Starch
Cornstarch being mixed with water
Identifiers
ChemSpider
  • none
ECHA InfoCard 100.029.696 Edit this at Wikidata
EC Number
  • 232-679-6
RTECS number
  • GM5090000
UNII
Properties
(C
6
H
10
O
5
)
n
+(H
2
O)
Molar mass Variable
Appearance White powder
Density Variable[1]
Melting point decomposes
insoluble (see starch gelatinization)
Thermochemistry
4.1788 kilocalories per gram (17.484 kJ/g)[2] (Higher heating value)
Hazards
410 °C (770 °F; 683 K)
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 15 mg/m3 (total) TWA 5 mg/m3 (resp)[3]
Safety data sheet (SDS) ICSC 1553
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Structure of the amylose molecule
Structure of the amylopectin molecule

Starch or amylum is a polymeric carbohydrate consisting of numerous glucose units joined by glycosidic bonds. This polysaccharide is produced by most green plants for energy storage. Worldwide, it is the most common carbohydrate in human diets, and is contained in large amounts in staple foods such as wheat, potatoes, maize (corn), rice, and cassava (manioc).

Pure starch is a white, tasteless and odorless powder that is insoluble in cold water or alcohol. It consists of two types of molecules: the linear and helical amylose and the branched amylopectin. Depending on the plant, starch generally contains 20 to 25% amylose and 75 to 80% amylopectin by weight.[4] Glycogen, the energy reserve of animals, is a more highly branched version of amylopectin.

In industry, starch is often converted into sugars, for example by malting. These sugars may be fermented to produce ethanol in the manufacture of beer, whisky and biofuel. In addition, sugars produced from processed starch are used in many processed foods.

Mixing most starches in warm water produces a paste, such as wheatpaste, which can be used as a thickening, stiffening or gluing agent. The principal non-food, industrial use of starch is as an adhesive in the papermaking process. A similar paste, clothing starch, can be applied to certain textile goods before ironing to stiffen them.

Etymology

The word "starch" is from its Germanic root with the meanings "strong, stiff, strengthen, stiffen".[5] Modern German Stärke (strength) is related and referring for centuries main application, the use in textile: sizing yarn for weaving and starching linen. The Greek term for starch, "amylon" (ἄμυλον), which means "not milled", is also related. It provides the root amyl, which is used as a prefix for several 5-carbon compounds related to or derived from starch (e.g. amyl alcohol).

History

Starch grains from the rhizomes of Typha (cattails, bullrushes) as flour have been identified from grinding stones in Europe dating back to 30,000 years ago.[6] Starch grains from sorghum were found on grind stones in caves in Ngalue, Mozambique dating up to 100,000 years ago.[7]

Pure extracted wheat starch paste was used in Ancient Egypt, possibly to glue papyrus.[8] The extraction of starch is first described in the Natural History of Pliny the Elder around 77–79 CE.[9] Romans used it also in cosmetic creams, to powder the hair and to thicken sauces. Persians and Indians used it to make dishes similar to gothumai wheat halva. Rice starch as surface treatment of paper has been used in paper production in China since 700 CE.[10]

Starch industry

Starch mill at Ballydugan (Northern Ireland), built in 1792
West Philadelphia Starch works at Philadelphia (Pennsylvania), 1850
Faultless Starch Company at Kansas City

In addition to starchy plants consumed directly, by 2008 66 million tonnes of starch were being produced per year worldwide. In 2011, production was increased to 73 million ton.[11]

In the EU the starch industry produced about 11 million tonnes in 2011, with around 40% being used for industrial applications and 60% for food uses,[12] most of the latter as glucose syrups.[13] In 2017 EU production was 11 million ton of which 9,4 million ton was consumed in the EU and of which 54% were starch sweeteners.[14]

The US produced about 27.5 million tons of starch in 2017, of which about 8.2 million tons was high fructose syrup, 6.2 million tons was glucose syrups, and 2.5 million tons were starch products.[clarification needed] The rest of the starch was used for producing ethanol (1.6 billion gallons).[15][16]

Energy store of plants

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Potato starch granules in cells of the potato
Starch in endosperm in embryonic phase of maize seed

Most green plants store energy as starch, which is packed into semicrystalline granules.[17] The extra glucose is changed into starch which is more complex than the glucose produced by plants. Young plants live on this stored energy in their roots, seeds, and fruits until they can find suitable soil in which to grow.[18] An exception is the family Asteraceae (asters, daisies and sunflowers), where starch is replaced by the fructan inulin. Inulin-like fructans are also present in grasses such as wheat, in onions and garlic, bananas, and asparagus.[19]

In photosynthesis, plants use light energy to produce glucose from carbon dioxide and water. The glucose is used to generate the chemical energy required for general metabolism, to make organic compounds such as nucleic acids, lipids, proteins and structural polysaccharides such as cellulose, or is stored in the form of starch granules, in amyloplasts. Toward the end of the growing season, starch accumulates in twigs of trees near the buds. Fruit, seeds, rhizomes, and tubers store starch to prepare for the next growing season.

Green algae and land-plants store their starch in the plastids, while red algae, glaucophytes, cryptomonads, dinoflagellates and the parasitic apicomplexa store a similar type of polysaccharide called floridean starch in their cytosol or periplast.[20]

Glucose is soluble in water, binds with water and then takes up much space and is osmotically active; glucose in the form of starch, on the other hand, is not soluble, therefore osmotically inactive and can be stored much more compactly. The semicrystalline granules generally consist of concentric layers of amylose and amylopectin which can be made bioavailable upon cellular demand in the plant.[21]

Amylose consist of long chains of glucose molecules connected by α-1,4-glycosidic linkage, while amylopectin consists of highly branched glucose chains with branches connected via α-1,6-glycosidic linkage.The same type of bond is found in the animal reserve polysaccharide glycogen. This is in contrast to many structural polysaccharides such as chitin, cellulose and peptidoglycan, which are bound by β-glycosidic bonds and exhibit greater resistance to hydrolysis.[22]

Biosynthesis

Plants synthesize starch in two types of tissues. The first type is storage tissues, for example, cereal endosperm, and storage roots and stems such as cassava and potato. The second type is green tissue, for example, leaves, where many plant species synthesize transitory starch on a daily basis. In both tissue types, starch is synthesized in a plastids (amyloplasts and chloroplasts).

The biochemical pathway involves conversion of glucose 1-phosphate to ADP-glucose using the enzyme glucose-1-phosphate adenylyltransferase. This step requires energy in the form of ATP. A number of starch synthases available in plastids then adds the ADP-glucose via α-1,4-glycosidic bond to a growing chain of glucose residues, liberating ADP. The ADP-glucose is almost certainly added to the non-reducing end of the amylose polymer, as the UDP-glucose is added to the non-reducing end of glycogen during glycogen synthesis.[23] The small glucan chain, further agglomerate to form initials of starch granules.

The biosynthesis and expansion of granules represent a complex molecular event that can be subdivided into four major steps, namely, granule initiation, coalescence of small granules,[24] phase transition, and expansion. Several proteins have been characterized for their involvement in each of these processes. For instance, a chloroplast membrane-associated protein, MFP1, determines the sites of granule initiation.[25] Another protein named PTST2 binds to small glucan chains and agglomerates to recruit starch synthase 4 (SS4).[26] Three other proteins, namely, PTST3, SS5, and MRC, are also known to be involved in the process of starch granule initiation.[27][28][29] Furthermore, two proteins named ESV and LESV play a role in the aqueous-to-crystalline phase transition of glucan chains.[30] Several catalytically active starch synthases, such as SS1, SS2, SS3, and GBSS, are critical for starch granule biosynthesis and play a catalytic role at each step of granule biogenesis and expansion.[31]

In addition to above proteins, starch branching enzymes (BEs) introduces α-1,6-glycosidic bonds between the glucose chains, creating the branched amylopectin. The starch debranching enzyme (DBE) isoamylase removes some of these branches. Several isoforms of these enzymes exist, leading to a highly complex synthesis process.[32]

Degradation

The transitory starch that is synthesized in plant leaves during the day, serves as an energy source at night. Starch degradation enzymes catalyze release of glucose molecules from the semi-crystalline starch granules. The insoluble, highly branched starch chains have to be phosphorylated in order to be accessible for degrading enzymes. The enzyme glucan, water dikinase (GWD) phosphorylates at the C-6 position of a glucose molecule, close to the chains 1,6-alpha branching bonds. A second enzyme, phosphoglucan, water dikinase (PWD) phosphorylates the glucose molecule at the C-3 position. A loss of these enzymes, for example a loss of the GWD, leads to a starch excess (sex) phenotype,[33] and because starch cannot be phosphorylated, it accumulates in the plastids.

After the phosphorylation, the first degrading enzyme, beta-amylase (BAM) can attack the glucose chain at its non-reducing end. Maltose is released as the main product of starch degradation. If the glucose chain consists of three or fewer molecules, BAM cannot release maltose. A second enzyme, disproportionating enzyme-1 (DPE1), combines two maltotriose molecules. From this chain, a glucose molecule is released. Now, BAM can release another maltose molecule from the remaining chain. This cycle repeats until starch is degraded completely. If BAM comes close to the phosphorylated branching point of the glucose chain, it can no longer release maltose. In order for the phosphorylated chain to be degraded, the enzyme isoamylase (ISA) is required.[34]

The products of starch degradation are predominantly maltose[35] and smaller amounts of glucose. These molecules are exported from the plastid to the cytosol, maltose via the maltose transporter, which if mutated (MEX1-mutant) results in maltose accumulation in the plastid.[36] Glucose is exported via the plastidic glucose translocator (pGlcT).[37] These two sugars act as a precursor for sucrose synthesis. Sucrose can then be used in the oxidative pentose phosphate pathway in the mitochondria, to generate ATP at night.[34]

Processing

Starches derived from potatoes, wheat, rice, corn, and tapioca are processed on an industrial scale to maltodextrin and glucose syrups and fructose syrups. These massive conversions are mediated by a variety of enzymes, which break down the starch to varying extents. Here breakdown involves hydrolysis, i.e. cleavage of bonds between sugar subunits by the addition of water. Some sugars are isomerized. The processes have been described as occurring in two phases: liquefaction and saccharification. The liquefaction converts starch into [[dextrin]s. Amylase is a key enzyme for producing dextrin. The saccharification converts dextrin into maltoses and glucose. Diverse enzymes are used in this second phase, including pullanase and other amylases.[38]

Corn starch, 800x magnified, under polarized light, showing characteristic extinction cross
Rice starch under transmitted light microscopy. A characteristic of rice starch is that granules have an angular outline and tend to clump.

Accumulated starch within plants is stored in semi-crystalline granules. Each plant species has a unique starch granular size: rice starch is relatively small (about 2 μm), potato starches have larger granules (up to 100 μm) and wheat and tapioca all in-between.[39] Unlike other botanical sources of starch, wheat starch has a bimodal size distribution, with both smaller and larger granules ranging from 2 to 55 μm.[39]

Some cultivated plant varieties have pure amylopectin starch without amylose, known as waxy starches. The most used is waxy maize, others are glutinous rice and waxy potato starch. Waxy starches undergo less retrogradation, resulting in a more stable paste. A maize cultivar with a relatively high proportion of amylose starch, amylomaize, is cultivated for the use of its gel strength and for use as a resistant starch (a starch that resists digestion) in food products.

Synthetic amylose made from cellulose has a well-controlled degree of polymerization. Therefore, it can be used as a potential drug deliver carrier.[40]

Dextrinization

If starch is subjected to dry heat, it breaks down to form dextrins, also called "pyrodextrins" in this context. This break down process is known as dextrinization. (Pyro)dextrins are mainly yellow to brown in color and dextrinization is partially responsible for the browning of toasted bread.[41]

Chemical tests

Main article: Iodine test

Granules of wheat starch, stained with iodine, photographed through a light microscope

A triiodide (I3) solution formed by mixing iodine and iodide (usually from potassium iodide) is used to test for starch; a dark blue color indicates the presence of starch. The details of this reaction are not fully known, but recent scientific work using single crystal X-ray crystallography and comparative Raman spectroscopy suggests that the final starch-iodine complex is similar to an infinite polyiodide chain like one found in a pyrroloperylene-iodine complex.[42] The strength of the resulting blue color depends on the amount of amylose present. Waxy starches with little or no amylose present will color red. Benedict's test and Fehling's test is also done to indicate the presence of starch.

Starch indicator solution consisting of water, starch and iodide is often used in redox titrations: in the presence of an oxidizing agent the solution turns blue, in the presence of reducing agent the blue color disappears because triiodide (I3) ions break up into three iodide ions, disassembling the starch-iodine complex. Starch solution was used as indicator for visualizing the periodic formation and consumption of triiodide intermediate in the Briggs-Rauscher oscillating reaction. The starch, however, changes the kinetics of the reaction steps involving triiodide ion.[43] A 0.3% w/w solution is the standard concentration for a starch indicator. It is made by adding 3 grams of soluble starch to 1 liter of heated water; the solution is cooled before use (starch-iodine complex becomes unstable at temperatures above 35 °C).

Each species of plant has a unique type of starch granules in granular size, shape and crystallization pattern. Under the microscope, starch grains stained with iodine illuminated from behind with polarized light show a distinctive Maltese cross effect (also known as extinction cross and birefringence).

Food

Sago starch extraction from palm stems

Starch is the most common carbohydrate in the human diet and is contained in many staple foods. The major sources of starch intake worldwide are the cereals (rice, wheat, and maize) and the root vegetables (potatoes and cassava).[44] Many other starchy foods are grown, some only in specific climates, including acorns, arrowroot, arracacha, bananas, barley, breadfruit, buckwheat, canna, colocasia, katakuri, kudzu, malanga, millet, oats, oca, polynesian arrowroot, sago, sorghum, sweet potatoes, rye, taro, chestnuts, water chestnuts, and yams, and many kinds of beans, such as favas, lentils, mung beans, peas, and chickpeas.

Before processed foods, people consumed large amounts of uncooked and unprocessed starch-containing plants, which contained high amounts of resistant starch. Microbes within the large intestine ferment or consume the starch, producing short-chain fatty acids, which are used as energy, and support the maintenance and growth of the microbes. Upon cooking, starch is transformed from an insoluble, difficult-to-digest granule into readily accessible glucose chains with very different nutritional and functional properties.[45]

In current diets, highly processed foods are more easily digested and release more glucose in the small intestine—less starch reaches the large intestine and more energy is absorbed by the body. It is thought that this shift in energy delivery (as a result of eating more processed foods) may be one of the contributing factors to the development of metabolic disorders of modern life, including obesity and diabetes.[46]

The amylose/amylopectin ratio, molecular weight and molecular fine structure influences the physicochemical properties as well as energy release of different types of starches.[47] In addition, cooking and food processing significantly impacts starch digestibility and energy release. Starch has been classified as rapidly digestible starch, slowly digestible starch and resistant starch, depending upon its digestion profile.[48] Raw starch granules resist digestion by human enzymes and do not break down into glucose in the small intestine - they reach the large intestine instead and function as prebiotic dietary fiber.[49] When starch granules are fully gelatinized and cooked, the starch becomes easily digestible and releases glucose quickly within the small intestine. When starchy foods are cooked and cooled, some of the glucose chains re-crystallize and become resistant to digestion again. Slowly digestible starch can be found in raw cereals, where digestion is slow but relatively complete within the small intestine.[50] Widely used prepared foods containing starch are bread, pancakes, cereals, noodles, pasta, porridge and tortilla.

During cooking with high heat, sugars released from starch can react with amino acids via the Maillard reaction, forming advanced glycation end-products (AGEs), contributing aromas, flavors and texture to foods.[51] One example of a dietary AGE is acrylamide. Recent evidence suggests that the intestinal fermentation of dietary AGEs may be associated with insulin resistance, atherosclerosis, diabetes and other inflammatory diseases.[52][53] This may be due to the impact of AGEs on intestinal permeability.[54]

Starch gelatinization during cake baking can be impaired by sugar competing for water, preventing gelatinization and improving texture.

Starch production

Glucose syrup

The starch industry extracts and refines starches from seeds, roots and tubers, by wet grinding, washing, sieving and drying. Today, the main commercial refined starches are cornstarch, tapioca, arrowroot,[55] and wheat, rice, and potato starches. To a lesser extent, sources of refined starch are sweet potato, sago and mung bean. To this day, starch is extracted from more than 50 types of plants.

Untreated starch requires heat to thicken or gelatinize. When a starch is pre-cooked, it can then be used to thicken instantly in cold water. This is referred to as a pregelatinized starch.

Starch sugars

Karo corn syrup advert 1917
Niagara corn starch advert 1880s
Pacific Laundry and Cooking Starch advert 1904

Starch can be hydrolyzed into simpler carbohydrates by acids, various enzymes, or a combination of the two. The resulting fragments are known as dextrins. The extent of conversion is typically quantified by dextrose equivalent (DE), which is roughly the fraction of the glycosidic bonds in starch that have been broken.

These starch sugars are by far the most common starch based food ingredient and are used as sweeteners in many drinks and foods. They include:

Modified starches

A modified starch is a starch that has been chemically modified to allow the starch to function properly under conditions frequently encountered during processing or storage, such as high heat, high shear, low pH, freeze/thaw and cooling.

The modified food starches are E coded according to European Food Safety Authority and INS coded Food Additives according to the Codex Alimentarius:[59]

INS 1400, 1401, 1402, 1403 and 1405 are in the EU food ingredients without an E-number.[60] Typical modified starches for technical applications are cationic starches, hydroxyethyl starch, carboxymethylated starches and thiolated starches.[61]

Use as food additive

As an additive for food processing, food starches are typically used as thickeners and stabilizers in foods such as puddings, custards, soups, sauces, gravies, pie fillings, and salad dressings, and to make noodles and pastas. They function as thickeners, extenders, emulsion stabilizers and are exceptional binders in processed meats.

Gummed sweets such as jelly beans and wine gums are not manufactured using a mold in the conventional sense. A tray is filled with native starch and leveled. A positive mold is then pressed into the starch leaving an impression of 1,000 or so jelly beans. The jelly mix is then poured into the impressions and put onto a stove to set. This method greatly reduces the number of molds that must be manufactured.

Use in pharmaceutical industry

In the pharmaceutical industry, starch is also used as an excipient, as tablet disintegrant, and as binder.

Resistant starch

Main article: Resistant starch

Resistant starch is starch that escapes digestion in the small intestine of healthy individuals. High-amylose starch from wheat or corn has a higher gelatinization temperature than other types of starch, and retains its resistant starch content through baking, mild extrusion and other food processing techniques. It is used as an insoluble dietary fiber in processed foods such as bread, pasta, cookies, crackers, pretzels and other low moisture foods. It is also utilized as a dietary supplement for its health benefits. Published studies have shown that resistant starch helps to improve insulin sensitivity,[62][63] reduces pro-inflammatory biomarkers interleukin 6 and tumor necrosis factor alpha[64][65] and improves markers of colonic function.[66] It has been suggested that resistant starch contributes to the health benefits of intact whole grains.[67]

Synthetic starch

In 2021, researchers reported the world's first artificial synthesis of starch in the laboratory. A cell-free chemoenzymatic process was used to synthesize starch from CO2 and hydrogen. If the process is viable and can be scaled, it could substantially reduce land-, pesticide- and water-use as well as greenhouse gas emissions while increasing food security. The chemical pathway of 11 core reactions was drafted by computational pathway design and converts CO2 to starch at a rate that is ~8.5-fold higher than starch synthesis in maize.[68][69]

Non-food applications

Starch adhesive
Gentleman with starched ruff in 1560

Papermaking

Papermaking is the largest non-food application for starches globally, consuming many millions of metric tons annually.[12] In a typical sheet of copy paper for instance, the starch content may be as high as 8%. Both chemically modified and unmodified starches are used in papermaking. In the wet part of the papermaking process, generally called the "wet-end", the starches used are cationic and have a positive charge bound to the starch polymer. These starch derivatives associate with the anionic or negatively charged paper fibers / cellulose and inorganic fillers. Cationic starches together with other retention and internal sizing agents help to give the necessary strength properties to the paper web formed in the papermaking process (wet strength), and to provide strength to the final paper sheet (dry strength).

In the dry end of the papermaking process, the paper web is rewetted with a starch based solution. The process is called surface sizing. Starches used have been chemically, or enzymatically depolymerized at the paper mill or by the starch industry (oxidized starch). The size/starch solutions are applied to the paper web by means of various mechanical presses (size presses). Together with surface sizing agents the surface starches impart additional strength to the paper web and additionally provide water hold out or "size" for superior printing properties. Starch is also used in paper coatings as one of the binders for the coating formulations which include a mixture of pigments, binders and thickeners. Coated paper has improved smoothness, hardness, whiteness and gloss and thus improves printing characteristics.

Corrugated board adhesives

Corrugated board adhesives are the next largest application of non-food starches globally. Starch glues are mostly based on unmodified native starches, plus some additive such as borax and caustic soda. Part of the starch is gelatinized to carry the slurry of uncooked starches and prevent sedimentation. This opaque glue is called a SteinHall adhesive. The glue is applied on tips of the fluting. The fluted paper is pressed to paper called liner. This is then dried under high heat, which causes the rest of the uncooked starch in glue to swell/gelatinize. This gelatinizing makes the glue a fast and strong adhesive for corrugated board production.

Clothing starch

Kingsford Oswego Starch advertising, 1885
Rice starch for ironing

Clothing or laundry starch is a liquid prepared by mixing a vegetable starch in water (unmodified starch only gels in water close to boiling point, while commercial products may not require heat), and is used in the laundering of clothes. Starch was widely used in Europe in the 16th and 17th centuries to stiffen the wide collars and ruffs of fine linen which surrounded the necks of the well-to-do. During the 19th and early 20th century it was stylish to stiffen the collars and sleeves of men's shirts and the ruffles of women's petticoats by starching them before the clean clothes were ironed. Starch gave clothing smooth, crisp edges, and had an additional practical purpose: dirt and sweat from a person's neck and wrists would stick to the starch rather than to the fibers of the clothing. The dirt would wash away along with the starch; after laundering, the starch would be reapplied. Starch is available in spray cans, in addition to the usual granules to mix with water.

Other

Another large non-food starch application is in the construction industry, where starch is used in the gypsum wall board manufacturing process. Chemically modified or unmodified starches are added to the stucco containing primarily gypsum. Top and bottom heavyweight sheets of paper are applied to the formulation, and the process is allowed to heat and cure to form the eventual rigid wall board. The starches act as a glue for the cured gypsum rock with the paper covering, and also provide rigidity to the board.

Starch is used in the manufacture of various adhesives or glues[70] for book-binding, wallpaper adhesives, paper sack production, tube winding, gummed paper, envelope adhesives, school glues and bottle labeling. Starch derivatives, such as yellow dextrins, can be modified by addition of some chemicals to form a hard glue for paper work; some of those forms use borax or soda ash, which are mixed with the starch solution at 50–70 °C (122–158 °F) to create a very good adhesive. Sodium silicate can be added to reinforce these formula.

Occupational safety and health

In the US, the Occupational Safety and Health Administration (OSHA) has set the legal limit (Permissible exposure limit) for starch exposure in the workplace as 15 mg/m3 total exposure and 5 mg/m3 respiratory exposure over an eight-hour workday. The National Institute for Occupational Safety and Health (NIOSH) has set a Recommended exposure limit (REL) of 10 mg/m3 total exposure and 5 mg/m3 respiratory exposure over an eight-hour workday.[74]

See also

References

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