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From Cereal Corn to Alcohol

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The Whisky Store


   

From Cereal Corn to Alcohol

maltose_6.jpg (6404 Byte)

Maltose Molecule
(pictures with friendly permission of Dr. Bernd Meynhardt/Universitaet Kiel)

Whisky by definition is a beverage distilled from grain. How do you produce alcohol from grains? By fermentation, of course. But you have to carry out a long series of chemical and biological reactions until you get alcohol.

[Karl Note:  One definition of fermentation:  A natural phenomenon, it is the transformation of sugars and grape juice into wine in the presence of yeasts. These yeasts convert the sugar into alcohol and carbonic gas.]

Sugar

Grains consist primarily of starch. Other constituents include proteins, fats and trace elements. Starch is the basic material required for alcohol production. For a simpler explanation of the chemical context, I would like to begin not with starch, but with sugar. Sugars and starch both belong to the carbohydrate group. If you understand the basic characteristics of sugar, then you can easily appreciate the properties of starch. 

Historically, our northern ancestors knew only of bee honey and fruits as a sugar supply. That changed with the development of contact to other parts of the world, when cane sugar from southern latitudes arrived. Only recently was sugar beet discovered as a sugar source. In the middle of the 19th century sugar plants were developed for northern latitudes. Today we produce sugar from sugar beet and starch sugar plants and additionally import substantial quantities of cane sugar into the European community (supplier e.g.: South Africa, Mauritius).

Everyone knows of some sugar forms from food advertisements. In addition to the sugars noted in the following chart, there are many other sugars, whose chemical structures are similar.

Description Chemical Description Formula
Cane Sugar Saccharose C12H22O11
(= 2*C6H12O6- H2O)
Dextrose (Grapes) Glucose C6H12O6
Fruit Sugar Fructose C6H12O6
Milk Sugar Lactose C12H22O11
Barley Sugar Maltose C12H22O11

Common to all these sugars is the basic chemical formula (C6H12O6). Thus a simple sugar molecule consists thus of six carbon, 12 hydrogen, and six oxygen atoms.

The following structure shows a stretched d-glucose-molecule.

glucose.gif (2622 Byte)

D-Glucose-Molecule

The important sugars Glucose and Fructose each have six carbon atoms (C6H12O6). Note that there are sugars with five or seven carbon atoms (example: Ribose) where a H-C-OH group is missing or is additionally inserted into the chain.

A fruit sugar (Fructose) has a slightly different structure in the chain. The second H-C-OH group has been replaced by a Carbonyl group (C=O); but the aldehyde function at the end of the chain is missing.

fructose.gif (2623 Byte)

D-Fructose-Molecule

What makes a sugar sweet? Sweetness is due to the OH groups, which react with the receptors on our tongue. But the quantity of the OH groups is not decisive; rather it is the relative positions of these OH groups in three-dimensional space. Only certain orientations can fit onto the sweet receptors on the tongue. There are non-sugar substances whose OH groups are arranged similarly in three-dimensional space (artificial sweeteners, Glycol...), and therefore also taste sweet.

2k - Glucose RingThe C1 and C5 atoms of the sugar molecule may be connected by the doubly bound oxygen atom of the upper aldehyde group to form a ring of five carbon and one oxygen atom. No atoms are lost during this addition and all atoms are built into the newly formed ring. The sixth carbon atom points laterally away from the ring. The ring is structured in space in the form of an easy chair. This ring structure is energetically more favorable than the straight chain. Statistically, a mixture of 99% rings and 1% chains are found in glucose solutions.

The important sugars for alcohol production (maltose, glucose) typically form these rings. However cane sugar consists not only of rings of six (carbon atoms) but also of rings of 5.

a_ring.gif (2443 Byte)

- Glucose

Alternately, the OH group at the first c-atom (formerly group of aldehydes in the chain) can be exchanged with the H-atom at the same C-atom. This results in another spatial configuration, called a beta arrangement.

b_ring.gif (2449 Byte)

- Glucose

 

Starch

Starch is constructed from Glucose by connecting several of these rings to form long chains, by the splitting off of water molecules. The water is eliminated between C1 and C4 atoms.

kette.gif (2814 Byte)

Linkage of two - Glucose molecules to the Maltose

This compound is the barley sugar. You may write this compound in the following way:

kette1.gif (1550 Byte)

Barley Sugar (Maltose)

Chemically you write for this connection also:

glc14.gif (1860 Byte)

This describes an alpha Glucose ring (Glc) connected by its first C-atom to a second ring via its fourth atom. Starch consists of repeated linkages of such sugars according to the generalized formula:

3k - 1->4 n Alpha Glucose

The formula above describes chemically pure starch, which is given the name Amylose. Pure Amylose is spatially bent. Natural starch is not structured quite so regularly. In addition to chains, branched forms appear.

If you chain beta glucose molecules by the same method you get cellulose, as found in the wood of whisky casks. Cellulose molecules are long chains which can connect themselves to each other and bind via hydrogen bonds. Therefore cellulose is fibrous and more stable than starch flour.

The enzyme Amylase, found in barley, can split grain starch at the O bonds. By contrast, it cannot detect the beta-forms of the sugar and thus does not react with cellulose. Goats are able to split cellulose by micro organisms in their intestine into sugars.

The enzyme attacks the chains, dividing them into two sugars (Dimere, Maltose) from the ends of the strand. If the entire chain is split, only two and three-chain constituents (Trimeres) remain. The Trimeres are not cut further by the enzyme.

SPECIAL FEATURE: The enzyme Amylase is exclusively present in the barley malt. It can divide into sugars not only the starch in barley but also starch derived from other grains. For this reason mashes for Bourbon and grain whisky usually contains 10% of barley malt with its enzyme.
Large grain distilleries, starch sugar factories and also the American whiskey distilleries make use of a special feature of starch. Starch can also be split at warm temperatures under acid conditions (acid-hydrolysis). The cookers of the Bourbon distilleries provide a sour, or acidic, environment (Sour Mash). The corn is cooked at 105 C under slight pressure for 25 min (1.14 bar = 2 psi pressure). This speeds the splitting of the starch.

Alcoholic Fermentation

The last step of cereal corn to alcohol reaction pathway is alcoholic fermentation.

Alcoholic fermentation is not performed by enzymes, but rather by yeasts. Yeasts are not bacteria but fungi. Yeasts are found in nature everywhere, particularly in the autumn when fruits ripen and their spores spread in large numbers in the air. These carry out a simple chemical reaction in sugar/water solutions according to the following formula:

maltose.gif (3050 Byte)

Wärme = Heat

The yeast fungi splits a Glucose molecule and produces two ethanol molecules (alcohol) and two carbon dioxide molecules per ring and energy in the form of heat. Additionally, fruity flavour materials (esters) develop, which provide a large taste variety to the whisky. The yeast fungi cannot act on pure starch, which remains untouched by the funghi.

In Scotland usually two different dry-yeasts (baker and brewery yeast) are used (see e.g.: Glen Moray or Dallas Dhu). The first yeast provides a fast start to the fermentation. At the same time the wash is acidified. The second yeast operates better in the sour environment and achieves its max. performance later. It ensures that the wash will have a high alcohol content by the end of the fermentation process. In America they especially favour the development of fruity components (esters) by the yeasts. Each Bourbon has therefore its own yeasts. These have been isolated from wild yeasts and patented by the companies. All yeasts are reproduced in their own private facilities (see e.g.: Four Roses and its laboratory) in large quantities. They are added to the wash in liquid form.

The carbon dioxide rises in the fermenting, bubbling solution and escapes to the air. The ethanol produced enriches itself in the solution. The fungus lives from the energy produced by the chemical reaction. This process persists for a long time, either until all the sugar is used up (typical for whisky) or until the alcohol concentration has increased so much that the yeast fungus is killed by its own products (typical for wine).

 

Vinegar - Acetic Acid - Vinegar Bacteria

Each distiller, brewer or winegrower has to confront himself with the existence of vinegar-producing bacteria. Vinegar bacteria are found in free nature in exactly the same environments as the yeast fungi. They nourish themselves on alcohol and produce acetic acid. If a fermentation container (wash back, fermenters) is stricken by vinegar bacteria, then the whole content is lost for the distiller. For this reason the wash backs in Scotland are cleaned with chemical substances and in the USA the fermenters are even sterilized with high temperature. The fundamental chemical reaction, which the vinegar bacteria execute, is as shown below:

3k - Umwandlung von Ethanol in Essigsäure

Transformation of Ethanol into Acetic Acid

Since the reaction needs oxygen, one can usually avoid an infection with vinegar bacteria by strict exclusion of air.

In addition to the vinegar bacteria, we described here, special bacteria exist, which produce initially alcohol and then acetic acid. There are also more highly developed fungi which compete with these vinegar bacteria and can work along the whole chain from the starch to the acetic acid.

Nature still performs miracles. But we can easily enjoy them without solving them.

If you have supplements or notes to this text, please send an eMail  to me.

 

Am Grundwassersee 4 · D-82402 Seeshaupt
Tel. 0 88 01 / 23 17 · Fax 0 88 01 / 26 37 · Faxabruf 0 88 01 / 91 22 32
Copyright © 1999-2002 The Whisky Store
letzte Änderung: 02. April 2002

 


The above process produces a liquid MASH -- of alcohol mixed with


Source

Spirits

    To begin with, a spirit is a beverage of high alcoholic content obtained by the distillation of fermented fruits or grains.  A spirit can be made from items like fermented grapes, potatoes, sugar cane or apples.

    What differentiates spirits from wine is distillation--a process whereby the water content of an alcoholic beverage is reduced by heat to prepare a liquid with a greater proportion of alcohol..  Since alcohol boils at a lower temperature than water, the alcohol vaporized first.  The distiller then captures those vapors and cools them so they condense again into liquid form.

    This is the basic step by which all whiskies, rums, vodkas, gins, tequilas and brandies are made.  It is also the basis for the making of liqueurs (also called cordials), which are highly refined spirits to which natural flavoring and sugar are added.

History

    Distilled spirits have been around for centuries.   The Celts, ancestors of the modern Scotch and Irish, called their distilled drink "visgebaugh" (pronounced wis-ge-baugh) which means "water of life."   The Russians and Poles named their favorite distilled spirit "vodka," after the diminutive, affectionate noun ending for the Slavic word for water ("voda"). Vodka literally means "dear little water."

    Distilled spirits hold a dear place in mankind's heart.   Some distilled spirits, like gin, were originally prepared (at least by the Dutch) for their supposed medicinal values.  And others, like tequila, were originally prepared to be drunk during Aztec religious ceremonies.

    Man has been making distilled spirits since recorded time, but our modern distillation process can be traced to Arabic alchemists of the 10th Century.

The Makin of Distilled Spirits

    As mentioned above, the distillation process involves separating water from alcohol via heat.  When this happens the percentage of alcohol to water in a distilled drink is strengthened.  This increased percentage is called "proof."

    A neutral spirit is an alcoholic spirit purified in the still to a minimum of 95% alcoholic purity.  At that degree of proof - 190 - the spirit is considered to have no important taste, and little body or flavor.  While they can be distilled from any material, almost always they are distilled from grain.   Neutral spirits are the base of other distilled drinks as the following chart shows:

Process:                                                                                                             Spirit:

Blended                                                                                                             Blended Whiskey

Original distillation or redistillation over juniper berries and other aromatics          Dry Gin

Filtered through charcoal                                                                                    Vodka

Base Spirit plus added Flavorings                                                                       Liqueurs

    Two type of stills are used in the distilling process: the pot still and the continuous or column still.  The pot still is the older of the two.  It is a simple device much like a huge kettle whose top tapers off into a spiraling pipe.  The continuous or column still resembles a tall cylinder about two or three stories high.  With the still pot, the liquid is heated in the kettle and the vapors rise through the cooling spiral where they condense and run off.  With the continuous still, the preheated liquid is pumped to the top of the still and flows down through baffle plates.  At the same time as the liquid is coming down, steam enters from the bottom of the still and rises through the baffle plates.  This steam distills and redistills the liquid as it rises and passes through the top of the still where it cools and condenses.

 


Alcoholic Beverages as Foods

Stephen Jon Gislason MD

Source

Alcoholic Beverages (ABs) are all are yeast fermentation products of staple foods, mostly grains and fruits. ABs are grape-yeast, grain-yeast, potato-yeast brews. The basic process of manufacturing an AB is mashing carbohydrate-rich fruit, grain, and vegetable material and then fermenting the mash in a container for a regulated time. The problem of ABs extends beyond ethanol itself.   (Click here for more on ethanol)

In the analysis of the adverse effects of alcoholic beverages, we have been too quick to blame ethanol for all the problems and have ignored other toxic and allergenic ingredients in the beverages. The fermented mash tends to be toxic with a complex chemistry. Ethanol is the dominant chemical/drug and usually considered the addictive "drug" in ABs.

Good AB makers know how to reduce the toxicity of their products so that people are less likely to get immediately and unmistakably ill after drinking the brew. They start with sterile containers; use cultivated yeasts; control the length of fermentation carefully; clarify and filter their products and let aging mellow the chemical mix.   Amateur wine and beer makers sometimes make themselves and their friends conspicuously ill because they lack the professional's finesse for reducing the toxicity of the fermentation products..

The sediments of wine, beer, and any alcoholic base for distillation contain the yeast corpses and substrate residues. Sediments are removed to improve the taste and clarity of the AB and to reduce its toxicity. Wine clarification removes the rest of the particulate matter before consumption. Red wines are made from the whole grape mash and tend to be more chemically complex than good white wines. The best white wines are supposed to be made from the juice of gently squeezed grapes and should be free of chemicals and contaminants associated with grape skins.

Distillation

Distillation of raw alcoholic brews concentrates the alcohol and leaves behind many chemicals that are not volatile at distillation temperatures. Whiskeys, therefore, are concentrates of ethanol and other volatile aromatic chemicals, which are chemical stressors. The chemical stressor value of whiskeys is increased by aging in devices such as charred oak caskets that give Scotch whiskeys their color and flavor. AB manufacturers spend a lot of money advertising their own charming version of the whiskey-aging process. These ads are supposed to appeal to the sophistication of the whiskey-connoisseur, but, rather, should alarm the reader as to the stressor and toxic properties added to the already harmful brew. Wine connoisseurs use the chemical sensors in their nose to select from among various aromatic chemicals present in the wines. The pretense of wine sampling in restaurants should allow you to screen for corks contaminated by obvious mold growths or wines that have turned to vinegar.

Beer and Ale

Ales and beers are raw filtered products of fermented grain mashes with hops, often chemically treated to manipulate color, foaming characteristics, and stability. These food liquors are somewhat nourishing, but they are also diuretic and may be toxic. Many male beer-drinkers get characteristic belly fat, breasts, and skinny limbs. It is hard to imagine how their deteriorating body shapes and soggy brains could be associated with manliness. Beer vendors tend to spend a lot of money advertising their imaginary link between beer drinking and healthy, athletic, fun-loving adults. There is no credible link between beer drinking and healthy athletes, or beer drinking and happy consumers at any age.

Beer can degrade athletic performance and any other skilled, energetic activity. Beer drinkers who over-indulge may get muscle disease, both in skeletal muscle and heart muscle. Cobalt salts, added to improve foaming, accelerate and intensify the process. Muscle wasting in the alcoholic increases with the amount of AB ingested. Muscle biopsy shows there is reduction of fast twitch Type 2B fibers, known to be susceptible to fatigue and metabolic derangement. The severity of the wasting correlated best with total ethanol consumption during the previous year. Research evidence points to direct toxicity of the AB, rather than vitamin deficiency, hormonal disturbance, peripheral nerve damage, or reduced physical activity. The effect of alcohol on the fast twitch anaerobic fibers of muscle is due to a reduction in the enzyme phosphofructokinase, a key catalyst in the breakdown of glycogen. Ethanol also impairs muscle activity by selective reduction of protein synthesis. Type 2B muscle fibers usually recover after abstention from drink, with significant improvement after three months and full recovery after a year

More realistic scenarios of beer-drinking, and all other AB ingestion would show the consequences of drinking too much, too often: noxious, smoked-filled rooms, demented discussions, arguments, illness, smashed cars, beaten wives, abused children, and wrecked careers. Our attention should focus on AB-caused illness; to the diarrhea, dermatitis, and dementia of the alcoholic pellagran; or to the staggering and absurd mutterings of the brain-damaged alcoholic with Wernicke's psychosis.

Wines

Red wines are rich in chemicals that are potentially troublesome. Non-nutrient amino acids such as tyramine are abundant in red wines and cheddar cheese. This favorite party combination can leave you with headache, confusion, and odd, inappropriate behavior. Tyramine may accumulate in people who have sluggish MAO enzyme activity. Tyramine acts something like a fight-and-flight hormone, increasing heart rate, blood pressure, and respiration, all with a sense of anxiety or panic. Drugs that inhibit MAO are prescribed as antidepressants and increase the toxic effect of ingested tyramine. The drug is prescribed along with a low tyramine diet which admonishes you to avoid red wine, beer, cheese, chocolate, bananas, yeasts, vanilla, and other neuroactive amine-containing foods.

Additives

Chemical additives used to control the fermentation process further complicate AB's. Allergenic sulfites are commonly used as disinfectants and bleaching agents in wine making. Sulfites such as Cambden tablets are used to stop fermentation. Methyl glycol has been deliberately added to some wines to sweeten the taste; Other wines have been recalled because of high pesticide content. Distilling of fermentation brews reduces the chemical load, but volatile products pass through the distiller along with alcohol. Only the water-clear AB's, like vodka, are relatively free of the chemical mix.

Food Allergy

All of the foods which are used to produce AB's by themselves can cause many of the symptoms of AB use. The "allergic" responses to cereal grains, grapes, and yeast all may cause physical illness associated with mental and behavioral aberrations. The adverse effects of alcohol beverages are a complex of problems such as alcohol poisoning, yeast allergy, grain or fruit allergy, nutrient deprivations and metabolic distortions. Sensitivity to the chemicals in AB's varies considerably from individual to individual. Many ABABs are hypersensitive to ABs and modest ingestion triggers powerful brain-confusing effects and flip-flops. Generalized illnesses may follow AB ingestion. These illness patterns are typical of food allergy and demonstrate that alcoholism is an illness that exceeds the drug effects of alcohol alone. AB abuse damages digestive function and makes GIT leaky to large molecules. This increased permeability is likely a major and unrecognized mechanism for the production of AB-related disease.

 


Ethanol & Alcohol Abuse

Source

Ethanol is a 2-carbon alcohol, responsible for the behavior-altering effects of Alcoholic Beverages, and for the devastation of the social and physical well being of alcoholics and their communities. This alcohol is a simple molecule, a carbohydrate, which is "burned" as a fuel supplying energy to cells.

Ethanol in its disguise as a fuel can be considered a non-essential nutrient. But before it is metabolized as a fuel, it is an active brain-drug and an all-purpose cellular toxin. It is important to understand the dual role of ethanol as a nutrient/drug, since it illustrates to us the programming principal that molecules are information carriers first.

As a brain drug, ethanol acts to depress brain function from the top down, very much in the style of an anesthetic. With low blood concentration, the cortical depression of ethanol seems to release behaviors that are otherwise inhibited. At this low level of mind intoxication, ethanol is useful and possibly pleasant. The relaxation of inhibitions releases playful behavior and laughter, promotes chatty talk, and facilitates socialization. If the use of AB's were constrained to occasional, low-dose cortical inhibition, we would likely praise AB's as socially useful drugs.

Even low doses of alcohol interfere with memory  and make it difficult for the hippocampus to process new information. "Somebody who drinks too much, the next day doesn't exactly remember what happened during that time, but yet at the same time has the ability, unfortunately in certain cases, to drive home after drinking a lot." 

With increasing doses, ethanol depresses more and more brain functions, rendering the intoxicant temporarily demented, with inappropriate behavior, incoordination, and poor judgment. The stubborn, irritable drunk often argues unreasonably; belligerent outbursts are characteristic of heavy intoxication. In many alcohol abusers, AB's release violent aggressive behaviors and result in fighting, assaults, and death by accident or murder.

The AB-intoxicated driver accounts for the majority of car accidents and road fatalities. Social attitudes are now changing, as the obvious relationship of AB and highway carnage is finally acknowledged. The belligerence and family violence of the drunk is the next level of criminal behavior which legislators will seek to better control. Women are the most vulnerable people when married to alcoholics and physical abuse of women is often related to male alcoholism. Children are the most vulnerable people when mother and/or father is an alcoholic.

Metabolism of Ethanol

The metabolism and toxicology of ethanol has been extensively studied. AB, like syphilis, are the "Great Imitators," since regular ingestion of AB in excess produces so many disease patterns involving every part of the body. Even moderate alcohol abuse distorts the personality, emotions, and intellect of the "social drinker," producing the commonest patterns of psychopathology which afflict our society. The personality distortion is a direct consequence of brain dysfunction cause by ethanol and other chemical pathogens in AB's.

Ethanol supplies cells with energy and replaces other foods at the level of basic fuel. Ethanol is metabolized to carbon dioxide and water with 2% being lost through the urine and through respiration. The rate of oxidation is about 75 mg per kilogram of body weight per hour. About half of a group of middle class alcoholics obtained 20 to 39 percent of their dietary calories from ABs while about one third of the individuals obtained between 40 and 59 percent. ABs had displaced other carbohydrates as a source of calories. The calories provided by an AB may be calculated by means of the following formula:

0.8 x proof x ounces = kilocalories.

The calorie contribution from the ethanol in wine or beer can be calculated by multiplying the percent alcohol by volume by two, and using this figure as the proof of the beverage. The oxidation of alcohol occurs in the following steps:

1. Ethanol ---> Acetaldehyde

2. Acetaldehyde ---> Acetate

3. Acetate ----> Carbon Dioxide + Water

Ethanol has a variable effect on body weight. It is ketogenic; ketones (like acetaldehyde) may produce a rapid weight loss of several pounds. Acetaldehyde is particularly toxic. The drug, disulfiram (Antabuse) impairs the enzymatic degradation of acetaldehyde. The accumulation of this chemical causes flushing of the face, shortness of breath, headache, fast and often irregular heart action, nausea, vomiting, weakness, fainting or collapse. Recovery follows in hours, after the ethanol and acetaldehyde have been metabolized. A person taking Antabuse is warned that even a small drink will make them ill. The immediate, rather than delayed, symptoms of AB ingestion are supposed to deter drinking.

Ethanol interferes with carbohydrate energy metabolism. Liver and muscle glycogen are depleted.

As cellular toxin, ethanol is catabolic and promotes structural tissue loss. The catabolic effect causes a greater loss of weight than caloric input can replace in the form of fat stores. Typically, fat distribution shifts to the belly and trunk, leaving the extremities skinny and weak. Men often grow female breasts, as estrogen accumulates in their system. Their psyches follow their body degeneration. Macho men turn to mushos and amygdaloids (people who have lost control of their rage response). There are a host of body responses to ethanol ingestion, as it acts in its drug/chemical pathogenic role.


 

 



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