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The Pharmageddon Herbal

Manufacturing the Solvents and Carriers 9.1
Apart from the crude drugs and exudates, the base materials of compounding (see Mod 10), are its solvents and carriers.

The solvents are alcohol (ethanol) and double distilled water. The carriers are solutions, emulsions, mucilage�s, syrups, water and alcohol. An essential part of some carrier substances are the fixed oils and waxes. By far, the most important substance is alcohol, without it, a complete extraction of herb constituents is not possible.

Alcohol 9.2
The alcohol of the British Pharmacopoeia is a 95% mixture of ethanol and water, which is obtained by the distillation of fermented sugars or by synthesis.

It is a clear, colorless, volatile liquid. It has a burning taste, with a characteristic odor and boils around 78�C. It is miscible with water in all proportions, however, when mixing with water, a contraction of volume and a rise in temperature occurs.

The mixture must cool to 20�C before it is adjusted to its final volume. Its SG at 20�/20�C (atmosphere 20�C - liquid 20�C), is 0.8119, for practical purposes we can say 0.800, its molecular formula is C₂H₅OH, sometimes given as C₂H₆O.

Synthetic alcohol can be manufactured by various chemical routes, from different starting substances, e.g.;

The most common starting substance is Ethylene; The alcohol produced by such methods is cheaper, and therefore, attractive. On analysis, its formula is C2H5OH, however, there are quite subtle differences that are unexplainable from a non Vitalist chemical viewpoint.

For want of better terminology, I will call such substances �dead alcohol�. The physiological effects are manifestly different to those of alcohol produced by fermentation methods. From the vitalist point of view, those differences are quite obvious.

What is produced is determined by the strain of the yeast and the material (substrata) upon which the yeast must work. The great perfume houses of the world know this to be a fact; and in spite of their high tech shiny laboratories, it still takes the human nose to detect what the chemist cannot. The perfumers preference, is for a grain based alcohol to produce the ethereal and elusive top notes of fine perfumes.

Whereas, for the Herbologist, a fruit or herb based alcohol is the preferred solvent. Such preferences are not a matter of philosophy or mere quirks of trade, but are the result of many generations of experience, that cannot be reduced to dry and tidy chemical formulae. What science cannot measure, it will turn a blind eye to.

Alcohol is produced within the body by the same, or similar, type of enzymes used by yeast, and the body recognizes the molecules produced by nature. In some countries it is illegal to use industrially produced alcohol for beverages or medicines. For ethical and safety reasons, the only alcohol to be used is that produced by the fermentation method.

�The fungi in common with other living organisms possess tools or reagents far more specific, more delicate and more powerful than those available in the laboratory'.
Lilly and Barnett
Physiology of the fungi 1951.

The tools or reagents referred to are, of course, �Enzymes�. The alchemists of life, which at bio-temperatures perform electron and proton chemistry at dazzling speed., e.g., one molecule of an enzyme called �urease�, can hydrolyze 30,000 molecules of �urea� in one second. Without urease, it would take around 3 million years.

All life functions are enzyme functions. There are many thousands of different enzymes that work upon different sub-strata for different results. We cannot make enzymes, we must borrow them from nature. Many of the enzymes will only work in the presence of co-enzymes, which are other substances, such as vitamins and minerals. Each type of enzyme produces co-enzymes that are required by other tribes.

The study of fungi, is embraced by biology and microbiology, and is called �Mycology� and more specifically, for our purposes, �Industrial Mycology�. The art of fermentation has a recorded history of around 8,000 years, its study as a science, covers around 250 years, and it is still in its infancy.

Yeasts are a single cell fungi. As micro-organisms, they are of great variety and differ in shape and function. They are of great importance in the pharmaceutical production of organic acids, antibiotics, vitamins and other enzyme preparations. The technology is relatively simple, because living organisms do the work, we need only provide materials and the right conditions.

The following figure is taken from �Lowsons Botany 8^th Edition 1939

There are many different types of micro-fungi which are cultivated to perform specific tasks. Our interest is in the production of alcohol for extraction of crude drugs.

We may do that by the use of �Bakers�, �Brewers�, or wine yeasts, which belong to a sub-family called �Saccharomycoideae�, or the �sugar fungi�.

The above mentioned yeasts belong to the tribe S.cerevisiae, and the variety S.ellipsoideus. The resulting alcoholic soup will be distilled to produce the ethanol required for extraction purposes, so we have no interest in bouquet or flavor.

As in all living things, yeast must eat, breathe, excrete and reproduce itself. The success or otherwise, of those functions is determined by its environment. For the purposes of this module, if the word �yeast� is used, it should be taken to mean members of the sugar fungi.

Yeasts utilize their nutrients in solution. The substrata, or food is dissolved by the extra cellular excretion of enzymes. The term �enzyme�, means �in yeast�. The enzymes are proteins and will often need co-enzymes to kick start them.

Some common co-enzymes are; Carbon, Nitrogen, Phosphorus, Potassium, Magnesium, Iron, Zinc, Copper, Manganese, Molybdenum and Calcium. Each of these elements should be freely available from plant substrata, however, if yeast were put to work on white sugar alone, it would also need to be fed vitamins and minerals to substitute for the missing co-enzymes. For example, lack of nitrogen during fermentation will cause the living yeast to break down the dead yeast cells to sequester the needed nitrogen. This process is called dehydrate-amination, which is the primary reason for the production of excess �Fusel Oils�. The term is from the German �evil spirit�, commonly called, �rot gut�. The Fusel oils are a mixture of the amyl alcohols, i.e., amyl, isoamyl, isobutyl, hexyl and propyl; all of which are extremely toxic and responsible for the headaches, nausea and gastric upsets caused by poor quality wines and spirits. So the better the substrata, the better the alcoholic soup. This means less waste and less work at a subsequent stage.

Fermentation may take place either in the presence of the atmosphere with free oxygen (aerobic), or when completely excluded from the atmosphere, which is called �anaerobic fermentation�. However, water and oxygen are essential to life, so that if the fermentation takes place anaerobically, then the oxygen will be taken from the water or breakdown products. It is usual to conduct the fermentation in anaerobic conditions, because of the danger of contamination, from unwanted yeasts, e.g., vinegar from the bacteria �Acetobacter�. The substrata, which is known as the �Must�, is usually sterilized by metabisulphite to kill any unwanted intruders, prior to the fermentation process.

The acidity of a �must� (fermentation liquid), will stimulate or inhibit the fermentation process. Experimental results suggest that sugar fungi give optimum performance in a liquid with a pH of 4 to 4.5. If fruit is the basis of the substrata, then there is usually sufficient organic acid, such as citric, malic or tartaric to acidify the liquid.

It is always prudent to test. If acidification is needed, then the readily available citric acid is most convenient. The purified compound may be used, but it is inferior to lemon juice. A small lemon approximates 3.5 g of citric acid. Under no circumstances should strong acids, such as hydrochloric, nitric or sulphuric, be used.

Enzymes facilitate biological reactions. All chemical reactions involve a release or transfer of energy, which may be detected as temperature fluctuations. If heat is absorbed from the environment in which the reaction is taking place, it is called an �endothermic� process and the temperature will drop. If heat is evolved from a reaction, it is an �exothermic� process and the temperature will rise.

The conversion of sugars to alcohol by enzymes is an exothermic process, and heat is evolved. This must be remembered if using heat for the temperature control of the fermentation liquid. Problems may be circumvented by using a thermostat.

The correct temperature will ensure a brisk and efficient fermentation. The best temperature is around 25�C. Temperatures of 30�C and over will result in the steady demise of a yeast colony. Low temperatures will cause the fermentation to become sluggish. Below 7�C fermentation will cease, which is a major reason for a stuck ferment. If this proves to be the case, then a rise in temperature will start the yeast working again.

The sugar fungi, as the name implies, use sugars for food and excrete ethanol (alcohol). The process is multi-stage and carried out by enzymes; like the production of starch, this is a process which is beyond our knowledge and we utilize the yeast, or the isolated enzymes to perform the molecular engineering involved.

The sugars belong to a class of substances called the carbohydrates, which are sometimes designated CHO. However, not all compounds that fit that description are carbohydrates, for example, Acetic acid C₂(H₂O)₂.

For our purpose, the most important carbohydrates are the sugar and starches. Sugars, which contain six or less carbon atoms in the molecule, are called �Monosaccharides�. Sugars that contain 12 Carbons per molecule are called �Disaccharides�.

The starches which have a large number of carbons per molecule are called �Polysaccharides�. The names of the different sugars always end in �Ose� e.g. Glucose, Fructose, which, because they have 6 carbon atoms per molecule, are known as �Hexose�s�, from the Greek �Hex� meaning six. Sucrose may be considered to be formed by the elimination of water (condensation reaction), from two hexose molecules, so it is a �disaccharide�. Di, is also from the Greek meaning twice.

The starches are formed from many (Poly) hexose units. An approximate molecular formula is (C₆H₁₀O5)₃₃₀, i.e. about 330 hexose units. The starches are found in all green plants, while the sugars are found in abundance throughout the plant kingdom; fruits, roots and leaves may be used in solution by enzymes. Alternatively, a hot water extract of the plant material can be used as the substrata for ethanol production.

Glucose is sometimes called Dextrose, or Grape sugar. It occurs naturally in grapes, honey, most sweet fruits, and may also be found in smaller quantities in many plants.

Glucose is manufactured on an industrial scale by hydrolyzing starch with dilute hydrochloric acid under pressure. The HCI is then neutralized, and the syrupy mixture evaporated under low pressure.

The syrup is sometimes called corn syrup, irrespective of the starch source. The syrup is not pure glucose and it may also contain dextrin and maltose. It is in great demand by the food and beverage industries. Corn syrup is suspect and especially in the USA where the bulk of it is made from GM organisms and that includes the yeast.

It must be mentioned that glucose is reduced with a sodium/mercury Na/Hg amalgam, to produce Sorbitol, which like glycerol, is used as a humectant (moisturizer). Glucose is soluble in water, but sparingly soluble in alcohol.

Glucose and Fructose are �isomers�. Glucose is optically active and rotates polarized light to the right, hence it is sometimes called �Dextrose�. Sucrose is the most common of all sugars, and is to be found throughout the plant kingdom.

The commercial source is from sugar beet, which can give up to 20% by weight of sucrose, or from sugar cane, which yields far higher; it is soluble in water but almost insoluble in alcohol. Its melting point is 180�C, at temperatures above that it starts to decompose. It can be hydrolyzed by boiling in water for around 20 minutes. Sucrose is dextra-rotary, and with boiling water it splits into an equimolar mixture of glucose and fructose, which is called �invert sugar�.

Inversion by the Boiling method

The yeast enzyme �sucrose�, or as it is sometimes called, �invertase�, carries out the process at low temperatures, from 30�C down to 10�C, and depending on the balance between the sugar and invertase, the reaction takes just seconds.

Starch is so common and in such abundance, that we tend to forget how important it is; without it animal life could not exist, so we are dependent on the synthesis of the green plants to produce it. We do not know how plants do that.

The plants use it as a reserve food supply. The bulk of the worlds commercial supplies are obtained from a relatively small number of plants, e.g., wheat, potatoes, maize, barley or rice. There are, of course, many other sources which are utilized. It is obtained by grinding, washing, filtering and drying the base material.

The microscopic examination of starch granules show a variation in shape from plant to plant. A typical green plant contains around 7% by weight, whereas, roots or tubers can contain upwards of 90%. Starch is a polysaccharide, it has large numbers of hexose units linked together, which must be broken down to obtain the sugars. The hydrolysis occurs in stages, and is not complete because the glucose syrup also contains dextrin and maltose, the probable pathway is as follows.

Starch - Dextrin - Maltose - Glucose.

This, of course, is the basis of the malting process of grains; for the brewing of beer; essentially the grains are sprouted, in this way enzyme activity is promoted to carry out the hydrolysis. The sprouted grains are then killed and brewed.

Sugars occur in all life forms in great numbers and great variety; they will also have an enzyme that facilitates their conversion to other substances needed for the life process. When an enzyme has completed its task, it passes the molecule to an enzyme of another type for a further modification. Only a very few of these production lines, or cycles, have been identified.

It is one thing to describe the microscopic form of a living object, and then to describe its product, as though the object were isolated and frozen in time. The reality is, that everything is happening at great speed, and when a neuron fires, every other neuron must know, because that is the only way in which life can maintain that synchronicity essential to viability. When an enzyme performs its task every other enzyme must also know.

The conversion of sugars by yeast to alcohol, is performed by enzymes; over a dozen have been identified; the total of which is called the �Zymaze Complex�, all of which are involved in the fermentation process. Not all of the functions are understood. The most important enzymes, from the alcohol production point of view, may be summarized as follows.

It must be clearly understood, that the clear cut divisions between substances and sugars that are shown in Table 9.11A, only indicate the major type of sugar to be found in a plant, for they will undoubtedly contain a complex of sugars, in the same way the yeast will secrete a complex of enzymes to handle the substrata. The processing and sequential ordering in such short time spans defies the imagination.

In human terms, we are talking of a combined oil refinery, sugar refinery and a distillery, which would employ large numbers of chemical engineers, chemists, technicians and tradesmen, plus the ancillary labor. Even after such enormous expenditures of money, time and energy it is no more than a pale shadow of the natural process. The sequential ordering of the process, depends upon the substrata on which the Zymaze complex goes to work. What we think happens, is as follows;

Starch - Water - Amylase - Maltose - Water - Maltase - Glucose - Zymaze = Alcohol + CO₂

Depending on the type of starch and other sugars present, this process could be considerably modified, and other pathways selected.

Glucose and Fructose are isomers, therefore the formula weights are identical.

1 mole of sugar is its formula weight, which corresponds to 180 gm. Figure 9 -12C, shows that 1 mol sugar yields 2 mol alcohol and 2 mol Carbon dioxide.

The formula weight of ethanol produced is 92 g, and that of carbon dioxide 88 g. On the basis of molecular weight, then 51.1% of the sugar is converted to alcohol and 48.9% to carbon dioxide. Obviously, that is the theoretical yield, because the yeast and the enzymes must use some of the sugar for their own metabolism.

The actual yield, under good conditions will vary between 40 to 48% ethanol per unit of sugar, i.e. 400 to 480g of alcohol per kg sugar; that will correspond to 352 to 423 ml of alcohol per kg of sugar, based on the density of the alcohol as 0.811 g/ml. It must be remembered, that the original sugar was in solution before conversion by the Zymaze complex, into alcohol.

The % of alcohol by volume, is dependent not only on the weight of the starting sugar, but also on the volume of the solution. The amount of alcohol produced per unit of sugar, is dependent on the yeast and its environment, therefore, a constant is not possible. Accordingly, further Figures and Tables will be based on the assumption of a 45% by weight conversion, of sugar to alcohol.

If 1 kg of sugar will convert to 45% by weight of alcohol, then 1g of sugar will produce 0.045% of alcohol by weight, so we may now set up a simple equation.

Weight of sugar in grams x 0.045 � by the volume of the solution = % of potential alcohol.

It will be understood from Table 9.11A, that most plant materials will yield some sugar or starch. If the starting material were grapes or other fruits, then they could be crushed and pulped and the juices fermented directly, or if the starting material was leaf, root or tuber, then they must be first chopped or ground, and the starches and sugars extracted by hot water treatment.

The method used to determine the sugar in solution, and therefore its potential alcohol, is by measuring the density of the solution. We could do this by weighing a volume, however, it is much more convenient to use a Hydrometer, which is simply �floated�, in the solution. The reading is compared with a set of Tables from which the appropriate values are taken.

In Module 4.32, we discussed the subject of �Relative Density�, or specific gravity (SG). Water is the substance, against which other substances are measured, in terms of their density.

Water is given the arbitrary number of �one�, and it is usually written as 1.000. If a miscible solute is lighter than water, its value will be below 1, e.g. 0.955, if it is heavier than water its value will be above 1, e.g., 1.110. Alcohol has an SG of 0.811 (lighter than water), therefore, if we add alcohol to water, we lower the density of the water.

Alcohol is miscible with water in all proportions, therefore, the density registered on a hydrometer, will be above 0.811 and below1.000 , e.g., if such a solution is 10% alcohol by volume, its SG is 0.986. If a solute is heavier than water, e.g., salt or sugar, then the density shown on the hydrometer will be above 1.000., e.g., if a volume of water contained 10% sugar by weight, its SG would be 1.075. Tables for sugar and alcohol will be given.

At the commencement of 4C there is an image of the old Sikes Hydrometer which was used by the revenue collecting agencies for determining the strength of alcohol in a solution. Today the hydrometer has been considerably improved and many different types of scales are available for differing purposes such as the measurement of sugar in solution. Also available are electronic instruments however they are dependent on a power source.

Figure 9.14A

On the left is shown a universal scale which would be suitable for alcohol and sugar solutions. Next to it is a hydrometer which contains the scale. The hydrometer shown is a sophisticated model that contains its own thermometer.

If the density of the water is lowered, by the addition of alcohol, the graduated hydrometer will sink lower; if the gravity is raised, by the addition of sugar, the hydrometer will rise. The hydrometer is simply a sealed glass, or plastic tube, which is weighted at one end. The tube is calibrated against distilled water at a given temperature, and then scaled in degrees according to the liquid it is designed to measure. For example, and for the purpose of taxation, the British authorities use the Sikes Hydrometer, of which the strength of an alcoholic solution is denoted as degrees over proof (o/p), or degrees under proof (u/p). The standard, or Proof Spirit, is legally defined as 57.07% v/v alcohol. (This is approximately 0.918 SG). The instrument used scientifically, is scaled to relative density or SG. There are three other scales in common use;

1. Degrees Baum� (Be�), named after Antoine Baum�, a French pharmacist. The scale is graduated to read the potential alcohol content of a must, or solution, prior to fermentation. Each degree indicates a possible 1% alcohol by volume, so it is related to the amount of sugar in the solution. Degrees Baum� will be used in conjunction with SG in the �Sugar Solution Table�.

2. Degrees Brix, sometimes called Balling. The scale is graduated to read the % of sugar by volume in a liquid. Each degree indicates 1% sugar by volume.

3. Degrees Twaddell (Tw�). The scale is graduated from 0 to 200�. An SG of 1.000 represents 0 Tw�. Each degree Twaddell represents 0.005 SG.

For practical purposes, the Twaddell scale is of more use to us than the Brix/Balling scale, for calculating the weight of sugar in a must or sugar solution. The Baum� scale may be used..to calculate the potential % of alcohol by volume of a sugar solution or must. Before we proceed to look at the relationship between the scales, let us assemble some conversion factors, whereby, the scales can be proved.

Sugar % by volume (ml) to % by weight (g) x 1.580
Sugar % by weight x 0.045 = Potential alcohol by volume.

1 g sugar will increase the volume of a liquid by 1.63 ml.

Or 1 kg increases 1 litre by 630 ml at 20�C.

Relationship of Density Scales, Tables 9.14B.

In the following Table, Tw� represents % sugar by volume, and Be� represents % of potential alcohol by volume. The sugar volume to weight ratio are based on 5 litre batches. For larger volumes, multiply by the factor shown.

SG and Weight/Volume Relationships, Table 9.14C.

Using the Tables 9.15

Distilled water is at its most dense at 4�C, at a higher temperature, a given volume of distilled water will increase in volume and decrease in density.

For this reason, most hydrometers are calibrated at 20�C. The reading is taken where the scale cuts the liquid. The calibration temperature will be given on the hydrometer.

Assume that we have prepared a �must� for fermentation, and bearing in mind that the sole purpose, is to produce a fermented liquid with the highest possible alcohol content, and the lowest possible level of unfermented sugar, we need to set a target level, for example 14.9% alcohol by volume.

Refer back to Table 9.14B, and seek out 14.9, in column 3, which is the Baum� Scale. The SG in column 1, reads 1.115. The sugar content in grams, column 5, is 1828.9; round that figure to 1830 grams per 5 litres. We proceed as follows.

A. Example; Take the SG of the must or liquid. Assume the SG is 1.032.

B. From that figure we deduct 0.007, to allow for un-fermentable solids, such as gums and pectin;

SG of must = 1.032  Deduct = 0.007  Correct SG = 1.025  An SG of 1.025 = 397.5 g sugar in 5 litres.

C. Target level 14.9 Alcohol SG 1.115, sugar 1830 g.

Target SG = 1.115 = Gravity 115 (column 6)

Actual SG = 1.025 = Gravity 25 (Column 6)

Gravity Difference = 90 (Column 6)

Seek out gravity 90, in column 6, then look to column 5, and you will find sugar 1431 g. That is the amount of sugar, to be added to the must, to reach the target level of 14.9% of alcohol by volume in 5 litres.

If we wish to produce 10, 15, or 25 litre batches, then the sugar weight in column 5, must be multiplied by the factor shown. The values given in columns 1, 2, 3 and 6 do not change.

Chapter Continues as 9B