Monograph Tapioca Pharma Starch

DEFINITION

Tapioca starch is obtained from the root of the cassava plant Manihot utilissima, Pehl (Fam. Euphorbi Aceae).

CHARACTERS

A very fine white powder practically insoluble in cold water and in alcohol. Tapioca starch does not contain starch grains of any other origin. It may contain a minute quantity, if any, of fragments of the tissue of the original plant.

IDENTIFICATION

A. Examined under a microscope using equal volumes of glycerol R and water R, it presents spherical granules with one truncated side, typically 5 μm to 35 μm in diameter, typically having a circular or several-rayed central clefts (Re.: BP).

B. Suspend 1 g in 50 ml of water R, boil for 1 min and cool. A thin cloudy mucilage is formed.

C. To 1 ml of the mucilage obtained in identification test B, add 0.05 ml of iodine solution R1. A dark-blue colour is produced which disappears on heating .

TESTS

pH (2.2.3). Shake 5.0 g with 25.0 ml of carbon dioxide-free water R for 60 s. Allow to stand for 15 min. The pH of the solution is 5.0 to 8.0.

Iron (2.4.9) Shake 1.5 g with 15 ml of dilute hydrochloric acid R. Filter. The filtrate complies with the limit test for iron (10 ppm).

Foreign matter (2.8.2). Examined under a microscope using a mixture of equal volumes of glycerol R and water R, not more than traces of cell walls and of cytoplasmic residues are present.

Total protein. Not more than 0.1 per cent of total protein (corresponding to 0.017 per cent N2, conversion factor: 5.7), determined on 6.0 g by sulphuric acid digestion (2.5.9) modified as follows: wash any adhering particles from the neck into the flask with 25 ml of sulphuric acid R; continue the heating until a clear solution is obtained; add 45 ml of strong sodium hydroxide solution R.

Oxidising substances (2.5.30). It complies with the test for oxidising substances.

Sulphur dioxide (2.5:29). Not more than 50 ppm.

Loss on drying (2.2.32). Not more than 14.0 per cent (Re.: BP), determined on 1.000 g by drying in an oven at 130 °C for 90 min.

Sulphated ash. (2.4.14). Not more than 0.6 per cent, determined on 1.0 g.

Microbial contamination. Total viable aerobic count (2.6.12) not more than 10³ bacteria and not more than 10² fungi per gram, determined by plate-count. It complies with the test for Escherichia coli (2.6.13)

adapted from international starch institute

Functional Properties of Starches in Foods

• specific viscosity (hot and cold)
• thin boiling (faster canning heat transfer)
• viscosity resistance acid/mechanical sheer
• freeze-thaw stability (natural / modified)
• gel texture, body at various temperatures
• clarity, opacity
• processing conditions tolerance
• oil retention, high or low
• resistance to . setback. (gel formation)
• high sheen
• flow properties
• emulsion stabilizing capacity
• mouthfeel, lubricity, palate-coating
• suspension characteristics
• adhesiveness
• crystallinity
• bland taste
• long shelf-life stability
• hygroscopicity
• colour
• anti-caking
• cold-water swelling or dispersibility
• swelling and resistance to swelling
• film-forming properties

Food Applications

Canning

• filling viscosity aid
• suspension aid for particulates
• opacity agent
• body or texture agent for soups, sauces, puddings and gravies
• aseptically canned products
• beverages such as coffee, teas or chocolate

Cereals and Snacks

• hot extruded snacks
• chips, pretzels, etc.
• extruded and fried foods
• ready-to-eat cereals

Bakery

• pies, tarts
• fillings, glazes
• custards and icings
• cakes, donuts, danish
• icing sugar

Batters and Breadings

• coated fried foods
• frozen battered vegetables, fish and meat
• dry mix coatings

Dressings, Soups and Sauces

• mayonnaise-type
• pourable salad dressings (high shear)
• spoonable dressings
• instant dry salad dressing mixes
• low-fat dressing
• canned gravies and sauces
• frozen gravies and sauces
• soups and chowders

Cooked Meat Binder

• water binder for formed meat
• smoked meats, low-fat meats
• pet foods (dried and canned)

Frozen Foods

• fruit fillings
• meat pies
• Oriental foods
• soups, sauces
• entrees
• cream-based products

Flavours and Beverage Clouds

• encapsulation of flavours, fats, oils vitamins, spices, clouding agents
• spray dried flavours for dry beverage mixes, bartender mixes,
• beverage emulsions
• liquid and powdered non-dairy creamers

Confectionery

• dusting powder
• licorice
• jelly gums
• hard gums
• panned candies
• confectioners sugar

Dairy Products

• yoghurt
• cheese and imitation cheese
• chilled desserts
• UHT Puddings
• low-fat products

Microwavable Products

• cheese sauces
• entrees

adapted from international starch institute

Tapioca Food Starch

Native Tapioca Starch is a food grade product refined from cassava roots.

Starch is an important constituent in many foods. It plays an obvious role in achieving the desired viscosity in such products as cornstarch pudding, sauces, pie fillings and gravies. It plays a more subtle role in potatoes, cereals, and baked products such as biscuits, muffins, popovers, pastry, cake and bread.

It is used as a water binding and texturizing agent. It has a high viscosity, water-holding capacity and binding abilities.

It is a white to off-white powder with a moisture below 13%. The pH of a slurry in water is neutral. Tapioca Starch is very bland and clean in flavor and is not masking the flavours used.

Cooked it forms a quite clear gel with a long and slightly stringy texture. Upon cooling, it sets to a soft gel. It loses most of its thickening ability during prolonged heating and under acidic conditions. The cooked gel resambles that of potato, but the texture is less stringy and the flavor i more neutral, making it a preferred thickener in delicate foods and desserts.

Special food applications: Extruded snacks, where it improves expansion, custard-type pie filling, where it reduces surface cracking and in baby foods as a bodying agent. In biscuits and in cream sandwiches 5-10 % tapioca starch softens the texture and renders the biscuit nonsticky.

In general it may be used as a thickener in foods not subject to rigorous processing.

For household cooking tapioca starch is the starch of choise in thickening fruit desserts - it gives a clear dessert but with improved and "shorter" texture compared to potato starch.

AMYLOSE AND AMYLOPECTIN Normal native starches consist of a mixture of 15-30 per cent. amylose and 70-85 per cent. amylopectin. Amylose structurally is a linear polymer of anhydroglucose units, of molecular weight approximately between 40 000 and 340 000, the chains containing 250 to 2000 anhydroglucose units.

Amylopectin is considered to be composed of anhydroglucose chains with many branch points; the molecular weight may reach as high as 80 000 000 (Re. WHO). Amylose is an unbranched chain which is coiled in the shape of a helix. If iodine is added to a solution containing amylose molecules, the iodine inserts itself into the helix making it rigid. This changes the color of the starch mixture to blue or purple depending on the length of the amylose molecule.

Amylopectin is a branching molecule which does not form a helical coil. Thus the iodine is not able to bind to the starch molecule. Amylose contributes to the gelling property of starch whereas amylopectin contributes high viscosity. This classic statement, however, may not be entirely valid. Both properties are used in the preparation of foods.

Starch Source	% Amylose
Waxy Rice	0
High Amylose Corn	70
Corn	28
Cassava	17
Waxy Sorghum	0
Wheat	26
Sweet Potato	18
Arrowroot	21
Sago	26
Potato	20

Refined Starch Plus Acid / Enzyme

The acid / enzyme process for continuous conversion of refined starch is mainly used where it is desired to combine a standard glucose syrup production with the possibility of producing high DE product DE 96 ) suitable forproduction of e.g. dextrose monohidrat.

The process is continuous, standard glucose syrup additionally equippedwith an enzymatic saccharification section. In the acid enzyme process a continuous acid liquifaction to alow DE takes place followed by enzymatic saccharificatio to approx. 96 DE by means of amyloglucosidase enzyme. This process is also suitable for production of special types of maltose and glucose syrup by changing the saccharifying enzyme.

Following the saccharificationthe product is passed through various refining steps such as filtration, decolorization, and in some cases deionization, all dependent on final product requirements. The refined product is continuously evaporated to specified dry substance content for either storage or, in the case of high DE product, for further processing into dextrose monohidrat.

The acid / enzyme process is suitable for all kinds of refined starches and the process equipment differs slightly, defendent on whether the starches originated from a cereal or a root (tuber). This is mainly the case in refining section, hwere it can be stated that a plant designed for handling starch from a cereal is also able to handle starch fro a root, but not alwaysthe other way round.

Refined Starch Plus Acid

Continuous conversition of starch into standard glucose syrup by using an acid catalyst is still extensively used within the industry. By means of the acid conversition process glucose product with DE - values between 35 - 65 can be produced by a slight adjustment of the automatic acidification or temperature control. ( 1 degree change of conversition temperature means a change in DE of 1.5 ).

Following of conversition the product is continuously neutralized and passed trought various refining stages such as filtration, decolorization and in some case deionization, all dependent on the quality of the raw material and the requirements of the final product.
Refining is followed by continuous evaporation to the specified dry substance content of the final standard glucose syrup.

The acid conversition process is suitable for all kind of refined starches, defendent on whethter the starches originated from a cereal or a root ( tuber ).

This is mainly the case in the refining section, where it can be stated that a plant designed for handling starch from a cereal is also able to handle starch from a root, but not always the other way round.

Starch Application

Food

Snacks

High amylose cornstarch is also used in extruded and fried snack products to obtain crisp, evenly browned product and hampers penetration of cooking oils. High amylose cornstarch requires higher cooking temperatures, typically 150-170 oC, to gelatinise properly.

Tapioca starch exhibits good clarity and bland flavour. It has good film-forming characteristics with resistance to cracking and chipping. It may be used at a concentration of twenty per cent. The film-forming properties of Tapioca dextrins make it effective as a replacement for gum Arabic in the pan coating of confections. This dextrin can be used as a non-tacky glaze for cakes, donuts, fruit, nuts and candies.

Baking

High maltose and high conversion syrups improve moisture retension and colour control in final product. Dextrose syrup improve crust and doug properties. High fructose syrups are used in frosting and fillings.

Baby food

Maltodextrin and starch is used as a nutrient with low fermentability. Dextrose as an energy source

Noodles

Adding potato starch or better a dual esterifed starch with low gelatinisation point and a high peak viscosity to noodles improves their consistency and mouthfeel. The starch will gelatinise and absorb water before the wheat flour takes over and dominate the viscosity profile.

Sauces

A pizza sauce gets improved eye appeal and mouthfeel from a cold water swelling pregelatinized starch. A cross-linked instant starch is easy to disperse in cold mixtures or oil and adds a pulpy and richer look to fruit based sauces. Cross-linking imparts the starch with resistance in acid foods and will even allow retorting.

Meat products

Modified waxy maize, potato or tapioca starch added at the chopping stage swells during heating and binds in poultry rolls and meat loaves as well as other cooked meats. The final texture will be firm and retained for prolonged periods. Starch may reduce drip during smoking of meats and weeping of vacuum packed foods. Starch is also used as a skim milk in replacer.

Low calorie foods

HFSS 90 is used in low calorie food applications, due to its high sweetening power to calorie ratio.

Tapioca based modified starch can be used as a fat mimetic in dairy systems due to its bland flavour. A low-fat product can be prepared with the organoleptic and textural properties of a traditional fat containing product.

Beverages

Soft drinks

High fructose starch-based syrup (HFSS), although originally introduced in 1967, it was the fructose level increase to 55% in 1978 which resulted in sugars loss of the soft drink market. HFSS can be produced at considerably lower costs than sugar, giving this product a competitive advantage over sugar.
High fructose starch-based syrups (HFSS) are used for soft drinks as a sugar replacement with similar sweetness. HFSS 55, is a most concentrated sweetener used primarily in beverages. It is a direct replacement of sugar. HFSS 42, an all-purpose sweetener, does also find uses in beverages. HFSS stabilize the flavour profile.

Beer

High maltose syrups find use as wort syrup in beer production. It is an excellent fermentation substrate and fermentation can be controlled by the sugar spectrum of the syrup. Some yeast species are sensitive to high concentrations of glucose but maltose does not have any suppression effect on yeast.

Alcohol

Very high DE glucose syrups are used as a fermentation booster in alcohol fermentation. Dextrose syrup has the advantage, that it is completely used up and do not add to by-products and may improve throughput when capacity is exhausted.

Instant coffee

Following conventional coffee cleaning and roasting the prepared coffee is ground and extracted in counter current column batteries using split or fraction technique to optimise yields or by using continuos extraction. The extract is concentrated in falling film evaporators or rotary thin film concentrators with final blending to produce a prime quality concentrate. A maltodextrin (low DE glucose syrup) may be added as a carrier or extender. The concentrate is conducted in a co-current nozzle tower and the coffee powder is discharged in cooled free-flowing form ready for packing. Further agglomeration produces a coarser product.

Confectionary

Ice cream

Starch products are used as crystal and texture controller. High maltose and high conversion syrups control softness and freezing characteristics. Recipee.

Today's ice cream has the following composition:

· greater than 10% milkfat - usually between 10% and as high as 16% fat in some premium ice creams
· 9 to 12% milk solids-not-fat: this component contains the proteins (caseins and whey proteins) and carbohydrates (lactose) found in milk
· 12 to 16% sweeteners: usually a combination of sucrose and glucose syrup
· 0.2 to 0.5% stabilizers and emulsifiers
· 55% to 64% water which comes from the milk or other ingredients

A sweet ice cream is usually desired by the consumer. As a result, sweetening agents are added to ice cream mix at a rate of usually 12 - 16% by weight. Sweeteners improve the texture and palatability of the ice cream, enhance flavors, and are usually the cheapest source of total solids. In addition, the sugars contribute to a depressed freezing point so that the ice cream has some unfrozen water associated with it at very low temperatures typical of their serving temperatures, -15° to -18° C. Without this unfrozen water, the ice cream would be too hard to scoop.
It has become common in the industry to substitute all or a portion of the sucrose content with sweeteners derived from starch syrup. This sweetener is reported to contribute a firmer and more chewy body to the ice cream, is an economical source of solids, and improves the shelf life of the finished product. Starch syrup in either its liquid or dry form is available in varying dextrose equivalents (DE). As the DE is increased by hydrolysis of the starch, the sweetness of the solids is increased and the average molecular weight is decreased. This results in an increase in the freezing point depression, in such foods as ice cream, by the sweetener. The lower DE starch syrup contains more dextrins which tie up more water in the mix thus supplying greater stabilizing effect against coarse texture.
HFSS High fructose starch-based syrup can be used to a much greater extent in sucrose replacement. However, these HFSS further reduce the freezing point producing a very soft ice cream at usual conditions of storage and dipping in the home. A balance is involved between sweetness, total solids, and freezing point.

Confectionery

High conversion glucose syrups replase sucrose and imparts products with less hygroscopicity and a better viscosity profile. High maltose syrups controls moisture and texture in soft confections.

Candy

High amylose cornstarch contains as much as 70% amylose compared to 25-28% in ordinary cornstarch. This makes it a particular strong gelling agent in the manufacture of fine jelly gum candies. High amylose cornstarch is used in combination with normal fluidity starches (thin boiling starches). Up to half the starch is commonly replaced by high amylose starch to obtain quick setting candy piece with an attractive texture.

Tapioca speciality dextrins replaces from 20% to 40% of gum Arabic in some hard gum candies.

High-Boiled Sweets

High-boiled sugar confectionery is expected not to be sticky or crystallised when reaching the consumer. The stability with respect to moisture pickup and stickiness depends on its ERH. The ERH of high- boiled sweets is approximately 30%, and since the atmospheric humidity is nearly always above this, there is a tendency to absorb moisture from the atmosphere.
Initially this occurs on the surface, with a thin film of a solution of lower solids forming with a lower viscosity. This in turn leads to crystallization of the sucrose (graining). To produce high-boiled sweets with a satisfactory shelf life, the final product must contain a minimum amount of residual moisture and the correct balance of sugar and glucose. To obtain a product with satisfactory texture and shelf life, a combination of sucrose and glucose in a 60:40 ratio is generally used. Medium conversion glucose syrup (42DE) is commonly used, which contains a wide range of simple to higher sugars. This is more resistant to water absorption from the atmosphere due to a raised ERH value and is less liable to grain, however, there are some downside effects - such as a higher viscosity, which makes the finished product difficult to crunch; the sweetness level is lower. Some of these can be overcome by the use of more specialized syrups such as High Maltose.

The use of invert sugar as a “doctor” in high-boiled sweets has all but been replaced by glucose syrup. Glucose syrup (42 DE) exhibits a higher relative vapour pressure and at the levels required to prevent sugar crystallization, the invert sugar will cause serious stickiness due to hygroscopicity.

Marshmallows

As marshmallows have a soluble solids content of 78-80%, the prevention of crystallization depends on the choice of an effective “doctor” carbohydrate. The hygroscopic nature of these products is again influenced by the ERH and marshmallows have an ERH range of 65-75%.

When considering an appropriate “doctor” for marshmallow, we find the use of invert sugar, 42DE glucose syrup and 63 DE glucose syrup. When comparing the relative vapour pressure, we find that where invert sugar is used, the relative vapour pressure (73.3%) is lower than when glucose syrups are used and therefore will pickup moisture from the atmosphere. This is important to remember if selling product in high humidity markets.

The use of 42 DE glucose will give lower moisture pickup, but may not deliver the desired sweetness or texture levels. It may be more desirable to use 63 DE glucose. This will retain more moisture and facilitate faster whipping, (due to a lower viscosity) and deliver a higher sweetness level.

Marmalade and jam

For proper texture, jellied fruit products require the correct combination of fruit, pectin, acid, and sugar.
Sugar serves as a preserving agent, contributes flavor, and aids in gelling. Cane and beet sugar are the usual sources of sugar for jelly or jam. Starch syrup may be used to replace part of the sugar in recipes, but too much will mask the fruit flavor and alter the gel structure. Too little sugar prevents gelling and may allow yeasts and molds to grow.
Medium high glucose syrup - 63 DE - replaces sugar in marmalade and jam. To provide good shelf life a high sugar concentration is required and for the purpose a 63 DE syrup is preferred to the traditional 42 De syrup. High conversion syrups and HFS adds more sweetness and increase osmotic pressure (better shelf life).

Canning

Maltodextrins and low conversions syrups add body to canned sauces. High conversion syrups add body and sweetness to canned fruit. HFS add seetness.

Foundries.

Starch is used as a core binder in castings (cast molds).

Animal feed

Starch is used as a binder and nutrient in animal feed pellets.
wet as is like roughage or dried. The dried pulp finds some use as a moisture absorber in soft foods for fur animals and fish.
Wheat gluten is used as a meat extender or replacer in pet food
Potato protein is a valuable protein for fur animals and small pigs.

Concrete

Starch finds use as a retarder in concrete. Starch products are used for reducing set-time in cement.

Oil drilling

Pregelatinized starch is used to increase viscosity of drilling mud and to reduce fluid loss by sealing the walls of boreholes . Cross-linking imparts higher temperature stability. Starch ethers impart tolerance to polyvalent cations and sea water. Starch are usedand for increasing the viscosity of transport and
cooling water.

Gypsum & Mineral Fiber

Starch is used as a binder in gypsum plaster, gypsum and mineral fibre board

Nappy / Diaper

Starch is used as an adhesive.

Diapers with superabsorbent gelling materials in their core has been developed with gelling materials capable of sequestering 80 times their weight of moisture. Starch based products may substitute high-molecular-weight, cross-linked sodium polyacrylate polymers as the absorbent.

Water

Starch products are used as flocculants in many industrial water treatment plants for flocculation purposes.

Coal

Briquettes made of coal dust and fines are bound with starch as a binder

Detergent

Starch finds use as a redeposition inhibitor of dirt once it has been released from the fabric.

Pharmacy

Starch acts as a binder in pharmaceutical tablets and as a disintegrating agent as well.

Special starch is used as dusting powder and surgical glove powder.

Agriculture

Copolymerizing starch with acrylonitril and alkaline hydrolysis gives a super absorbing polymer, "Super-Slurper" used for coating of seeds to improve presence of water for faster germination and to improve water capacity of soil for potted plants.

Stain remover

To remove a stain with an absorbent powder, sprinkle a layer of starch powder over the stain. Spread the starch round, and as soon as it becomes gummy lift, shake or brush it off. Repeat this until nothing further is being absorbed. If a mark still remains after this, mix the powder to a paste, using water for non-greasy stains and a grease solvent (see "for greasy marks"). Leave standing till dry, then brush off.

Dusting powders

Dusting powder consists of finely powdered substances free of grittiness. They are used on normal intact skin prophylactically to reduce friction (talc) or moisture (starch). By cross-linking starch can be stand sterilising in autoclave and be used as surgical dusting powder.

Paper

Thin-boiling starches is used as sizing on most paper. Cationic starches are used as wet-end additives improving filler retension and reducing effluent load. Starch is used for for coating.

Corrugated board

Native starch in mixture with pregelatinized starch is applied on top of the corrugated flute before lining. The native starch acts as an instant glue with good tack when heat is applied.

Card board may be produced by gluing liners together with a starch based glue.

Textile

Starch is used for sizing yarn to improve abrasion resistance in fast looms. Starch is is used for finishing fabrics to add feel, stiffness or to provide a good printing surface. Thin-boiling starches are preferred.

Plastics & Packaging

In plastics starches improve the biodegradability of plastic and finished products.

Foamed Starch

Starch can be environmentally friendly blown into a foamed material using water steam. Foamed starch is antistatic, insulating and shock absorbing, therefore a good replacement for polystyrene foam. It can be used as packaging material or can be pressed into starch-based sheet for thin-walled products, such as trays, disposable dishes, cups etc or used as loose-fill for packaging. It offers numerous disposal alternatives and can be a good substitute of CFCs-blown PS.

adapted from International Starch Institute

Starch ... a renewable raw material

Starch is abundant. All major agricultural crops contain starch. Colder climates favour potato growing, the tropics cassava, while grain varieties are grown all over the world. With sun and water as the main limitations, fifteen tons of starch dry mater can be achieved per hectare.

Modern techniques enable starch to be extracted from agricultural crops with high yield and extreme purity, making starch the most versatile raw material used within the food and chemical industries. The starch granule is a compact package of pure glucose polymer.

The purity and efficient moisture absorbing properties of starch have made it indispensable in the production of medicinal tablets and as a moisture regulator.

Polymer releases from the granule during cooking. At 60 ^oC, the polymer begins to hydrate, adding its viscosity and gelling power to the water. This is the way puddings are made in the home - just by using native starch. The food industry also employs native starch as a binder and thickening agent in snacks, meat products, sausages, etc.

Although native starch does have its industrial uses, most often industry requires the functionality of modified starch. The modification is achieved in one of two ways - either by the starch producer, who modifies the starch without disrupting the granules, or by the end-user who cooks and modifies the starch in a single step operation. The first method results in a granular product good for storage and the other in a ready-to-use paste. The two methods do not always act as a substitute for the other.

The single largest consumer of modified starch is the paper industry.

Starches are used as wet-end additives, as size press starches, as binders in coatings and as adhesives. Cationic starches provide retention at the wet-end and reduce the amount of pollutants released. Oxidised starch is a good film-forming product - a favoured material for coating and surface sizing. Thin boiling starches produced by acid or enzyme treatment are used as well.

Special starch produced by esterification or combined treatments are used in coatings, glues, the production of cardboard, etc.

The Stein Hall process of manufacturing corrugated cardboard employs both cooked and uncooked starch. Cooked starch adds viscosity while uncooked starch swells up as the cardboard liner passes the heating rolls, giving instant bond. Pre-swollen starch is used alone in no-carrier adhesives.

The process of drilling for oil uses starch in the suspension of excavated mud. During this process, starch is either employed alone or in combination with other stabilisers, e.g. xanthan gum. Within the textile industry, thin boiling starch has made a comeback in the competition with petrochemicals.

The addition of chemical groups to the starch chain improves the clarity and stability of the gel during cooking, mixing and freezing. These chemicals include propylene oxide, acetic acid, and metaphosphates. They form tailor-made hydrocolloids, which go into desserts, ice cream, puddings, wine gums, etc.

Starch is the cheap and reliable source of energy for the biochemical manufacturing of alcohol, enzymes and fine chemicals. When broken down by enzymes or acids it becomes the basic ingredient for producing glucose, fructose and sorbitol.

adapted from International Starch Institute

Sweetners

Carbohydrates are an important dietary nutrienet which is mostly used to supply energy to the body, as well as, a carbon source for synthesis of other needed chemicals.

In addition mono- and disaccharides are craved because of their sweetness. All carbohydrate sweeteners (sugar, evaporated cane juice, turbinado sugar, honey, high fructose corn syrup, maple syrup, juice concentrates) contain primarily sugars and do not provide significant amounts of vitamins and minerals. We value sugar and other natural sweeteners because they enhance taste and enjoyment of a wide variety of nutritious foods.

USDA estimates that for 1997 about 67 pounds of sugar (cane and beet); 86 pounds of corn sweeteners; and 1 pound of other sweeteners (honey, maple syrup) per capita were delivered into the food supply. That adds up to a total carbohydrate sweetener availability of about 154 pounds per capita.

Saccharides have varying degrees of sweetness on a relative scale as illustrated in the table on the left. Fructose is the sweetest, while lactose is only slightly sweet by comparison.

Originally the needs of diabetics and more recently the soft drink industry has provided the stimulus in the search of other sweetners.

Discovery of Non-Carbohydrate Sweetners:

Saccharin was discovered in 1879 by Constantine Fahlberg, while working in the laboratory of Ira Remsen, quite by accident as were most other sweetners. While working in the lab, he spilled a chemical on his hand. Later while eating dinner, Fahlberg noticed a more sweetness in the bread he was eating. He traced the sweetness back to the chemical, later named saccharin, by tasting various residues on his hands and clothes (unsanitary conditions) and finally chemicals in the lab (not a safe lab practice).

By 1907, saccharin was used as a replacement for sugar in foods for diabetics. Since it is not metabolized in the body for energy, saccharin is classified as a noncaloric sweetner. By the 1960s it was used on a massive scale in the "diet" soft drink industry.

Aspartame: In 1965, Jim Schlatter, a chemist at G.D. Searle was working on a on a project to discover new treatments for gastric
ulcers. One of the steps in the research process was to make a dipeptide intermediate, aspartyl-phenylalanine methyl ester. He accidently and unknownly spilled some on his hand. Later he licked his finger as he reached for a piece of paper (unsanitary lab technique), and noticed the sweet taste. He and a friend decided to test some in coffee and confirmed the identify of the chemical with the sweet taste. The result was the sweetner, aspartame.

Cyclamate: Michael Sveda, while a graduate student at the University of Illinois, discovered cyclamate by smoking a cigarette. While working on the synthesis of anti-pyretic (anti-fever) drugs in the laboratory in 1937, he put his cigarette down on the lab bench. When he put it back in his mouth, he discovered the sweet taste of cyclamate (unsanitary lab technique).

Acesulfame was discovered by another chemist, Karl Clauss, in 1967. He noticed a sweet taste when he licked his finger to pick up a piece of paper (unsanitary lab technique).

Sucralose may have the strangest "accidental discovery" story. Tate & Lyle, a British sugar company, was looking for ways to use sucrose as a chemical intermediate. Halogenated sugars were being synthesized and tested. A foreign graduate student, Shashikant Phadnis, misunderstood a request for "testing" of a chlorinated sugar as a request for "tasting," leading to the discovery that many chlorinated sugars are sweet with potencies some hundreds or thousands of times as great as sucrose. Substituting three chlorine ions for hydroxyl groups on an ordinary sucrose molecule makes Sucralose.

adapted from www.elmhurst.edu

Starch - Iodine

Starch:

Plants store glucose as the polysaccharide starch. The cereal grains (wheat, rice, corn, oats, barley) as well as tubers such as potatoes are rich in starch.

Starch can be separated into two fractions--amylose and amylopectin. Natural starches are mixtures of amylose (10-20%) and amylopectin (80-90%).

Amylose forms a colloidal dispersion in hot water whereas amylopectin is completely insoluble. The structure of amylose consists of long polymer chains of glucose units connected by an alpha acetal linkage.
Starch - Amylose - shows a very small portion of an amylose chain. All of the monomer units are alpha -D-glucose, and all the alpha acetal links connect C # 1 of one glucose to C # 4 of the next glucose.

Starch Coil or Spiral Structure:

As a result of the bond angles in the alpha acetal linkage, amylose actually forms a spiral much like a coiled spring. See the graphic on the left which show four views in turning from a the side to an end view.

Chemical Test for Starch or Iodine:

Amylose in starch is responsible for the formation of a deep blue
color in the presence of iodine. The iodine molecule slips inside of the amylose coil.

Iodine - KI Reagent: Iodine is not very soluble in water, therefore the iodine reagent is made by dissolving iodine in water in the presence of potassium iodide. This makes a linear triiodide ion complex with is soluble. The triiodide ion ion slips into the coil of the starch causing an intense blue-black color.

Starch Test: Add Iodine-KI reagent to a solution or directly on a potato or other materials such as bread, crackers, or flour. A blue-black color results if starch is present. If starch amylose is not present, then the color will stay orange or yellow. Starch amylopectin does not give the color, nor does cellulose, nor do disaccharides such as sucrose in sugar.

Iodine Test: When following the changes in some inorganic oxidation reduction reactions, iodine may be used as an indicator to follow the changes of iodide ion and iodine element. Soluble starch solution is added. Only iodine element in the presence of iodide ion will give the characteristic blue black color. Neither iodine element alone nor iodide ions alone will give the color result.

adapted from www.elmhurst.edu

Starch Sweetener Syrups

Chemistry.

Glucose is formed in plants from carbon dioxide absorbed from the air using sun light as energy source. Part of the glucose is polymerised into long chains of glucose and stored as starch in granules as a reserve. In spring starch is broken down again to support new growth.

This break down of starch can be imitated in a our factories by applying acid or enzymes to cooked starch. The way we do it cause the starch to hydrolyse into a variety of mixtures of glucose and intermediates and the way we characterise these various mixtures is by its DE number. DE means Dextrose Equivalent. The analytical procedure measures reducing end groups and attach a DE of 100 to pure glucose (glucose = dextrose) and a DE of 0 to pure starch.

Only glucose solution of high DE can crystallise easily and yield a product in powder or granular form. A most popular crystallised product is dextrose monohydrate with applications in medicine and used in chewing tablets by people doing sport. Dextrose monohydrate is pure glucose. A less purified product known as Total Sugar is produced by instant crystallising a 97 DE syrup leaving no hydrol (mother liquor) to dispose off.

Standard Acid converted 42 DE Syrup.

Lowering the DE, the syrup loose gradually its tendency to crystallise and below approximately 45 DE the syrup can be evaporated into a stable, non-crystallising and auto sterile liquid. These qualities are one of the reasons behind the success and wide spread use of the standard 42 DE syrup. Starch is hydrolysed by acid or enzymes to 40 - 42 DE and evaporated to a viscous liquid with a dry matter of 80% - 84%.

This standard product has a bland sweet taste, stores and ship well in drums or tank lorries. It find applications in canned fruit preserves, ice cream, bakery products, jam, soft drinks, candy and all kinds of confectionery. Large quantities are also used as a booster in the fermentation of alcohol The relative sweetness of 42 DE to sucrose is 40 - 45%.

High quality starch is supplied either as a slurry from a starch factory or a slurry of approximately 21 oBe is prepared from ordinary native dried starch. Acid - preferably hydrochloric acid, HCl is added to the slurry in order to acidify before cooking. The acidified slurry is heated to the desired temperature by injecting steam of 9 bar.

The liquefaction temperature is kept for a few minutes. The degree of liquefaction (hydrolysis) is controlled by the temperature in the holding zone. The acid is neutralised and the hydrolysate enters a cyclone - via a back pressure valve - where the hydrolysate is flashed down to atmospherical pressure. The crude hydrolysate is refined by means of activated carbon in order to remove discoloration from the interaction of protein and other starch constituents during hydrolysation.

Filter aid is added as body feed and the filtered off on a filter press. The purified hydrolysate passes a check filter and the water clear hydrolysate is evaporated until the dry substance reaches 80 - 84 %. From the evaporator the final product can be drummed off. Dependent on raw material and end product requirements various filtration steps and deionization etc. may be added to the process

Enzymes as catalysts.

The acid catalyst allows the manufacture of intermediate conversion products ranging from 35 - 55 DE. Intermediate and higher conversion products for special purposes can also be made by substituting acid with enzymes - typically in a two step process. For the first step, the liquefaction, termostable a-amylase or acid is used. After cooling and pH adjustment a saccharification enzyme like amyloglucosidase is applied.

Except for a different holding time the processes are in principles identical regardless of catalyst. However, enzymes and acid breaks down starch differently resulting in different sugar composition for identical DE, but it is possible to work around that problem and even produce the classic 42 DE syrup by an all-enzyme process only. With enzymes it is possible to produce syrups with DE from 28 and up to 98. Glucose syrups may be grouped according to the degree of conversion:

Conversion Groups

Conversion	DE
Low	20-38
Intermediate	38-58
High	58-73
Very high	73

Glucose Composition

DE	28	38	42	63	98
Catalyst	A/E	A	A	A/E	E
Glucose	5	12	18	37	96
Maltose	8	10	13	34	2
Maltotriose	16	10	12	16	1
Higher sugars	71	68	57	13	1

A=Acid E=Enzyme A/E=Acid liquefaction plus enzyme saccharification

High DE syrups are intermediates for fructose syrup, sorbitol, and many fermentation products and find uses in beverages, foods etc. Glucose syrup and maltose syrup are referred to as wort syrups in breweries, where they substitute malt improving capacity, adjusting protein, taste, mouthfeel etc.

Sugar confections will either pickup or lose moisture to the atmosphere, depending on the external conditions to which they are subjected. Therefore the water activity of the sweetener is an important property. This value is known as the equilibrium relative humidity (ERH).

Water Activity of Sweeteners

Syrup	Conversion	Solids	Water Acitity
42 DE	A	75	0.81
		80	0.77
		85	0.70
60 DE	A/E	75	0.78
		80	0.71
		85	0.64
94 DE	E	74	0.72
High Fructose	E	70	0.76
Liquid Sucrose		67	0.85

HFSS.

High Fructose Starch-based Syrups are produced from refined very high DE glucose syrups. An enzymatic process using isomerase fixated on a resin facilitates the conversion of glucose to fructose. By using more resin columns in parallel the enzyme activity is completely exhausted before a refill.

The isomerase catalyses the formation of 42% fructose in equilibrium with glucose. This syrup may be refined and evaporated as such and it is an excellent all-purpose sweetener.

In order to obtain a more perfect match with sucrose based liquid sugar (cane and beet sugar) the fructose content has to be increased to 55% by enrichment. A stream of HFSS-42 is fractionated. Previous attempts to do this by crystallisation have never gained industrial acceptance. The fractionation is done more elegantly by chromatography. By auto-matically switching the injection point an endless ring column is simulated and the HFSS-42 is fractionated in fructose and glucose. Water or condensate is used to eluate the column. The fructose fraction is backmixed with the HFSS-42 to make up an HFFS-55. In this way a perfect match with traditional sucrose based liquid sugar is obtained. The HFSS-55 finds widespread use as sweetener in soft drinks.

The fructose fraction from the chromatographic column can of course be refined and evaporated to a syrup separately as HFSS-90 finding applications in low calorie foods.

Demineralisation throughout the HFSS-process and precautions against de-cross-linking by oxygen extends the lifetime of the resins. An HFSS-section should preferably run continuously non-stop.

Starch & Sweetener Process Flow Chart in Principle

Corn ↓	Cassava Potato ↓	Native Starch ↓
Cleaning
Steeping	Washing
Milling	Rasping
Separation	Extraction
Concentration
Refining		Slurry preparation
Purified starch milk
		Prepara tion	Liquefaction
			Saccharification
			Refining
			Ion exchange
		Reaction	Hydrolysate
				Evaporation
				Crystal lisation	Hydro genation	Isomerisation
				Separa tion		Refining
		Finishing				Ion exchange
						Evapora tion
						Enrich ment
					Ion exchange
Drying					Evaporation
Granular Starch Products			Hydrolysed Starch products
Native Corn Starch	Native Tuber Starch	Modified Starch	Malto dextrin	Dextrose Mono hydrate	Sorbitol	HFSS 55	HFSS 42	High DE Glucose syrup	Glucose syrup

adapted from international starch institute

Di-, Poly-Carbohydrates

General names for carbohydrates include sugars, starches, saccharides, and polysaccharides. The term saccharide is derived from the Latin word " sacchararum" from the sweet taste of sugars.

Monosaccharides contain one sugar unit such as glucose, galactose, fructose, etc.

Disaccharides contain two sugar units. In almost all cases one of the sugars is glucose, with the other sugar being galactose, fructose, or another glucose. Common disaccharides are maltose, lactose, and sucrose.

Polysaccharides contain many sugar units in long polymer chains of many repeating units. The most common sugar unit is glucose. Common poly saccharides are starch, glycogen, and cellulose.

Common Carbohydrates
Name	Derivation of name and Source
Monosaccharides
Glucose	From Greek word for sweet wine; grape sugar, blood sugar, dextrose.
Galactose	Greek word for milk--"galact", found as a component of lactose in milk.
Fructose	Latin word for fruit--"fructus", also known as levulose, found in fruits and honey; sweetest sugar.
Ribose	Ribose and Deoxyribose are found in the backbone structure of RNA and DNA, respectively.
Disaccharides - contain two monosaccharides
Sucrose	French word for sugar--"sucre", a disaccharide containing glucose and fructose; table sugar, cane sugar, beet sugar.
Lactose	Latin word for milk--"lact"; a disaccharide found in milk containing glucose and galactose.
Maltose	French word for "malt"; a disaccharide containing two units of glucose; found in germinating grains, used to make beer.

Common Polysaccharides
Name	Source
Starch	Plants store glucose as the polysaccharide starch. The cereal grains (wheat, rice, corn, oats, barley) as well as tubers such as potatoes are rich in starch.
Cellulose	The major component in the rigid cell walls in plants is cellulose and is a linear polysaccharide polymer with many glucose monosaccharide units.
Glycogen	This is the storage form of glucose in animals and humans which is analogous to the starch in plants. Glycogen is synthesized and stored mainly in the liver and the muscles.

adapted from www.elmhurst.edu

Carbohydrates

General names for carbohydrates include sugars, starches, saccharides, and polysaccharides. The term saccharide is derived from the Latin word " sacchararum" from the sweet taste of sugars.

The name "carbohydrate" means a "hydrate of carbon." The name derives from the general formula of carbohydrate is C_x(H₂O)_y - x and y may or may not be equal and range in value from 3 to 12 or more. For example glucose is: C₆(H₂O)₆ or is more commonly written, C₆H₁₂O₆.

The chemistry of carbohydrates most closely resembles that of alcohol, aldehyde, and ketone functional groups. As a result, the modern definition of a CARBOHYDRATE is that the compounds are polyhydroxy aldehydes or ketones. The chemistry of carbohydrates is complicated by the fact that there is a functional group (alcohol) on almost every carbon. In addition, the carbohydrate may exist in either a straight chain or a ring structure. Ring structures incorporate two additional functional groups: the hemiacetal and acetal.

A major part of the carbon cycle occurs as carbon dioxide is converted to carbohydrates through photosynthesis. Carbohydrates are utilized by animals and humans in metabolism to produce energy and other compounds.

Carbohydrate Functions:

Carbohydrates are initially synthesized in plants from a complex series of reactions involving photosynthesis.

-Store energy in the form of starch (photosynthesis in plants) or glycogen (in animals and humans).

-Provide energy through metabolism pathways and cycles.

-Supply carbon for synthesis of other compounds.

-Form structural components in cells and tissues.

Photosynthesis is a complex series of reactions carried out by algae, phytoplankton, and the leaves in plants, which utilize the energy from the sun. The simplified version of this chemical reaction is to utilize carbon dioxide molecules from the air and water molecules and the energy from the sun to produce a simple sugar such as glucose and oxygen molecules as a by product. The simple sugars are then converted into other molecules such as starch, fats, proteins, enzymes, and DNA/RNA i.e. all of the other molecules in living plants. All of the "matter/stuff" of a plant ultimately is produced as a result of this photosynthesis reaction.

Metabolism:

Metabolism occurs in animals and humans after the ingestion of organic plant or animal foods. In the cells a series of complex reactions occurs with oxygen to convert for example glucose sugar into the products of carbon dioxide and water and ENERGY. This reaction is also carried out by bacteria in the decomposition/decay of waste materials on land and in the water.

Combustion occurs when any organic material is reacted (burned) in the presence of oxygen to give off the products of carbon dioxide and water and ENERGY. The organic material can be any fossil fuel such as natural gas (methane), oil, or coal. Other organic materials that combust are wood, paper, plastics, and cloth.

The whole purpose of both processes is to convert chemical energy into other forms of energy such as heat.

Fossil Fuels

Hydrocarbons in Fossil Fuels Name Molecular Formula Boiling Point (oC) State at 25oC methane CH4 -164 gas Natural Gas is composed mainly of methane, but also may contain small quantities of ethane, propane, and butane. After refining, it is almost pure methane as it is moved by pipeline to commercial users and homes. In most areas of the country, natural gas is the fuel of choice for combustion and conversion into energy for residential use. It is burned in the furnace, hot water tank, clothes dryer, and stove. ethane C2H6 -89 propane C3H8 -42 Propane in small tanks is the gas used for mobile applications such as campers and Bar-B-Q. LPG or Liquefied Petroleum Gas, contains propane and butane and finds uses in larger tanks in rural areas for residential use. butane C4H10 -0.5 Butane is the fuel in cigarette lighters. A flint or piezo electric spark ignites the butane gas vapor. pentane C5H12 36 liquid hexane C6H14 69 heptane C7H16 98 Naphthas are a general name given to the the C5 - C7 hydrocarbons. These may be found in a variety of solvents for paint, paint thinners, and Bar-B-Q lighter fluids. These are easily vaporized and highly combustible. octane C8H18 125 nonane C9H20 151 decane C10H22 174 Gasoline is a mixture of many straight chain, branched, and aromatic hydrocarbon molecules in the range of C7 through C11 or 12. undecane C11H24 196 dodecane C12H26 216 Kerosene, jet fuel, and diesel fuel contain hydrocarbons in the range of C12 to C20. Fuel Oil has a range of hydrocarbons of C20 to C40. eicosane C20H42 343 solid triacontane C30H62 450 solid Tar and asphalt bitumen, which are solids, contain hydrocarbons in the range of C40 to C70.

adapted from www.elmhurst.edu