the predawn of paper chromatography

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The Predawn of PaperChromatography 2001, 54 409-414 L.S. Ettre Department of Chemical Engineering,Yale University, New Haven, CT, USA l) Key Words History of chromatography Paper chromatography F.F. Runge's pattern figures Capillary analysis Summary The activities of F.F. Runge, F.GoppeJsroeder and R.E.Liesegang are outlined. The technique of capillary analysis is described and its shortcomings elaborated. Tswett's use of filter paper to imitate plant tissues is explained and finally, the considerations of Izmailov and Shraiber even- tually leading to thin-layer chromatography are summarized. Introduction Today, paper chromatography is almost completely superseded by thin-layer chro- matography (TLC). However, the two are closely related. TLC was a logical exten- sion of paper chromatography, providing the possibility for the use of different ad- sorbents as the stationary phase, with in- creased sample size, while maintaining the simplicity of the technique. Paper chromatography occupies a very important place in the evolution of the chromatographic techniques: through it chromatography became everybody's tool, and it revolutionized the way bio- chemical investigations were carried out. As pointed out by W.J. Whelan, professor 1) Mailing address: P.O. Box 6274, Bridgeport, CT 06606, USA emeritus at the University of Miami School of Medicine (Miami, FL, USA), who in 1945-1948 was a graduate student in England [1], "The technological advance repre- sented (by paper chromatography) was astonishing. Amino acids ... could now be separated in microgram amounts and visualized.... (Paper chromato- graphy) would allow one within the space of one week to carry out first a test for homogeneity and then a struc- tural analysis of an oligosaccharide, which until then could very well have occupied the three years of a Ph.D. dis- sertation using (classical methods)." It is important to investigate the begin- nings of paper chromatography because of its significance in the evolution of the chromatographic techniques. R.L.M. Synge, the co-inventor of parti- tion chromatography in 1941, for which achievement he received together with A.J.P. Martin the 1952 Chemistry Nobel Prize, wrote some time ago a little known short paper entitled "How the Robinsons Nearly Invented Partition Chromatogra- phy in 1934" [2]. In it he was referred to an experiment of Robert Robinson at Oxford University in which he tried to use a 20-ft long surgical bandage, hung vertically in one of the staircases, in the fashion paper chromatography was carried out a decade later, for the separation of anthocyanins. The present discussion is similar to Synge's: none of the works mentioned here led to the actual development of the techni- que although each had the potential for it. Development of paper chromatogra- phy is generally credited to A.J.P. Martin and his group [3]. However, they were not the first who carried out some kind of ma- nipulation on (filter) paper, and Martin, in his Nobel Lecture [4], mentions that he was aware of the use of filter paper by dye- stuff chemists to check the quality of the dyes; in fact, he admits that he followed their practice. Actually, similar methods had already been used 1900 years earlier by the Romans to check the quality of the dye extracted from the fish sea purple, used to color the border of their robes [5, 6a]. A similar method was also used to check for possible adulteration of verdi- gris (essentially copper acetate), a popular medication in Rome [5, 6b]. However, these tests, performed on a piece of pa- pyrus, the paper of the Ancient Ages, can- not be termed as chromatography since no systematic separation was involved. Historical Paper 0009-5893/00/02 Chromatographia 2001, 54, September (No. 5/6) 409- 06 $ 03.00/0 9 2001 Friedr. Vieweg & Sohn Verlagsgesellschaft mbH 409

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The activities of F.F. Runge, F. GoppeJsroeder and R.E. Liesegang are outlined. The technique ofcapillary analysis is described and its shortcomings elaborated. Tswett's use of filter paper toimitate plant tissues is explained and finally, the considerations of Izmailov and Shraiber eventuallyleading to thin-layer chromatography are summarized.

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Page 1: The Predawn of Paper Chromatography

The Predawn of Paper Chromatography

2001, 54 409-414

L. S. Ettre

Department of Chemical Engineering,Yale University, New Haven, CT, USA l)

Key Words

History of chromatography Paper chromatography F.F. Runge's pattern figures Capillary analysis

Summary The activities of F.F. Runge, F. GoppeJsroeder and R.E. Liesegang are outlined. The technique of capillary analysis is described and its shortcomings elaborated. Tswett's use of filter paper to imitate plant tissues is explained and finally, the considerations of Izmailov and Shraiber even- tually leading to thin-layer chromatography are summarized.

Introduction

Today, paper chromatography is almost completely superseded by thin-layer chro- matography (TLC). However, the two are closely related. TLC was a logical exten- sion of paper chromatography, providing the possibility for the use of different ad- sorbents as the stationary phase, with in- creased sample size, while maintaining the simplicity of the technique.

Paper chromatography occupies a very important place in the evolution of the chromatographic techniques: through it chromatography became everybody's tool, and it revolutionized the way bio- chemical investigations were carried out. As pointed out by W.J. Whelan, professor

1) Mailing address: P.O. Box 6274, Bridgeport, CT 06606, USA

emeritus at the University of Miami School of Medicine (Miami, FL, USA), who in 1945-1948 was a graduate student in England [1 ],

"The technological advance repre- sented (by paper chromatography) was astonishing. Amino acids ... could now be separated in microgram amounts and visualized . . . . (Paper chromato- graphy) would allow one within the space of one week to carry out first a test for homogeneity and then a struc- tural analysis of an oligosaccharide, which until then could very well have occupied the three years of a Ph.D. dis- sertation using (classical methods)."

It is important to investigate the begin- nings of paper chromatography because of its significance in the evolution of the chromatographic techniques.

R.L.M. Synge, the co-inventor of parti- tion chromatography in 1941, for which achievement he received together with A.J.P. Martin the 1952 Chemistry Nobel Prize, wrote some time ago a little known short paper entitled "How the Robinsons Nearly Invented Partition Chromatogra- phy in 1934" [2]. In it he was referred to an experiment of Robert Robinson at Oxford University in which he tried to use a 20-ft long surgical bandage, hung vertically in one of the staircases, in the fashion paper chromatography was carried out a decade later, for the separation of anthocyanins. The present discussion is similar to Synge's: none of the works mentioned here led to the actual development of the techni- que although each had the potential for it.

Development of paper chromatogra- phy is generally credited to A.J.P. Martin and his group [3]. However, they were not the first who carried out some kind of ma- nipulation on (filter) paper, and Martin, in his Nobel Lecture [4], mentions that he was aware of the use of filter paper by dye- stuff chemists to check the quality of the dyes; in fact, he admits that he followed their practice. Actually, similar methods had already been used 1900 years earlier by the Romans to check the quality of the dye extracted from the fish sea purple, used to color the border of their robes [5, 6a]. A similar method was also used to check for possible adulteration of verdi- gris (essentially copper acetate), a popular medication in Rome [5, 6b]. However, these tests, performed on a piece of pa- pyrus, the paper of the Ancient Ages, can- not be termed as chromatography since no systematic separation was involved.

Historical Paper

0009-5893/00/02

Chromatographia 2001, 54, September (No. 5/6)

409- 06 $ 03.00/0 �9 2001 Friedr. Vieweg & Sohn Verlagsgesellschaft mbH

409

Page 2: The Predawn of Paper Chromatography

Figure 2. Spot test of Runge [1 la]. A = dark spot consisting of the precipitate from a mix- ture of a tree bark extract and lead acetate so- lution, surrounded by a turbid ring of the pre- cipitate's suspension; B = clear outer ring con- sisting either of pure water or excess lead acet- ate solution; C = pale yellow spot of K2CrO4 solution; D = dark yellow PbCrO4 solution (in- dicating an excess of the lead acetate reagen 0.

Figure 1. A typical picture produced by Runge (No.6 in [13]). It was the result of interaction of solu- tions of CuSO4, (NH4)H2PO4 and K4Fe(CN)6 on the filter paper.

Runge's Pictures

In the chromatographic literature one can often find the German physician-che- mist Friedlieb Ferdinand Runge (1794 1867) mentioned as the precursor or even as the "inventor" of paper chromatogra- phy [7]. His life story is fascinating and, on the occasion of the bicentennial of his birth, it was discussed in detail in this journal [8]. He had two doctorates, in medicine and chemistry, but he never practiced as a physician. Between 1826 and 1832 he was associated with a textile factory and the university in Breslau (to- day Wroclaw, Poland) and then in 1832 he joined a chemical factory in Oranien- burg, a town just north of Berlin (today a town in the state of Brandenburg) as an industrial chemist where he did pioneer- ing work on the investigation of coal tar. In the last 15 years of his life Runge lived on a royal pension granted him by the king of Prussia.

Runge had a lifelong interest in textile dyeing and in color formation in general. Between 1834 and 1850 he published three volumes on Farbenchemie (the chemistry of color and coloring) [9 11], mainly as an aid to textile manufacturing. Slowly he became more and more involved in study- ing the formation of colored patterns through reactions on filter paper, and be- tween 1850 and 1866 he published three books, full of beautiful illustrations in full

color [12 14]. At first glance these look almost like circular paper chromato- grams; however, they have nothing to do with chromatography.

Runge's aim was to create unique pic- tures through the mutual action of reagent solutions spotted on filter paper. In a book published in 1985, Harsch and Bus- semas dealt in detail with Runge's activ- ities, with many illustrations in full color [15], explaining also the way these pictures were created. As an example, we want to mention the preparation of one of his fig- ures (No.6 in [13]). The filter paper was first impregnated with copper sulfate [CuSO4] solution and let dry. Next, one drop of ammonium dihydrogen phos- phate [(NH4)H2PO4] solution was added to the paper; finally, one drop of potas- sium ferrocyanide [K4Fe(CN)6.3H20] so- lution was spotted on the middle of the colorless phosphate spot and four drops on the periphery of this spot. The resulting picture was mostly pink, with rays around a white center, and blue spots on the outer ring. Figure 1 provides a copy of Runge's original multicolored illustration.

However, Runge did not only pro- duced these figures "for the friends of beauty" as indicated in the title of his book [12]. He more and more moved to- ward a philosophical and almost mystical interpretation, believing that these color pictures "grew independently," and that their formation represented a manifesta-

tion of a special natural force, which he then later called the "Od".

While Runge's pictures have nothing to do with chromatography, they are ac- tually close to the spot tests first devised in 1859 by Hugo Schiff and then elabo- rated in details from 1918 on by Fritz

Feigl (1891 1970), first at the University of Vienna and, from 1940 on, in Brazil. In Feigl's T@felanalyse drops of reagents were added to a drop of the sample solu- tion, spotted on a piece of filter paper, and the analyte was identified through characteristic color formation or chemi- cal changes [16]. It may be interesting to mention the little known fact that in his earlier work, Runge had already followed exactly the same principles. An example is described in the third volume of his Farbenchemie [11]. His aim was to estab- lish the amount of a pigment in a tree bark extract, and he carried this out by precipitation with lead acetate: its solu- tion was added to the sample solution un- til there was as excess of lead in the fil- trate. The problem, however, was that the addition of even a small amount of the lead salt resulted in a dark, turbid suspen- sion, prohibiting the observation of any additional precipitate upon the addition of further reagent solution, and it was dif- ficult to filter this suspension. Runge sim- plified the investigation by developing a spot test [1 la] (Figure 2). When a drop of the turbid suspension was spotted on fil-

410 Chromatographia 2001, 54, September (No. 5/6) Historical Paper

Page 3: The Predawn of Paper Chromatography

ter paper, a dark spot was formed, sur- rounded by a turbid zone and then by a clear ring which consisted either of water (in the case of incomplete precipitation) or excess lead acetate solution. If now a drop of diluted (light yellow) potassium chromate was spotted next to the clear ring, it spread into it: in the case of the presence of excess lead acetate, dark yel- low led chromate formed, indicating that the precipitation of the pigment was com- plete.

This discussion clearly showed that while some of Runge's work may be con- sidered as the precursor of the spot tests, his beautiful multicolored pictures mir- rored his fantasy, and not chromatogra- phy. His work was aptly characterized as "the most original scientific playing" [17].

CapillaryAnalysis This technique started in 1864 with the observation of Christian Friedrich Schoenbein (1799 1868), professor at the University of Basel and the discoverer of ozone, that when dipping a filter paper strip into an aqueous solution, the solvent and the dissolved substances will travel up in the paper at different speeds, the sol- vent (water) being the fastest [18]. Frie- drich Goppelsroeder (1837 1919) was Schoenbein's student and he immediately followed his teacher's observation with his own work, describing the possibility of recognizing individual dyes in their mix- tures [19].

From then on, Goppelsroeder spent practically his whole productive life ex- ploring various aspects of this method which he named capillary analysis (Kapil- laranalyse); he published scores of papers reporting on his observations when inves- tigating the widest possible variety of nat- ural substances. He also collected these papers in a few books, with some addi- tional comments [20 22]. However, as noted by A. Griine in her detailed study of the evolution of capillary analysis, "it is usually very tiring to read (these publica- tions), because they report on a large number of individual observations with- out any clear line and without any obser- vable advances" [23].

Goppelsroeder used long, narrow filter paper strips and had their lower end im- mersed in the sample solution: in other words, instead of adding a finite amount of sample, the sample was continuously

Figure 3. Goppelsroeder's set-up for capillary analysis [20]. Some of the paper strips were placed under a bell-glass.

fed to the paper strip. Usually a dozen such strips were affixed to a rack (Figure 3); sometimes the system was also placed in a vacuum chamber or under pressure. Periodically, Goppelsroeder also ex- tracted the various colored zones from the paper strip by alcohol and then repeated the investigation with this solution. He al- ways carefully recorded the observation (height of the advanced zones) but with- out identification of the individual zones and without any conclusions. No visualiz- ing technique was used, thus the behavior of colorless substances could not be ob- served. It should also be mentioned that capillary analysis was a slow process: the experiments took many hours.

Schoenbein, in his original work, clear- ly attributed the movement of the sample components on the filter paper to capil- lary action. In his explanation Goppels- roeder thought that a number of physical phenomena are involved, but he had no clear understanding of their basic princi- ples. According to R.L.M. Synge, "Gop- pelsroeder hopelessly confused adsorp- tion, surface tension, diffusion and other effects and arrived at no satisfying expla- nations for his phenomena" [24]. Gop- pelsroeder considered selective adsorption as one of the phenomena causing the dif- ferent speed of the upward travel of the sample components and in this point he was strongly opposed by Tswett, the in- ventor of chromatography.

Mikhail Semenovich Tswett (1872 1919) carefully followed the work of Gop- pelsroeder and investigated the possible relationship of his new technique, chro- matographic adsorption analysis, with Goppelsroeder's capillary analysis. In his magnum opus' published in 1910 [25] Tswett devoted a whole chapter (Chapter VII) to the comparison of the two techni- ques. He particularly objected Goppels- roeder's assumption that adsorption has a role in capillary analysis and, based on some experiments, concluded that capil- lary analysis had nothing to do with ad- sorption, i.e., with chromatography.

With our present knowledge we realize that Tswett's assessment of capillary ana- lysis was not entirely correct: among a number of phenomena (e.g., capillary ac- tion and selective diffusion) adsorption also had an influence on the overall effect of capillary analysis. The correct assess- ment was properly formulated by Synge who characterized it as "frontal chroma- tography on paper" [24], and we may add to this definition that capillary analysis can be characterized as frontal adsorption analysis on paper.

While emphasizing the superiority of his new technique, the chromatographic adsorption analysis (in column), over Goppelsroeder's capillary analysis, Tswett also realized that there are substances or solvent systems which cannot be or can only inadequately analyzed by the chro-

Historical Paper Chromatographia 2001, 54, September (No. 5/6) 411

Page 4: The Predawn of Paper Chromatography

Figure 4. The capillary analysis arrangement of Platz [28].

Figure 5. The capillary analysis system used by Liesegang [30]. The container is covered by two wooden plates: the lower one has a slit and the filter paper strip is pulled through it. The pur- pose of the top plate is to hold the paper strip in place.

matographic adsorption technique (e.g., aqueous solutions). He pointed out that for such cases, capillary analysis could play a role. However, capillary analysis in the form carried out by Goppelsroeder is "rough and imperfect" and may "distort the actual content of a complex pigment." Therefore, further refinement of capillary analysis would be needed before it could be used successfully for the analysis of such samples, and he specifically men- tioned the need to change from continu- ous introduction of the sample solution to a finite sample and development with pure solvent. In other words, methodology should follow that of chromatography, but now carrying it out on a filter paper in- stead of on a column [26b].

As already mentioned, the fundamen- tal shortcoming of Goppelsroeder's tech- nique was the fact that the sample was continuously fed and thus, there was no clear separation of the zones of the indivi- dual sample components: they overlapped each other. As remarked by Newesely, "if Goppelsroeder would have tried only once to add a finite sample to the paper and then washed it with the pure solvent, then he might be named the father of modern chromatography, and paper chromatography would have been in- vented 80 years earlier" [27].

One further difference should also be pointed out between capillary analysis and paper chromatography as developed by Martin's group, and this had already been pointed out in their first paper de- scribing the technique [3]. While in capil- lary analysis, separation depends on a number of phenomena including adsorp- tion of the solutes on cellulose, in paper chromatography it depends on the differ- ences in the partition coefficients between the mobile phase and water, saturating

the cellulose: the paper is playing only the role of an inert support. This fact was also emphasized in the title of their paper which referred to "a partition chromato- graphic method using paper" [3].

After Goppelsroeder's death the use of capillary analysis was further widened. According to H. Platz, it was included in 1922 in the Dutch [28] and later in the German Homeopathic Pharmacopeia, and it remained there even after the ad- vent of paper chromatography [29]. How- ever, the methodology changed very little as compared to Goppelsroeder's original technique (Figure 4).

Capillary analysis was significantly modified by R.E. Liesegang (1869 1947). In 1927 he placed the filter strips into a closed chamber so that the atmosphere surrounding it was saturated with the sol- vent vapor (Figure 5) [30]. A further radi- cal change in 1943 was to spot the sample on the paper and then developing it by dipping the end of the paper strip into pure solvent [31]. This, of course, was not anymore "capillary analysis", but true elution development, identical to the method of paper chromatography. Liese- gang also introduced another variant which he called Kreutzkapillaranalyse (cross capillary analysis): after spotting the sample in one corner of the paper and developing it in one direction, he turned the paper 90 o and carried out a second de- velopment, with another solvent [32]. This was practically identical to the methodol- ogy of two-dimensional paper chromato- graphy, described one year later by Con- sden, Gordon, and Martin in their funda- mental paper [3].

There is no question that capillary ana- lysis as modified by Liesegang was very close to paper chromatography, as devel- oped by Martin's group. However, the

two groups were not even aware of the other's activities and Liesegang's work had no impact on the further develop- ment. Let us not forget that at that time, the war was raging on and there was no communication between Germany and England. Also, Liesegang was a colloid chemist with no particular interest in ana- lytical chemistry or biochemistry. At that time he was already 74 years old, had no formal academic affiliation; and he had no followers. Thus, his work was not con- tinued after his death and represented a dead-end street in the evolution of chro- matography.

Tswett and His Followers It is generally not known that in the early part of his study of plant pigments, Tswett utilized filter paper as a model for the plant's fibers. In his first report presented in 1903 in Warsaw [33], Tswett described his observations on the extraction of pig- ments from leaves. Carotenes could be ex- tracted easily using naphtha or petrol ether, * but for the extraction of the chlor- ophylls, a polar solvent such as ethanol was needed. On the other hand, the ex- tracted chlorophyllic pigments were solu- ble in the non-polar solvents. His assump- tion was that in the plant, the chlorophyl- lic pigments are attracted by adsorption to the tissue, and one needs a solvent having a dissolving power stronger than these ad- sorption forces. However, once separated from the plant tissue, there are no adsorp- tion forces which would retain the pig-

* Petrol ether consists mainly of C5-C6 hydro- carbons with a boiling range of 35 80 ~ while naphtha (ligroin) consists of higher paraffins, with more than 80% boiling between 130 and 145 ~

412 Chromatographia 2001, 54, September (No. 5/6) Historical Paper

Page 5: The Predawn of Paper Chromatography

ments: therefore, pure chlorophylls can be easily dissolved in the non-polar solvents.

Tswett wanted to check in a controlled experiment whether his assumption is cor- rect. He selected filter paper to serve as the "plant tissue" because both consist of cellulose fibers. To create a "leaf," he eva- porated the solvent of a pigment extract in the presence of filter paper. The paper be- came green just like leaves and also be- haved like leaves: carotenes could be ex- tracted with petrol ether, but for the ex- traction of the chlorophylls (the green pig- ments), ethanol had to be added to the sol- vent. In addition, he also observed that dipping filter paper into a solution of chlorophylls in naphtha, it will adsorb the dissolved pigments [33]. These experi- ments showed the validity of his assump- tions.

During the development of the chro- matographic adsorption analysis Tswett systematically investigated the (selective) adsorption properties of over 100 sub- stances of the widest possible variety. These were tabulated in his 1910 book [26d]. The discussion of this table in the book would imply that these substances were tested in powdered form, used as col- um n packings. It is, however, interesting to note that filter paper is also listed in the table. Because no further information is given, we cannot be sure whether Tswett actually tried to carry out "paper chroma- tography", or this reference is related to his previously mentioned experiments.

In his assessment of capillary analysis mentioned earlier, Tswett made an impor- tant statement: he drew an analogy be- tween the filter paper strip of capillary analysis and the adsorption column of chromatography [26b]. This statement al- most led to the development of paper chromatography, six years before the re- sults of Martin 's group.

We have to jump now 25 years, to the mid 1930s, and to Kharkov, in the U.S.S.R. (in Ukraine). The university had an Institute of Experimental Pharmacy and within this a physical chemistry la- boratory. Its head was a young scientist, Nikolai Arkad'evich Izmailov (1907 1961) who was just joined by a new gradu- ate student, Maria Semenova Shraiber (1904 1992). Forty years later, she pub- lished her reminiscences and thus, we have a first-hand account of the happenings [34, 35].

At that time, most of the pharmaceuti- cals were still galenic preparations and problems existed in their quality, because

of the lack of suitable analytical methods. Therefore, the task set for Shraiber was to improve methodology and develop more reliable control methods.

Izmailov was well acquainted with Tswett 's work and they had been using column adsorption chromatography for the analysis of complex mixtures, com- bined with fluorimetry for the identifica- tion of the separated substances. How- ever, this technique was too time-consum- ing, unsuitable for routine pharmaceutical analysis. Therefore, another way had to be found. Evidently they read Tswett's 1910 book [25] (most likely, it was avail- able in the university's library) and re- membered his analogy between the prop- erties of an adsorption column and a strip of filter paper. Thus, they were thinking that using such an open, fiat surface would accelerate the separation process. They also remembered Tswett 's criticism against capillary analysis, that complete separation could only be achieved having a finite sample and development by pure solvent in other words, using the techni- que adapted six years later for paper chro- matography by Martin 's group. However, soon they realized that a simple filter pa- per will still not have the needed separa- tion power: for this, adsorbents of higher selectivity are needed. As a conclusion, they prepared an adsorbent layer, added one drop of the sample solution and drops of a suitable solvent. In other words, in- stead of inventing paper chromatography, Izmailov and Shraiber invented thin-layer chromatography [36].

But this is another story.

References

[1] Whelan, W.J. FASEB Journal 1995, 9, 287 288.

[2] Synge. R.L.M. Notes and Records of the RoyalSoe. 1992,46, 309 312.

[3] Consden, R.; Gordon, A.H.; Martin A.J.P. Bioehem.J. 1944,38, 224 232.

[4] Martin, A.J.P. In NobelLectures: Chemis- try 1942 1962, Elsevier, Amsterdam, 1964; pp. 355 373.

[5] Ettre, L.S.J . High Resolut. Chromatogr. 1995,18, 277 278.

[6] Gaius Plinius Secundus (Pliny the Elder), Natural History. Bilingual edition in ten volumes, translated and edited by H. Rackham, Harvard University Press, Cambridge, MA, 1938-1963; (a) Book IX, Chapters LXI-LXIII; (b) Book XXXIV, Chapters XXV XXVI.

[7] Weil, H.; Williams, T.I. Naturwiss. 1953, 40,1 7.

[8] Bussemas, H.H.; Harsch, G.; Ettre, L.S. Chromatographia1994,38, 243 254.

[9] Range, F.F. Farbenchemie, 1: Lehrbuch der praktischen Baumwollfiirberei (Chem- istry of the Color, I.: Textbook of Practi- cal Wool Dyeing). Mittler Verlag, Berlin, 1834.

[10] Range, F.F. Farbenchemie, 11: Die Kunst zu Drucken. (Chemistry of Color, II: The Art of Printing). Mittler Verlag, Berlin, 1942.

[11] Range, F.F. Farbenchemie, 111: Die Kunst der Farbenbereitung. (The Art of Dye Pre- paration). E.S. Mittler & Sohn, Berlin, 1850; (a) pp. 15 16.

[12] Range, F.F. Zur Farbenchemie. Muster- bilder j~r Freunde des Sch6nen and zum Gebrauch j~r Zeichner, Maler, Verzierer und Zeugdrucker, dargestellt durch che- mische Wechselwirkung. (On the Chemis- try of Color. Pattern Pictures for the Friends of Beauty and for the Use of Draftsmen, Painters, Decorators and Tex- tile Printers. Prepared by Chemical Reac- tions.) E.S. Mittler & Sohn, Berlin, 1850.

[13] Range, F.F. Der Bildungstrieb der Stoffe, veranschaulicht in selbsti~ndig gewachsenen Bildern. (The Driving Force for Forma- tion of Substances, Visualized by Self- grown Pictures.) Published by the author, Oranienburg, 1855.

[14] Runge, F.F. Das Od als Bildungstrieb der StojJe, veransehaulieht in selbsti~ndig ge- waehsenen Bildern. (The Od as the Driving Force for Formation of Substances, Vi- sualized by Self-grown Pictures.) Pub- lished by the author, Oranienburg, 1866. (This book is identical to [13] except for a changed title page. According to our knowledge, only one copy of this book ex- ists: it is in the Beinecke Rare Book & Manuscript Library of Yale University.)

[15] Harsch, G.; Bussemas, H.H. Bilder die sieh selber malen. Der Chemiker Runge und seine "'Musterbilder j~r Freunde des Sch6- hen. "" (Self-coloring Pictures. The Chemist Range and his "Patter Pictures for the Friends of Beauty.") DuMont Verlag, K61n, 1985.

[16] Feigl, F. Qualitative Analyse mit Hilje von Ti~pjelreaktionen," Theoretische Grundlage, Praktische Au~j~hrung und Anwendung. (Qualitative Analysis with Help of Spot Reactions; Theoretical Basis and Practical Execution.) Akademische Verlagsgesell-

n d schaft, Leipzig, 1931; 2 ed., 1935. [17] Bechhold, H. Z. phys. Chem. 1905, 52,

185 199. [18] Schoenbein, C.F. Verh. Naturjbrsch. Ges.

Basel 1861, 3, 249 255. [19] Goppelsroeder, F. Verh. Naturjbrsch. Ges.

Basel, 1861,3, 268 275. [20] Goppelsroeder, F. Capillaranalyse, beru-

hend auf Capillarit~ts- und Adsorptions- erscheinungen. (Capillary Analysis, Based on Capillarity and Adsorption Phenom- ena.) Emil Birkhfiuser Verlag, Basel, 1901.

[21] Goppelsroeder, F. Anregung zum Studium der auf Capillarit~ts- und Adsorption- serscheinungen beruhenden Capillarana- lyse. (Stimulus to Capillary Analysis, Based on Capillarity- and Adsorption Phenomena.) Helbing & Lichtenhalm Vet- lag, Basel, 1906.

[22] Goppelsroeder, F. Capillaranalyse beru- hend auf Capillarit~ts- und Adsorption- serscheinungen. (Capillary Analysis, Based on Capillarity and Adsorption Phenom- ena.) SteinkopffVerlag, Dresden, 1910.

Historical Paper Chromatographia 2001, 54, September (No. 5/6) 413

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[23] Grfine, A. Osterr. Chem. Z. 1959, 60, 301 311.

[24] Synge, R.L.M. In Goodwin, Ed., British Biochemistry Past and Present (Biochem, Soc. Symposium No.30), Academic Press, London, 1970; pp. 175 182.

[25] Tswett, M.S. Khromojilly v Rastitel'nom i Zhivotnom Mire (Chlorophylls in the Plant and Animal World.) Karbasnikov Publishers, Warsaw, 1910; For a partial English translation see [26a].

[26] Berezkin, V.G. Ed. Chromatographic Ad- sorption Analysis. Selected Works o f M. S. Tswett. Ellis Harwood, New York, Lon- don, 1990; (a) pp. 35 93; (b) pp. 70 74; (c) pp. 9 19;(d) pp. 49 51.

[27] Newesely, M. Chromatographia 1990, 30, 595 596.

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Received: May 23, 2001 Accepted: June 5, 2001

414 Chromatographia 2001, 54, September (No. 5/6) Historical Paper