Anal Bioanal Chem (2007) 389:3–9 DOI 10.1007/s00216-007-1465-y

ANALYTICAL CHALLENGE

“Doctrine of Signatures” challenge Stephen G. Saupe & Katherine E. Sharpless

Published online: 24 July 2007 # Springer-Verlag 2007

We would like to invite you to participate in the Analytical Challenge, a series of puzzles to entertain and challenge our readers. This special ABC feature has established itself as a truly unique quiz series, with a new scientific puzzle published every second month. Readers can access the complete collection of published problems, with their solutions, on the Analytical and Bioanalytical Chemistry homepage at http://www.springer.com/abc. Test your knowledge and tease your wits in diverse areas of analytical and bioanalytical chemistry by viewing this collection. In the present challenge the “Doctrine of Signatures” is the topic. And please note that there is a prize to be won (a Springer book of your choice up to a value of € 75). Please read on...

Meet the “Doctrine of Signatures” challenge

“Though sin and Satan have plunged mankind into an ocean of infirmities, yet the mercy of God, which is over all His workes, maketh grasse to growe upon the mountains and herbes for the use of men, and hath not only stamped upon them a distinct forme, but also S. G. Saupe (*) Biology Department, College of St. Benedict, St. Joseph, MN 56374, USA e-mail: [email protected] K. E. Sharpless Analytical Chemistry Division, National Institute of Standards and Technology, Gaithersburg, MD 20899, USA e-mail: [email protected]

given them particular signatures, whereby a man may read even in legible characters the use of them.” William Coles Art of Simpling (1656)

The quote from William Coles, a seventeenth-century British herbalist and physician, reflects a common belief of the period that the appearance of a plant provides a clue, or signature, to its potential medicinal use [1]. In Europe, this idea became known as the “Doctrine of Signatures” and, as a consequence, a plant or part that looked like a diseased organ, or like a venomous animal, or had a color similar to that of the disease was used to treat the respective condition [2]. For example, the kidney-shaped seeds of milk-vetch (Astragalus) were used to treat kidney stones and testicleshaped orchid tubers (Orchis) were used to treat impotence. The snake-like roots of snakeroot (Rauwolfia serpentina) were used to treat snakebites and plants with yellow sap or fruits, such as barberry (Berberis) and Italian buckthorn (Rhamnus alaternus), were used to treat jaundice and hepatitis [2]. Although the earliest formal account of the Doctrine of Signatures was published by Theophrastus Bombast von Hohenheim (1493–1541), who was better known as Paracelsus, this idea certainly arose much earlier and independently throughout the world. The early Egyptians and Chinese, classical Greeks, and medieval Europeans all selected medicines on the basis of this idea [2]. North American Indians had an equivalent system and ate wormlike plants to eliminate worms and used plants with a milky sap to promote lactation [3]. The adoption of this idea by various peoples around the world is not surprising. There has always been a need to identify treatments for a particular ailment. Any technique

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beyond simple trial and error would certainly have been welcome. An added benefit of the Doctrine of Signatures is that it provides a visual way of associating a disease with its treatment thereby making it easier to remember. The scientific validity of the Doctrine of Signatures has long been discredited. Although a variety of secondary metabolites have been isolated from putative medicinal plants suggested by the Doctrine of Signatures, there is no correlation between the appearance of the plant and its chemistry. However the common names of many plants, such as boneset (Eupatorium perfoliatum), eyebright (Euphrasia officinalis), toothwort (Dentaria sp.), liverleaf (Hepatica sp.), and maidenhair fern (Adiantum pedatum), still retain the vestiges of their origin in the Doctrine of Signatures. Though virtually no scientists support this idea, it persists in homeopathic medicine.

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses? Plant 2

The challenge For each of the images: 1. Identify the plant by selecting the appropriate name from the Name list; 2. Select from the Treatment list the use to which this plant was ascribed via the Doctrine of Signatures; 3. Identify compounds that have been found in the plant from the Chemical constituents list; and 4. Indicate (yes or no) whether the plant has any value treating the condition to which the Doctrine of Signatures ascribed. 5. Does the plant have any other medicinal uses unrelated to the Doctrine of Signatures? If so, indicate.

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Plant 3

Plant 1

Anal Bioanal Chem (2007) 389:3–9

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

5

Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Plant 6 Plant 4

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Plant 5

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses? Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list):

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Anal Bioanal Chem (2007) 389:3–9

Plant 7

Plant 9

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Plant 8

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Anal Bioanal Chem (2007) 389:3–9

Plant 10

7

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Plant 12

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Plant 11 Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

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Anal Bioanal Chem (2007) 389:3–9

Plant 13

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses?

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses? Plant 15

Plant 14

Name (letter from Name list): Use suggested by Doctrine of Signatures (letter from Treatment list): Secondary Metabolite (letter from Chemical constituents list): Doctrine of Signatures Efficacy (yes or no): Other medicinal uses? Names list a. Barberry (Berberis sp.; Berberidaceae - Barberry family) b. Birthwort (Aristolochia clematitis; Aristolochiaceae Dutchman’s-Pipe family)

Anal Bioanal Chem (2007) 389:3–9

c. Bleeding heart (Dicentra spectabilis; Papaveraceae Poppy family) d. Bloodroot (Sanguinaria canadensis; Papaveraceae Poppy family) e. Boneset (Eupatorium perfoliatum; Asteraceae - Sunflower family) f. Dutchman’s breeches (Dicentra cucullaria; Papaveraceae - Poppy family) g. Eyebright (Euphrasia sp.; Orobanchaceae - Broomrape family) h. Kidney bean (Phaseolus vulgaris; Fabaceae - Legume family) i. Lungwort (Pulmonaria officinalis; Boraginaceae Borage family) j. Maidenhair fern (Adiantum pedatum; Pteridaceae Maidenhair Fern family) k. Mandrake (Mandragora officinarum; Solanaceae Tomato family) l. Onion (Allium cepa; Alliaceae - Onion family) m. Spleenwort (Asplenium sp.; Aspleniaceae - Spleenwort family) n. St. John’s wort (Hypericum perforatum; Clusiaceae Saint-John’s-Wort family) o. Walnut (Juglans sp.; Juglandaceae - Walnut family)

Treatment list a. b. c. d. e. f. g. h. i. j. k. l. m. n. o.

Ailments of the spleen Blood disease Brain ailments Dermatological problems Difficult births General panacea Hair and scalp problems Healing broken bones Heart problems Improving vision Jaundice Kidney problems Lung diseases Treat wounds Venereal diseases

Chemical constituents list a. Alkaloids including scopolamine, mandragorine, hyoscyamine b. Allantoin, quercetin, kaempferol c. Allyl propyl disulfide, flavonoids d. Aporphine, protoberberine, protopine, and related isoquinoline alkaloids

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e. f. g. h. i. j. k. l. m. n. o.

Aristolochic acid Berberine, berbamine, oxyacanthine Corycavine, bulbocapnine and corydin Flavonol glycosides, proanthocyanidins, phytohaemagglutinin Iridoid glycosides, phenolic acids, phenylpropanoid glycosides Naphthodianthrones (hypericin, pseudohypericin), flavonoids, proanthocyanidins, hyperforin, phenolic acids Sanguinarine (pseudochelerythrine), chelerythrine, protopine, homochlidonine Sesquiterpene lactones, flavonoids, phytosterols Tannins, juglone, essential fatty acids Triterpenoids Xanthone glycosides

We invite our readers to participate in the Analytical Challenge by solving the puzzle above. Please send the correct solution to [email protected] by October 20, 2007. Make sure you enter “Doctrine of Signatures challenge” in the subject line of your e-mail. The winner will receive notice via e-mail and his/her name will be published on the “Analytical and Bioanalytical Chemistry” website at http://www.springer.com/abc and in the Journal. Readers will find the solution and a short explanation on the “Analytical and Bioanalytical Chemistry” website after October 20, 2007, and in the Journal (Issue 390/1). The next Analytical Challenge will be published in Issue 389/5, November 2007. If you have enjoyed solving this Challenge you are invited to try the previous puzzles on the “Analytical and Bioanalytical Chemistry” website. Disclaimer The above information should not be construed as medical advice or recommendations; the Chemical constituents list may not include all constituents.

References 1. Tippo O, Stern WL (1977) Humanistic botany. Norton, New York 2. Dafni A, Lev E (2002) Econ Bot 56:328–334 3. Klein RM (1987) The green world. An introduction to plants and people. Harper and Row, New York

Picture Credits Plants 1, 3, 11, and 13 – K. Sharpless Plants 2 and 5 – West Virginia University Herbarium, courtesy of Smithsonian Institution Plants 4, 6, and 9 – S. Saupe Plant 7 – E. Haug, courtesy of Smithsonian Institution Plant 8 – G.A. Cooper, courtesy of Smithsonian Institution Plant 10 – W.L. Wagner, courtesy of Smithsonian Institution Plants 12, 14, and 15 – R.A. Howard, courtesy of Smithsonian Institution