Eduard Farber

“ At about that time (1833) , the Duke of Richmond proved that the fertilizing value of bones resided not in the gelatin, nor in the calcium, but in the phosphoric acid. Thus, he confirmed what Théodore de Saussure had said in 1804, that “we have no reason to believe” that plants can exist without phosphorus. Unknowingly at first, the farmer had supplied this element by means of the organic fertilizers he used: manure, excrements, bones, and horns. Now, with the value of phosphorus known, a search began for mineral phosphates to be applied as fertilizers. ”

“ During the intervening three centuries numerous other chemical miracles have been found, yet phosphorus retains a special aura of universal importance in chemistry. Many investigators have occupied themselves with this element and its diverse chemical compounds. Further enlightenment and insight into the ways of nature can be expected from these efforts. ”

“ What makes phosphorus so important that they cannot grow without it? The next insight was that animals acquire it from their plant food. It is then found in bones, in fat and nerve tissue, in all cells and particularly in the cell nuclei. What are its functions there?
The answers to such questions were developed from the study of a long-known process, the conversion of carbohydrates into carbon dioxide and alcohol by yeast. It started with Eduard Buchner’s discovery of 1890, that fermentation is produced by a preparation from yeast in which all living cells have been removed. ”

“ Thus, the study of organic phosphates progressed from the comparatively simple esters connected with fatty substances of organisms to the proteins and the nuclear substances of the cell. The proportional amount of phosphorus in the former was larger than in the latter; the actual importance and function in the life of organisms, however, is not measured by the quantity but determined by the special nature of the compounds. ”

“ Phosphates as Plant Nutrients
One hundred years after the discovery of “cold light,” the presence of phosphorus in plants and animals was ascertained, and its form was established as a compound of phosphoric acid. This knowledge had little practical effect until the “nature” of the acid, in its various forms, was explained through the work of Thomas Graham. ”

“ Salts are formed when a “basis,” i.e., a metal oxide, replaces water. When potassium-acid sulfate is neutralized by sodium base, the acid-salt divides into Glauber’s salt and potassium sulfate, which proves the acid-salt to be a mixture of the neutral salt with its acid. Sodium-acid phosphate behaves quite differently. After neutralization by a potassium “base” (hydroxide) , the salt does not split up; a uniform sodium-potassium phosphate is obtained. Therefore, phosphoric acid is truly three-basic! ”

“ The beneficial effects were obvious enough to increase the use of phosphates as plant nutrients and to call for new sources of supply. Active developments of phosphate mining and treating started in South Carolina in 1867, and in Florida in 1888. [25]
In a reciprocal action, more phosphate application to soils stimulated increasing research on the conditions and reactions obtaining in the complex and varying compositions called soil. The findings of bacteriologists made it clear that physics and chemistry had to be amplified by biology for a real understanding of fertilizer effects. ”

“ Figure 23.—Melvin Calvin (b. 1911) received the Nobel Prize in Chemistry in 1961 for his research in photosynthesis, in which he specified the function of phosphoglyceric acid as an intermediate in the synthesis of carbohydrates from carbon dioxide and water by green plants.
The story of phosphorus, which began 300 years ago, has acquired new importance in this century. Many scientists have contributed to it: 13 of them have received Nobel Prizes for work directly bearing on the chemical and biological importance of phosphorus compounds. ”

“ In the system of chemistry, as it developed in the first half of the 19th century, the new development can be characterized as the turn from inorganic to organic phosphates, from the substance of minerals and strong chemical interactions to the components in which phosphate groups remained combined with carbon-containing substances.
Phosphatides and Phosphagens
The important phosphorus compounds in organisms are much more complex than the simple salts, to which Nietzsche attributed such influence on man’s character. ”

“ Hankwitz [9] described methods for obtaining this acid, and Marggraf showed its chemical peculiarities. They did not necessarily establish phosphorus as a new element. To do that was not as important, at that time, as to conjecture on analogies with known substances. Underlying all its unique characteristics was the analogy of phosphorus with sulfur. Like sulfur, phosphorus can burn in two different ways, either slowly or more violently, and form two different acids. ”

“ Under the influence of ATP, phosphoglyceric acid is synthesized and further built up by way of carbohydrate phosphates to hexose sugars and finally to starch. In many starchy fruits, a small proportion of phosphate remains attached to the end product.
The synthesis of proteins is under the control of deoxyribonucleic acid or ribonucleic acid, abbreviated by the symbols DNA and RNA. The genes in the nucleus are parts of a giant DNA molecule. RNA is a universal constituent of all living cells. Where protein synthesis is intense, the content in RNA is high. ”

“ This newest phase developed out of an accidental discovery concerning one of the oldest organic-chemical industries, the production of alcohol by the fermentative action of yeast on sugar. A transition of carbohydrates through phosphate compounds to the end products of the fermentation process was found, and it gradually proved to be a kind of model for a host of biological processes.
Specific phosphates were thus found to be indispensable for life. In reverse, the wrong kind of phosphates can destroy life. ”

“ Many of the enzymes are closely related to vitamins. Thus, cocarboxylase A, which takes part in the separation of carbon dioxide from an intermediate fermentation product, is the phosphate of vitamin B1. Others of the B vitamins contain phosphate groups, for example those of the B2 and B6 group, and in B12, one lonely phosphate forms a bridge in the large molecule that contains one atom of cobalt: C63H90N14O14PCo. The formation of vitamin A from carotine occurs under the influence of ATP.
The first stages in fermentation are like those in respiration, which ends with carbon dioxide and water. ”

“ Yeast itself is considered to be a valuable food additive.
On the other hand, there are phosphate compounds that act as poisons. One group of such compounds was discovered in 1929 by W. Lange, who wrote: “Of interest is the strong action of mono-fluorophosphate esters on the human body—the effect is produced by very small quantities.” [40] Diisopropyl fluorophosphate has since become a potential agent for chemical warfare. It inactivates an enzyme which controls the transmission of nerve impulses to muscle, acetylcholine esterase. ”

“ Otherwise, enzymes would have decomposed it. Through more recent work, four enzymes have been separated, which act specifically in decomposing lecithin. Enzyme A removes one fatty acid and leaves a complex residue, called lysolecithin, intact. Enzyme B attacks this residue and splits off the remaining fatty acid group from it, enzyme C liberates only the choline from lecithin, and enzyme D opens lecithin at the ester bond between glycerol and phosphoric acid. ”

“ Bilious people have too little sodium sulfate, the melancholics are lacking in potassium sulfate and phosphate; too little calcium phosphate in the phlegmatics. Courageous natures have an excess of iron phosphate. ”

“ Thus, from phosphatides, phosphoric acid is generated, and they could also be called phosphagens. Since 1926, however, the name phosphagens has been reserved for a group of organic substances that release their phosphoric acid very readily. The link between phosphorus and carbon is provided by oxygen in the phosphatides, by nitrogen in the phosphagens. In vertebrates, the basis for the phosphoric acid is creatine, whereas invertebrates have arginine instead.
Creatine Phosphate
Arginine phosphate Nuclein and Nucleic Acids
All parts of an organism are essential for life. ”

“ A compound of adenine, ribose, and phosphoric acid was found in yeast, blood, and in skeletal muscle of mammals. From 100 grams of such muscle, 0.35-0.40 grams of this compound were isolated. If the muscle is at rest, the compound contains three molecules of phosphoric acid, linked through oxygen atoms. ”

“ The finding of polybasicity was extended to other acids and formed the model that helped to recognize the polyfunctionality in other compounds, like alcohols and amines. The hydrogen theory of acids was fundamental for further advance. In another dimension, it is particularly interesting to see that large-scale applications followed almost immediately and directly from the new theoretical insight. The first and foremost of these applications was in agriculture. ”

“ Its phosphate content was easily discovered, but to find the exact proportions and the nature of the other components required special methods of separation from phosphatides and other proteins. It was difficult to develop such methods at a time when little was known about the properties, and particularly [Pg 193] the stability, of a nuclein. For preparing nuclein from yeast cells, Felix Hoppe-Seyler (1825-1895) described the following details: Yeast is dispersed in water to extract soluble materials, like salts or sugars. ”

“ To obtain phosphorus, a good proportion of coal (regarded as a type of phlogiston) was added to urine, previously thickened by evaporation and preferably after putrefaction, and the mixture was heated to the highest attainable temperature. It was obvious that phlogiston entered into the composition of the distillation product. The question remained whether this product was generated de novo. In his research of 1743 to 1746, Andreas Sigismund Marggraf (1709-1782) provided the answer. ”

“ Any new material immediately became the hope of ailing mankind—and of striving inventors. [16] Phosphorus was prescribed, in liniments with fatty oils or as solution in alcohol and ether, for external and internal application. ”

“ This third substance was the same as one previously noticed when nerves had been subjected to an extraction by boiling water and acid and, therefore, called nerve-substance or neurine. Adolf Friedrich Strecker (1822-1871) established the identity of this neurine with a product he had extracted from bile and which went under the name of choline. Adolphe Wurtz (1817-1884) succeeded in synthesizing this substance from ethylene oxide, CH2.O.CH2 and trimethylamine N (CH3) 3. ”

“ Refining the techniques of Gay-Lussac (1816) and several other investigators, Graham characterized the three phosphoric acids as “a terphosphate, a biphosphate, and phosphate of water.” Actually, this was the wrong terminology for what he meant and formulated as trihydrate, bihydrate, and monohydrate of phosphorus oxide. In [Pg 183] his manner of writing the formulas, each dot over the symbol for the element was to indicate an atom of oxygen; thus, he wrote:
... :: .. ... . .
H3 P H2 P and H P. [22]
Figure 5.—Oven for the calcination of bones, about 1870. ”