium. Also, gels from amidated pectin are thermo-reversible – they can be heated and after cooling solidify again, whereas conventional pectin-gels will afterwards remain liquid.

Within high ester pectins, the speed by which pectin gels set is faster with higher than with lower ester pectins. On the other hand, reactions with calcium increases as the degree of esterification falls. Similary, lower pH-values or higher soluble solids (normally sugars) increase gelling speed. Suitable pectins can therefore be selected for jams and for jellies, or for higher sugar confectionery jellies.

Sources and Production
Apples, quince, plums, gooseberries and oranges contain much pectin, while soft fruits like cherries, grapes and strawberries contain little pectin.

Typical levels of pectin in plants are (fresh weight):

apples, apricot approx. 1%

oranges 0.5 - 3.5%

carrots approx. 1.4%

The main raw-materials for pectin production are dried citrus peel or apple pomace, both by-products of juice production. Pomace from sugar-beet is also used to a small extent.

From these materials, pectin is extracted by adding hot dilute acid at pH-values from 1.5 – 3.5. During several hours of extraction, the protopectin loses some of its branching and chain-length and goes into solution. After filtering, the extract is concentrated in vacuum and the pectin then precipitated by adding ethanol or isopropanol. An old technique of precipitating pectin with aluminium salts is no longer used (apart from alcohols and polyvalent cations; pectin also precipitates with proteins and detergents).

Precipitated pectin is then separated, washed and dried. Treating the initial pectin with dilute acid leads to low-esterified pectins. When this process includes ammonium hydroxide, amidated pectins are obtained. After drying and milling pectin is usually standardised with sugar and sometimes calcium-salts or organic acids to have optimum performance in a particular application.

Worldwide, approximately 40,000 metric tons of pectin are produced every year.

Uses
The main use for pectin is as a gelling agent, thickening agent and stabilizer in food. The classical application is giving the jelly-like consistency to jams or marmalades, which would otherwise be sweet juices. For household use, pectin is an ingredient in jelling sugar (sometimes sold as “sugar with pectin”) where it is diluted to the right concentration with sugar and some citric acid to adjust pH. In some countries, pectin is also available as a solution or an extract, or as a blended powder, for home jam making. For conventional jams and marmalades that contain above 60% sugar and soluble fruit solids, high-ester pectins are used. With low-ester pectins and amidated pectins less sugar is needed, so that diet products can be made. Pectin can also be used to stabilize acidic protein drinks, such as drinking yogurt, and as a fat replacer. Typical levels of pectin used as a food additive are between 0.5 – 1.0% - this is about the same amount of pectin as in fresh fruit.

In medicine, pectin increases viscosity and volume of stool so that it is used against constipation and diarrhea. Until 2002, it was one of the main ingredients used in Kaopectate, along with kaolinite. Pectin is also used in throat lozenges as a demulcent. In cosmetic products, pectin acts as stabilizer. Pectin is also used in wound healing preparations and specialty medical adhesives, such as colostomy devices.

In ruminant nutrition, depending on the extent of signification of the cell wall, pectin is up to 90% digestible by bacterial enzymes. Ruminant nutritionists recommend that the digestibility and energy concentration in forages can be improved by increasing pectin concentration in the forage.

Pectin is also a substitute for fat in baked goods.

In the cigar industry, pectin is considered an excellent substitute for vegetable glue and many cigar smokers and collectors will use pectin for repairing damaged tobacco wrapper leaves on their cigars.

Legal status
Pectins, including high and low -ester and amidated, are used in food all over the world. At the FAO/WHO joint Expert Committee on Food Additives and in the EU, no numerical acceptable daily intake (ADI) has been set, as pectin is considered safe.

In the US, pectin is GRAS – Generally recognized as safe. In most foods it can be used according to good manufacturing practices in the levels needed for its application, “quantum satis”.

In the International Numbering System (INS) pectin has the number 440. In Europe it is differentiated into E440(i) for non-amidated pectins and E440 (ii) for amidated pectins. There are specifications in all national and international legislation defining its quality and regulating its use.

History
Pectin was first isolated and described in 1825 by Henri Braconnot, though the action of pectin to make jams and marmalades was known long before. To obtain well set jams from fruits that had little or only poor quality pectin, pectin-rich fruits or their extracts were mixed into the recipe.

During industrialization, the makers of fruit preserves soon turned to producers of apple juice to obtain dried apple pomace that was then cooked to extract pectin.

Later, in the 1920s and 1930s, factories were built that commercially extracted pectin from dried apple pomace and later citrus-peel in regions that produced apple juice in both the USA and in Europe.

At first pectin was sold as a liquid extract, but nowadays pectin is often used as dried powder that is easier to store and handle than a liquid.