Starch

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

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. Glycogen, the glucose store of animals, is a more branched version of amylopectin.

Starch is processed to produce many of the sugars in processed foods. Dissolving starch in warm water gives wheatpaste, which can be used as a thickening, stiffening or gluing agent. The biggest industrial non-food use of starch is as adhesive in the papermaking process. Starch can be applied to parts of some garments before ironing, to stiffen them.

Etymology
The word "starch" is from a Germanic root with the meanings "strong, stiff, strengthen, stiffen". Modern German Stärke (starch) is related.

"Amylum" for starch is from the Greek αμυλον, "amylon" which means "not ground at a mill". The root amyl is used in biochemistry for several compounds related to starch.

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. Starch grains from sorghum were found on grind stones in caves in Ngalue, Mozambique dating up to 100,000 years ago.

Pure extracted wheat starch paste was used in Ancient Egypt possibly to glue papyrus. The extraction of starch is first described in the Natural History of Pliny the Elder around AD 77-79. 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, from 700 AD onwards.

In addition to starchy plants consumed directly, 66 million tonnes of starch were being produced per year world-wide by 2008. In the EU this was around 8.5 million tonnes, with around 40% being used for industrial applications and 60% for food uses, most of the latter as glucose syrups.

Energy store of plants
Most green plants use starch as their energy store. An exception is the family Asteraceae (asters, daisies and sunflowers), where starch is replaced by the fructan inulin.

In photosynthesis, plants use light energy to produce glucose from carbon dioxide. The glucose is stored mainly in the form of starch granules, in plastids such as chloroplasts and especially 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.

Glucose is soluble in water, hydrophilic, 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.

Glucose molecules are bound in starch by the easily hydrolyzed alpha bonds. 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 beta bonds and are much more resistant to hydrolysis.

Biosynthesis
Plants produce starch by first converting glucose 1-phosphate to ADP-glucose using the enzyme glucose-1-phosphate adenylyltransferase. This step requires energy in the form of ATP. The enzyme starch synthase then adds the ADP-glucose via a 1,4-alpha glycosidic bond to a growing chain of glucose residues, liberating ADP and creating amylose. Starch branching enzyme introduces 1,6-alpha glycosidic bonds between these chains, creating the branched amylopectin. The starch debranching enzyme isoamylase removes some of these branches. Several isoforms of these enzymes exist, leading to a highly complex synthesis process.

Glycogen and amylopectin have the same structure, but the former has about one branch point per ten 1,4-alpha bonds, compared to about one branch point per thirty 1,4-alpha bonds in amylopectin. Amylopectin is synthesized from ADP-glucose while mammals and fungi synthesize glycogen from UDP-glucose; for most cases, bacteria synthesize glycogen from ADP-glucose (analogous to starch).

In addition to starch synthesis in plants, starch can be synthesized from non-food starch mediated by an enzyme cocktail. In this cell-free biosystem, beta-1,4-glycosidic bond-linked cellulose is partially hydrolyzed to cellobioase. Cellobiose phosphorylase cleaves to glucose 1-phosphate and glucose; the other enzyme—potato alpha-glucan phosphorylase can add glucose unit from glucose 1-phosphorylase to the non-ruducing ends of starch. In it, phosphate is internally recycled. The other product—glucose—can be assimilated by a yeast. This cell-free bioprocessing does not need any costly chemical and energy input, can be conducted in aqueous solution, and does not have sugar losses. As a result, cellulosic starch could be used to feed the world because cellulose resource is about 50 times of starch resource.

Degradation
Starch is synthesized in plant leaves during the day, in order to serve as an energy source at night. Starch is stored as granulates. These insoluble highly branched 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. Because starch cannot be phosphorylated, it accumulates in the plastid.

After the phosphorylation, the first degrading enzyme, beta-amylase (BAM) is able to 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 less 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.

The products of starch degradation are to the major part maltose and to a less extensive part glucose. These molecules are now exported from the plastid to the cytosol. Maltose is exported via the maltose transporter. If this transporter is mutated (MEX1-mutant), maltose accumulates in the plastid. Glucose is exported via the plastidic glucose translocator (pGlcT). Now, these two sugars act as a precursor for sucrose synthesis. Sucrose can the be used in the oxidative pentose phosphate pathway in the mitochondria, in order to generate ATP at night.

Structure


While amylose was traditionally thought to be completely unbranched, it is now known that some of its molecules contain a few branch points. Although in absolute mass only about one quarter of the starch granules in plants consist of amylose, there are about 150 times more amylose molecules than amylopectin molecules. Amylose is a much smaller molecule than amylopectin.

Starch molecules arrange themselves in the plant in semi-crystalline granules. Each plant species has a unique starch granular size: rice starch is relatively small (about 2μm) while potato starches have larger granules (up to 100μm).

Starch becomes soluble in water when heated. The granules swell and burst, the semi-crystalline structure is lost and the smaller amylose molecules start leaching out of the granule, forming a network that holds water and increasing the mixture's viscosity. This process is called starch gelatinization. During cooking, the starch becomes a paste and increases further in viscosity. During cooling or prolonged storage of the paste, the semi-crystalline structure partially recovers and the starch paste thickens, expelling water. This is mainly caused by retrogradation of the amylose. This process is responsible for the hardening of bread or staling, and for the water layer on top of a starch gel (syneresis).

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 have less retrogradation, resulting in a more stable paste. High 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.

Hydrolysis
The enzymes that break down or hydrolyze starch into the constituent sugars are known as amylases.

Alpha-amylases are found in plants and in animals. Human saliva is rich in amylase, and the pancreas also secretes the enzyme. Individuals from populations with a high-starch diet tend to have more amylase genes than those with low-starch diets;

Beta-amylase cuts starch into maltose units. This process is important in the digestion of starch and is also used in brewing, where amylase from the skin of seed grains is responsible for converting starch to maltose (Malting, Mashing).

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.

Chemical tests


Iodine solution is used to test for starch; a dark blue color indicates the presence of starch. The details of this reaction are not yet fully known, but it is thought that the iodine (I3− and I5− ions) fit inside the coils of amylose, the charge transfers between the iodine and the starch, and the energy level spacings in the resulting complex correspond to the absorption spectrum in the visible light region. 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.

Starch indicator solution consisting of water, starch and iodine 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. 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
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). Many other starchy foods are grown, some only in specific climates, including acorns, arrowroot, arracacha, bananas, barley, breadfruit, buckwheat, canna, colacasia, 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.

Widely used prepared foods containing starch are bread, pancakes, cereals, noodles, pasta, porridge and tortilla.

Digestive enzymes have problems digesting crystalline structures. Raw starch will digest poorly in the duodenum and small intestine, while bacterial degradation will take place mainly in the colon. When starch is cooked, the digestibility is increased. Hence, before humans started using fire, eating grains was not a very useful way to get energy.

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

Starch industry
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, wheat, rice and potato starch. To a lesser extent, sources include rice, sweet potato, sago and mung bean. Historically, Florida arrowroot was also commercialized. 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
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 sweetener in many drinks and foods. They include:


 * Maltodextrin, a lightly hydrolyzed (DE 10–20) starch product used as a bland-tasting filler and thickener.
 * Various glucose syrups (DE 30–70), also called corn syrups in the US, viscous solutions used as sweeteners and thickeners in many kinds of processed foods.
 * Dextrose (DE 100), commercial glucose, prepared by the complete hydrolysis of starch.
 * High fructose syrup, made by treating dextrose solutions with the enzyme glucose isomerase, until a substantial fraction of the glucose has been converted to fructose. In the United States sugar prices are two to three times higher than in the rest of the world, which makes high fructose corn syrup significantly cheaper, so that it is the principal sweetener used in processed foods and beverages. Fructose also has better microbiological stability. One kind of high fructose corn syrup, HFCS-55, is sweeter than sucrose because it is made with more fructose, while the sweetness of HFCS-42 is on par with sucrose.
 * Sugar alcohols, such as maltitol, erythritol, sorbitol, mannitol and hydrogenated starch hydrolysate, are sweeteners made by reducing sugars.

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 the International Numbering System for Food Additives (INS):
 * 1400 Dextrin
 * 1401 Acid-treated starch
 * 1402 Alkaline-treated starch
 * 1403 Bleached starch
 * 1404 Oxidized starch
 * 1405 Starches, enzyme-treated
 * 1410 Monostarch phosphate
 * 1412 Distarch phosphate
 * 1413 Phosphated distarch phosphate
 * 1414 Acetylated distarch phosphate
 * 1420 Starch acetate
 * 1422 Acetylated distarch adipate
 * 1440 Hydroxypropyl starch
 * 1442 Hydroxypropyl distarch phosphate
 * 1443 Hydroxypropyl distarch glycerol
 * 1450 Starch sodium octenyl succinate
 * 1451 Acetylated oxidized starch

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

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.

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 into 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 or as binder.

Resistant starch
Resistant starch is starch that escapes digestion in the small intestine of healthy individuals. High amylose starch from 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 Type 2 resistant corn helps to improve insulin sensitivity, increases satiety and improves markers of colonic function. It has been suggested that resistant starch contributes to the health benefits of intact whole grains.

Papermaking
Papermaking is the largest non-food application for starches globally, consuming millions of metric tons annually. 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
Clothing or laundry starch is a liquid that is prepared by mixing a vegetable starch in water (earlier preparations also had to be boiled), 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 century and early 20th century, it was stylish to stiffen the collars and sleeves of men's shirts and the ruffles of girls' petticoats by applying starch to them as the clean clothes were being ironed. Aside from the smooth, crisp edges it gave to clothing, it served practical purposes as well. Dirt and sweat from a person's neck and wrists would stick to the starch rather than to the fibers of the clothing, and would easily wash away along with the starch. After each laundering, the starch would be reapplied. Today, the product is sold in aerosol cans for home use.

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 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 – to create a very good adhesive. Sodium silicate can be added to reinforce these formula.


 * Textile chemicals from starch: warp sizing agents are used to reduce breaking of yarns during weaving. Starch is mainly used to size cotton based yarns. Modified starch is also used as textile printing thickener.
 * In oil exploration, starch is used to adjust the viscosity of drilling fluid, which is used to lubricate the drill head and suspend the grinding residue in petroleum extraction.


 * Starch is also used to make some packing peanuts, and some drop ceiling tiles.
 * In the printing industry, food grade starch is used in the manufacture of anti-set-off spray powder used to separate printed sheets of paper to avoid wet ink being set off.
 * For body powder, powdered corn starch is used as a substitute for talcum powder, and similarly in other health and beauty products.


 * Starch is used to produce various bioplastics, synthetic polymers that are biodegradable. An example is polylactic acid based on glucose form starch.
 * Glucose from starch can be further fermented to biofuel corn ethanol using the so-called wet milling process. Today most bioethanol production plants use the dry milling process to ferment corn or other feedstock directly to ethanol.
 * Hydrogen production could use glucose form starch as the raw material, using enzymes.