Pectin

Introduction
Pectins are polysaccharides enriched in galacturonic acid and galacturonic acid methyl ester units

Combined with proteins and other polysaccharides, pectins forms skeletal tissues of plants, which are chemically stable and physically strong
With high molecular weight and a polyanionic nature, pectins react to their environments to form dense gels to dilute solutions These properties enable pectin polymers to carry signal molecules and support various biologically active substances In addition, pectins closely imitate the structure of polysaccharides found in the extracellular matrices of mammals useful for biomaterials

Industrial production (extraction) of pectin

Apple residue (pomace) or citrus peel are collected from juice producers. The material has been washed and dried so it can be transported and stored without spoilage. The raw material is added to hot water containing a processing aid (usually a mineral acid like diluted HNO3). After time to extract the pectin, the remaining solids are separated (by filtration or centrifugation) The solution clarified and concentrated by removing some of the water. The concentrated liquid is mixed with an alcohol (primarily iso-propanol or ethanol) to precipitate the pectin. The pectin can be partly de-esterified at this stage

Industrial production (extraction) of pectin

The precipitate is separated, washed with more alcohol to remove impurities, and dried. The presence of little salts or alkalis may convert pectin to a partial salt form (sodium, potassium, calcium, ammonium) The alcohol (usually isopropanol) is recovered and reused to precipitate further pectin. Before or after drying, the pectin may be treated with ammonia to produce an amidated pectin if required. The dry solid is ground to a powder, tested, and blended with sugar or dextrose to a standard gelling power or other functional property such as viscosity or stabilising power.

Pectins are also sold blended with other approved food additives for use in specific products.
(May, 1990)

Degree of esterification (DE)

It is the percent of the total number of carboxyl groups esterified or as the percent of methoxyl content of total pectin (Walter, 1991) Determined by FTIR analysis Theoretically the degree of esterification (DE) can range from 0 to 100% Pectins with DE >50% are known as high methoxyl (HM) pectins and consequently low methoxyl (LM) pectins have a DE< 50% (Walter, 1991) The DE and therefore the charge on a pectin molecule is important to the functional properties in the plant cell wall. It also significantly affects their commercial use as gelling and thickening agents. HM pectins form gels at low pH (<4.0) or in the presence of a low amount of soluble solids, usually sucrose (>55%). HM pectin gels are stabilised by hydrophobic interactions. Conversely, LM pectins form electrostatically stabilised gel networks with divalent metal cations, usually calcium.

Effect of DE on pectin gelation

For high DE pectins, the formation of hydrophobic areas parallel to the helix axes can expand to dramatically reduce the solubility of pectin. High DE pectins also form gel in the presence of large concentrations of sugar. Aqueous solutions of univalent salts of pectins exhibit low viscosity at physiological pH. Univalent salts of low DE pectins are highly water soluble and form gel only at extremely low solution pH or in the presence of divalent cations. The introduction of amide groups in low DE pectin reduces the hydrophilic property with an increasing tendency to form gels.

Factors influencing gelling property of pectin

Types and concentrations of pectin Degree of esterification (DE)

The modifications of hydroxyl group

Solution pH and temperature The presence of cations

Under similar conditions, degree of gelation, gel strength and gelling temperature increase proportionately
Each of these properties is proportional the molecular weight and inversely proportional to the DE of pectin

Factors influencing gelling property of pectin

Pectins can gel in various ways depending on the type and structure of the pectin molecule. Gelling can be induced by acid, by cross-linking with calcium ion, or by synergistic reaction with alginate. At low pH (<4.0) the ionization of carboxylate groups on pectins is repressed. Pectin molecules no longer repel each other over their entire chains, and thus can associate over a portion of their chains to form acid-pectin gels. For acid-induced pectin gels, the hydration of pectin is reduced and there is less water incorporated into inter-chain entanglements. At high pH, the polycarboxylate groups are ionized, and able to react with calcium ions to form calcium-pectinate gels. The interaction of calcium ions and the carboxylate groups in pectin involves intermolecular chelate binding of the cation leading to the formation of macromolecular aggregates. When pectin is mixed with alginate in the presence of d-glucono-delta-lactone, gelling occurs by a synergistic reaction, which is referred to as the strong inter-chain contact between the protonated GG-blocks in alginate and the methoxy groups in pectin. The acid-inducing and calcium cross-linking pectin gels have been used most often for the development of pectin-based drug delivery systems.

P(LGA)
(Composite matrices of pectin and poly-lactide-coglycolide) It has been used clinically for tissue repair and organ regeneration for decades. This hydrophobic polymer is biocompatible, biodegradable, and easily processed into a variety of sizes and shapes with good mechanical properties. It support cell attachment and cell growth. Does not impart signals to the cells. This deficiency is currently overcome by synthesizing block or graft copolymers of lactic acid and lysine or other segments carrying side chain functional groups.

(Liu et al., 2004)

Pectin-applications
Effect of modified pectin molecules on the growth of bone cells
(Kokkonen et al., 2007)

Pectins have shown promise in engineering drug carriers for oral drug delivery. (Liu et al, 2004) Pectin-based systems for colon-specific drug delivery via oral route
(Liu et al., 2003)

Pectin-based injectable biomaterials for bone tissue engineering 3D matrix for bone issue development, attachment facilitated with RGD motif. (Munarin et al., 2011) Facilitating the delivery of specific sequences of amino acids, antiinflammatory agents, anti-coagulants, and wound healing substances to tissue sites. Pectin based composites can be formed into membranes, microspheres, scaffolds, or injectable gels. (Munarin et al., 2011)