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
*** 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 Wolfenbüttel, 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, _Précis de Chimie industrielle_, Paris,
1849; reproduced from HUGO FLECK, _Die Fabrikation chemischer Produkte
aus thierischen Abfällen_, 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 _Méthode 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 François 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 Émile Kopp (1844), by Wilhelm Hittorf
(1824-1914) and, in its practical application, by Anton Schrötter
(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° 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 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. 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-Kröner, 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, Théophile 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 Böttger, 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 Théodore Gobley[27] (1811-1876), because he obtained it from egg
yolk (in Greek, _lékidos_). 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 Willstätter 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, _Mémoires Académie, 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 Wörterbuch_, 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, _Mémoires Académie_ (Paris, 1682); _Akademie der
Wissenschaften, Miscellanea Berolinensia_ (Berlin, 1710), vol. 1, p. 91.
[6] JEAN HELLOT, _Mémoires Académie 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,"
_Mémoires Académie 1777_, (Paris, 1780), pp. 65-78.
[11] GUYTON DE MORVEAU and others, _Méthode de Nomenclature Chimique_,
Proposée 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] ÉMILE KOPP, _Comptes-rendus hebdomadaires des Séances de l'Académie
des Sciences, Paris_ (1844), vol. 18, p. 871; WILHELM HITTORF, _Annalen
der Chemie und Pharmazie_, suppl. to vol. 4, p. 37; ANTON SCHRÖTTER,
_Annales de Chimie et de Physique_, series 3, vol. 24 (1848), p. 406;
see also Schrötter's report on "Phosphor und Zündwaaren" in A. W. VON
HOFMANN, _Bericht über 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. Nordenskiöld (Stockholm: Norstedt, 1892), pp. 38, 144.
[21] J. J. BERZELIUS, _Lehrbuch_, transl. F. Wöhler (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 für 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 für 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, Jöns 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, Théodore, 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 Théodore, 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, Émile, 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, Théophile Juste, 189
Rouelle, Guillaume François, 181
Scheele, Karl W., 182
Schmiedeberg, Oswald, 193
Schrader, Gerhard, 199
Schrötter, Anton, 181
Stoklasa, Julius, 186
Strecker, Adolf Friedrich, 191
Thudichum, Ludwig, 192
Todd, Lord Alexander, 200
Willm, Edmond, 182
Willstätter, Richard, 191
Wurtz, Adolphe, 185, 191
Transcriber's Notes
The following typographical errors have been corrected:
Page 180 "_Abfällen_, 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 "Gähn"
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 33766-8.txt or 33766-8.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. Special rules,
set forth in the General Terms of Use part of this license, apply to
copying and distributing Project Gutenberg-tm electronic works to
protect the PROJECT GUTENBERG-tm concept and trademark. Project
Gutenberg is a registered trademark, and may not be used if you
charge for the eBooks, unless you receive specific permission. If you
do not charge anything for copies of this eBook, complying with the
rules is very easy. You may use this eBook for nearly any purpose
such as creation of derivative works, reports, performances and
research. They may be modified and printed and given away--you may do
practically ANYTHING with public domain eBooks. Redistribution is
subject to the trademark license, especially commercial
redistribution.
*** START: FULL LICENSE ***
THE FULL PROJECT GUTENBERG LICENSE
PLEASE READ THIS BEFORE YOU DISTRIBUTE OR USE THIS WORK
To protect the Project Gutenberg-tm mission of promoting the free
distribution of electronic works, by using or distributing this work
(or any other work associated in any way with the phrase "Project
Gutenberg"), you agree to comply with all the terms of the Full Project
Gutenberg-tm License (available with this file or online at
https://gutenberg.org/license).
Section 1. General Terms of Use and Redistributing Project Gutenberg-tm
electronic works
1.A. By reading or using any part of this Project Gutenberg-tm
electronic work, you indicate that you have read, understand, agree to
and accept all the terms of this license and intellectual property
(trademark/copyright) agreement. If you do not agree to abide by all
the terms of this agreement, you must cease using and return or destroy
all copies of Project Gutenberg-tm electronic works in your possession.
If you paid a fee for obtaining a copy of or access to a Project
Gutenberg-tm electronic work and you do not agree to be bound by the
terms of this agreement, you may obtain a refund from the person or
entity to whom you paid the fee as set forth in paragraph 1.E.8.
1.B. "Project Gutenberg" is a registered trademark. It may only be
used on or associated in any way with an electronic work by people who
agree to be bound by the terms of this agreement. There are a few
things that you can do with most Project Gutenberg-tm electronic works
even without complying with the full terms of this agreement. See
paragraph 1.C below. There are a lot of things you can do with Project
Gutenberg-tm electronic works if you follow the terms of this agreement
and help preserve free future access to Project Gutenberg-tm electronic
works. See paragraph 1.E below.
1.C. The Project Gutenberg Literary Archive Foundation ("the Foundation"
or PGLAF), owns a compilation copyright in the collection of Project
Gutenberg-tm electronic works. Nearly all the individual works in the
collection are in the public domain in the United States. If an
individual work is in the public domain in the United States and you are
located in the United States, we do not claim a right to prevent you from
copying, distributing, performing, displaying or creating derivative
works based on the work as long as all references to Project Gutenberg
are removed. Of course, we hope that you will support the Project
Gutenberg-tm mission of promoting free access to electronic works by
freely sharing Project Gutenberg-tm works in compliance with the terms of
this agreement for keeping the Project Gutenberg-tm name associated with
the work. You can easily comply with the terms of this agreement by
keeping this work in the same format with its attached full Project
Gutenberg-tm License when you share it without charge with others.
1.D. The copyright laws of the place where you are located also govern
what you can do with this work. Copyright laws in most countries are in
a constant state of change. If you are outside the United States, check
the laws of your country in addition to the terms of this agreement
before downloading, copying, displaying, performing, distributing or
creating derivative works based on this work or any other Project
Gutenberg-tm work. The Foundation makes no representations concerning
the copyright status of any work in any country outside the United
States.
1.E. Unless you have removed all references to Project Gutenberg:
1.E.1. The following sentence, with active links to, or other immediate
access to, the full Project Gutenberg-tm License must appear prominently
whenever any copy of a Project Gutenberg-tm work (any work on which the
phrase "Project Gutenberg" appears, or with which the phrase "Project
Gutenberg" is associated) is accessed, displayed, performed, viewed,
copied or distributed:
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
1.E.2. If an individual Project Gutenberg-tm electronic work is derived
from the public domain (does not contain a notice indicating that it is
posted with permission of the copyright holder), the work can be copied
and distributed to anyone in the United States without paying any fees
or charges. If you are redistributing or providing access to a work
with the phrase "Project Gutenberg" associated with or appearing on the
work, you must comply either with the requirements of paragraphs 1.E.1
through 1.E.7 or obtain permission for the use of the work and the
Project Gutenberg-tm trademark as set forth in paragraphs 1.E.8 or
1.E.9.
1.E.3. If an individual Project Gutenberg-tm electronic work is posted
with the permission of the copyright holder, your use and distribution
must comply with both paragraphs 1.E.1 through 1.E.7 and any additional
terms imposed by the copyright holder. Additional terms will be linked
to the Project Gutenberg-tm License for all works posted with the
permission of the copyright holder found at the beginning of this work.
1.E.4. Do not unlink or detach or remove the full Project Gutenberg-tm
License terms from this work, or any files containing a part of this
work or any other work associated with Project Gutenberg-tm.
1.E.5. Do not copy, display, perform, distribute or redistribute this
electronic work, or any part of this electronic work, without
prominently displaying the sentence set forth in paragraph 1.E.1 with
active links or immediate access to the full terms of the Project
Gutenberg-tm License.
1.E.6. You may convert to and distribute this work in any binary,
compressed, marked up, nonproprietary or proprietary form, including any
word processing or hypertext form. However, if you provide access to or
distribute copies of a Project Gutenberg-tm work in a format other than
"Plain Vanilla ASCII" or other format used in the official version
posted on the official Project Gutenberg-tm web site (www.gutenberg.org),
you must, at no additional cost, fee or expense to the user, provide a
copy, a means of exporting a copy, or a means of obtaining a copy upon
request, of the work in its original "Plain Vanilla ASCII" or other
form. Any alternate format must include the full Project Gutenberg-tm
License as specified in paragraph 1.E.1.
1.E.7. Do not charge a fee for access to, viewing, displaying,
performing, copying or distributing any Project Gutenberg-tm works
unless you comply with paragraph 1.E.8 or 1.E.9.
1.E.8. You may charge a reasonable fee for copies of or providing
access to or distributing Project Gutenberg-tm electronic works provided
that
- You pay a royalty fee of 20% of the gross profits you derive from
the use of Project Gutenberg-tm works calculated using the method
you already use to calculate your applicable taxes. The fee is
owed to the owner of the Project Gutenberg-tm trademark, but he
has agreed to donate royalties under this paragraph to the
Project Gutenberg Literary Archive Foundation. Royalty payments
must be paid within 60 days following each date on which you
prepare (or are legally required to prepare) your periodic tax
returns. Royalty payments should be clearly marked as such and
sent to the Project Gutenberg Literary Archive Foundation at the
address specified in Section 4, "Information about donations to
the Project Gutenberg Literary Archive Foundation."
- You provide a full refund of any money paid by a user who notifies
you in writing (or by e-mail) within 30 days of receipt that s/he
does not agree to the terms of the full Project Gutenberg-tm
License. You must require such a user to return or
destroy all copies of the works possessed in a physical medium
and discontinue all use of and all access to other copies of
Project Gutenberg-tm works.
- You provide, in accordance with paragraph 1.F.3, a full refund of any
money paid for a work or a replacement copy, if a defect in the
electronic work is discovered and reported to you within 90 days
of receipt of the work.
- You comply with all other terms of this agreement for free
distribution of Project Gutenberg-tm works.
1.E.9. If you wish to charge a fee or distribute a Project Gutenberg-tm
electronic work or group of works on different terms than are set
forth in this agreement, you must obtain permission in writing from
both the Project Gutenberg Literary Archive Foundation and Michael
Hart, the owner of the Project Gutenberg-tm trademark. Contact the
Foundation as set forth in Section 3 below.
1.F.
1.F.1. Project Gutenberg volunteers and employees expend considerable
effort to identify, do copyright research on, transcribe and proofread
public domain works in creating the Project Gutenberg-tm
collection. Despite these efforts, Project Gutenberg-tm electronic
works, and the medium on which they may be stored, may contain
"Defects," such as, but not limited to, incomplete, inaccurate or
corrupt data, transcription errors, a copyright or other intellectual
property infringement, a defective or damaged disk or other medium, a
computer virus, or computer codes that damage or cannot be read by
your equipment.
1.F.2. LIMITED WARRANTY, DISCLAIMER OF DAMAGES - Except for the "Right
of Replacement or Refund" described in paragraph 1.F.3, the Project
Gutenberg Literary Archive Foundation, the owner of the Project
Gutenberg-tm trademark, and any other party distributing a Project
Gutenberg-tm electronic work under this agreement, disclaim all
liability to you for damages, costs and expenses, including legal
fees. YOU AGREE THAT YOU HAVE NO REMEDIES FOR NEGLIGENCE, STRICT
LIABILITY, BREACH OF WARRANTY OR BREACH OF CONTRACT EXCEPT THOSE
PROVIDED IN PARAGRAPH 1.F.3. YOU AGREE THAT THE FOUNDATION, THE
TRADEMARK OWNER, AND ANY DISTRIBUTOR UNDER THIS AGREEMENT WILL NOT BE
LIABLE TO YOU FOR ACTUAL, DIRECT, INDIRECT, CONSEQUENTIAL, PUNITIVE OR
INCIDENTAL DAMAGES EVEN IF YOU GIVE NOTICE OF THE POSSIBILITY OF SUCH
DAMAGE.
1.F.3. LIMITED RIGHT OF REPLACEMENT OR REFUND - If you discover a
defect in this electronic work within 90 days of receiving it, you can
receive a refund of the money (if any) you paid for it by sending a
written explanation to the person you received the work from. If you
received the work on a physical medium, you must return the medium with
your written explanation. The person or entity that provided you with
the defective work may elect to provide a replacement copy in lieu of a
refund. If you received the work electronically, the person or entity
providing it to you may choose to give you a second opportunity to
receive the work electronically in lieu of a refund. If the second copy
is also defective, you may demand a refund in writing without further
opportunities to fix the problem.
1.F.4. Except for the limited right of replacement or refund set forth
in paragraph 1.F.3, this work is provided to you 'AS-IS' WITH NO OTHER
WARRANTIES OF ANY KIND, EXPRESS OR IMPLIED, INCLUDING BUT NOT LIMITED TO
WARRANTIES OF MERCHANTIBILITY OR FITNESS FOR ANY PURPOSE.
1.F.5. Some states do not allow disclaimers of certain implied
warranties or the exclusion or limitation of certain types of damages.
If any disclaimer or limitation set forth in this agreement violates the
law of the state applicable to this agreement, the agreement shall be
interpreted to make the maximum disclaimer or limitation permitted by
the applicable state law. The invalidity or unenforceability of any
provision of this agreement shall not void the remaining provisions.
1.F.6. INDEMNITY - You agree to indemnify and hold the Foundation, the
trademark owner, any agent or employee of the Foundation, anyone
providing copies of Project Gutenberg-tm electronic works in accordance
with this agreement, and any volunteers associated with the production,
promotion and distribution of Project Gutenberg-tm electronic works,
harmless from all liability, costs and expenses, including legal fees,
that arise directly or indirectly from any of the following which you do
or cause to occur: (a) distribution of this or any Project Gutenberg-tm
work, (b) alteration, modification, or additions or deletions to any
Project Gutenberg-tm work, and (c) any Defect you cause.
Section 2. Information about the Mission of Project Gutenberg-tm
Project Gutenberg-tm is synonymous with the free distribution of
electronic works in formats readable by the widest variety of computers
including obsolete, old, middle-aged and new computers. It exists
because of the efforts of hundreds of volunteers and donations from
people in all walks of life.
Volunteers and financial support to provide volunteers with the
assistance they need are critical to reaching Project Gutenberg-tm's
goals and ensuring that the Project Gutenberg-tm collection will
remain freely available for generations to come. In 2001, the Project
Gutenberg Literary Archive Foundation was created to provide a secure
and permanent future for Project Gutenberg-tm and future generations.
To learn more about the Project Gutenberg Literary Archive Foundation
and how your efforts and donations can help, see Sections 3 and 4
and the Foundation web page at https://www.pglaf.org.
Section 3. Information about the Project Gutenberg Literary Archive
Foundation
The Project Gutenberg Literary Archive Foundation is a non profit
501(c)(3) educational corporation organized under the laws of the
state of Mississippi and granted tax exempt status by the Internal
Revenue Service. The Foundation's EIN or federal tax identification
number is 64-6221541. Its 501(c)(3) letter is posted at
https://pglaf.org/fundraising. Contributions to the Project Gutenberg
Literary Archive Foundation are tax deductible to the full extent
permitted by U.S. federal laws and your state's laws.
The Foundation's principal office is located at 4557 Melan Dr. S.
Fairbanks, AK, 99712., but its volunteers and employees are scattered
throughout numerous locations. Its business office is located at
809 North 1500 West, Salt Lake City, UT 84116, (801) 596-1887, email
[email protected]. Email contact links and up to date contact
information can be found at the Foundation's web site and official
page at https://pglaf.org
For additional contact information:
Dr. Gregory B. Newby
Chief Executive and Director
[email protected]
Section 4. Information about Donations to the Project Gutenberg
Literary Archive Foundation
Project Gutenberg-tm depends upon and cannot survive without wide
spread public support and donations to carry out its mission of
increasing the number of public domain and licensed works that can be
freely distributed in machine readable form accessible by the widest
array of equipment including outdated equipment. Many small donations
($1 to $5,000) are particularly important to maintaining tax exempt
status with the IRS.
The Foundation is committed to complying with the laws regulating
charities and charitable donations in all 50 states of the United
States. Compliance requirements are not uniform and it takes a
considerable effort, much paperwork and many fees to meet and keep up
with these requirements. We do not solicit donations in locations
where we have not received written confirmation of compliance. To
SEND DONATIONS or determine the status of compliance for any
particular state visit https://pglaf.org
While we cannot and do not solicit contributions from states where we
have not met the solicitation requirements, we know of no prohibition
against accepting unsolicited donations from donors in such states who
approach us with offers to donate.
International donations are gratefully accepted, but we cannot make
any statements concerning tax treatment of donations received from
outside the United States. U.S. laws alone swamp our small staff.
Please check the Project Gutenberg Web pages for current donation
methods and addresses. Donations are accepted in a number of other
ways including including checks, online payments and credit card
donations. To donate, please visit: https://pglaf.org/donate
Section 5. General Information About Project Gutenberg-tm electronic
works.
Professor Michael S. Hart was the originator of the Project Gutenberg-tm
concept of a library of electronic works that could be freely shared
with anyone. For thirty years, he produced and distributed Project
Gutenberg-tm eBooks with only a loose network of volunteer support.
Project Gutenberg-tm eBooks are often created from several printed
editions, all of which are confirmed as Public Domain in the U.S.
unless a copyright notice is included. Thus, we do not necessarily
keep eBooks in compliance with any particular paper edition.
Most people start at our Web site which has the main PG search facility:
https://www.gutenberg.org
This Web site includes information about Project Gutenberg-tm,
including how to make donations to the Project Gutenberg Literary
Archive Foundation, how to help produce our new eBooks, and how to
subscribe to our email newsletter to hear about new eBooks.
