2.2 Angiosperm resins I – Fabales

465 Pages·2013·14.31 MB·English

by  Gundel Schmidtbauer

The Vigani Cabinet –
Analysis of historical resinous materials by gas
chromatography - mass spectrometry and infrared
spectroscopy
D I S S E R T A T I O N
Submitted in fulfilment of the requirements
for the degree of
Doctor rerum naturalium
(Dr. rer. nat.)
presented at
the Department of Mathematics and Natural Sciences
at the Technical University Dresden
by
Diplom-Naturwissenschaftlerin Gundel Steigenberger
born 20 July 1979 in Karl-Marx-Stadt
Submitted on 03.01.2013

Die Dissertation wurde von Januar 2007 bis Dezember 2012 am Insitut für Biochemie der
Technischen Universität Dresden und am Labor für Archaeomtrie an der Kunsthochschule
Dresden angefertigt. Tag der Einreichung war der 3. Januar 2013, die Verteidigung fand am
14. Mai 2013 am Institut für Biochemie statt. Gutachter waren Prof. Karl-Heinz van Pée (TU
Dresden) und Prof. Christoph Herm (Kunsthochschule Dresden).
Teilergebnisse der Arbeit wurden in folgenden Beiträgen veröffentlicht und auf Konferenzen
präsentiert:
Steigenberger, Gundel; Herm, Christoph: Natural resins and balsams from a 18th century
pharmaceutical collection, Analytical and Bioanalytical Chemistry, 401, 2011, 1771-1784
Steigenberger, Gundel: GC-MS investigations of natural resins from a 300 years old material
collection, MaSC Meeting Cambridge/Massachusetts, 2001
Steigenberger, Gundel; Herm, Christoph: The Vigani Cabinet - investigations of natural resins
from 1703 using GC-MS, Chemistry for Cultural Heritage, Ravenna, 2010
Steigenberger, Gundel; Herm, Christoph; Fuhrmann, Annegret: Pitch, tar and resinous
materials in 18th century nomenclatures, Poster, MaSC Meeting, London, 2009

Acknowledgements

The dissertation thesis presented here benefitted from the help and support of many people.
First and foremost I thank my supervisors, Prof. Dr. Christoph Herm and Prof. Dr. Karl-Heinz
van Pée, who guided me through the process of the dissertation and supported me in many
ways. I also owe Prof. Ulrich Schießl, who died in Dresden at the 25th July 2011. Prof. Schießl
initiated the co-operation between the TU Dresden and the Queens’ College Cambridge on
which this dissertation project is based. He also supported this work with samples and advice.
I also wish to thank Dr. Brian Callingham and his wife Margaret for supporting my work and
providing me pictures of the Cabinet, and The President and Fellows of Queens’ College
Cambridge for allowing the samples from the Vigani Cabinet to be taken.
The dissertation builds on previous work done on the Vigani Cabinet by Dr. Lisa Wagner. The
analyses reported in the study benefited from help and exchange with Annegret Fuhrmann,
researcher at the HfBK Dresden. I thank Dr. Patrick Dietemann for fruitful exchange and the
provision of mass spectra for my analyses and Anja Schüler, Andreas Steigenberger and Dr.
Norbert Steigenberger for comments on earlier versions of this thesis.
Various people and institutions supported me by providing samples for the reference anal-
yses: Dr. Ulrich Pietzarka, Forest Botanical Garden Tharandt, Babara Dietsch, Botanical Gar-
den of the Technical University of Dresden, Dr. Heidemarie Nowak-Krawietz, Botanical Gar-
den Berlin-Dahlem at the Free University of Berlin, Christian Gruber, Bayerisches Landesamt
für Denkmalpflege, Andreas Schulze, Landesamt für Denkmalpflege Sachsen, and Nanke
Schellmann.
This work would not have been possible without financial support from Kulturstiftung der
Dresdner Bank (KulturInvest), organized by the Stifterverband der Deutschen Wissenschaft,
and the Land of Saxony. I am grateful for the funding I received.

Summary
Natural resins have been in use for a long time and for manifold purposes resulting in a long
and complex terminological history. The investigation of this history has so far been based
on the connection between nomenclature and chemical composition. Because resin chemis-
try and the botanical classification of source plants are connected as well, the investigation
of natural resins can be enhanced by adding taxonomy as an additional dimension, providing
a more complex and complete picture of resin chemistry and resin use.
The Vigani Cabinet, a collection of 300-year-old pharmaceutical and chemical materials
owned by Queens’ College, Cambridge (UK), allows doing just that. The materials are in a
very good state of conservation, with their original labels still attached. The Cabinet was
compiled by John Francis Vigani, who held the first Chair for Chemistry in Cambridge, at the
beginning of the Enlightenment era, and is an important part of the developing and intensi-
fying scientific research of that era. A wide range of historical literature provides information
about contemporary terminology, botanical and geographical origin, manufacture, trade and
properties of resinous materials from the 18th century. This contemporary context is a par-
ticular feature of the Cabinet, which allows adding a historical dimension to the correlations
between terminology, chemical composition and taxonomy.
The dissertation thesis presented here provides an investigation of 17 botanical, 80 refer-
ence materials and samples from 24 natural resins from the Vigani Cabinet, studying these
complex correlations and changes over time. The association of insights gained from the
analysis of a broad spectrum of historical literature with comprehensive data profiles ob-
tained from chemical analyses results in a new understanding of the link between historical
and modern terminology and the chemotaxonomy of natural resins.
The analytical method employed in this study was gas chromatography-mass spectrometry
(GC-MS) with and without methylation with trimethylsulfoniumhydroxide. This technique
provided detailed molecular compositions of the studied materials. The work contributes
systematic data for the differentiation of Pinaceae, Cupressaceae and Pistacia resins, im-
proving their chemotaxonomical data profile. A wide range of reference samples from Co-
paifera provided an improved data profile for the differentiation of Copaiba sources by
marker molecules. The mass spectra of phenylpropanoid methylesters found in commercial
Balsam of Peru and Tolu (Myroxylon resins) are discussed. The analysis of legume copals
from Fabaceae and Burseraceae resins revealed insights into the connection between termi-
nology and chemical composition, which could be used to fill knowledge gaps regarding the
wide range of similarly labelled materials from these groups. Finally, the identification of
Baltic amber based on the analysis of its solvent-soluble fraction was investigated.
Materials from the Vigani Cabinet analysed in this work were labelled as "turpentines", "pix
burgundica", "sandaracha", "copaiba", "balsamum peruvianum and tolutanum", "mastiche",
"anime", "copal", "elemi", "tacamahaca" and "succinum". Historical nomenclature of natural
resins has not always been unequivocally associated with a botanical origin. The availability
of natural resins changed throughout the centuries. Lack of knowledge, in particular about
resins from over-seas, or adulterations resulting from changing harvesting methods, led to
changes in trade names or variations in the composition of products traded under the same
name. Generic names were used for resins with similar properties but different botanical
(and geographical) origin. The thesis shows that a chemotaxonomic reference system is suit-
able for the identification of unknown resinous materials, and a number of new insights into
the nomenclature of natural resins from the 17th and 18th century is obtained. The study of
historical literature contributed in a significant way to the historico-cultural and archeomet-
ric research of the samples from the Vigani Cabinet and of natural resins in general and pro-
vided a basis for the interpretation of the chemical data from the Vigani samples. Table S.1
below summarises historical and modern names, botanical origin, chemotaxonomical mark-
ers and the scope of the investigation presented here.
The investigated "turpentines" (Cabinet number 1/8-1/11, 1/13) originated mainly from the
family of Pinaceae. With reference to their historical reported botanical origin, the "Stras-
burg", "Venice" and "Chios turpentines" were adulterated, while a number of analyzed "tur-
pentines" made from pine resin showed a strong connection to resin producing regions in
South France reported in contemporary sources. The only exception from these findings was
"Cyprus turpentine" (1/14), which turned out being a "Pistacia turpentine" from a Pistacia
species, probably Pistacia therebinthus L. Another conifer resin was "Pix Burgundica" (A/24),
which could be attributed to the resin of Picea abies Karst. in contrary to modern reference
samples, which are obtained from pines. Main marker compounds for the Pinaceae resins
were pimaric and sandaracopimaric acids and neutral labdane diterpenes. Based on the
marker compounds hydroxy-sandaracopimaric, dehydroabietic acids and the phenols totarol
and ferruginol, "sandaracha" (A/26) was obtained from the Sandarac cypress Tetraclinis ar-
ticulata Mast., despite the tree was still unknown at the time of Vigani, which is why the
material was named "juniper gum" in some of the sources. Several South American balsam
resins called "Copaiba", "Balsamum Peruvianum or Tolutanum" (1/4, 1/31, 2/1, Z/17) could
be characterized based on the results of the reference analysis, which shed some light on the
confusing historical literature about these at the time of Vigani widely unknown South-
American trees.
Another Pistacia resin was "mastiche" (A/11), which was obtained from Pistacia lentiscus L.
A further group included the terminological connected materials labeled as "copal", "anime",
"elemi" and "tacamahaca". "Anime" (A/5), a term which is if at all used today for American
Hymenaea or Protium resins, could be attributed – by the presence of ent-labdane acids – to
African Fabaceae resins as well as an unlabeled material from one of the lower drawers
(La2/7). It could be shown that African legume copals were called "anime" at the time of
Vigani. The term originally was used for antique African resins and was transferred by Portu-
guese traders to American materials. Other materials from this group (A/21, A/22, Z/1, A/24)
belonged to the triterpene Burseraceae resins. The two "copal" and "elemi" resins originated
from a Protium or Canarium species. The resins of both genera are composed so similar –
markers are - and -amyrin, brein, maniladiol and tirucallane acids –, that a differentiation
was not possible. Additionally, historical sources mention both "oriental" as well as "occi-
dental" sorts of both "copal" and "elemi", which corresponds with the geographical distribu-
tion of Canarium and Protium. The today nearly unknown "tacamahaca" originated from a
Bursera species, a genus connected to American "copals" today. Bursera resins can be dis-
tinguished from other American triterpene resins, for example from Protium species, by the
presence of lupanes and the 3-epimers of - and -amyrin.
The last group contained four samples labeled "succinum" (E/13-E/16). Their solvent soluble
fraction contained the characteristic markers of Baltic amber. They were investigated addi-
tionally by FT-IR. A "black amber" variety, which appeared very similar to jet, showed the
characteristic soluble fraction as well but lacked the Baltic shoulder in its FT-IR spectrum.
Modern name Historical name # Botanical origins Botanical origin Marker compounds Research focus
Vigani (historical) (Vigani)
Strasburg turpentine Therebinthia 1/8 Abies alba Mill. Pinus sp. Pimaric and dihydroagathic acids Adulteration, aging
Argentoratensis
Venice turpentine Therebintina 1/10 Larix decidua L., Pinus sp. Pimaric and dihydroagathic acid Nomenclature, adultera-
Veneta Abies alba Mill., Pinus tion, aging
1/11 Mixture of Larix de- Epimanoyloxide, iso-abienol, abi-
sp.
cidua L. & Abies alba enol, D8, D10 and L9, no pimaric Ibid.
Mill acid
Common turpentine Therebinthina 1/9 Pinus sp., Picea sp., Pinus sp. Pimaric and dihydroagathic acids Nomenclature, adultera-
vulgaris Larix sp. tion, aging
Pistacia turpentine Chios Turpenti- 1/13 Pista- Pinus sp. Pimaric and dihydroagathic acids Nomenclature, adultera-
ne cia terebinthus L. P. tion, aging
atlantica Desf.,
Pistacia turpentine Cyprus Turpen- 1/14 Pista- Pistacia sp. Triterpenes (oleananes, tirucallan- Nomenclature, trade
tine cia terebinthus L. P. es, dammaranes)
atlantica Desf.
Burgundy pitch Pix Burgundica A/23 Picea abies Karst., Picea abies Karst. Pimaric and sandaracopimaric Nomenclature, manufac-
Pinus sp. acids; cembrene, 13-cis- ture
neoabienol, abienol, cis- and trans-
abienol
Sandarac Sandaracha A/26 Tetraclinis articulata Tetraclinis articulata Oxygenated sandaracopimaric and Botanical origin, trade
Mast. Mast. dehydroabietic acids, phenols name
Copaiba balsam Copaiba, Capivi 1/4 Copaifera sp. Copaifera sp. -selinene, -bisabolene, kauran- Botanical origin, diversity
19-oic, polyalthic acids, eL17, of Copaifera species

cativic, ent-pinifolic acids used
Modern name Historical name # Botanical origins Botanical origin Marker compounds Research focus
Vigani (historical) (Vigani)
Balsam of Peru Balsamum Pe- 1/31, Myroxylon balsamum Myroxylon balsamum Benzylbenzoate, -cinnamate, cin- Botanical origin, different
ruvianum 2/1 Harms var. pereirae Harms var. pereirae namylbenzoate, -cinnamate, benzo- sorts used
ic, cinnamic acids, trans-nerolidol
Balsam of Tolu Balsamum To- Z/17 Myroxylon balsamum Myroxylon balsamum Benzylbenzoate, -cinnamate, cin- Botanical origin, origin of
lutanum Harms var. balsamum Harms var. pereirae namylcinnamate, benzoic, cinnamic adulteration
acids
Mastic Mastiche A/11 Pistacia lentiscus L. Pistacia lentiscus L. Triterpenes (oleananes, tirucallan- Botanical origin, aging
es, dammaranes)
Anime Gum Anime A/5 (West or East) African Daniellia or Guibour- 18-hydroxy-, 18-methoxy-labda- Botanical origin, transfer
trees, Hymenaea tia sp. (Fabaceae) 8(20)-en-15-oic acids, hydroxy- of the term to American
courbaril L., Mexican labden-18-oic acid, 18-hydroxy-15- resins, confusion with
Bursera or Protium methoxy-labdane copal
sp.
Copal Gum copal A/21 Hymenaea sp., Rhus Protium or Canarium - and -amyrin, brein, maniladiol, Botanical origin, transfer
copallifera L., Protium sp. tirucallane acids of the term to African &
& Bursera sp. Asian resins, confusion
with anime
Elemi Gum elemi A/24 Canarium sp., Bos- Protium or (African) - and -amyrin, brein, maniladiol, Botanical origin, transfer
wellia frereana Canarium sp. tirucallane acids of the term to American
Birdw., Dacryodes resins
edulis Lam., Protium
sp., Amyris elemifera
L.