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diff --git a/33766.txt b/33766.txt new file mode 100644 index 0000000..a74635c --- /dev/null +++ b/33766.txt @@ -0,0 +1,2157 @@ +The Project Gutenberg EBook of History of Phosphorus, by Eduard Farber + +This eBook is for the use of anyone anywhere at no cost and with +almost no restrictions whatsoever. You may copy it, give it away or +re-use it under the terms of the Project Gutenberg License included +with this eBook or online at www.gutenberg.org + + +Title: History of Phosphorus + +Author: Eduard Farber + +Release Date: September 20, 2010 [EBook #33766] + +Language: English + +Character set encoding: ASCII + +*** START OF THIS PROJECT GUTENBERG EBOOK HISTORY OF PHOSPHORUS *** + + + + +Produced by Chris Curnow, Joseph Cooper, Louise Pattison +and the Online Distributed Proofreading Team at +https://www.pgdp.net + + + + + + + + + +Transcriber's Note. + +This is Paper 40 from the Smithsonian Institution United States National +Museum Bulletin 240, comprising Papers 34-44, which will also be +available as a complete e-book. + +The front material, introduction and relevant index entries from the +Bulletin are included in each single-paper e-book. + +Corrections are listed at the end of the e-book. + + + + +SMITHSONIAN INSTITUTION + +UNITED STATES NATIONAL MUSEUM + +BULLETIN 240 + + +[Illustration] + +SMITHSONIAN PRESS + + +MUSEUM OF HISTORY AND TECHNOLOGY + +CONTRIBUTIONS FROM THE MUSEUM OF HISTORY AND TECHNOLOGY + + _Papers 34-44_ + _On Science and Technology_ + +SMITHSONIAN INSTITUTION . WASHINGTON, D.C. 1966 + + + + +_Publications of the United States National Museum_ + + +The scholarly and scientific publications of the United States National +Museum include two series, _Proceedings of the United States National +Museum_ and _United States National Museum Bulletin_. + +In these series, the Museum publishes original articles and monographs +dealing with the collections and work of its constituent museums--The +Museum of Natural History and the Museum of History and +Technology--setting forth newly acquired facts in the fields of +anthropology, biology, history, geology, and technology. Copies of each +publication are distributed to libraries, to cultural and scientific +organizations, and to specialists and others interested in the different +subjects. + +The _Proceedings_, begun in 1878, are intended for the publication, in +separate form, of shorter papers from the Museum of Natural History. +These are gathered in volumes, octavo in size, with the publication date +of each paper recorded in the table of contents of the volume. + +In the _Bulletin_ series, the first of which was issued in 1875, appear +longer, separate publications consisting of monographs (occasionally in +several parts) and volumes in which are collected works on related +subjects. _Bulletins_ are either octavo or quarto in size, depending on +the needs of the presentation. Since 1902 papers relating to the +botanical collections of the Museum of Natural History have been +published in the _Bulletin_ series under the heading _Contributions from +the United States National Herbarium_, and since 1959, in _Bulletins_ +titled "Contributions from the Museum of History and Technology," have +been gathered shorter papers relating to the collections and research of +that Museum. + +The present collection of Contributions, Papers 34-44, comprises +Bulletin 240. Each of these papers has been previously published in +separate form. The year of publication is shown on the last page of each +paper. + +FRANK A. TAYLOR _Director, United States National Museum_ + + + + + CONTRIBUTIONS FROM + THE MUSEUM OF HISTORY AND TECHNOLOGY: + PAPER 40 + + + + + HISTORY OF PHOSPHORUS + + _Eduard Farber_ + + + + + THE ELEMENT FROM ANIMALS AND PLANTS 178 + + EARLY USES 181 + + CHEMICAL CONSTITUTION OF PHOSPHORIC ACIDS 182 + + PHOSPHATES AS PLANT NUTRIENTS 185 + + FROM INORGANIC TO ORGANIC PHOSPHATES 187 + + PHOSPHATIDES AND PHOSPHAGENS 189 + + NUCLEIN AND NUCLEIC ACIDS 192 + + PHOSPHATES IN BIOLOGICAL PROCESSES 197 + + MEDICINES AND POISONS 198 + + + + +_Eduard Farber_ + + + + +HISTORY OF PHOSPHORUS + + + _The "cold light" produced by phosphorus caused it to be + considered a miraculous chemical for a long time after its + discovery, about 1669. 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._ + + _Not only is the story of phosphorus a major drama in the + history of chemistry; it also illustrates, in a spectacular + example, the growth of this science through the discovery of + connections between apparently unrelated phenomena, and the + continuous interplay between basic science and the search for + practical usage._ + + THE AUTHOR: _Eduard Farber is a research professor at American + University, Washington, D.C., and has been associated with the + Smithsonian Institution as a consultant in chemistry._ + + +When phosphorus was discovered, nearly three centuries ago, it was +considered a miraculous thing. The only event that provoked a similar +emotion was the discovery of radium more than two centuries later. The +excitement about the _Phosphorus igneus_, Boyle's _Icy Noctiluca_, was +slowly replaced by, or converted into, chemical research. Yet, if we +would allow room for emotion in research, we could still be excited +about the wondrous substance that chemical and biological work continues +to reveal as vitally important. It is a fundamental plant nutrient, an +essential part in nerve and brain substance, a decisive factor in muscle +action and cell growth, and also a component in fast-acting, powerful +poisons. The importance of phosphorus was gradually recognized and the +means by which this took place are characteristic and similar to other +developments in the history of science. This paper was written in order +to summarize these various means which led to the highly complex ways of +present research. + + + + +The Element from Animals and Plants + + +It was a little late to search for the philosophers' stone in 1669, yet +it was in such a search that phosphorus was discovered. Wilhelm Homberg +(1652-1715) described it in the following manner: Brand, "a man little +known, of low birth, with a bizarre and mysterious nature in all he +did, found this luminous matter while searching for something else. He +was a glassmaker by profession, but he had abandoned it in order to be +free for the pursuit of the philosophical stone with which he was +engrossed. Having put it into his mind that the secret of the +philosophical stone consisted in the preparation of urine, this man +worked in all kinds of manners and for a very long time without finding +anything. Finally, in the year 1669, after a strong distillation of +urine, he found in the recipient a luminant matter that has since been +called phosphorus. He showed it to some of his friends, among them +Mister Kunkel [sic]."[1] + +Neither the name nor the phenomenon were really new. Organic +phosphorescent materials were known to Aristotle, and a lithophosphorus +was the subject of a book published in 1640, based on a discovery made +by a shoemaker, Vicenzo Casciarolo, on a mountain-side near Bologna in +1630.[2] Was the substance new which Brand showed to his friends? Johann +Gottfried Leonhardi quotes a book of 1689 in which the author, Kletwich, +claims that this phosphorus had already been known to Fernelius, the +court physician of King Henri II of France (1154-1189).[3] To the same +period belongs the "Ordinatio Alchid Bechil Saraceni philosophi," in +which Ferdinand Hoefer found a distillation of urine with clay and +carbonaceous material described, and the resulting product named +escarbuncle.[4] It would be worth looking for this source; although +Bechil would still remain an entirely unsuccessful predecessor, it does +seem strange that in all the distillations of arbitrary mixtures, the +conditions should never before 1669 have been right for the formation +and the observation of phosphorus. + +[Illustration: Figure 1.--THE ALCHEMIST DISCOVERS PHOSPHORUS. A painting +by Joseph Wright (1734-1779) of Derby, England.] + +For Brand's contemporaries at least, the discovery was new and exciting. +The philosopher Gottfried Wilhelm von Leibniz (1646-1716) considered it +important enough to devote some of his time (between his work as +librarian in Hanover and Wolfenbuettel, his efforts to reunite the +Protestant and the Catholic churches, and his duties as Privy Councellor +in what we would call a Department of Justice) to a history of +phosphorus. This friend of Huygens and Boyle tried to prove that Kunckel +was not justified in claiming the discovery for himself.[5] Since then, +it has been shown that Johann Kunckel (1630-1703) actually worked out +the method which neither Brand nor his friend Kraft wanted to disclose. +Boyle also developed a method independently, published it, and +instructed Gottfried Hankwitz in the technique. Later on, Jean Hellot +(1685-1765) gave a meticulous description of the details and a long +survey of the literature.[6] + +[Illustration: Figure 2.--GALLEY-OVEN, 1869. The picture is a cross +section through the front of the oven showing one of the 36 retorts, the +receivers for the distillate, and the space in the upper story used for +evaporating the mixture of acid solution of calcium phosphate and coal. +(According to ANSELME PAYEN, _Precis de Chimie industrielle_, Paris, +1849; reproduced from HUGO FLECK, _Die Fabrikation chemischer Produkte +aus thierischen Abfaellen_, Vieweg, Braunschweig, 1862, page 80 of volume +2, 2nd group, of P. BOLLEY'S _Handbuch der chemischen Technologie_.)] + +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. He found the +new substance in edible plant seeds, and he concluded that it enters the +human system through the plant food, to be excreted later in the urine. +He did not convince all the chemists with his reasoning. In 1789, +Macquer wrote: "There are some who, even at this time, hold that the +phosphorical ('phosphorische') acid generates itself in the animals and +who consider this to be the 'animalistic acid.'"[7] + +Although Marggraf was more advanced in his arguments than these +chemists, yet he was a child of his time. The luminescent and +combustible, almost wax-like substance impressed him greatly. "My +thoughts about the unexpected generation of light and fire out of water, +fine earth, and phlogiston I reserve to describe at a later time." These +thoughts went so far as to connect the new marvel with alchemical wonder +tales. When Marggraf used the "essential salt of urine," also called +_sal microcosmicum_, and admixed silver chloride ("horny silver") to it +for the distillation of phosphorus, he expected "a partial conversion of +silver by phlogiston and the added fine vitrifiable earth, but no trace +of a more noble metal appeared."[8] + +Robert Boyle had already found that the burning of phosphorus produced +an acid. He identified it by taste and by its influence on colored plant +extracts serving as "indicators." 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. The analogy can, therefore, be extended to explain the +results in both groups in the same way. In the process of burning, the +combustible component is removed, and the acid originally combined with +the combustible is set free. Whether the analogy should be pursued even +further remained doubtful, although some suspicion lingered on for a +while that phosphoric acid might actually be a modified sulfuric acid. +Analogies and suspicions like these were needed to formulate new +questions and stimulate new experiments. They are cited here for their +important positive value in the historical development, and not for the +purpose of showing how wrong these chemists were from our point of +view, a point of view which they helped to create. + +The widespread interest in the burning of sulfur and of phosphorus, +naturally, caught Lavoisier's attention. In his first volume of +_Opuscules Physiques et Chimiques_ (1774), he devoted 20 pages to his +experiments on phosphorus. He amplified them a few years later[10] when +he attributed the combustion to a combination of phosphorus with the +"eminently respirable" part of air. In the _Methode de Nomenclature +Chimique_ of 1787, the column of "undecomposed substances" lists sulfur +as the "radical sulfurique," and phosphorus, correspondingly, as the +"radical phosphorique." The acids are now shown to be compounds of the +"undecomposed" radicals, the complete reversion of the previous concept +of this relationship. A part of the old analogy remained as far as the +acids are concerned: sulfuric acid corresponds to phosphoric; sulfurous +acid to phosphorous acid with less oxygen than in the former.[11] + + + + +Early Uses + + +In the 18th century, phosphorus was a costly material. It was produced +mostly for display and to satisfy curiosity. Guillaume Francois Rouelle +(1703-1770) demonstrated the process in his lectures, and, as Macquer +reports, he "very often" succeeded in making it.[12] Robert Boyle had +the idea of using phosphorus as a light for underwater divers.[13] A +century later, "instant lights" were sold, with molten phosphorus as the +"igniter," but they proved cumbersome and unreliable.[14] Because white +phosphorus is highly poisonous, an active development of the use in +matches occurred only after the conversion of the white modification +into the red had been studied by Emile Kopp (1844), by Wilhelm Hittorf +(1824-1914) and, in its practical application, by Anton Schroetter +(1802-1875).[15] + +[Illustration: Figure 3.--DISTILLATION APPARATUS (1849) for refining +crude phosphorus. The crude phosphorus is mixed with sand under hot +water, cooled, drained, and filled into the retort. The outlet of the +retort, at least 6 cm. in diameter, is partially immersed in the water +contained in the bucket. A small dish, made from lead, with an iron +handle, receives the distilled phosphorus. (From HUGO FLECK, _Die +Fabrikation chemischer Produkte ..._ page 90.)] + +The most exciting early use, however, was in medicine. It is not +surprising that such a use was sought at that time. 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. A certain Dr. Kramer found it efficient against epilepsy +and melancholia (1730). A Professor Hartmann recommended it against +cramps.[17] However, in the growing production of phosphorus for +matches, the workers experienced the poisonous effects. In the plant of +Black and Bell at Stratford, this was prevented by inhaling turpentine. +Experiments on dogs were carried out to show that poisoning by +phosphorus could be remedied through oil of turpentine.[18] + +[Illustration: Figure 4.--APPARATUS FOR CONVERTING WHITE PHOSPHORUS into +the red allotropic form, 1851. Redistilled phosphorus is heated in the +glass or porcelain vessel (g) which is surrounded by a sandbath (e) and +a metal bath (b). Vessel (j) is filled with mercury and water; together +with valve (k), it serves as a safety device. The alcohol lamp (l) keeps +the tube warm against clogging by solidified vapors. Because of hydrogen +phosphides, the operation, carried out at 260 deg. C., had to be watched +very carefully. (According to Arthur Albright, 1851; reproduced from +HUGO FLECK, _Die Fabrikation chemischer Produkte ..._, page 112.)] + + + + +Chemical Constitution of Phosphoric Acids + + +In a long article on phosphorus, Edmond Willm wrote in 1876: "For a +century, urine was the only source from which phosphorus was obtained. +After Gahn, in 1769, recognized the presence of phosphoric acid in +bones, Scheele indicated the procedure for making phosphorus from +them."[19] Actually, Gahn used at first hartshorn (_Cornu cervi +ustum_), and Scheele doubted, until he checked it himself, that his +esteemed friend was right. A few years later, Scheele corrected Gahn's +assumption that the _sal microcosmicum_ was an ammonia salt; instead, it +is "a tertiary neutral salt, consisting of _alkali minerali fixo_ (i.e., +sodium), _alkali volatili_, and _acido phosphori_."[20] + +In the years after 1770, phosphorus was discovered in bones and many +other parts of various animals. Treatment with sulfuric acid decomposed +these materials into a solid residue and dissolved phosphoric acid. Many +salts of this acid were produced in crystalline form. Heat resistance +had been considered one of the outstanding characteristics of phosphoric +acid. Now, however, in the processes of drying and heating certain +phosphates, it became clear that three kinds of phosphoric acids could +be produced: _ortho_, _pyro_, and _meta_. + +Berzelius cited these acids as examples of compounds which are ISOMERIC. +This word was intended to designate compounds which contain the same +number of atoms of the same elements but combined in different manners, +thereby explaining their different chemical properties and crystal +forms. It was in 1830 that Berzelius propounded this companion of the +concept, ISOMORPHISM, which was to collect all cases of equal crystal +form in compounds in which equal numbers of atoms of different elements +are put together in the same manner. Together, the two concepts of +isomerism and isomorphism seemed to cover all the known exceptions from +the simplest assumption as to specificity and chemical composition. + +However, only a few years later Thomas Graham (1805-1869) proved that +the three phosphoric acids are not isomeric. He used the proportion of 2 +P to 5 O in the oxide which Berzelius had thought justified at least +until "an example of the contrary could be sufficiently +established."[21] 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 his manner of writing the formulas, each dot over the symbol +for the element was to indicate an atom of oxygen; thus, he wrote: + + ... :: .. ... . . + H^{3} P H^{2} P and H P.[22] + +[Illustration: Figure 5.--OVEN FOR THE CALCINATION OF BONES, about 1870. +"The operation is carried out in a rather high oven, such as shown.... +The fresh bones are thrown in at the top of the oven, B. First, fuel in +chamber F is lighted, and a certain quantity of bones is burnt on the +grid D. When these bones are burning well, the oven is gradually filled +with bones, and the combustion maintains itself without addition of +other fuel. A circular gallery, C, surrounds the bottom of the oven and +carries the products of combustion into the chimney, H. The calcined +bones are taken out at the lower opening, G, by removing the bars of +grid B." (Translation of the description from FIGUIER, _Merveilles de +l'industrie_, volume 3, 1874, page 537.)] + +[Illustration: Figure 6.--AN ADVERTISEMENT with view of plant for +manufacturing superphosphate about 1867. (From E. T. FREEDLEY, +_Philadelphia and its Manufacturers in 1867_, page 288.)] + +Graham had come to this understanding of the phosphoric acids through +his previous studies of "Alcoates, definite compounds of Salts and +Alcohol analogous to the Hydrates" (1831). Liebig started from analogies +he saw with certain organic acids when he formulated the phosphoric +acids with a constant proportion of water (aq.) and varying proportions +of "phosphoric acid" (P) as follows: + + 2 P 3 aq. phosphoric acid + 3 P 3 aq. pyrophosphoric acid + 6 P 3 aq. metaphosphoric acid. + +[Illustration: Figure 7.--FLORIDA HARD-ROCK PHOSPHATE MINING. (From +Carroll D. Wright, _The Phosphate Industry of the United States_, sixth +special report of the Commissioner of Labor, Government Printing Office, +Washington, 1893, plate facing page 43.)] + +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![23] + +This result has later been confirmed, but the analogy by means of which +it had been obtained was very weak, in certain parts quite wrong. + +The acids from the two lower oxides of phosphorus were also considered +as three-basic. Adolphe Wurtz (1817-1884) formulated them in 1846, +according to the theory of chemical types: + + (PO)... + O^{3} phosphoric acid + H^{3} + + (PHO).. + O^{2} phosphorus acid + H^{2} + + (PH^{2}O). + O hypophosphorous acid.[24] + H + +Further proof for these constitutions was sought in the study of the +esters formed when the acids react with alcohols. + +Among the analogies and generalizations by which the research on +phosphoric acid was supported, and to the results of which it +contributed a full share, was the new theory of acids. Not oxygen, +Lavoisier's general acidifier, but reactive hydrogen determines the +character of acids. In this brief survey, it seems sufficient just to +mention this connection without describing it in detail. + +The study of phosphoric acids led to important new concepts in +theoretical chemistry. 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. + + + + +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. From it, there started +a considerable technical development. + +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 Theodore 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. Jean Baptiste Boussingault (1802-1887), an agricultural +chemist in Lyons, traveled to Peru to see the guano deposits. Garcilaso +de la Vega (ca. 1540 to ca. 1616) noted in his history of Peru (1604) +that guano was used by the Incas as a fertilizer. Two hundred years +later, Alexander von Humboldt revived this knowledge, and Humphry Davy +wrote about the benefits of guano to the soil. Yet, the application of +this fertilizer developed only slowly, until Justus Liebig sang its +praise. Imports into England rose and far exceeded those into France +where, between 1857 and 1867, about 50,000 tons were annually received. + +The other great advance in the use of phosphatic plant nutrients started +with Liebig's recommendation (1840) to treat bones with sulfuric acid +for solubilization. This idea was not entirely new; since 1832, a +production of a "superphosphate" from bones and sulfuric acid had been +in progress at Prague. At Rothamsted in 1842, John Bennet Lawes +obtained a patent on the manufacture of superphosphate. Other +manufactures in England followed and were successful, although James +Muspratt (1793-1886) at Newton lost much time and "some thousands of +pounds" on Liebig's idea of a "mineral manure." + +[Illustration: Figure 8.--FLORIDA LAND-PEBBLE PHOSPHATE MINING. (From +Carroll D. Wright, _The Phosphate Industry of the United States ..._, +plate facing page 58.)] + +It was difficult enough to establish the efficacy of bones and +artificially produced phosphates in promoting the growth of plants under +special conditions of soils and climate; therefore, the question as to +the action of phosphates in the growing plant was not even seriously +formulated at that time. 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. +After 1900, for example, Julius Stoklasa (1857-1936) pointed out that +bacterial action in soil solubilizes water-insoluble phosphates and +makes them available to the plants.[26] + +[Illustration: Figure 9.--FLORIDA RIVER-PEBBLE PHOSPHATE MINING. (From +Carroll D. Wright, _The Phosphate Industry of the United States ..._, +plate facing page 64.)] + +The insight into the importance of phosphorus in organisms, especially +since Liebig's time, is reflected in the work of Friedrich Nietzsche +(1844-1900). This "re-valuator of all values" who modestly said of +himself: "I am dynamite!" once explained the human temperaments as +caused by the inorganic salts they contain: "The differences in +temperament are perhaps caused more by the different distribution and +quantities of the inorganic salts than by everything else. 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." (See +volume 12 of _Nietzsche's Works_, edit. Naumann-Kroener, Leipzig, 1886.) +In this strange association of inorganic salts with human temperaments, +the role of iron phosphate as a producer of courage is particularly +interesting. What would a modern philosopher conclude if he followed the +development of insight into the composition and function of complex +phosphate compounds in organisms? + + + + +From Inorganic to Organic Phosphates + + +By the middle of the 19th century, the source of phosphorus in natural +phosphates and the chemistry of its oxidation products had been +established. The main difficulty that had to be overcome was that these +oxidation products existed in so many forms, not only several stages of +oxidation, but, in addition, aggregations and condensations of the +phosphoric acids. Once the fundamental chemistry of these acids was +elucidated, the attention of chemists and physiologists turned to the +task of finding the actual state in which phosphorus compounds were +present in the organisms. It had been a great advance when it had been +shown that plants need phosphates in their soil. This led to the next +question concerning the materials in the body of the plant for which +phosphates were being used and into which they were incorporated. +Similarly, the knowledge that animals attain their phosphates from the +digested plant food called, in the next step of scientific inquiry, for +information on the nature of phosphates produced from this source. + +The method used in this inquiry was to subject anatomically separated +parts of the organisms to chemical separations. The means for such +separations had to be more gentle than the strong heat and destructive +chemicals that had been considered adequate up to then. The +interpretation of the new results naturally relied on the general +advance of chemistry, the development of new methods for isolating +substances of little stability, of new concepts concerning the +arrangements of atoms in the molecules, and of new apparatus to measure +their rates of change. + +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. + +[Illustration: Figure 10.--ELECTRIC FURNACE FOR PRODUCING ELEMENTAL +PHOSPHORUS, invented by Thomas Parker of Newbridge, England, and +assigned to The Electric Construction Corporation of the same place. The +drawing is part of United States patent 482,586 (September 13, 1892). +The furnace was patented in England on October 29, 1889 (no. 17,060); in +France on June 23, 1890 (no. 206,566); in Germany on June 17, 1890 (no. +55,700); and in Italy on October 23, 1890 (no. 431). The following +explanation is cited from the U.S. patent: + +Figure 1 [shown here] is a vertical section of the furnace, and Fig. 2 +is a diagram to illustrate the means for regulating the electro-motive +force or quantity of current across the furnace. + +F is the furnace containing the charge to be treated. It has an +inlet-hopper at _a_, with slides AA, by which the charge can be admitted +without opening communication between the interior of the furnace and +the outer air. + +B is a screw conveyer by which the charge is pushed forward into the +furnace. + +_c'c'_ are the electrodes, consisting of blocks or cylinders or the like +of carbon fixed in metal socket-pieces _c c_, to which the +electric-circuit wires _d_ from the dynamo D are affixed. The current, +as aforesaid, may be either continuous or alternating. _c^{2}c^{2}_ are +rods of metal or carbon, which are used to establish the electric +circuit through the furnace, the said rods being inserted into holes in +conductors _c^{3}_ (in contact with the socket-pieces _c_) and in the +furnace, as shown. + +_g_ is the outlet for the gas or vapor, _h_ the slag-tap hole, and _x_ +the opening for manipulating the charge, the said openings being closed +by clay or otherwise when the furnace is at work. + +I use coke or other form of carbon in the charge between the electrodes +_c'_, the said coke being in contact with the said electrodes, so that +complete incandescence is insured. + +A means for varying the electro-motive force or quantity of current +across the furnace with the varying resistance of the charge is +illustrated by the diagram, Fig. 2. _c' c^{2}_ indicate the electrodes +in the furnace, as in Fig. 1, and D is the dynamo and T its terminals. E +represents the exciting-circuit. R R are resistances, and R S is the +resistance-switch, which is operated to put in more or less resistance +at R as the resistance of the charge in the furnace lessens or +increases. This switch may be automatically operated, and a suitable +arrangement for the purpose is a current-regulator such as is described +in the specification of English Letters Patent No. 14,504, of September +14, 1889, granted to William Henry Douglas and Thomas Hugh Parker.] + +[Illustration: + + T. PARKER. + ELECTRICAL FURNACE. + + Patented Sept. 13, 1892. + + FIG. 1.] + +[Illustration: FIG. 2. + + _Inventor + Thomas Parker_ + + _By his attorneys + Howson and Howson_ + + _Witnesses: + George Baumann + John Revell_] + +[Illustration: Figure 11.--DIPPING OF MATCHSTICKS in France, about 1870. +The frame which holds the matches so that one end protrudes at the +bottom, is lowered over a pan containing molten sulfur. The +sulfur-covered matches are then dropped into a phosphorous paste. See +figure 12. (From FIGUIER, _Merveilles de l'industrie_, volume 3, 1874, +page 575.)] + + + + +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. Long before he wrote, it was known that phosphoric acid +combines not only with inorganic bases to form salts, but with alcohols +to form esters. In the middle of the 19th century, Theophile Juste +Pelouze (1807-1867) extended this knowledge to an ester of glycerol. +This proved to be significant in several respects. Glycerol had been +shown by Michel Chevreul (1786-1889) as the substance in fats that is +released in the process of soap boiling, when the fatty acids are +converted into their salts. That it has the nature of an alcohol had +been demonstrated by Marcellin Berthelot. Instead of one "alcoholic" +hydroxyl group, OH, like ethanol (the alcohol of fermentation), or two +hydroxyl groups (like ethylene glycol), glycerol contains three such +groups. It was the only "natural" alcohol known at that time. That this +alcohol would combine with phosphoric acid could be predicted, but that +the ester, as obtained by Pelouze, still contained free acidic functions +and formed a water-soluble barium salt was a new experience. + +[Illustration: Figure 12.--PAN FOR DIPPING MATCHSTICKS into phosphorus +paste, about 1870. The letters on the picture are: A, matches; B, water +bath; C, frame; D, plate; E, phosphorus paste; F, oven. The phosphorus +paste of Boettger, 1842, contained 10 phosphorus, 25 antimony sulfide, +12.5 manganese dioxide, 15 gelatin. According to Figuier (page 579), R. +Wagner substituted lead dioxide for the manganese dioxide. (From +FIGUIER, volume 3, 1874, page 576.)] + + +ALCOHOLIC FERMENTATION + + (C_{6}H_{10}O_{5})_{_n_} C_{6}H_{12}O_{6} C_{6}H_{12}O_{6} + glycogen glucose fructose + ^| ^| ^| + || H_{3}PO_{4} || <-- ATP || <--ATP + |v |v |v + ---------------+ ------+ + H--C--OPO_{3}H_{2}| H--C--OH | H _{2}C--OH + | | | | | + H--C--OH | H--C--OH | C--(OH)--+ + | | | | | | + HO--C--H O <==> HO--C--H O <=======> HO--C--H | + | | | | | O + H--C--OH | H--C--OH | H--C--OH | + | | | | | | + H--C--------------+ H--C-----+ H--C--------+ + | | | + CH_{2}OH H_{2}C--OPO_{3}H_{2}+ADP H_{2}C--OPO_{3}H_{2}+ADP + + glucose-1-phosphate glucose-6-phosphate fructose-6-phosphate + (Cori-ester) (Robison-ester) (Neuberg-ester) + ^ | + | | <-- ATP + +----| | + | +------| + | | + | v + H_{2}C--OPO_{3}H_{2} + | + C(OH)--+ + | | + HO--C--H | + fructose-1,6-diphosphate | O + (Harden-Young-ester) H--C--OH | + | | + H--C------+ + | + H_{2}C--OPO_{3}H_{2} + ADP + ^| + || O + || // + CH_{2}OPO_{3}H_{2} || CH + | |v | 3-phosphoglycer-aldehyde + dihydroxyacetone-phosphate C=O <=============> CHOH (Fischer-ester) + | | + CH_{2}OH CH_{2}OPO_{3}H_{2} + || + coenzyme + H_{3}PO_{4} + O=C--OPO_{3}H_{2} + | + 1,3-diphosphoglyceric acid CHOH + dihydro-coenzyme + (Negelein-ester) | + CH_{2}OPO_{3}H + ^| + ADP --> || + || O + |v// + C--OH + | +---+ + 3-phosphoglyceric acid CHOH + |ATP| + (Nilsson-ester) | +---+ + CH_{2}OPO_{3}H_{2} + ^| + |v + COOH + 2-phosphoglyceric acid | + CHOPO_{3}H_{2} + | + CH_{2}OH + ^| + |v + COOH + | + phosphopyruvic acid COPO_{3}H_{2} + (enol-) || + CH_2 + ADP --> || + COOH + +------+ | +---+ + |CO_{2}| + CH_3CHO <-------- C=O + |ATP| + +------+ acetaldehyde | +---+ + carbon | CH_{3} + dioxide | + dihydro-coenzyme pyruvic acid + | + v + +----------------+ + | CH_{3}CH_{2}OH | + coenzyme + +----------------+ + ethyl alcohol + +[Illustration: Figure 13.--SURVEY OF ALCOHOLIC FERMENTATION, 1951. The +"well-known scheme of alcoholic fermentation" according to Albert Jan +Kluyver (1888-1956), presented before the Society of Chemical Industry +in the Royal Institution, March 7, 1951. In _Chemistry & Industry_, +1952, page 136 ff., Kluyver restates that "... the fermentation of one +molecule of glucose is indissolubly connected with the formation of two +molecules of adenosine triphosphate (ATP) out of two molecules of +adenosine diphosphate (ADP)."] + +Shortly after this experience had been gained, it became valuable for +understanding the chemical nature of a new substance extracted from a +natural organ. This substance was named lecithin by its discoverer, +Nicolas Theodore Gobley[27] (1811-1876), because he obtained it from egg +yolk (in Greek, _lekidos_). He used ether and alcohol for this +extraction. Had he used water and mineral acid instead, he would not +have found lecithin, but only its components. As Gobley and, slightly +later, Oscar Liebreich (1839-1908), subjected lecithin to treatment with +boiling water and acid, they separated it into three parts. One of them +was the glycerophosphoric acid of Pelouze, the second was the well-known +stearic acid of Chevreul, but the third was somewhat mysterious. 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, CH_2.O.CH_2 and trimethylamine N(CH_3)_3.[28] Thus, all +three parts were identified, and Strecker put them together to construct +a chemical formula for lecithin, glycerophosphoric acid combined with a +fatty acid and with choline (a hydrate of neurine). + + { OH } + N { (CH_3)_3 } Choline + { C_2H_4O } + + + C_18H_33O_2 } HO } + } } PO + C_16H_31O_2 } C_3H_5O } + + Fatty Acids Glycerophosphate + \--------v-------/ + Lecithin + according to Strecker + +This formula was not quite correct. Richard Willstaetter showed that an +internal neutralization takes place between the amino group and the free +acidic residue. This is expressed in his lecithin formula of 1918. + + CH_{2}.O.R + | + CH_{2}.O.R_2 + | + | O.CH_{2}.CH_{2} + | / \ + CH_{2}.O--P=O N(CH_{3})_{3} + \ / + \---O----/ + +[Illustration: Lecithin (1918)] + +When the aim was to distill elementary phosphorus out of an organic +material, it did not matter whether this was fresh or putrified. For +obtaining lecithin out of egg yolk and similar materials, it was +essential to use it in fresh condition. 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. This is shown in the following diagram. + + ENZYMATIC SPLITTING OF LECITHINS + + ENZYME SUBSTRATE PRODUCTS + + A Lecithin Lysolecithin and fatty + acids. + + B Lysolecithin Glycero-phospho-choline + and fatty acids. + + C Lecithin Phosphatidic acid and + choline. + + D Lecithin Phosphoryl choline and + diglyceride. + +Several fatty acids can be present in lecithin from various sources: +palmitic and oleic acid, besides the stearic acid which at first had +been thought the only one involved. In another group of extracts from +brain or nerve tissue, amino-ethanol H_{2}NCH_{2}CH_{2}OH is found +instead of the choline of lecithin. The variations include the alcohol, +to which the fatty acids and choline phosphate are attached, for +example, glycerol can be replaced by the so-called meat-sugar, inositol, +which has six hydroxyl groups in its hexagon-shaped molecule +C_{6}H_{6}(OH)_{6}. + +[Illustration: Figure 14.--EDUARD BUCHNER (1860-1917) received the Nobel +Prize in Chemistry for his discovery of cell-free fermentation, the +first step in finding the role of phosphate in fermentations (1907).] + +The generally similar behavior of these phosphate-and fat-containing +substances was emphasized by Ludwig Thudichum (1829-1901). He coined the +name phosphatides for this group of substances from seeds and +nerves.[29] His work on the phosphates in brain substance aroused +particular interest. When William Crookes drew his highly imaginative +picture of an "evolution" of the chemical elements, he put into it +"phosphorus for the brain, salt for the sea, clay for the solid +earth...."[30] But phosphatides occur in many places of organisms, in +bacteria, in leaves and roots of plants, in fat and tissues of animals. +And where phosphatides are found, there are also enzymes that +specifically act on them. They are called phosphatases to imply that +they split the phosphatides. In addition, enzymes are present, which +transfer phosphate groups from one compound to another. They are more +abundant in seeds of high fat content than in the more starch-containing +seeds, but even potatoes and orange juice have phosphatases.[31] + +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. + + H OH OH + | / / + N--P=O NH--P=O + / \ / \ + C=NH OH C=NH OH + \ \ + N--CH_{2}COOH NH + | | + CH_{3} CH_{2} + | + Creatine phosphate CH_{2} + | + CH_{2} + | + CHNH_{2} + | + COOH + + Arginine phosphate + + + + +Nuclein and Nucleic Acids + + +All parts of an organism are essential for life. Only with this in mind +does it make sense to say that the most important part of the cell is +its nucleus. From the nuclei of cells in pus and in salmon sperm, Johann +Friedrich Miescher (1811-1887) obtained a peculiar kind of substance, +which he named nuclein (1868). 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 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. After a few hours, the insoluble material is separated, +washed once more with water, and then extracted with a very dilute +solution of sodium hydroxide. The slightly alkaline solution, freed from +insoluble residues, is slowly added to a weak hydrochloric acid. A +precipitate forms which is separated by filtration, washed with dilute +acid, then with cold alcohol, and finally extracted by boiling alcohol. +The dried residue is the nuclein.[32] It contains six percent +phosphorus. A little more washing with water, a slightly longer +treatment with acid or alcohol gives products of lower phosphorus +content. Many experimental variations were necessary to establish the +procedure that leads to purification without alteration of the natural +substance. + +This was also true for the methods of chemical degradation, carried out +in order to find the components of nucleins in their highest state of +natural complexity. It was learned for example, that the special kind of +carbohydrate present in nucleins was very susceptible to change under +the conditions of hydrolysis by acids. Phoebus Aaron Theodor Levine +(1869-1940), therefore, used the digestion by a living organism. With E. +S. London, he introduced a solution of nucleic acid into, e.g., the +gastrointestinal segment of a dog through a gastric fistula and withdrew +the product of digestion through an intestinal fistula. Fortunately, the +products obtained in such degradations were not new in themselves. The +carbohydrate in this nucleic acid proved to be identical with D-ribose, +which Emil Fischer had artificially made from arabinose and named ribose +to indicate this relationship (1891). The nitrogenous products of the +degradation were identical with substances previously prepared in the +long study of uric acid. In the course of this study, Emil Fischer +established uric acid and a number of its derivatives as having the +elementary skeleton of what he called "pure uric acid," abbreviated to +purine. Out of Adolf Baeyer's work on barbituric acid came the knowledge +of pyrimidine and its derivatives. + +[Illustration: Figure 15.--ALBRECHT KOSSEL (1853-1927) received the +Nobel Prize in Medicine and Physiology in 1910 for his work on nucleic +substances, which contain a high proportion of phosphorus. The chemical +bonds of this phosphorus in the molecules of nucleic substances were +determined in later work. (_Photo courtesy National Library of Medicine, +Washington, D.C._)] + +From these findings, together with what Oswald Schmiedeberg (1838-1921) +had established concerning the presence of four phosphate groups in the +molecule (1899), Robert Feulgen (1884-1955) constructed the following +scheme of a nucleic acid. Feulgen's formula of 1918 is: + + Phosphoric acid--Carbohydrate--Guanine + Phosphoric acid--Carbohydrate--Cytosine + Phosphoric acid--Carbohydrate--Thymine + Phosphoric acid--Carbohydrate--Adenine + +Of the four basic components on the right, thymine occurs in the nucleic +acid from the thymus gland. Yeast contains uracil instead. The +difference between these two bases is one methyl group: thymine is a +5-methyluracil. In all of these basic substances, the structure of urea + + NH_{2} + / + C=O + \ + NH_{2} + +is involved, and they form pairs of oxidized and reduced states: + + PURINE PYRIMIDINE + + (reduced) Adenine + (oxidized) Thymine + (oxidized) Guanine + (reduced) Cytosine + + 3N = CH4 + | | + 2H--C CH5 + || || + 1N--CH6 + + Pyrimidine + + 1N==CH6 + | | H + | | 7/ N==C--NH_{2} + 2H--C C--N | | + || ||5 \ H--C C--NH + || || \ || || \ + || || CH8 || || CH + || || // || || // + 3N--C--N N--C--N + 4 9 + Adenine + Purine + + HN--C=O + | | + NH_{2}--C C--NH N==C--NH_{2} H--N--C=O + || || \ | | | | + || || CH O=C C--H O=C CH + || || // | || | || + N--C--N H--N--CH HN--CH + + Guanine Cytosine Uracil + + The carbohydrate is ribose or deoxyribose. + + CHO CHO + | | + H--C--OH HO--C--H + | | + HO--C--H HO--C--H + | | + HO--C--H HO--C--H + | | + CH_{2}OH CH_{2}OH + + Arabinose L-Ribose + + Fischer and Piloty, 1891 + + H + \(1)/-----O-----\(4) (5) + C CH--CH_{2}OH + / \(2) (3)/ + HO CH_{2}--HC(OH) + + Deoxyribose + +The exact position of phosphoric acid was established after long work +and verified by synthesis.[33] + +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. It was named adenosine triphosphate or +adenyltriphosphoric acid,[34] usually abbreviated by the symbol ATP. It +releases one phosphoric acid group very easily and goes over in the +diphosphate, ADP, but it can also lose 2 P-groups as pyrophosphoric acid +and leave the monophosphate, AMP. + + N==C--NH_{2} + | | + HC C--N +----O----+ + || || \\ | | + || || CH | OH OH | H OH + || || / | | | | | / + N--C--N-----C--C---C--C--C--O--P=O + | | | | | \ + H H H H H OH + \---------/\---------------/\--------/ + Adenine D-Ribose Phosphoric + acid + +This change of ATP was considered to be the main source of energy in +muscle contraction by Otto Meyerhof.[35] The corresponding derivatives +of guanine, cytosine, and uracil were also found, and they are active in +the temporary transfer of phosphoric acid groups in biological +processes. + +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. + +[Illustration: Figure 16.--OTTO MEYERHOF (1884-1951) received one-half +of the Nobel Prize in Medicine and Physiology in 1922 for his discovery +of the metabolism of lactic acid in muscle, which involves the action of +phosphates, especially adenosine duophosphates. (_Photo courtesy +National Library of Medicine, Washington, D.C._)] + +[Illustration: Figure 17.--ARTHUR HARDEN (1865-1940), left, AND HANS A. +S. VON EULER-CHELPIN (b. 1875), right, shared the Nobel Prize in +Chemistry in 1929. Harden received it for his research in fermentation, +which showed the influence of phosphate, particularly the formation of a +hexose diphosphate. Euler-Chelpin received his award for his research in +fermentation. He found coenzyme A which is a nucleotide containing +phosphoric acid.] + +[Illustration: Figure 18.--GEORGE DE HEVESY (b. 1885) received the Nobel +Prize in Chemistry in 1943 for his research with isotopic tracer +elements, particularly radiophosphorus of weight 32 (ordinary phosphorus +is 31).] + +[Illustration: Figure 19.--CARL F. CORI (b. 1896) AND HIS WIFE, GERTY T. +CORI (1896-1957) received part of the Nobel Prize in Medicine and +Physiology in 1947 for their study on glycogen conversion. In the course +of this study, they identified glucose 1-phosphate, now usually referred +to as "Cori ester," and its function in the glycogen cycle. (_Photo +courtesy National Library of Medicine, Washington, D.C._)] + +The study of this function is the newest phase in the history of +phosphorus and represents the culmination of the previous efforts. 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. As a result, an +important part of the new phase in phosphorus history consisted in the +study--and use--of antibiotic phosphorus compounds. + + + + +Phosphates in Biological Processes + + +The first indication that phosphorus is important for life came from the +experience that plants take it up from the substances in the soil. They +incorporate it in their body substance. 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. When yeast is dead-ground and +pressed out, the juice still has the ability to produce fermentation. + +It is strange, but in many ways characteristic for the process of +science, that the "riddle" of phosphorus in life was solved by first +eliminating life. In such "lifeless" fermentations, Arthur Harden found +that the conversion of sugar begins with the formation of a hexose +phosphate (1904). The "ferment" of yeast, called zymase, proved to be a +composite of several enzymes. Hans von Euler-Chelpin isolated one part +of zymase, which remains active even after heating its solution to the +boiling point. From 1 kilogram of yeast, he obtained 20 milligrams of +this heat-stable enzyme, which he called cozymase and identified as a +nucleotide composed of a purine, a sugar, and phosphoric acid.[36] In +the years between the two World Wars, zymase was further resolved into +more enzymes, one of them the coenzyme I, which was shown to be ADP +connected with another molecule of ribose attached to the amide of +nicotinic acid, or diphosphopyridine nucleotide: + + ^ NH_{2} + / \\ | + / \\ N ^ + || |-CONH_{2} //\ / \\ + || | | || N + \ // | || | + N_{+} N--+ | + | | \// + | | N + H--C------+ H--C------+ + | | | | + H--C--OH | H--C--OH | + | O | O + H--C--OH | H--C--OH | + | | | | + H--C------+ O O H--C------+ + | || || | + CH_{2}--O--P--O--P--O--CH_{2} + | | + O- OH + + Coenzyme I + +[Illustration: Figure 20.--FRITZ A. LIPMANN (b. 1899) shared with Hans +Adolf Krebs the Nobel Prize in Medicine and Physiology in 1953 for his +work on coenzyme A. He discovered acetyl phosphate as the substance in +bacteria, which transfers phosphate to adenylic acid.] + +[Illustration: Figure 21.--ALEXANDER R. TODD (b. 1907) received the +Nobel Prize in Chemistry in 1957 for his research on nucleotides. He +determined the position of the phosphate groups in the molecule and +confirmed it by synthesis of dinucleotide phosphates.] + +Its function is connected with the transfer of hydrogen between +intermediates formed through phosphate-transferring enzymes. +Fermentation proceeds by a cascade of processes, in which phosphate +groups swing back and forth, and equilibria between ATP with ADP play a +major role. + +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 B_{1}. +Others of the B vitamins contain phosphate groups, for example those of +the B_{2} and B_{6} group, and in B_{12}, one lonely phosphate forms a +bridge in the large molecule that contains one atom of cobalt: +C_{63}H_{90}N_{14}O_{14}PCo. 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. These two are the materials for the +reverse process in photosynthesis. When light is absorbed by the +chlorophyll of green plants, one of the initial reactions is a transfer +of hydrogen from water to a triphosphopyridine nucleotide, which later +acts to reduce the carbon dioxide. 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. Thus, the spinning glands of silkworms are +extraordinarily rich in RNA.[37] + +In his research on the radioactive isotope P^32, George de Hevesy gained +some insight into the surprising mobility of phosphates in organisms: "A +phosphate radical taken up with the food may first participate in the +phosphorylation of glucose in the intestinal mucose, soon afterwards +pass into the circulation as free phosphate, enter a red corpuscle, +become incorporated with an adenosine triphosphoric-acid molecule, +participate in a glycolytic process going on in the corpuscle, return to +circulation, penetrate into the liver cells, participate in the +formation of a phosphatide molecule, after a short interval enter the +circulation in this form, penetrate into the spleen, and leave this +organ after some time as a constituent of a lymphocyte. We may meet the +phosphate radical again as a constituent of the plasma, from which it +may find its way into the skeleton."[38] Much has been added in the last +30 years to complete this picture in many details and to extend it to +other biochemical processes, including even the changes of the pigments +in the retina in the visual process, or in the conversion of chemical +energy to light by bacteria and insects. + + + + +Medicines and Poisons + + +In the delicate balance of these processes, disturbances may occur which +can be remedied by specific phosphate-containing medicines. Thus, +adenosine phosphate has been recommended in cases of angina pectoris +and marketed under trade names like sarkolyt, or in compounds named +angiolysine. A considerable number of physiologically active organic +phosphates can be found in the patent literature.[39] 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. + +Organic esters of phosphoric acids are used as insecticides. The +hexa-ethylester of tetraphosphoric acid, prepared by Gerhard Schrader by +heating triethylphosphate with phosphorus oxychloride,[41] actually +contains tetraethylpyrophosphate (TEPP) among others. Bayer's Dipterex, +the dimethyl ester of 2,2,2-trichloro-1-hydroxyethyl-phosphonate, has +been modified to dimethyl-2,2-dichlorovinyl-phosphate and is especially +active against the oriental fruit fly.[42] + +[Illustration: Figure 22.--ARTHUR KORNBERG (b. 1918) AND SEVERO OCHOA +(b. 1905) shared the Nobel Prize in Medicine and Physiology in 1959. +Kornberg received it for research on the biological synthesis of +deoxyribonucleic acid. In particular, he found that four triphosphate +components and a small amount of the end product as a "template" had to +be present for the enzymatic synthesis. Ochoa received his share of the +prize for research in ribonucleic acid and deoxyribonucleic acid. In +particular, Ochoa synthesized polyribonucleotides and used the +radioactive isotope, P^{32}. The synthetic polyribonucleotides were +found to resemble the natural substances in all essentials.] + + Cl H O + | | || OCH_{3} + | | ||/ + Cl--C--C--P Bayer's L 13/59 + | | \ (Dipterex) + | | OCH_{3} + Cl OH + + (CH_{3})_{2}N O O N(CH_{3})_{2} + \|| ||/ + P--O--P Schradan + / \ + (CH_{3})_{2}N N(CH_{3})_{2} + + Octamethylpyrophosphoramide + +[Illustration: 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 +chronological order, they are: Eduard Buchner, Albrecht Kossel, Otto +Meyerhof, Arthur Harden, Hans von Euler-Chelpin, George de Hevesy, Carl +F. Cori, Gerty T. Cori, Fritz Lipmann, Lord Alexander Todd, Arthur +Kornberg, Severo Ochoa, and Melvin Calvin. The developers of industrial +production and commercial utilization of phosphate compounds have had +other rewards. + +Some impression of the continuing growth in this field[43] can be gained +from the following data. + +PHOSPHATE ROCK + +annually "sold or used by producer" in the United States in million long +tons (2,240 lbs.) + + 1880 0.2 + 1890 0.5 + 1900 1.5 + 1910 2.655 + 1920 4.104 + 1930 3.926 + 1940 4.003 + 1945 5.807 + 1950 11.114 + 1955 12.265 + 1955 (world: about 56) + 1960 17.202 + 1962 19.060 + +Sources: U.S. Bureau of the Census. _Historical Statistics of the United +States 1789-1945_ (1949); _Statistical Abstract of the United States._ + +ELEMENTAL PHOSPHORUS + +annually produced in the United States in short tons (2,000 lbs.) + + 1939 43,000 + 1944 85,679 + 1950 153,233 + 1956 312,200 + 1958 335,750 + 1959 366,350 + 1960 409,096 + 1961 430,617 + 1962 451,970 + +Source: U.S. Department of Commerce. + + + + +FOOTNOTES: + + +[1] WILHELM HOMBERG, _Memoires Academie, 1666-1699_ (Paris, 1730), vol. +10, under date of April 30, 1692, pp. 57-61. + +[2] FORTUNIO LICETUS, _Lithiophosphorus sive de lapide Bononiensi_ +(Venice, 1640). + +[3] Cited in PETER JOSEPH MACQUER _Chymisches Woerterbuch_, 2nd ed. +(Leipzig: Weidmann, 1789), vol. 4, p. 508, footnote "c" as "Kletwich (de +phosph. liqu. et solid. 1689, Thes. II)." + +[4] FERDINAND HOEFER, _Histoire de la Chimie_ (Paris, 1843), vol. 1, p. +339. + +[5] G. W. VON LEIBNIZ, _Memoires Academie_ (Paris, 1682); _Akademie der +Wissenschaften, Miscellanea Berolinensia_ (Berlin, 1710), vol. 1, p. 91. + +[6] JEAN HELLOT, _Memoires Academie 1737_ (Paris, 1766), under date of +November 13, 1737, pp. 342-378. + +[7] MACQUER, op. cit. (footnote 3), p. 551. + +[8] A. S. MARGGRAF, _Akademie der Wissenschaften, Miscellanea +Berolinensia_ (Berlin, 1743), vol. 7, 342 ff.; see also WILHELM OSTWALD +_Klassiker der Exakten Naturwissenschaften_ (Leipzig: Engelmann, 1913), +no. 187. + +[9] G. HANCKEWITZ, [Hankwitz], _Philosophical Transactions of the Royal +Society of London_, 1724-1734, abridged (London, 1809), vol. 7, pp. +596-602. + +[10] ANTOINE LAURENT LAVOISIER, "Sur la Combustion du Phosphore de +Kunckel, Et sur la nature de l'acide qui resulte de cette Combustion," +_Memoires Academie 1777_, (Paris, 1780), pp. 65-78. + +[11] GUYTON DE MORVEAU and others, _Methode de Nomenclature Chimique_, +Proposee par MM. de Morveau, Lavoisier, Bertholet, & de Fourcroy (Paris, +1787), plate 9. + +[12] MACQUER, op. cit. (footnote 3), p. 513. + +[13] MARIE BOAS, _Robert Boyle and Seventeenth Century Chemistry_ (New +York: Cambridge University Press, 1958), p. 226; see also WYNDHAM MILES, +"The History of Dr. Brand's Phosphorus Elementarus," _Armed Forces +Chemical Journal_ (November-December 1958), p. 25. + +[14] ARCHIBALD CLOW and NAN L. CLOW, _The Chemical Revolution_ (London: +Batchworth Press, 1952), p. 451. + +[15] EMILE KOPP, _Comptes-rendus hebdomadaires des Seances de l'Academie +des Sciences, Paris_ (1844), vol. 18, p. 871; WILHELM HITTORF, _Annalen +der Chemie und Pharmazie_, suppl. to vol. 4, p. 37; ANTON SCHROeTTER, +_Annales de Chimie et de Physique_, series 3, vol. 24 (1848), p. 406; +see also Schroetter's report on "Phosphor und Zuendwaaren" in A. W. VON +HOFMANN, _Bericht ueber die Entwicklung der Chemischen Industrie_ +(Braunschweig: Vieweg, 1875), pp. 219-246. + +[16] R. GLAUBER, _Furni Novi Philosphici_ (Amsterdam, 1649), vol. 2, pp. +12 ff. + +[17] HERMANN SCHELENZ, _Geschichte der Pharmazie_ (Berlin: Springer, +1904), p. 598. + +[18] J. PERSONNE, _Comptes-rendus ..._, Paris (1869), vol. 68, pp. +543-546. + +[19] A. WURTZ, _Dictionnaire de Chimie_ (Paris, 1876), vol. 2, part 2, +p. 951. + +[20] KARL W. SCHEELE, _Nachgelassene Briefe und Aufzeichnungen_, edit. +A. E. Nordenskioeld (Stockholm: Norstedt, 1892), pp. 38, 144. + +[21] J. J. BERZELIUS, _Lehrbuch_, transl. F. Woehler (Dresden, 1827), +vol. 3, part 1, p. 96. + +[22] THOMAS GRAHAM, _Philosophical Transactions of the Royal Society of +London_ (1833), pp. 253-284. + +[23] JUSTUS LIEBIG'S _Annalen der Pharmacie_ (1838), vol. 26, p. 113 ff. + +[24] A. WURTZ, _Annales de Chimie et de Physique_, series 3, vol. 16 +(1846), p. 190. + +[25] CARROLL D. WRIGHT, _The Phosphate Industry in the United States_, +sixth special report of the Commissioner of Labor (Washington, 1893). + +[26] J. STOKLASA, _Biochemischer Kreislauf des Phosphat-Ions im Boden, +Centralblatt fuer Bakteriologie ..._ (Jena: Fischer, March 22, 1911), +vol. 29, nos. 15-19. + +[27] N. T. GOBLEY, _Comptes-rendus_ ..., Paris (1845), vol. 21, p. 718. + +[28] A. WURTZ, _Comptes-rendus_ ..., Paris (1868), vol. 66, p. 772. + +[29] L. THUDICHUM, _Die chemische Constitution des Gehirns des Menschen +und der Tiere_ (1901); see also H. WITTCOFF, THE PHOSPHATIDES (New York: +Reinhold, 1951). + +[30] WILLIAM CROOKES, _British Association for the Advancement of +Science, Reports_ (1887), sec. B, p. 573. + +[31] J. E. COURTOIS and A. LINO, _Progress in the Chemistry of Organic +Natural Products_, edit. L. Zechmeister (Vienna: Springer Verlag, 1961), +vol. 19, p. 316-373. + +[32] A. WURT, _Dictionnaire de Chimie_, supp. part 2, [n.d.] p. 1087; A. +KOSSEL, _Zeitschrift fuer physiologische Chemie_, series 3 (1879), p. +284. + +[33] ALEXANDER TODD, _Les Prix Nobel en 1957_ (Stockholm). + +[34] HANS VON EULER-CHELPIN, _Les Prix Nobel en 1929_ (Stockholm). + +[35] O. MEYERHOF and E. LUNDSGAARD, _Naturwissenschaften_ (Berlin, +1930), vol. 18, pp. 330, 787. + +[36] K. LOHMANN, _Naturwissenschaften_ (Berlin, 1929), vol. 17, p. 624; +C. H. FISKE and Y. SUBBAROW, _Science_ (Washington, 1929), vol. 70, p. +381 f. + +[37] J. BRACHET, _Scientia, Revista di Scienza_ (1960), vol. 95, p. 119. + +[38] GEORGE DE HEVESY, _Les Prix Nobel en 1940_ (Stockholm). See also +EDUARD FARBER, _Nobel Prize Winners in Chemistry_, 2nd ed. (New York: +Schuman, 1963), p. 179. + +[39] See, e.g., _Chemical Week_, vol. 77 (September 3, 1955), p. 79 f.; +J. BOLLE, _Chimie et Industrie_ (1960), vol. 83, p. 252. + +[40] W. LANGE, _Berichte der Deutschen Chemischen Gesellschaft_ (Berlin, +1929), vol. 62, p. 793; vol. 65 (1932), p. 1598. + +[41] GERHARD SCHRADER, U.S. patent 2,336,302 of 1943 (priority in +Germany, 1938); S. A. HALL and M. JACOBSON, _Industrial and Engineering +Chemistry_ (1943), vol. 40, p. 694. + +[42] A. M. MATTSEN and others, _Journal of Agriculture and Food +Chemistry_ (1955), vol. 3, p. 319. + +[43] JOHN B. VAN WAZER, _Phosphorus and its Compounds_, 2 vols. +(vol. 1, _Chemistry_; vol. 2 _Technology, Biological Functions and +Applications_, New York: Interscience, 1958, 1961. + + * * * * * + +U.S. GOVERNMENT PRINTING OFFICE: 1965 + +For sale by the Superintendent of Documents, U.S. Government Printing +Office Washington, D.C. 20402--Price 25 cents + + + + +INDEX + + +Aristotle, 179 + + +Baeyer, Adolf, 193 + +Bechil, Achild, 179 + +Berthelot, Marcellin, 189 + +Berzelius, Joens Jakob, 182 + +Black and Bell, plant at Stratford, 182 + +Boussingault, Jean Baptiste, 185 + +Boyle, Robert, 178, 179 + +Brand, H., 178, 179 + +Buchner, Hans, 197, 200 + + +Calvin, Melvin, 200 + +Casciarolo, Vicenzo, 179 + +Chevreul, Michel, 189 + +Cori, Carl F., 200 + +Cori, Gerti T., 200 + +Crookes, William, 192 + + +Davy, Sir Humphry, 185 + +De Hevesy, George, 198, 200 + +De la Vega, Garcilaso, 185 + +De Saussure, Theodore, 185 + + +Euler-Chelpin, Hans von, 197, 200 + + +Fernelius, Jean, 179 + +Feulgen, Robert, 193 + +Fischer, Emil, 193 + + +Gahn, Johann Gottlieb, 182 + +Gay-Lussac, Joseph Louis, 182 + +Gobley, Nicolas Theodore, 191 + +Graham, Thomas, 182, 183, 185 + + +Hankwitz, Gottfried, 180 + +Harden, Arthur, 197, 200 + +Hartmann, Immanuel Peter, 181 + +Hellot, Jean, 180 + +Henry II, King of France, 179 + +Hittorf, Wilhelm, 181 + +Hoefer, Ferdinand, 179 + +Holmberg, Wilhelm, 178 + +Hoppe-Seyler, Felix, 193 + +Humboldt, Alexander von, 185 + +Huygens, Christiaan, 179 + + +Incas, 185 + + +Kletwich, Johann Christopher, 179 + +Koppe, Emile, 181 + +Kornberg, Arthur, 200 + +Kossel, Albrecht, 200 + +Kraft, Johann Daniel, 179 + +Kramer, Dr. ----, 181 + +Kunckel, Johann, 179 + + +Lange, W., 199 + +Lavoisier, Antoine Laurent, 181, 185 + +Laws, John Bennet, 186 + +Leibnitz, Gottfried Wilhelm von, 179 + +Lennox, Charles, third Duke of Richmond, 185 + +Leonhardi, Johann Gottfried, 179 + +Levine, Phoebus Aaron Theodor, 193 + +Liebig, Justus, 183, 185, 186 + +Liebreich, Oscar, 191 + +Lipmann, Fritz, 200 + +London, E. S., 193 + + +Macquer, Peter Joseph, 180 + +Marggraf, Andreas Sigismund, 180 + +Meyerhof, Otto, 194, 200 + +Miescher, Johann Friedrich, 192 + +Muspratt, James, 186 + + +Nietzsche, Friedrich, 186, 187, 189 + + +Ochoa, Severo, 200 + + +Pelouze, Theophile Juste, 189 + + +Rouelle, Guillaume Francois, 181 + + +Scheele, Karl W., 182 + +Schmiedeberg, Oswald, 193 + +Schrader, Gerhard, 199 + +Schroetter, Anton, 181 + +Stoklasa, Julius, 186 + +Strecker, Adolf Friedrich, 191 + + +Thudichum, Ludwig, 192 + +Todd, Lord Alexander, 200 + + +Willm, Edmond, 182 + +Willstaetter, Richard, 191 + +Wurtz, Adolphe, 185, 191 + + + + +Transcriber's Notes + + +The following typographical errors have been corrected: + + Page 180 "_Abfaellen_, Vieweg, Braunschweig," - had "Viewig". + Page 188 "wires _d_ from the dynamo D" - had "dynano". + Page 191 "phosphate are attached, for example," - had "attached, For". + Page 192 "But phosphatides occur" - had "phosphatide soccur". + Page 193 "the nucleic acid from the thymus" - had "nucleidic". + Page 199 "acetylcholine esterase." - had "acetylcholin". + Page 200 "George de Hevesy, Carl F. Cori," - comma added after Hevesy. + Footnote [39] "See, e.g., _Chemical Week_, vol. 77" - had "See. e.g." + Index Entry: "Gahn, Johann Gottlieb, 182" - had "Gaehn" + +The spelling of "Bertholet" [Claude Louis Berthollet] is as given on the +original title page of the work referenced in this paper. + +Inconsistent hyphenation of chemical names has been retained. + + + + + +End of the Project Gutenberg EBook of History of Phosphorus, by Eduard Farber + +*** END OF THIS PROJECT GUTENBERG EBOOK HISTORY OF PHOSPHORUS *** + +***** This file should be named 33766.txt or 33766.zip ***** +This and all associated files of various formats will be found in: + https://www.gutenberg.org/3/3/7/6/33766/ + +Produced by Chris Curnow, Joseph Cooper, Louise Pattison +and the Online Distributed Proofreading Team at +https://www.pgdp.net + + +Updated editions will replace the previous one--the old editions +will be renamed. + +Creating the works from public domain print editions means that no +one owns a United States copyright in these works, so the Foundation +(and you!) can copy and distribute it in the United States without +permission and without paying copyright royalties. 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