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History of chromatography : ウィキペディア英語版
History of chromatography
The history of chromatography spans from the mid-19th century to the 21st. Chromatography, literally "color writing",〔(【引用サイトリンク】url=http://www.etymonline.com/index.php?term=chromatography&allowed_in_frame=0 )〕 was used—and named— in the first decade of the 20th century, primarily for the separation of plant pigments such as chlorophyll (which is green) and carotenoids (which are orange and yellow). New forms of chromatography developed in the 1930s and 1940s made the technique useful for a wide range of separation processes and chemical analysis tasks, especially in biochemistry.
==Precursors==

The earliest use of chromatography—passing a mixture through an inert material to create separation of the solution components based on differential adsorption—is sometimes attributed to German chemist Friedlieb Ferdinand Runge, who in 1855 described the use of paper to analyze dyes. Runge dropped spots of different inorganic chemicals onto circles of filter paper already impregnated with another chemical, and reactions between the different chemicals created unique color patterns. According to historical analysis of L. S. Ettre, however, Runge's work had "nothing to do with chromatography" (and instead should be considered a precursor of chemical spot tests such as the Schiff test).〔Ettre (2001), p. 410.〕〔L.S. Ettre = Leslie Stephen Ettre (1922-2010), Hungarian-American chemist, author of several publications on the history of chromatography.〕
In the 1860s, Christian Friedrich Schönbein and his student Friedrich Goppelsroeder published the first attempts to study the different rates at which different substances move through filter paper.〔Christian Schönbein (1861) ("Ueber einige durch die Haarröhrchenanziehung des Papiers hervorgebrachten Trennungswirkungen" ) (On some separation effects produced by capillary attraction of paper), ''Verhandlungen der Naturforschenden Gesellschaft zu Basel'', 3 (2) : 249-255.〕〔Friedrich Goppelsröder (1861) ("Ueber ein Verfahren, die Farbstoffe in ihren Gemischen zu erkennen" ) (On a method for detecting the colorings in mixtures of them), ''Verhandlungen der Naturforschenden Gesellschaft zu Basel'', 3 (2) : 268-275.
See also: Friedrich Goppelsroeder, (''Capillaranalyse beruhend auf Capillaritäts- und Adsorptionserscheinungen'' … ) (analysis based on phenomena of capillarity and adsorption … ) (Basel, Switzerland: Emil Birkhäuser, 1901).〕 Schönbein, who thought capillary action (rather than adsorption) was responsible for the movement, called the technique capillary analysis, and Goppelsroeder spent much of his career using capillary analysis to test the movement rates of a wide variety of substances. Unlike modern paper chromatography, capillary analysis used reservoirs of the substance being analyzed, creating overlapping zones of the solution components rather than separate points or bands.〔Ettre (2001), pp. 411-412.〕〔However, in his book ''Capillaranalyse … '' (1901), Goppelsroeder stated (p. 168) that he had been separating plant colorants since 1880, and that he had achieved complete separations of those colorants. From p. 166:
''"Bietet sich auch dem Auge bei Betrachtung der verschiedenen Pflanzenorgane eine wunderbare Mannigfaltigkeit der Farben und Farbenabstufungen dar, so bleibt ihm doch die wichtige Thatsache verborgen, dass meist nicht nur ein einziger Farbstoff, sondern mehrere nebeneinander in demselben Organe vorkommen. Während das Auge nur eine Färbung erkennt und wir desshalb glauben, dass dieselbe einem bestimmten einzelnen Farbstoff angehöre, lässt uns die Capillaranalyse meist mehrere verschieden gefärbte Zonen auf den Capillarstreifen in bestimmer, sehr oft von farblosen Zonen unterbrochener Reihenfolge erkennen. Das Chlorophyll oder Blattgrün z.B. findet sich nicht nur in den grünen, sonder auch in anders gefärbten Organen, beispielsweise verdeckt durch die rote Färbung des Zellsafts in den Blättern der Blutbuche neben dem roten Anthokyan, sowie neben roten Phycoerythrin in den Rotalgen, den Florideen. Diese verschiedenen Farbstoffe lassen sich durch Capillaranalyse in den gemeinschaftlichen Auszügen, ohne irgend welche sonstige Trennungsmanipulationen nebeneinander nachweisen. Sind sie capillarisch in Zonen getrennt, dann genügt deren spectroscopische und chemische Prüfung zur endgiltigen Feststellung ihrer Natur."''
(If a wonderful variety of colors and color gradations presents itself to the eye when looking at the different plant organs, yet the important fact remains hidden to it: that usually not only a single colorant but several occur side by side in the same organs. While the eye perceives only one color and we believe therefore that it belongs to a certain individual colorant, capillary analysis (paper chromatography ) allows us to detect usually several differently colored zones on the capillary strips in certain sequences (are ) very often interrupted by colorless zones. Chlorophyll or leaf green, for example, is found not only in the green, but also in differently colored organs; for example, obscured by the red color of the protoplasm in the leaves of the copper beech together with red anthocyanin, as well as together with red phycoerythrin in red algae, the ''Florideae''. These various colorants can be detected by capillary analysis in extracts where they are present in combination, without any other concurrent separation treatments. If they are separated into zones by capillarity, then their spectroscopic and chemical examination suffices for the conclusive ascertaining of their nature.)〕
Work on capillary analysis continued, but without much technical development, well into the 20th century. The first significant advances over Goppelsroeder's methods came with the work of Raphael E. Liesegang: in 1927, he placed filter strips in closed containers with atmospheres saturated by solvents, and in 1943 he began using discrete spots of sample adsorbed to filter paper, dipped in pure solvent to achieve separation. This method, essentially identical to modern paper chromatography, was published just before the independent—and far more influential—work of Archer Martin and his collaborators that inaugurated the widespread use of paper chromatography.〔Ettre (2001), p. 412.〕
In 1897, the American chemist David Talbot Day (1859-1915), then serving with the U.S. Geological Survey, observed that crude petroleum generated bands of color as it seeped upwards through finely divided clay or limestone.〔David T. Day (1897) ("A suggestion as to the origin of Pennsylvania petroleum," ) ''Proceedings of the American Philosophical Society'', 36 (154) : 112-115. From page 115: " … by experimental work it may easily be demonstrated that if we saturate a limestone such as the Trenton limestone with the oils characteristic of that rock and exert slight pressure upon it, so that it may flow upward through finely divided clay, it is easy to change it in its color … "〕 In 1900, he reported his findings at the First International Petroleum Congress in Paris, where they created a sensation.〔See:
* Day, David T() (1900) "La variation des caracteres des huiles brutes de Pensylvanie et de l'Ohio" (Variation of the character of crude oil from Pennsylvania and Ohio), ''Congrès international du pétrole, première session, Paris, 1900. Notes, mémoires et documents '', Paris, 1 : 52-56.
* Reprinted in: Day, David F. (November 1901) ("La variation des caracteres des huiles brutes de Pensylvanie et de l'Ohio" ) (Variation of the character of crude oil from Pennsylvania and Ohio), ''Revue de Chimie industrielle'', 12 (143) : 308-310.
* Reprinted in English in: David T. Day (1900) ("The variation in the character of Pennylvania and Ohio crude oils," ) ''The Petroleum Review'', supplement to volume 3, 3 : 9-10.〕〔Soon after David T. Day's discovery, other researchers investigated the diffusion of petroleum through finely divided earths; viz, the German organic chemist Karl Engler (1842-1925) of the Technical University Karlsruhe and the American chemist Joseph Elliot Gilpin (1866-1924) of Johns Hopkins University. See:
* L. S. Ettre (February 1995) "Early petroleum chemists and the beginnings of chromatography," ''Chromatographia'', 40 : 207-216.
* Herbert Weil and Trevor I. Williams (1950 Dec. 9) Letters to Nature: "History of chromatography," ''Nature'', 166 : 1000-1001.
* C. Engler and E. Albrecht (1901) ("On filtering petroleum with fuller's earth," ) ''The Petroleum Review'', 5 : 354-357.
* Karl Oswald Viktor Engler and Hans Höfer von Heimhalt, ''Das Erdöl: seine Physik, Chemie, Geologie, Technologie und Wirtschaftsbetrieb'' (Petroleum: Its physics, chemistry, geology, technology and commercial operation), vol. 1 (Leipzig, Germany: S. Hirzel, 1913) ; see especially (page 130. ) From page 130: ''"Die Dayschen Versuche erregten damals Aufsehen, da er sie in Beziehung zur Genesis der Erdöle brachte, … "'' (Day's experiments created a sensation at that time, since he related them (his experiments ) to the creation of petroleum, … )
* Gilpin, J. Elliott, and Cram, Marshall P. (1908) ("The fractionation of crude petroleum by capillary diffusion," ) ''Bulletin of the U.S. Geological Survey'', no. 365. Reprinted in: Gilpin and Cram (1908) ("The fractionation of crude petroleum by capillary diffusion," ) ''American Chemical Journal'', 40 (6) : 495-537.
* Gilpin, J. Elliott and Bransky, Oscar E. (1911) ("The diffusion of crude petroleum through fuller's earth with notes on its geologic significance," ) ''Bulletin of the U.S. Geological Survey'', no. 475. Reprinted in: Gilpin and Bransky (1910) ("The diffusion of crude petroleum through fuller's earth," ) ''American Chemical Journal'', 44 (3) : 251-303.
* J. Elliott Gilpin and P. Schneeberger (1913) ("Fractionation of California petroleum by diffusion through fuller's earth," ) ''American Chemical Journal'', 50 (2) : 59-100.〕

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