Identity of Modified Starches

According to Regulation (EC) No 1333/2008, “modified starches” are edible starches that have been chemically, physically, or enzymatically treated, including acid or alkali treatment, bleaching, or thinning. Some types of modified starches, like white or yellow dextrin, roasted or dextrinated starch, and physically modified starch are not considered food additives. However, JECFA considers other types, like dextrin roasted starch (INS 1400), acid-treated starch (INS 1401), alkaline-treated starch (INS 1402), bleached starch (INS 1403), and enzyme-treated starch (INS 1405) as food additives with separate rules.

Starch is made up of two types of glucose polymers, called amylose and amylopectin. Amylose is almost linear while amylopectin is highly branched. Amylose has glucose monomers linked by alpha-1,4-glycosidic links, while amylopectin contains additional alpha-1,6-glycosidic bonds. Most commercial starches have 20-25% amylose and 75-80% amylopectin. High amylose starches usually have 50-80% amylose and 20-50% amylopectin.

Commercial starches come from potatoes, cereals, and other sources. These “native” starches can be modified chemically, which means they can undergo oxidation, esterification, and etherification. This allows for a variety of modifications to the chemical structure of the starch.

Food additiveCAS NoEC noSynonyms
Oxidised starch (E 1404)910452-67-4Modified starch, INS No 1404; starch, oxidised
Monostarch phosphate (E 1410)63100-01-6Modified starch, INS No 1410; starch, dihydrogen phosphate
Distarch phosphate (E 1412)55963-33-2611-338-9Modified starch, INS No 1412; starch, hydrogen phosphate
Phosphated distarch phosphate (E 1413)11120-02-8601-054-3Modified starch, INS No 1413; starch, phosphate
Acetylated distarch phosphate (E 1414)68130-14-3Modified starch, INS No 1414; starch, hydrogen phosphate acetate
Acetylated starch (E 1420)9045-28-7618-556-3Modified starch, INS No 1420; starch, acetate
Acetylated distarch adipate (E 1422)63798-35-6613-382-4Modified starch, INS No 1422; starch, acetate hexanedioate
Hydroxypropyl starch (E 1440)9049-76-7618-565-2Modified starch, INS No 1440; starch, 2- hydroxypropyl ether
Hydroxypropyl distarch phosphate (E 1442)53124-00-8610-966-0Modified starch, INS No 1442; starch, hydrogen phosphate, 2-hydroxypropyl ether
Starch sodium octenyl succinate (E 1450)66829-29-6Modified starch, INS No 1450; starch, hydrogen 2-(octen-1-yl)butanedioate, sodium salt; SSOS; OSA-modified starch
Acetylated oxidised starch (E 1451)68187-08-6614-359-1Modified starch, INS No 1451; starch, acetylated oxidised
Starch aluminium octenyl succinate (E 1452)9087-61-0618-671-9Starch, hydrogen 2-(octen-1-yl) butanedioate, aluminium salt; starch octenyl succinate aluminium salt
Table. Identity of modified starches

In order to minimize uncertainties with the identification of modified starches, the CAS Registry numbers and EC numbers in the table were confirmed. According to Starch Europe, CAS numbers cannot easily match E-numbers for modified starches because the requirements for identifying chemicals in each system are different. While CAS numbers do not directly address safety concerns, E-numbers aim to reflect the safety aspects of modified starches. Therefore, Starch Europe members do not believe that assigning a CAS number reference to an E-number identity would be useful or appropriate for identifying a particular modified starch, as it may suggest unrealistic safety aspects.

Starch Europe has pointed out that it can be challenging to accurately identify modified starches with CAS numbers due to the complex nature of their chemical structures. However, the Panel believes that assigning CAS numbers to these structures is the best way to identify them.

According to the Commission Regulation (EU) No 231/2012, all modified starches described in the present document are white or nearly white powder or granules or (if pregelatinized) flakes, amorphous powder or coarse particles. The particle size of commercial starches has been reported to be greater than 0.5 µm.

Oxidised starch (E 1404)

Oxidised starch (E 1404) is made by treating starch with sodium hypochlorite, according to Commission Regulation (EU) No 231/2012. Oxidised starches are typically whiter than unmodified starches since any pigments in the molecules are bleached. When heated in water, oxidised starches create clear fluid solutions that remain stable upon cooling, unlike their acid-converted counterparts, which tend to thicken and form gels or pastes.

Monostarch phosphate (E 1410)

Monostarch phosphate (E 1410) is a type of modified starch according to the EU Regulation. It is made by esterifying starch with ortho-phosphoric acid, sodium or potassium ortho-phosphate, or sodium tripolyphosphate. The phosphoric ester groups are attached to the glucopyranose units of the starch. The amount of residual phosphate is limited by the EU Regulation.

Starch phosphates are more water-soluble and have a greater water-binding capacity than native starch. The higher the level of phosphate substitution, the greater these characteristics are. The phosphorylation of starch leads to higher viscosities and greater clarity of the dispersions.

Distarch phosphate (E 1412)

Distarch phosphate (E 1412) is a type of starch that has been cross-linked with sodium trimetaphosphate or phosphorus oxychloride, forming phosphate groups that connect neighboring glucose molecules. The amount of phosphate groups per glucopyranose unit varies depending on the production process, but is limited to a certain amount by Commission Regulation (EU) No 231/2012.

Distarch phosphate has different properties compared to native starch, including higher viscosity and water-binding capacity, which increase with the degree of cross-linking. The properties of distarch phosphate also vary depending on the origin of the starch. While slightly cross-linked starch preparations show a decrease in viscosity with acidification, medium and high cross-linked preparations show an increase in viscosity.

Phosphated distarch phosphate (E 1413)

Phosphated distarch phosphate (E 1413) is a type of starch that has been treated with a combination of treatments as described for monostarch phosphate and for distarch phosphate. According to Commission Regulation (EU) No 231/2012, its residual phosphate content is limited to 0.5% bound P for wheat and potato starches, and 0.4% for starches from other sources. It is mostly made up of phosphated starch (≥ 70%), residual unreacted starch (7–14%), water (10–14%), lipids (0.8%) and proteins (0.8%) (EFSA NDA Panel, 2010).

Acetylated distarch phosphate (E 1414)

Acetylated distarch phosphate (E 1414) is a type of starch cross-linked with sodium trimetaphosphate or phosphorus oxychloride and esterified by acetic anhydride or vinyl acetate. The content of residual phosphate is limited by the EU purity criteria to 0.14% bound P for wheat and potato starches, 0.04% for other starch sources, and 2.5% acetyl groups. Its behavior in aqueous solutions is similar to distarch phosphate (E 1412), and its viscosity decreases as the level of cross-linking increases. Acidification affects it depending on the degree of cross-linking. While the viscosity decreases in slightly cross-linked starch, the viscosity of medium and high cross-linked starch is higher at pH 3.5 than at pH 5.5.

Acetylated starch (E 1420)

Acetylated starch (E 1420) is a type of starch that has been treated with acetic anhydride or vinyl acetate, as defined in Commission Regulation (EU) No 231/2012. The content of acetyl groups is limited to a maximum of 2.5%, which corresponds to a maximum degree of substitution (DS) of 0.1. Acetylated starch has increased water solubility and water-binding capacity compared to native starch. However, the effects on viscosity are inconsistent, with some studies reporting lower viscosity and others reporting higher viscosity. Acetylated starch is stable under mild to moderate acidic conditions, but is sensitive to alkaline hydrolysis.

Acetylated distarch adipate (E 1422)

Acetylated distarch adipate (E 1422) is a type of modified starch defined by Commission Regulation (EU) No 231/2012. It is made by cross-linking starch with adipic anhydride and esterifying it with acetic anhydride, forming crosswise bindings between adjacent chains of glucose rests. The content of adipate is limited to 0.135%, while the content of acetyl groups is limited to 2.5%. When dissolved in water, it forms viscous solutions, which decrease in viscosity slowly with decreasing pH. Research has shown that it has improved acid resistance, salt tolerance, and good viscosity breakdown properties when compared to native starch, especially potato starch.

Hydroxypropyl starch (E 1440)

Hydroxypropyl starch (E 1440) is made by mixing starch with propylene oxide under alkaline conditions. The resulting product has a maximum of four ether linkages per 10 glucopyranose units, and a hydroxypropyl content ranging from 3.3% to 11.5%. The hydroxypropyl groups are mainly found on the secondary hydroxyl at the C-2 position of the glucose units. When added to water, it forms a viscous solution whose thickness varies with the shear rate. Higher levels of hydroxypropyl substitution result in lower pasting temperatures. At a certain level of substitution, the starches become cold water-swelling.

Hydroxypropyl distarch phosphate (E 1442)

Hydroxypropyl distarch phosphate (E 1442) is a type of modified starch that is cross-linked with sodium trimetaphosphate or phosphorus oxychloride and etherified with propylene oxide. This creates phosphate groups that form crosswise bonds between the neighboring chains of glucose molecules. The amount of phosphorus allowed in the starch is limited to 0.04% to 0.14% bound P, depending on the starch’s origin, while the amount of hydroxypropyl groups is limited to 7%.

Starch sodium octenyl succinate (E 1450)

Starch sodium octenyl succinate (E 1450) is starch modified with octenyl-succinic anhydride. The amount of octenyl-succinyl groups in the product is limited to 3% and the content of octenyl-succinic acid residue to a maximum of 0.3%. The product has a DS of 0.02. The modification of starch with starch sodium octenyl succinate increases its water-holding power, tendency to swell in cold water and viscosity. The degree of cold water swelling and viscosity increase with higher levels of substitution. The viscosity is highest at neutral pH and is reduced in acidic conditions.

Acetylated oxidised starch (E 1451)

Acetylated oxidised starch (E 1451) is made by treating starch with sodium hypochlorite followed by esterification with acetic anhydride. It becomes more soluble in water as the acetyl content increases. This modification improves the gel strength and clarity of the starch, making it gummy and transparent. However, it hydrolyses slowly in strong acids.

Starch aluminum octenyl succinate (E 1452)

Starch aluminum octenyl succinate (E 1452) is a type of modified starch that is treated with octenylsuccinic anhydride and aluminum sulfate. It is similar to starch sodium octenyl succinate (E 1450), but aluminum is present instead of sodium. It has a reduced tendency to form gels and loses clarity when compared to native starch. It also has polyelectrolyte properties due to the introduction of succinate ester groups. The EU has set limits on the content of octenylsuccinyl groups, octenylsuccinic acid residue, and aluminum.

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