Development of chromatography - Analytical Chemistry (ACS

Leslie S. Ettre. Anal. Chem. , 1971, 43 (14), pp 20A–31a. DOI: 10.1021/ac60308a022. Publication Date: December 1971. ACS Legacy Archive. Cite this:A...
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The Development of Chromatography THE

TEARS 1971-72 represent three important anniversaries related to the various chromatographic techniques: the 100-year anniversary of the birth of Tswett, the inventor of adsorption chromatography ; the 30-year anniversary of the development of partition chromatography; and the 20-year anniversary of the first paper on gas-liquid partition chromatography. The purpose of this report is, 011 the occasion of the Seventh International Symposium on the Advances in Chromatography, to note

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the importance of these anniversaries and summarize the results of the pioneers that led to the techniques used today. The development of chromatographic techniques alone would assure a permanent place for the pioneers-11. S. Tswett, A. J. P. Martin, R . L. AI. Synge, and A. T. ,James-in the history of chemistry. However, their merit is more than t h a t ; they not only described new techniques but also properly interpreted them, summarized the theoretical basis of the techniques, and showed the possibilities of practical

applications. Thus, their work is an example of how scientific work should be carried out. Twsett, Martin, Synge, and James represent the starting points in a line of distinguished scientists, all of n.hom contributed greatly to the advancement of chromatography. It is impossible t o deal in this report with their activities; also, we cannot deal here with the development of ion exchange, thinlayer, and gas adsorption chromatographic techniques, each of which probably would merit a report in itself. Holyever. it should be em-

REPORT FOR ANALYTICAL CHEMISTS

On the occasion of the Seventh International Symposium on Advances in Chromatography, this Report deals with the importance of the work of Tswett and the circumstances which led to the development of liquid-liquid and gas-liquid partition chromatography

phasized that the pioneers only represent the start, and without the achievements of many known and unknown chemists and scientist,, we would not be where we are today. Adsorption Chromatography: The Life and Work of Tswett

For almost every invention, one can find persons who worked earlier and more or less carried out similar investigations but who are still not considered as the inventors of given techniques, processes, or machinery. Usually, the person recognized as the real inventor not only utilized or

described a phenomenon but also could interpret it and apply it knowingly for some purpose. The situation is not different in chromatography. Tswett certainly had his forerunners who described separation obtained by selective retardation on a column containing a solid substance. The most important person in this field was David Talbot D a y (1859-1925), who was connected with the US.Geological Survey for 28 years and served as the director of its Division of ?\Tinera1 Resources for 21 years. H e demonstrated in 1897 that when

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crude oil fractions are pressed through pulverized Fuller's earth, a certain fractionation takes place and, in the forthcoming years, investigated this phenomenon in detail. H e reported on his results in 1900 a t the First International Petroleum Congress in Paris and then three years later a t the 43rd meeting of the U S . Geological Society in Kashington, D.C. (For details on the activities of D a y and his collaborators and their publications, see ref. 1 and 2 . ) It should be noted, however, that, although D a y recognized the analytical potential

CHEMISTRY, VOL. 43, NO. 14, DECEMBER 1971

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Report for Analytical Chemists

of the process icvestigated, he and his co-workers interpreted incorrectly the physicochemical basis of the separation, calling it a capillary diffusion process. This is mainly the reason why today, Tswett and not D a y is recognized as the inventor of adsorption chromatography. llichael S. Tswett's life and activities are fairly well documented (3-6) although some of the statements in these summaries are contradictory. His life was a fascinating one, and a typical example of the troubled life encountered later by so many other European scientists mho, due t o the events beyond their control, had to settle a t places far from their homes or find refuge after losing everything. His scientific work shows the activity of one of the clearest and most conclusive minds. Michael S. Tswett was born on M a y 14, 1872, in ,4sti, Piemonte, Italy, as the son of Simeon Tswett, a Russian subject, and his wife Maria Dorosza, an Italian. H e grew up in Switzerland, studied there, and graduated with a P h D ; in 1896, he moved t o Russia and, in ,January 1901, after spending a few years in minor jobs, he found a permanent position a t the University of Warsaw (Poland was then part of Russia). H e successively served as assistant, associate, and full professor a t the University, the School of Veterinary Medicine, and the Institute of Technology of Warsaw until Korld War I interrupted his life. I n 1915, he left Warsaw with the Institute of Technology which was evacuated to Nishi Novgorod (today: Gorkiy) before the advancing German troops. I n 1917 he became ill and spent some time in the Caucasus recuperating, then accepted the chair of botany a t the Vniversity of *Jurjeff. [This was then the name of the city; its German name is Dorpat. After World War I, this area became Estonia, and the city's name was changed from the Russian Jurjeff to the Estonian name Tartu. When, in 1940, Estonia again became part of Russia (the Soviet Union), the Estonian name was kept.] I n the fall of 1918, the University was evacuated to Voronezh before the advancing German troops; he first decided to stay but, a t the

last minute, followed the University group. His illness a t t h a t time was already advanced, and he died in Voronezh on June 26, 1919, probably of heart disease. H e was buried in the cemetery around a monastery which (and this is the last intervention of history in Tsmett's life) was destroyed in World War I1 during the fighting with the German troops, and thus, his grave cannot be located anymore. I n practically his whole working life, Tswett dealt with investigations related to chlorophyll. Toward the end of the 19th century, many scientists showed interest in the pigments occurring in the leaves of plants, but there was no real way to separate them from each other and to check their identity in different plants. Since these substances are very labile, one could not be sure whether material obtained through chemical manipulation really corresponded to the form existing in the living plant. Tswett's approach was different ; he was looking for a physical method which would permit the separation of these pigments from each other and from closely related compounds that others felt to represent the same substances. For he was convinced that chlorophyll, as isolated by other researchers, was not a single substance. I n his work, he systematically checked a large number of solvents capable of extracting the pigments from vegetable matter, and more than 100 solid substances capable of selective retardation of the individual pigments through adsorption, and he also deducted a number of important rules for the adsorption phenomenon. His first paper in which his preliminary work was summarized was presented on March 21, 1903, before the Biological Section of the Warsaw Society of Yatural Sciences and published in Russian in the proceedings of the Society (7) ; it is also available in English translation ( 4 ) . The title of the paper is "On a Kew Category of Adsorption Phenomena and Their Application to Biochemical Analysis," and in it, he, in essence, describes chromatography without yet naming it as such. Three years later, in his

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A two remarkable papers entitled “Physico-Chemical Studies of Chlorophyll. T h e Adsorptions” (14), and “Adsorption Analysis and the Chromatographic Method. Application in the Chemistry of Chlorophyll” (9) published in the journal of the German Botanical Society, he very clearly defined the technique. It is worthwhile to quote from his first paper (8a) : “When a petroleum ether solution is filtered through a column of an adsorbent (I use mainly calcium carbonate which is tamped firmly into a narrow glass t u b e ) , then the pigments are resolved, according to the adsorption sequence, from top to bottom, into various colored zones, since the more strongly adsorbed pigments displace the more weakly adsorbed ones, and force them farther downward. This separation becomes practically complete when, after the pigment solution has flowed through, a stream of pure solvent is passed through the adsorbing column. Like light rays in the spectrum, the different components of a pigment mixture, obeying a law, are resolved on the calcium carbonate column and then can be qualitatively and quantitatively determined. I call such a preparation a chromatogram and the corresponding method the chromatographic method.”

It is generally assumed that the word “chromatography” has its origin in the Greek words chroma (color), and graphe (writing). However, already Tswett ( 8 b ) emphasized that:

“It is self-evident that the adsorption phenomena described are not restricted to the chlorophyll pigments, and one must assume t h a t all kinds of colored and colorless chemical compounds are subject to the same laws.” Actually, one may question whether Tswett really meant (‘color writing” when coining the name chromatography ( 1 0 ) . The interesting fact is t h a t the surname of

Tswett, in Russian, is identical with the Russian word for color ( 4BET) and, as expressed by Purnell ( l l ) , “It would be nice to think t h a t Tswett, whose name, in Russian, means color, took advantage of the opportunity to indulge his sense of humour.” I n his later papers, Tswett developed even further his technique -the separation of substances by retardation through selective adsorption. Tswett did not invent adsorption; this had been described well before him and also explained from the theoretical point of view (e.g., in the books of W. Ostwald from 1891-95). Also, scientists before him had separated plant pigments by selective solution. Tswett’s merits are in the generalization of the technique as a n analytical method and in the detailed investigations of the role of various adsorbents and solvents. As pointed out by Zechmeister ( 1 ) , “Tswett’s achievement is superior to Day’s in two respects. First, he recognized and correctly interpreted chromatographic processes; and second, he devised a useful laboratory method t h a t includes as an important feature the development of chromatograms by pure solvents. The distances between the individual zones are thus increased and complete resolutions advised within minutes.” Although Tswett published his most important papers in German journals (German was then the general language of chemistry), his work and the importance of the chromatographic technique were probably not understood immediately. It is interesting to note t h a t Palmer ( l e ) rein 1922 in the US., ported on a number of chromatographic experiments, giving credit to Tswett, but his work went largely unnoticed. Only 25 years after the publication of Tswett’s two basic papers was his work taken out of oblivion by Kuhn e t al. (IS, 14) who applied it successfully to the separation of carotene and egg yolk xanthophyll into their isomeric compounds. From there on, the development of adsorption chromatography was straightforward. ANALYTICAL CHEMISTRY, VC

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It is rare in the history of science that somebody can claim a number of major inventions. One of those men is A. J. P. Martin. Thirty years ago, together with Synge, he invented partition chromatography and demonstrated its use with a liquid carrier ( 1 5 ) . Three years later, together with Consden and Gordon, he described paper chromatography as a simple variant of liquid partition chromatography ( 1 6 ) . Then, 20 years ago, in cooperation with James, he showed the validity of their prediction in the first paper on partition chromatography that a gas could be used as well as the carrier instead of a liquid ( 1 7 ) . K i t h this publication, the unparalleled growth of gas-liquid partition chromatography began. Today, one could not even imagine chemistry and biochemistry without partition chromatography, and its importance is best demonstrated by the fact that Martin and Synge received the 1952 Sobel prize in chemistry for their work. thus joining the few scientists who have received the Sobel prize for a development in analytical chemistry. The history of the development of the three techniques is fascinating and is described in detail by Martin (18) and James ( 1 9 ) . As Martin explained, he early became interested in distillation columns. I n 1931, when Winterstein (who, two years earlier with Kuhn and Lederer, brought back adsorption chromatography from oblivion) demonstrated a t Cambridge Vniversity the separation of carotene on a chalk column, Martin realized that the processes involved in the separation are similar in both techniques. This early thinking resulted later in the expression of the efficiency of chromatographic columns by using terms established in distillation theory (HETP, number of theoretical plates). A t Cambridge University, when working on the separation of carotenes, Martin developed a very complicated countercurrent extraction apparatus and continued to utilize this technique for the separation of amino acids in wool when, in 1938, he moved to the Wool Industries' Research Association where Synge became his collaborator.

Report for Analytical Chemists

However, the whole system was extremely complicated and difficult to operate, and therefore, he tried to develop some other technique which would do the job. As described by bIartin (18):

“In 1940, it occurred to me that the crux of the problem was that we were trying to b o r k two liquids in opposite directions simultaneously . . . Then I suddenly realized that it rvas not necessary to moye both the liquids; if I just moved one of them, the required conditions were fulfilled. I was able to devise a suitable apparatus the very next day, and a modification of this eventually became the partition chromatograph with which we are now familiar.” I n their early work, chloroform containing a small amount of alcohol was used as the mobile phase, water as the stationary phase, and silica gel as the support; they could separate the monoamino monocarboxylic acids, and, according to Martin, “One foot of tubing in this apparatus could do substantially better separations than all the machinery n.e had constructed until then.” I n their paper, Martin and Synge ( 1 5 ) emphasized that, by the selection of suitable mobile phase-stationary phase combinations, the technique can be used for many other separations. and they predicted t h a t : “The mobile phase need not be a liquid but may be a vapour. We show below that the efficiency of contact between the phases (theoretical plates per unit length of column) is far greater in the chromatogram than in ordinary distillation or extraction columns. Very refined separation of volatile substances should therefore be possible in a column in which permanent gas is made to flow over gel impregnated with a nonvolatile solvent in which the substances to be separated approximately obey Raoult’s law.” I t is interesting to note that, although this prediction clearly and unequivocally predicted the possibility of gas-liquid partition chromatography, nobody picked it up,

and it took 10 years until Martin, then wit,h A. T. James, proved its great potential.

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Paper Chromatography

Liquid partition chromatography, as described originally by Martin and Synge, had superior separation power. However, in their original work, using water as the stationary phase and silica gel as the support, they were unable to separate the dicarboxylic and basic amino acids. They realized that the problem lay in the adsorptive power of silica gel and thus, were looking for some other support. As Martin explained, he had seen a “paper chromatogram” of dyes before and thus their first choice was paper. First, they used circles of papers in a Petri dish containing water; a drop of the amino acid solution was placed in the center of the paper, and water-saturated butanol was fed to the center of the paper; when i t reached the edge, the paper was dried and sprayed with ninhydrin, a substance found by Gordon to give proper color reaction with the amino acids, enabling the detection of their spots. Later, they used paper strips in boxes, in an atmosphere saturated with water, and the edge of the paper was dipped into the solvent (the moving phase). They also learned to run the paper in two dimensions. This is how paper chromatography, which revolutionized biochemical analysis, was born ( 1 6 ) . Gas-Liquid Partition Chromatography

As mentioned earlier, Martin and Synge predicted, in their original paper, the possibility of using a gas as the moving phase in partition chromatography. However, nobody thought to test experimentally this prediction a t that time although gas adsorption chromatography underwent an important development in the 1940’s. (See, e.g., the works of G. Hesse, E. Cremer, S. Claesson. E. Glueckauf, and C. S. G. Phillips; for a listing of their papers, see Bibliography, ref. 20). I n 1948, Martin moved to the National Institute for Xedical Research, where -4. T. James, who had previously been working with Synge. joined him. They were engaged in research work which did

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not result in any success, and Dr. James became so discouraged that Martin suggested that they switch to a project that surely must workto test the prediction of the possibility of gas-liquid partition chromatography. A request to try to develop a more advanced method for fatty acid analysis came as a good model for the investigations. Their work succeeded fairly rapidly, and soon the new technique was born; their paper was submitted for publication on June 5, 1951, and published in the first part of 1952 in Biochemical Journal ( 1 7 ) . I n their original work, James and lllartin added the sample by a pipet a t the front of the column and determined the eluted fractions by titration, and it was fairly difficult to record the “chromatogram.” I n the same year, D . H. Desty of British Petroleum, K. H. R a y of I.C.I., and R. P. IT7. Scott of Benzole Producers -4ssn. contacted Martin about the separation of hydrocarbony and then the possibility of using a thermal conductivity detector (applied at that time by Claesson) in gas adsorption chromatography was raised. I n the next three years, the applicability of the new technique to a \Tide variety of problems was sholvn, and in 1955, the first commercial instrument appeared on the market. The rest is history which those of us who “joined the club” in its early period will never forget. Sometime ago I read about life in the Spanish ports in the years after Columbus’ return from the S e w World, lvhere every ship brought something n e r , interesting. and exciting in treasures, people, and tales about new discoveries. We ivho have participated in the development of gas-liquid partition chromatography since its beginning, probably felt similarly ; every new issue of the journals, every meeting we have attended has brought something new and interesting that everybody wanted to try out in his own laboratory the next day. It is o proper to quote D r . Lipsky ~ l i finished one of his lectures (21) by paying tribute to D r . Martin: “He has twice made outstanding contributions to this field-in his discovery of partition chromatog-

Report for Analytical Chemists

raphy and in his pione,ering work on gas chromatograph y. H e has thus altered, for the better, the lives of many of us. TWe, his scientific colleagues, thaiik him for allowing us to share with him this wonderful adventure.” Interaction of ChromatographieTech niques

It is interesting to note that, until fairly recently, some art1ificial classification harriers have 1.ieen dividing the various types ci f chromatography, and scientists rarely deserted their own fields, IMartin being a rare expection. A few years ago, however, these artiificial barriers started to corrode. Scientists who, during the genesis of gas chro..2LL matography became i d e nLu: cu. Jw .W IUI it, started to be active in the other branches of chromatography. As a result of this healthy development, chromatography is treated today more and more by a unifying approach. This happening is a natural one, and the proper way development of a complex method is carried out. It starts in different channels which, for some time, look like separate techniques with nothing in common. But, sooner or later, it becomes clear t h a t these channels are not parallel but approach each other and, a t a given time, converge.

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From this point on, they are developed together, benefiting from each other’s achievements. Today, chromatography is the most widely used analytical technique, and there is practically no laboratory in the world where i t is not practiced. It permits results which otherwise would be impossible. Present-day chemists who, in less than 30 min, can separate a complex multicomponent mixture and establish its concentration often do not realize that, until fairly recently, the solution of this problem would probaby have required weeks of hard work. All of us who are active in this field should therefore appreciate the genius of the pioneers of this technique.

(6) X. Sakodynsky, Chromatographia, 3, 9 2 4 (1970). (7) M. S. Tswett, PTOC. Warsaw Sac. Nat. 56. Biol. Sect.. 14. minute No.6 (1903). , ~ (8) M. Tswett, Be?’. Deut. Bot. Ges., 24, 313-26 (1%) ; the two quothtions are from n 322 and 323~ ~~~~~~. (9) M. Tswett, Ber. Deut. Bot. Ges., 24, 384-93 (1906). (10) 1,. S. Ettre, Chromatographia, 3, 9 5 4 (1970). (11) H. Purnell, Gas Chromatography, P 1. Wilcy 8- Sons, New York, N.Y., 1962. (12) L. S. Palmer, “Camtinoids and Related Pigments,” Chemical Catalog Co., NPWYork. N.Y.. 1922. ~

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(16) R. Consden,, A. H. Gordon, and A

References

(1) L. Zechmeister, “Historical Introduction,” in “Chromatographv.” E. Heftmann, Ed., 2nd ed., pp 3-10, Reinhold, Xew York, N.Y., 1967. (2) V. Heines, Chem. Tech., 1, 280-5 (1971). (3) C. DhkrP, Condollea (Geneva), 10, 23-73 (1943). (4) G Hessp and H . Weil, Michael Tswett’.T F m t Paper on Chronatogmphy, M. Woelm, Eschwege, Germany, 1954.

1 Prktihe 6f Yilev & Sans, Xew

Leslie S. Ettre is ezecutive editor of the 18-volume “Encyclopedia of Industrial Chemical Analysis,” published by John Wiley & Sons, Inc. Mr. Ettre graduated in 1945 from the Faculty of Chemical Engineering o f the Institute of Technology, Budapest, Hungary. He became interested in chromatography in 1957 while employed at LURGI-Companies in Frankfurt am Main, Germany. From 1958 to 1968, he was working in gas chromatography at Perkin-Elmer Corp., serving in the last years as chief applications chemist. He has over 70 publications, mostly in the field of gas chromatography, is author of the book, “Open Tubular Columns in Gas Chromatography,” and editor o f the books, “The Practice of Gas Chromatography,” (with A. Zlat-

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(17) A. T. James and A. J. P. Martin, Biochem. J., 50, 67%90 (1952). (18) A. J. P. Martin, “Historical Backaround,” in Gas Chromatopmohy in Biology and Medicine,’: R.Porter, Ed., PP 2-10, J. & A . Churchill Ltd., London, Endand, 1969. (19) A. T.$mes, “The Development of an Idea, in “Gas Chromatography.” H . J. Noebels, N. Urenner. and R. F. Wall, Eds., pp 247-54, Academic Press, 1961. (20) R. L. Pecsok, Ed., “Principles and Practice of Gas Chromatoeraphy,” Wiley & Sons, New York, N.Y., 1959, pp 154-6. (21) S. R. Lipsky, “Gas Chramataaraphy; The Anatomy of a Scientific Revolution,” in “Gas Chromatography in Uiology and Medicine,” R. Porter, Ed., pp 11-16, J. & A. Churchill Ltd., London, Endand, 1969.

kis) and “Ancillary Techniques of Gas Chromatography” (with W . H. McFadden). He is a member of the editorial advisory board of the Journal of Chromatographic Science, one of the regional editors of Chromatographia, and serves as chairman of the Subcommittee on Nomenclature of ASTM Committee E-19 on Chromatography. Mr, Ettre is a member o f ACS, ISA, the New York Academy o f Sciences, the British Society for Analytical Chemistry and Gas Chromatography Discussion Group, and a fellow of the American Institute of Chemists. Lesl ie Ettre has cooperated 7uith Albert Zlatkis in the organization o f ,,-”,;“*“7r I u G L v I I u L the InL-! ucf” y~rbpy” o;”L u ^^ Advances in Chromatography since t heir beginning. I__^

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