Phytochemistry Letters 4 (2011) 59–68

Contents lists available at ScienceDirect

Phytochemistry Letters
journal homepage: www.elsevier.com/locate/phytol

Invited mini review

Triterpenoid saponins of the Caryophyllaceae and Illecebraceae family

Stefan Böttger, Matthias F. Melzig *
Institut für Pharmazie – Pharmazeutische Biologie, Freie Universität Berlin, Königin-Luise-Str. 2+4, 14195 Berlin, Germany

A R T I C L E I N F O A B S T R A C T

Article history: The closely related plant families of Caryophyllaceae and Illecebraceae are reviewed for their saponins.
Received 26 June 2010 An overview with special attention on the contained sapogenins and their linkage of sugar moieties are
Received in revised form 22 July 2010 provided. Gypsogenin, gypsogenic acid and quillaic acid turned out to be widely spread in the family of
Accepted 9 August 2010
Caryophyllaceae. Gypsogenin is found in 46% of the examined species. The occurrence of gypsogenin is
Available online 21 August 2010
1.5-fold higher than that of gypsogenic acid or quillaic acid, which occur with the same frequency. The
genus Gypsophila L. of the family of Caryophyllaceae has the highest accumulation of gypsogenin. 75% of
Keywords:
the examined species contain gypsogenin. It appears 3-fold more often than gypsogenic acid or quillaic
Gypsogenin
Gypsogenic acid
acid in this genus. In contrast, all examined species of the family of Illecebraceae lack of gypsogenin.
Quillaic acid Since certain bisdesmosidic gypsogenin-based saponins of Gypsophila paniculata L. recently showed the
Caryophyllaceae ability to drastically amplify the toxicity of cellular membrane-impermeable type I ribosome-
Illecebraceae inactivating proteins (type I RIPs), the analysis reveals other possible natural sources for further testing.
Saponins ß 2010 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.
Sapogenins
Genins
Triterpenes
Sugar moieties
Type I ribosome-inactivating proteins

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
1.1. Caryophyllaceae and Illecebraceae. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
1.2. Saponins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
1.3. RIPs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2. Aim . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3. Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.1. Occurrence of saponins in Caryophyllaceae and Illecebraceae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
3.2. Properties of saponins occurring in Caryophyllaceae and Illecebraceae. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66

1. Introduction were united in the family of Caryophyllaceae. Today, the family of

1.1. Caryophyllaceae and Illecebraceae
The families of Caryophyllaceae and Illecebraceae present a
bulky group of plants spread over almost the whole landsite of the
earth with its centres of biodiversity in the moderate to warm
temperature regions of Europe and Asia. The two families formerly
* Corresponding author. Tel.: +49 30 838 51451; fax: +49 30 838 51461.
E-mail address: melzig@zedat.fu-berlin.de (M.F. Melzig).
Caryophyllaceae contains 104 genera with more than 2000 species.
The family of Illecebraceae contains 27 genera with about 500
species. The plants of both families are mostly of herbaceous
habitus with annual as well as perennial growth. Cross-opposite
leaves and flowers, swollen nodes, dichasial crotch of stem and
entire, elongate leaves are also part of the macroscopic appearance.
Unusual characteristic of these families is the stable and endurable
foam that appears, when parts of the plants are put into water and
are shaken. This behaviour is due to the occurrence of saponins.
The name saponin is derived from the Latin word ‘‘sapo’’, which
means soap, because saponin molecules may form the soap-like

1874-3900/$ – see front matter ß 2010 Phytochemical Society of Europe. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.phytol.2010.08.003
60 S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68
foam. The yield of saponins can reach up to 20% (dry weight) in
some species (Kolodziejski and Stecka, 1965), but may vary by
period of growth, part of the plant and season. The highest yield of
saponins within a plant, depending on the species, is usually
located in the roots or seeds (Kolodziejski and Stecka, 1965; Henry
et al., 1991). Crude saponins appear as white powder, with bitter
taste and easily provoke sneezing.
1.2. Saponins
Saponins are secondary plant compounds with a molecular
weight ranging from 600 to 2000 Da. Their hydrocarbon structure
is complex and may be subdivided into an aglycone or sapogenin
and one or more sugar chains, i.e. monodesmosidic- (one),
bisdesmosidic- (two), trisdesmosidic- (three) linkage, of different
length and branching. Sapogenins may be classified to the steroid
or triterpenoid skeletons. This review only deals with triterpenoid
sapogenins. Thirty carbon atoms forming four or five rings with or
without side chains present the typical framework for the
triterpenoid aglycone. The molecular structures of dammarane,
hopane, lupane, oleanane, taraxasterane, tirucallane and ursane
are defined to be the prototypes for these triterpenes. The
oleanane-type saponins present the main fraction of saponins in
the families of Caryophyllaceae and Illecebraceae and were of
special interest for this review. Sugars present in oleanane-type
saponins may be: apiose, arabinose, fucose, galactose, glucose,
glucuronic acid, N-acetyl glucosamine, quinovose, rhamnose,
ribose and xylose (Vincken et al., 2007).
The possession of distinct hydrophobic and hydrophilic regions
is responsible for the surfactant behaviour when saponins are
dissolved in water. But the same feature, that forms endurable
foam in water has the ability to interfere with cellular membranes,
inducting cytotoxicity even at low concentrations. The haemolytic
activity is based on this characteristic, for example, a solution of
bovine blood becomes transparent when the erythrocyte mem-
branes are destroyed by saponins. This haemolysis test was used to
identify and to quantify saponins in mixtures and drugs for a long
time. A mixture of saponins from Gypsophila arrostii Guss. and
Gypsophila paniculata L., called Saponinum album or Merck
Saponin, formed a standard in activity for this test in the German
pharmacopeia DAB 7 (Hänsel and Steinegger, 1992).
1.3. RIPs
Our recent research revealed another characteristic feature of
some saponins from Saponinum album, respectively from G.
arrostii Guss. and G. paniculata L. This showed the ability to amplify
the toxicity of type I ribosome-inactivating proteins (type I RIPs),
lectins like saporin and agrostin in a synergistic manner
(Hebestreit et al., 2006). A number of type I ribosome-inactivating
proteins, usually unable to penetrate the cellular membrane,
remove adenine residues from the 28S ribosomal RNA as part of a
process, that leads to inhibition of protein synthesis. The
synergistic amplification of toxicity was not based on the damage
of cellular membranes by the saponins. Moreover, it was not based
on a simple increase in endocytosis for the type I RIPs, but a
triggerage of clathrin-mediated endocytosis by the saponins
(Weng et al., 2008, 2009). This brings up a strong enhancement
of toxicity for the naturally membrane-impermeable type I RIPs,
making them as toxic as the membrane-permeable type II RIPs, like
viscumin and ricin at same concentrations. We also investigated
the efficacy of a receptor-specific chimeric toxin consisting of
saporin, epidermal growth factor and a molecular adapter,
previously shown to reduce side effects on non-target cells. The
used concentration of saponins, chimeric toxins or type I RIPs
either, were not toxic for any of the tested human cancer cell lines
in vitro, whereas the pre-appliance of saponins enhanced the
cytotoxic effects, dependent on the cell line between 1000 and
100,000-fold (Heisler et al., 2005). This underlines the synergistic
manner of the detected effects that were strictly target-cell specific
in case of the chimeric toxins. Saponins that provided the highest
synergistic toxicity were those, whose triterpenoid components
were gypsogenin or quillaic acid—both of oleanane-type. Bisdes-
mosidic linkage of sugar chains at C-3 and C-28 seemed to be
another essential structure characteristic.
2. Aim
The purpose of this review was to screen the genera of the
families for their triterpenoid saponins. Due to the presumed
structural likeness, it should be possible to identify saponins,
which are conforming to the structural conditions mentioned
above. Only few reviews have been published yet, providing
information about structural details of triterpenoid saponins in
groups of plants, for example, Kondratenko et al. (1981) and
Vincken et al. (2007). Table 1 shows the occurrence of gypsogenin
and quillaic acid. Moreover it shows the presence of gypsogenic
acid in several species. Based on structural similarities, an activity
similar to gypsogenin and quillaic acid might be probable and
should be worth to be tested for saponins containing gypsogenic
acid too. Although Table 1 makes no claim to be really complete,
the shown information represent the most up do date published
results of phytochemical research in the families of Caryophylla-
ceae and Illecebraceae. Furthermore, we tried to provide additional
information about the usage and particular origin of some species.
3. Results and discussion
3.1. Occurrence of saponins in Caryophyllaceae and Illecebraceae
As Table 1 shows, the majority of saponins in the family of
Caryophyllaceae possess gypsogenin, gypsogenic acid or quillaic
acid as aglyconic components, with a light preference on
gypsogenin (structures are given in Fig. 1). In 46% of the listed
species of the family of Caryophyllaceae, gypsogenin forms the
aglyconic component. Gypsogenic acid occurs in 31%, quillaic acid
in 33% of the listed species of this family. That means, the
occurrence of gypsogenin is 1.5-fold higher than that of gypsogenic
acid or quillaic acid, which occur with the same frequency.
Especially the genus Gypsophila L. has the highest accumulation of
gypsogenin. It can be found in 75% of the listed species of this
genus, whereas gypsogenic acid occurs in 25% and quillaic acid
occurs in 30% of them. Therefore, in this genus the appearance of
Gypsogenin is 3-fold more often than that of gypsogenic acid or
quillaic acid, which appear with nearly the same frequency. The
exposed existence of gypsogenin might mark a typical pattern for
the secondary plant compounds in the whole family of Caryo-
phyllaceae. This observation might be confirmed by the fact that
none of the genera of the family of Illecebraceae described below
seems to contain gypsogenin. Medicagenic acid and its derivatives
are present in all listed species of Herniaria L. But none of the two
families can exclusively be associated with just a single sapogenin.
Usually several oleanane-type saponins are accompanied in one
species. 12% of all listed species contain saponins that are based on
three or even more different sapogenins, namely: Acanthophyllum
gypsophiloides Rgl., G. arrostii Guss., G. capillaries (Forssk.) C. Chr.,
Gypsophila oldhamiana Miq., G. pacifica Kom., Herniaria glabra L., H.
hirsuta L., Melandrium firmum Rohrb., Saponaria officinalis L. and
Vaccaria segetalis (Neck.) Garcke. Further species might be
identified in future analytics. In any case, it is possible to speak
of repetitive occurrences of the three sapogenins, listed in the table
within the Caryophyllaceae family, especially when considering
Table 1
Sapogenins of the families of Caryophyllaceae and Illecebraceae.

Family Genus Species Sapogenins and linkage of sugar moieties Reference

Gypsogenin Gypsogenic Quillaic Others

acid acid

C Acanthophyllum C.A. Mey adenophorum Freyn x(2) Amanmuradov and Tanyurcheva (1969)
gypsophiloides Rgl. x(2) x(?) x(2) Putieva et al. (1970), Belous and Ryabinin
(1967), Kondratenko et al. (1981)
pachystegium K.H. x(1) x(2) Haddad et al. (2004)
paniculatum Rgl. x(1) Kondratenko et al. (1981)
squarrosum Boiss. x(2) x(2) Gaidi et al. (2001a)
subglabrum Schischk. x(?) Belous and Ryabinin (1967)

I Achyronychia Torr. & A. Gray n.i.

C Agrostemma L. githago L. x(1+2) x(?) 28-Methyl ester of gypsogenin Siepmann et al. (1998), Tschesche and
Schulze (1974)
gracilis Boiss. Oleanolic acid, echinocystic acid Koz et al. (2010)

S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68

C Allochrusa Bunge ex Boiss. gypsophiloides Rgl. (x) Arifkhodzhaev and Rakhimov (1992)
paniculata Rgl. (x) Arifkhodzhaev (1995)

C Alsinanthe (Fenzl) Rchb. = n.i.

Minuartia L.
C Alsine Gaertn. = Minuartia L. n.i.
C Alsine L. = Stellaria L. n.i.
C Alsinidendron H. Mann n.i.
C Ankyropetalum Fenzl n.i.
I Anychia Michx. n.i.

C Arenaria L. brevipetala Y.W. Tsui & L.H. Zhou (x) Zhou et al. (2009)
filicaulis Boiss. x(1) Camilliagenin A, snatzkein A Soliman et al. (1999, 2001)
graminifolia Schrad. x(?) Bukharov and Shcherbak (1973)
juncae M. Bieb. x(2) x(?) 3-Sulfate ester of gypsogenic acid Gaidi et al. (2005, 2001b), Liu and Qin (2007)
kansuensis Maxim. (x) Xu et al. (2009)

C Bolanthus (Ser.) Rchb. n.i.

C Brachystemma D. Don n.i.
C Brewerina A. Gray n.i.
C Bufonia L. n.i.
C Calycotropis Trucz. = n.i.
Polycarpaea Lam.
I Cardionema DC. n.i.
C Cerastium L. n.i.
C Cerdia Moc. & Sesse n.i.
I Chaetonychia (DC.) Sweet n.i.
C Charesia E.A. Busch = Silene L. n.i.
C Colobanthus Bartl. n.i.
I Cometes L. surattensis L. (x) Aynehchi et al. (1982)
C Coronaria Guett. = Lychnis L. n.i.
C Cucubalus L. baccifer L. x(?) Oleanane-type (no common name) Strzalka and Sendra (1979), Cheng et al. (2001)
C Cyathophylla Bocquet & Strid n.i.
C Dianthella Clauson ex Pomel = n.i.
Petrorhagia (Ser.) Link

C Dianthus L. barbatus L. x(?) Cordell et al. (1977)

calocephalus Boiss. (x) Sezik and Turkoz (1987)
caryophyllus L. x(1+2) Gumnicka and Oleszek (1998)
chinensis L. x(1+2) Hong-Yu et al. (1994)
deltoides L. x(2) x(1) Kondratenko et al. (1981)
superbus L. x(1+2) 23-Methyl ester of gypsogenic acid Oshima et al. (1984)

61
versicolor Fisch. ex Link. x(1+2) x(1+2) Ma et al. (2009)
 62
Table 1 (Continued )

Family Genus Species Sapogenins and linkage of sugar moieties Reference

Gypsogenin Gypsogenic Quillaic Others

acid acid

C Diaphanoptera Rech.f. n.i.

I Dicheranthus Webb n.i.

C Drymaria Willd. ex Schult. arenarioides H.B.K. (x) Williams (1978)

diandra Blume Oleanolic acid acetate, Yang et al. (2003)
drummondii Hook. Oleanolic acid acetate, Dominguez et al. (1975)
a-amyrin acetate
C Drypis L. n.i.
C Eremogene Fenzl = Arenaria L. n.i.
C Fimbripetalum (Turcz.) Ikonn. = n.i.
Stellaria L.
C Gastrocalyx Schischk. = Silene L. n.i.
I Geocarpon Mack. n.i.
C Gooringia F.N. Williams = Arenaria L. n.i.

S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68

C Gouffeia Robill. & Castagne ex Lam. & n.i.
DC. = Arenaria L.
I Gymnocarpos Forssk. n.i.

C Gypsophila L. acutifolia Fisch. x(2) Chirva et al. (1974)

altissima L. x(1+2) Chen et al. (2010)
aretioides Boiss. (x) Gladkikh et al. (1965)
arrostii Guss. x(2) x(?) x(2) Hydroxylated gypsogenin isomers Frechet et al. (1991a), Mostada and
Doehl (1987)
bermejoi G. López x(1) 23-Sulfate ester of hederagenin Acebes et al. (1998a,b)
bicolor Freyn et Sint x(?) Gypsogenin lactone Tagiev and Ismailov (1978)
capillaris (Forssk.) C. Chr. x(1) x(1+2) x(1) Elgamala et al. (1995)
capitata M. Bieb. x(?) Iskenderov et al. (1967)
eriocalyx Boiss. (x) Sezik and Turkoz (1987)
muralis L. x(?) Pauthe-Dayde et al. (1990)
oldhamiana Miq. x(1+2) x(?) x(1+2) Echinocystic acid, neogypsogenin Bai et al. (2007), Luo and Kong (2006),
A and B, Luo et al. (2008, 2006)
segetalic acid,
hedragenin, oleanaolic acid and
derivatives
pacifica Kom. x(2) x(1+2) x(2) Gypsogenin lactone, hydroxylated Nie et al. (2010), Kochetkov et al. (1963)
gypsogenin isomers
paniculata L. x(2) x(2) Frechet et al. (1991b)
patrinii Ser. x(1+2) Kondratenko et al. (1981)
petraea (Baumg.) Rchb. x(?) Pauthe-Dayde et al. (1990)
repens L. x(2) x(1+2) Lupane-type Elbandy et al. (2007a,b)
simonii Hub. Mor. Gypsogenin ester Cevrimli et al. (2007)
tekirae Stef. (x) Todorov and Todorov (1995)
trichotoma Wend. x(2) Sulfated oleanane-type Krasteva et al. (2009), Luchanskaya
et al. (1971)
vicolor Freyn x(?) Kondratenko et al. (1981)

C Habrosia Fenzl n.i.

I Hafunia Chiov. = Sphaerocoma n.i.
T. Anderson
I Haya Balf.f. n.i.
C Heliosperma Rchb. = Silene L. n.i.

I Herniaria L. fontanesii J. Gay Medicagenic acid Mbark et al. (1995)

glabra L. x(?) x(?) Medicagenic acid and derivatives Freiler et al. (1996), Klein et al. (1982),
Tamas et al. (1978)
hirsuta L. x(?) x(?) Medicagenic acid and derivatives Mbark et al. (2000), Klein et al. (1982),
Tamas et al. (1978)
C Holosteum L. n.i.
C Honckenya Ehrh. n.i.
C Hymenella Moc. & Sesse = n.i.
Minuartia L.
I Illecebrum L. n.i.
I Kabulia Bor & C. Fisch n.i.
C Kohlrauschia Kunth = Petrorhagia n.i.
(Ser.) Link
C Krascheninikovia Turcz. Ex Fenzl = n.i.
Pseudostellaria Pax
C Krauseola Pax & K. Hoffm. n.i.
C Kuhitangia Ovcz. n.i.
C Lepyrodicilis Fenzl n.i.
C Lidia A. Love & D. Love = Minuartia L. n.i.
I Lochia Balf.f. n.i.
C Loeflingia L. n.i.

C Lychnis L. alba Mill. (x) Kazerovskis (1962)

flos-cuculi L. x(?) Hederagenin Bukharov et al. (1974)
viscaria L. x(?) Bukharov and Bukharova (1974)

S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68

C Melandrium Roehl. = Vaccaria Wolf firmum Rohrb. x(?) x(?) x(?) Melandrigenin, oleanane-type Woo et al. (1992), Chang et al. (1989)
(no common name)
sylvestre Roehl. (x) Vetter and Haraszti (1987)

C Melandryum Rchb. = Silene L. n.i.

C Mesostemma Vved. n.i.
C Microphyes Phil. n.i.
C Minuartia L. n.i.
C Minuopsis W.A.Weber = Minuartia L. n.i.
I Mniarum J.R. Forst. & G. Forst. = Scleranthus L. n.i.
C Moehringia L. n.i.
C Moenchia Ehrh. n.i.
C Myosoton Moench n.i.
C Ochotonophila Gilli n.i.
C Ortegia L. n.i.

I Paronychia Mill. argentea Lam. Polygalacic acid Braca et al. (2008)

chionaea Boiss. x(2) Avunduk et al. (2007)

I Pentacaena Bartl. = Cardionema DC. n.i.

C Pentastemonodiskus Rech.f. n.i.
C Petrocoptis A. Braun ex Endl. n.i.
C Petrorhagia (Ser.) Link n.i.
I Philippiella Speg. n.i.
C Phryna (Boiss.) Pax & K. Hoffm. n.i.
C Phrynella Pax. & K. Hoffm. n.i.
C Pinosia Urb. n.i.
C Pirinia M. Kral n.i.
C Pleioneura Rech.f. n.i.
I Plettkea Mattf. n.i.
I Pollichia Aiton n.i.
C Polycarpaea Lam. corymbosa Lam. Camelliagenin A, A1-barrigenol Chiang (1978)

C Polycarpon L. loeflingiae Benth. & Hook.f. Saikogenin derivatives Bhandaria et al. (1990)
prostratum (Forssk.) Asch. & Schweinf. Saikogenin derivatives Ding et al. (2003)
succulentum J. Gay Hopane-type Meselhy and Aboutabi (1997)

C Polytepalum Suess. & Beyerle n.i.

C Porsildia A. Love & D. Love = Minuartia L. n.i.
C Provancheria B. Boivin n.i.
C Psammophila Ikonn. = Gypsophila L. n.i.

63
 64
Table 1 (Continued )

Family Genus Species Sapogenins and linkage of sugar moieties Reference

Gypsogenin Gypsogenic Quillaic Others

acid acid

C Psammophiliella Ikonn. = Gypsophila L. n.i.

C Pseudosaponaria (F.N.Williams) Ikonn. = n.i.
Gypsophila L.
C Pseudostellaria Pax heterophylla (Miq.) Pax (x) Peng et al. (2006)
I Pteranthus Forssk. n.i.
C Pycnophyllopsis Skottsb. n.i.
C Pycnophyllum J. Remy n.i.
C Queria L. = Minuartia L. n.i.
C Reesia Ewart = Polycarpaea Lam. n.i.
C Rhodalsine J. Gay = Minuartia L. n.i.
C Robbairea Boiss. n.i.
C Sagina L. japonica (Sw. ex Steud.) Ohwi (x) Huang et al. (1980)
C Sanctambrosia Skottsb. Ex Kuschel n.i.

C Saponaria L. kotschyi Boiss. (x) Sezik and Turkoz (1987)

S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68

officinalis L. x(2) x(1+2) x(2) Hydroxygypsogenic acid Koike et al. (1999), Jia et al. (1998),
and derivatives Kondratenko et al. (1981)

C Schiedea Cham. & Schltdl. n.i.

C Schischkiniella Steenis = Silene L. n.i.
C Scleranthopsis Rech.f. n.i.
I Scleranthus L. annuus L. (x) Tamas et al. (1978)
I Sclerocephalus Boiss. n.i.
I Scopulophila Torrey & A. Gray n.i.
C Selleola Urb. = Minuartia L. n.i.

C Silene L. brahuica Boiss. (x) Sokol’skaya and Magzumov (1958)

cucubalus Wib. x(1) x(1) Larhsinia et al. (2003)
dichotoma Ehrh. (x) Sezik and Turkoz (1987)
fortunei Wis. x(2) Lacaille-Dubois et al. (1999)
jenisseensis Willd. x(2) Lacaille-Dubois et al. (1997)
latifolia Poir. x(?) Tegisbaev et al. (1965)
nutans L. x(2) Kondratenko et al. (1981)
rubicunda A. Dietr. x(2) Tan et al. (1996)
succulenta Forssk. x(?) Oleanolic acid Karawya et al. (1991)
szechuensis F.N. Williams x(2) Zou et al. (1999)
vulgaris (Moench) Garcke x(2) x(2) Glensk et al. (1999)

I Siphonychia Torrey & A. Gray n.i.

C Spergula L. n.i.

C Spergularia (Pers.) J. Presl. & C. Presl. arbuscula I.M. Johnst.
marginata DC
media (L.) C. Presl
ramosa Cambess.
Equinocistic acid, oleanolic acid Appel et al. (1964), Kondratenko
et al. (1981)
Oleanane-type; no common name Kondratenko et al. (1981)
(x) Bouche (1955)
x(2) x(2) De Tommasi et al. (1998)

I Sphaerocoma T. Anderson n.i.

C Stellaria L. media (L.) Cyr. x(?) Hydroxylated oleanolic acid Hodisan and Sancraian (1989),
derivatives Hu et al. (2009a)
C Stipulicida Michx. n.i.
M Telephium L. n.i.
C Thurya Boiss. & Balansa n.i.
C Thylacospermum Fenzl n.i.
C Tryphane Rchb. = Minuartia L. n.i.
C Tunica Ludw. = Dianthus L. n.i.
 [()TD$FIG]
S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68 65

C = Caryophyllaceae (KEW, 2010a); I = Illecebraceae (KEW, 2010b); M = Mollunginaceae (KEW, 2010c); x(1) = monodesmosidic saponins; x(2) = bisdesmosidic saponins; x(1 + 2) = mono- and bisdesmosidic saponins; x(?) = linkage of
Koike et al. (1998), Balsevich et al. (2006)

Kondratenko et al. (1981)

Hickie et al. (2009)

sugar moieties unknown; (x) = saponins are present, but sapogenins are not specified or published; n.i. = no information for species containing saponins published.
3,4-Secogypsogenic acid

Fig. 1. Structures of gypsogenin, gypsogenic acid and quillaic acid.

the large number of oleanane-type triterpenes that are probable to

be present. As Vincken et al. (2007) analyzed, the oleanane-
skeleton is the most common triterpenoid skeleton for sapogenins
and it is present in most orders of the plant kingdom.
n.i.

n.i.
n.i.

n.i.

n.i.
n.i.
n.i.
n.i.
(x)

Above all, the table illustrates as far as is known whether the

linkage of the sugar chains to the sapogenins is monodesmosidic or
x(2)

bisdesmosidic. The linking points for sugar moieties to the

triterpenoid skeletons in the family of Caryophyllaceae usually
are at C-3 and C-28. Only the genus Dianthus L. seems to be an
exception to this observation. The species D. chinensis L., D.
x(1+2)

superbus L. and D. versicolor Fisch. ex Link. bring up saponins,

whose sugars may be linked to C-23 (Hong-Yu et al., 1994; Oshima
et al., 1984; Ma et al., 2009). Despite bisdesmosidic linkage of sugar
chains, these saponins are not fitting the conditions described
above. Trisdesmosidic saponins have not been identified within
x(2)

x(2)

the family of Caryophyllaceae yet. The appearance of sulphated or

sulphur-containing saponins is quite rare, only the species Arenaria
juncae M. Bieb., Gypsophila bermejoi G. López and G. trichotoma
Wend. are reported within the Caryophyllaceae family (Acebes
et al., 1998a; Gaidi et al., 2005; Krasteva et al., 2009). G. repens L.
and Polycarpon succulentum J. Gay are the only species that are
segetalis (Neck.) Garcke

reported to contain saponins of lupane- or hopane-type (Meselhy

pyramidata Medik.

and Aboutabi, 1997; Elbandy et al., 2007b). Hopanes seem to be

specific for the order of Caryophyllales (Vincken et al., 2007).
viscosa Bernh.

3.2. Properties of saponins occurring in Caryophyllaceae and

Illecebraceae

In ancient times saponin bearing herbs where used as a soap

substitute. But even today they are still part of organic cosmetics
and cleansing detergents (Rudnicki et al., 1990; Aghela et al., 2007;
Wangerinia E. Franz = Microphyes Phil.

Yang et al., 2009). Saponins from Acanthophyllum squarrosum Boiss.

Tytthostemma Nevski = Stellaria L.

were used to develop a natural hair shampoo. Added thickeners,

Wierzbickia Rchb. = Minuartia L.
Tunica Mert. & W.D.J. Koch =

glycerine and preservatives, the formulation abstained from

harmful and problematic surfactants (Aghela et al., 2007). The
Petrorhagia (Ser.) Link

seeds of the species Agrostemma githago L. var. githago presented a

source of contamination of grain from antiquity till the beginning
Uebelinia Hochst.

Wilhelmsia Rchb.

of the twentieth century. This problem in agriculture led to

Vaccaria Wolf

Viscaria Rohl.

Xerotia Oliv.

widespread intoxications of the population. The principle of this

Velezia L.

intoxication was not only based on the contained saponins, but on

the synergistic amplification of cytotoxic effects of the included
type I ribosome-inactivating protein agrostin in the manner
described above (Hebestreit, 2005). Other species known for
containing type I RIPs are: Dianthus barbatus L., D. caryophyllus L.
C

C
C

C
C
C
C
C
I

and D. sinensis L. containing dianthin (Prestle et al., 1992;

66 S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68
Messeguer et al., 1999; Cho et al., 2000; Fermani et al., 2003),
Gypsophila elegans M. Bieb. containing gypsophilin (Yoshinari et al.,
1997), Lychnis chalcedonica L. containing lychnin (Fermani et al.,
2003; Chambery et al., 2006), and Saponaria officinalis L. containing
the above-mentioned saporin (Carzaniga et al., 1994). The type I
RIPs found in Saponaria ocymoides L. and Vaccaria pyramidata
Medik. are not named yet. Above all, there are further variants for
each of the named type I RIPs slightly differing in the amino acid
sequences (Bolognesi et al., 1995; Fermani et al., 2009). Saponin
bearing herbs are also a problem for grazing cattle. The toxicity of
saponins from Drymaria arenarioides H.B.K. and D. pachyphylla
Wooten & Standl. has been scrutinized and is responsible for the
poisoning of cattle, sheep, goats and chickens (Mathews, 1933;
Dollahite, 1959; Williams, 1978; Williams and Fierro, 1980). In the
Traditional Chinese Medicine saponin-containing drugs are still
used to treat a large amount of ailments, like cardiovascular and
cerebrovascular diseases (Hu et al., 2009a,b), arrhythmia (Yu et al.,
2008), several types of pain (Sun, 2008), respiratory diseases (Tu
et al., 2007) or osteoporosis (Zheng et al., 2007a). Recently
published results could confirm the validity of some of these
customs for Dianthus superbus L. and other drugs (Hikino et al.,
1984). Different species of the genus Dianthus L. have been used in
Traditional Chinese Medicine in particular. Furthermore, antiviral
(Simões et al., 1999), antifungal (Marston et al., 1988; Rajasekaran
et al., 1993; Fave et al., 1994), molluscicidal (Marston et al., 1988),
herbicidal (Krol et al., 1995), spermicidal (Rajasekaran et al., 1993),
antitumoral (Hickie et al., 2009) or antihepatotoxic (Hikino et al.,
1984) properties were revealed for certain saponins of other plant
families. The ability to inhibit a-glucosidase activity might offer
the use of saponins found in some species as a antidiabetic remedy.
Especially saponins from Gypsophila oldhamiana Miq. showed a
very strong inhibitory activity (Luo et al., 2008). Besides, saponins
from G. oldhamiana Miq. showed inhibitory activity of pancreatic
lipase as well as antitumoral properties (Bai et al., 2007; Zheng
et al., 2007b). H. glabra L. has been used as a diuretic in former
times. Antihypertensive effects of the saponins of this plant could
be noted in rats (Rhiouani et al., 2001). Latest systematic
classification of the plant families and genera classified the genus
Herniaria L. into the family of Illecebraceae instead of Caryophyl-
laceae. In folk medicine, drugs rich in saponins are used as
expectorants to treat respiratory disorders. Saponins from Silene
vulgaris (Moench) Garke and S. fortunei Wis. have immuno-
modulatory activity and are able to influence lymphocyte
proliferation (Gasiorowski et al., 1999; Gaidi et al., 2002). Species
of the genus Vaccaria Wolf were traditionally used to treat breast-
related diseases, like inflammation, galactostasia or even breast-
cancer (Fu and Fu, 2008; Hickie et al., 2009). V. segetalis (Neck.)
Garcke was used to increase galactopoesis in the Traditional
Chinese Medicine. Saponins therein are able to increase the b-
casein production in mouse mammary cells (Qin et al., 2008).
4. Conclusion
Saponins fulfilling the above-mentioned conditions – for
example, based on gypsogenin, gypsogenic acid or quillaic acid
and bisdesmosidic linkage of sugar chains at C-3 and C-28 – could
be identified in 29 species.
Phytochemical data about the presence of saponins or their
structures are not published for all genera until now. The authors
are researching into species of the genus Gypsophila L. Moreover,
we suggest further analysis of species of the genus Dianthus L. In
our opinion the presence of biologically active saponins has
promise. The genus contains numerous species, which are widely
spread over different climes. This large number of variables might
result in a large number of different secondary plant compounds.
At least some species of Dianthus L. have already been used in the
Chinese folk medicine and the effects have been confirmed by
modern measuring methods (Hickie et al., 2009). Finally, the fact
that the type I RIP dianthin is present in some species of Dianthus L.
(Prestle et al., 1992; Messeguer et al., 1999; Cho et al., 2000;
Fermani et al., 2003) might amplify the probability of the
occurrence of other saponins, which are able to enhance the
synergistic toxicity of dianthin itself or other type I RIPs. Other
genera worth to be soon assayed for similar reasons are Arenaria L.,
Lychnis L., Saponaria L. and Vaccaria L.
Nevertheless, Table 1 presents a complete and up to date
compilation of the genera of the Caryophyllaceae family as well as
the Illecebraceae family. It refers to the latest classification of
genera according to the Royal Botanic Gardens, KEW (2010a,b).
Adding the genus Telephium L., which now belongs to the family of
Mollunginaceae (KEW, 2010c), Table 1 shows all genera that were
formerly part of the family of Caryophyllaceae, referring to an older
classification of genera in the family of Caryophyllaceae of the
Royal Botanic Gardens, KEW (MOBOT, 2010). Synonyms exist for
many genera and are presented as well.
References
Acebes, B., Bernabé, M., Dı́az-Lanza, A.M., Bartolome, C., 1998a. Two new sulfated
saponins from the roots of Gypsophila bermejoi. Journal of Natural Products 61,
1557–1559.
Acebes, B., Dı́az-Lanza, A.M., Bernabé, M., 1998b. A saponin from the roots of
Gypsophila bermejoi. Phytochemistry 49, 2077–2079.
Aghela, N., Moghimipourb, E., Dana, A.R., 2007. Formulation of a herbal shampoo
using total saponins of Acanthophyllum squarrosum. Iranian Journal of Pharma-
ceutical Research 6, 167–172.
Amanmuradov, K., Tanyurcheva, T.N., 1969. Triterpenic glycoside from Acantho-
phyllum adenophorum. Chemistry of Natural Compounds 5, 276.
Appel, H.H., Lobos, E., Overton, K.H., 1964. The saponin and the sapogenin of
Spergularia arbuscula. Scientia (Valparaiso) 30, 123–126.
Arifkhodzhaev, A.O., 1995. Polysaccharides of saponin-bearing plants. VII. Study of
the polyssaccharides of the roots of Allochrusa paniculata. Chemistry of Natural
Compounds 31, 455–456.
Arifkhodzhaev, A.O., Rakhimov, D.A., 1992. Polysaccharides of saponin-bearing
plants. V. Polysaccharides of the epigeal organs of Allochrusa gypsophiloides.
Chemistry of Natural Compounds 28, 379.
Avunduk, S., Lacaille-Dubois, M.-A., Miyamoto, T., Bedir, E., Senol, S.G., Caliskan,
Ö.A., 2007. Chionaeosides A–D, triterpene saponins from Paronychia chionaea.
Journal of Natural Products 70, 1830–1833.
Aynehchi, Y, Sormaghi, M.H.S., Amin, G.H., Soltani, A., Qumehr, N., 1982. Survey of
Iranian plants for saponins, alkaloids, flavonoids and tannins. II. International
Journal of Crude Drug Research 20, 61–70.
Bai, H., Zhong, Y., Xie, Y.-Y., Wang, Y.-S., Liu, L., Zhou, L., Wang, J., Mu, Y.-L., Zuo, C.-X.,
2007. A major triterpenoid saponin from Gypsophila oldhamiana. Chemistry &
Biodiversity 4, 955–960.
Balsevich, J.J., Bishop, G.G., Ramirez-Erosa, I., 2006. Analysis of bisdesmosidic
saponins in Saponaria vaccaria L. by HPLC-FAD-MS: identification of new
quillaic acid and gypsogenin 3-O-trisaccharides. Phytochemical Analysis 17,
414–423.
Belous, V.N., Ryabinin, A.A., 1967. Gypsogenic acid from the roots of Acanthophyllum
subglabrum and A. gypsophiloides. Chemistry of Natural Compounds 3, 79–80.
Bhandaria, S.P.S., Agrawal, P.K., Garg, H.S., 1990. A triterpenoid saponin from
Polycarpone loeflingiae. Phytochemistry 29, 3889–3892.
Bolognesi, A., Olivieri, F., Battelli, M.G., Barbieri, L., Falasca, A.I., Parente, A., Del
Vecchio Blanco, F., Stirpe, F., 1995. Ribosome-inactivating proteins (RNA N-
glycosidases) from the seeds of Saponaria ocymoides and Vaccaria pyramidata.
European Journal of Biochemistry 228, 935–940.
Bouche, R., 1955. Chemical study of the saponin of an adulterated Polygala senega,
Spergularia marginata or Spergularia media. Journal de Pharmacie de Belgique
169–191.
Braca, A., Bader, A., Siciliano, T., De Tommasi, N., 2008. Secondary metabolites from
Paronychia argentea. Magnetic Resonance in Chemistry 46, 88–93.
Bukharov, V.G., Bukharova, I.L., 1974. Triterpenoid glycoside from Viscaria. Chem-
istry of Natural Compounds 10, 550.
Bukharov, V.G., Chirva, V.Y., Bukharova, I.L., 1974. Triterpene glycosides from
Coronaria flos-cuculi. Pharmazie 29, 540.
Bukharov, V.G., Shcherbak, S.P., 1973. Triterpene glycosides from Arenaria grami-
nifolia. Chemistry of Natural Compounds 9, 123.
Carzaniga, R., Sinclair, L., Fordham-Skelton, A.P., Harris, N., Croy, R.R.D., 1994.
Cellular and subcellular distribution of saporins, type-1 ribosome-inactivating
proteins, in soapwort (Saponaria officinalis L.). Planta 194, 461–470.
Cevrimli, B.S., Kariptas, E., Yucekutlu, A.N., 2007. Isolation of saponin from dried
roots of Gypsophila simonii Hub. Mor. Pakistan Journal of Biological Sciences:
PJBS 10, 1944–1946.
 S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68
Chambery, A., De Donato, A., Bolognesi, A., Polito, L., Stirpe, F., Parente, A., 2006.
Sequence determination of lychnin, a type 1 ribosome-inactivating protein
from Lychnis chalcedonica seeds. Biological Chemistry 387, 1261–1266.
Chang, I.S., Han, Y.B., Woo, W.S., Kang, S.S., Lotter, H., Wagner, H., 1989. Sapogenins
from Melandrium firmum. Planta Medica 55, 544–547.
Chen, Q., Luo, J.-G., Kong, L.-Y., 2010. Triterpenoid Saponins from Gypsophila
altissima L. Chemical & Pharmaceutical Bulletin 58, 412–414.
Cheng, Y.X., Zhou, J., Dai, H.F., Ding, D.T., 2001. Cucubalugenin A, a new triterpenoid
from Cucubalus baccifer. Fitoterapia 72, 848–849.
Chiang, H.-C., 1978. Studies on the constituents of Polycarpaea corymbosa Lam.
Taiwan Yaoxue Zazhi 30, 114–120.
Chirva, V.Y., Kintya, P.K., Mel’nikov, V.N., Paukov, V.N., 1974. Structure of the
triterpenoid glycoside from Gypsophila acutifolia. Chemistry of Natural Com-
pounds 10, 336–338.
Cho, H.J., Lee, S.J., Kim, S., Kim, B.D., 2000. Isolation and characterization of cDNAs
encoding ribosome-inactivating protein from Dianthus sinensis L. Molecules and
Cells 10, 135–141.
Cordell, G.A., Lyon, R.L., Fong, H.H.S., Benoit, P.S., Farnsworth, N.R., 1977. Biological
and phytochemical investigations of Dianthus barbatus cv. ‘‘China Doll’’ (Car-
yophyllaceae). Lloydia 40, 361–363.
De Tommasi, N., Piacente, S., Gacs-Baitz, E., De Simone, F., Pizza, C., Aquino, R., 1998.
Triterpenoid saponins from Spergularia ramosa. Journal of Natural Products 61,
323–327.
Ding, Z., Yang, X., Bao, Z., Ye, J., 2003. Two new monoglycosides from Polycarpon
prostratum. Zhongcaoyao 34, 388–390.
Dollahite, J.W., 1959. Toxicity of Drymaria arenarioides for cattle, sheep and goats.
Journal of the American Veterinary Medical Association 132, 125–127.
Dominguez, X.A, Marroquin, J., Gutierrez, M.M., 1975. Triterpene acetates and D-(+)-
pinitol from Drymaria drummondii. Phytochemistry 14, 815–816.
Elbandy, M., Miyamoto, T., Lacaille-Dubois, M.-A., 2007a. New triterpenoidal sapo-
nins from Gypsophila repens. Helvetica Chimica Acta 90, 260–270.
Elbandy, M., Miyamoto, T., Lacaille-Dubois, M.-A., 2007b. Sulfated lupane triterpene
derivatives and a flavone C-glycoside from Gypsophila repens. Chemical &
Pharmaceutical Bulletin 55, 808–811.
Elgamala, M.H.A., Solimana, H.S.M., Karawyab, M.S., Mikhovac, B., Duddeck, H.,
1995. Isolation of triterpene saponins from Gypsophila capillaris. Phytochemis-
try 38, 1481–1485.
Fave, A., Steinmetz, M.D., Regli, P., Vidal-Ollivier, F., Elias, R., Balansard, G., 1994. In
vitro antifungal activity of triterpenoid saponins. Planta Medica 60, 50–53.
Fermani, S., Falini, G., Ripamonti, A., Bolognesi, A., Polito, L., Stirpe, F., 2003.
Crystallization and preliminary x-ray diffraction analysis of two ribosome-
inactivating proteins: lychnin and dianthin 30. Acta Crystallographica, Section
D: Biological Crystallography D59, 1227–1229.
Fermani, S., Tosi, G., Farini, V., Polito, L., Falini, G., Ripamonti, A., Barbieri, L.,
Chambery, A., Bolognesi, A., 2009. Structure/function studies on two type 1
ribosome-inactivating proteins: bouganin and lychnin. Journal of Structural
Biology 168, 278–287.
Frechet, D., Christ, B., Monegier du Sorbier, B., Fischer, H., Vuilhorgne, M., 1991a.
Four triterpenoid saponins from dried roots of Gypsophila species. Phytochem-
istry 30, 927–931.
Frechet, D., Christ, B., Monegier du Sorbier, B., Fischer, H., Vuilhorgne, M., 1991b.
New triterpene sapogenins from Gypsophila useful for pharmaceuticals. Pat. DE
4017766 (A1).
Freiler, M., Reznicek, G., Schubert-Zsilavecz, M., Reiner, J., Haslinger, E., Jurenitsch, J.,
Kubelka, W., 1996. Structures of triterpene saponins from Herniaria glabra.
Scientia Pharmaceutica 64, 359–365.
Fu, L., Fu, J., 2008. Traditional Chinese medicinal soft capsule for treating mammary
gland diseases and its preparation method. Faming Zhuanli Shenqing Gongkai
Shuomingshu 22.
Gaidi, G., Miyamoto, T., Lacaille-Dubois, M.-A., 2001a. Junceosides A–C, new tri-
terpene saponins from Arenaria juncea. Journal of Natural Products 64, 1533–
1537.
Gaidi, G, Miyamoto, T., Lacaille-Dubois, M.-A., 2005. An unusual new sulfated
triterpene saponin from Arenaria juncea. Pharmazie 60, 635–637.
Gaidi, G., Miyamoto, T., Laurens, V., Lacaille-Dubois, M.-A., 2002. New acylated
triterpene saponins from Silene fortunei that modulate lymphocyte prolifera-
tion. Journal of Natural Products 65, 1568–1572.
Gaidi, G., Miyamoto, T., Rustaiyan, A., Lacaille-Dubois, M.-A., 2001b. Three new
acylated triterpene saponins from Acanthophyllum squarrosum. Journal of Nat-
ural Products 64, 920–924.
Gasiorowski, K., Brokos, B., Glensk, M., Schöpke, T., 1999. Immunomodulatory
activity of the saponin-rich fraction from roots of Silene vulgaris Garcke: initial
study. Pharmazie 54, 864–866.
Gladkikh, A.S., Gubanov, I.A., Meshcheryakov, A.A., 1965. Content of saponins in
plants of Turkmenia. Seriya Biologicheskikh Nauk 22–35.
Glensk, M., Wray, V., Nimtz, M., Schöpke, T., 1999. Silenosides A–C, triterpenoid
saponins from Silene vulgaris. Journal of Natural Products 62, 717–721.
Gumnicka, O, Oleszek, W., 1998. Triterpene saponins from the aerial parts of
Dianthus caryophyllus var. remontant Hort. Acta Societaris Botanicorum Poloniae
67, 65–68.
Haddad, M., Miyamoto, T., Ramezani, M., Lacaille-Dubois, M.-A., 2004. New triterpene
saponins from Acanthophyllum pachystegium. Helvetica Chimica Acta 87, 73–81.
Hänsel, R., Steinegger, E., 1992. Pharmakognoise, 5. Aufl. Springer-Verlag, Berlin.
Hebestreit, P., 2005. Untersuchung zum Synergismus von Saponinen und Toxinen
bei in vitro kultivierten Säugetierzellen. Dissertation. Humboldt-Universität zu
Berlin.
67
Hebestreit, P., Weng, A., Bachran, C., Fuchs, H., Melzig, M.F., 2006. Enhancement of
cytotoxicity of lectins by Saponinum album. Toxicon 47, 330–335.
Heisler, I., Sutherland, M., Bachran, C., Hebestreit, P., Schnitger, A., Melzig, M.F.,
Fuchs, H., 2005. Combined application of saponin and chimeric toxins drasti-
cally enhances the targeted cytotoxicity on tumor cells. Journal of Controlled
Release 106, 123–137.
Henry, M., Rochid, M., Bennini, B., 1991. Biosynthesis and accumulation of saponins
in Gypsophila paniculata. Phytochemistry 30, 1819–1821.
Hickie, R., Balsevich, J., Ramirez-Erosa, I., Dunlop, D., Bishop, G., Deibert, L., Arnison,
P., 2009. Saponin extract from Saponaria spp. for treating cancer. Pat. WO 2009
117828 (A8).
Hikino, H., Ohsawa, T., Kiso, Y., Oshima, Y., 1984. Analgesic and antihepatotoxic
actions of dianosides, triterpenoid saponins of Dianthus superbus var. long-
icalycinus Herbs. Planta Medica 50, 353–355.
Hodisan, V., Sancraian, A., 1989. Triterpenoid saponins from Stellaria media (L.) Cyr.
Farmacia 37, 105–109.
Hong-Yu, L., Koike, K., Ohmoto, T., 1994. Triterpenoid saponins from Dianthus
chinensis. Phytochemistry 35, 751–756.
Hu, J., Jin, L., Liu, C., Wang, F., Yu, Y., Lu, B., Yan, Z., Wang, X., 2009a. Chinese medical
composition for treating cardiovascular and cerebrovascular diseases. Faming
Zhuanli Shenqing Gongkai Shuomingshu 12.
Hu, Y.M., Wang, H., Ye, W.C., Qian, L., 2009b. New triterpenoid from Stellaria media
(L.) Cyr. Natural Products Research, Part A: Structure and Synthesis 23, 1274–
1278.
Huang, H.-P., Cheng, C.-F., Ren, G.-Y., Lin, W.-Q., 1980. Antitumor activity and
preclinical pharmacologic study of the flavone of Sagina japonica. Yaoxue
Tongbao 15, 1–2.
Iskenderov, G.B., Aliev, R.K., Libizov, N.I., 1967. Saponins from Gypsophila capitata.
Farmatsiya 16, 29–34.
Jia, Z., Koike, K., Nikaido, T., 1998. Major triterpenoid saponins from Saponaria
officinalis. Journal of Natural Products 61, 1368–1373.
Karawya, M.S., Elgamal, M.H.A., Shalaby, N.M.M., Soliman, H.S.M., Duddeck, H.,
1991. Saponins of Silene succulenta Forssk. growing locally. Egyptian Journal of
Pharmaceutical Sciences 32, 879–887.
Kazerovskis, K.K., 1962. Preliminary phytochemical study of Lychnis alba saponin.
Journal of Pharmaceutical Sciences 51, 352–354.
KEW, Royal Botanic Gardens, 2010a. http://data.kew.org/cgi-bin/vpfg1992/gen-
list.pl?CARYOPHYLLACEAE (2010-02-18).
KEW, Royal Botanic Gardens, 2010b. http://data.kew.org/cgi-bin/vpfg1992/genlist.-
pl?ILLECEBRACEAE (2010-02-18).
KEW, Royal Botanic Gardens 2010c. http://data.kew.org/cgi-bin/vpfg1992/gen-
list.pl?MOLLUGINACEAE (2010-02-18).
Klein, G., Jurenitsch, J., Kubelka, W., 1982. Structure of the sapogenins from Herba
Herniariae (Herniaria glabra L. and Herniaria hirsuta L.). Scientia Pharmaceutica
50, 216–233.
Kochetkov, N.K., Khorlin, A.J., Ovodov, J.S., 1963. The structure of gypsoside—
triterpenic saponin from Gypsophila pacifica Kom. Tetrahedron Letters 4,
477–482.
Koike, K., Jia, Z., Nikaido, T., 1998. Triterpenoid saponins from Vaccaria segetalis.
Phytochemistry 47, 1343–1349.
Koike, K., Jia, Z., Nikaido, T., 1999. New triterpenoid saponins and sapogenins from
Saponaria officinalis. Journal of Natural Products 62, 1655–1659.
Kolodziejski, I.J., Stecka, L., 1965. Occurrence of saponins in various parts of
Gypsophila paniculata and Gypsophila altissima. Farmacja Polska 21, 751–
754.
Kondratenko, E.S., Putieva, Z.M., Abubakirov, N.K., 1981. Triterpene glycosides of
plants of the family Caryophyllaceae. Chemistry of Natural Compounds 17,
303–317.
Koz, O., Bedil, E., Masullo, M., Alankus-Caliskan, O., Piacente, S., 2010. Triterpene
glycosides from Agrostemma gracilis. Phytochemistry 71, 663–668.
Krasteva, I., Jenett-Siems, K., Kaloga, M., Nikolov, S., 2009. 3-O-Sulfo-triterpenoid
saponins from Gypsophila trichotoma Wend. Zeitschrift für Naturforschung B
64b, 319–322.
Krol, M., Pawlowska, J., Jurzysta, M., 1995. Phytotoxic activity of alfalfa (Medicago
sativa L.) saponins to some cereal species. Materialy Sesji Naukowej Instytutu
Ochrony Roslin (Poznan) 35, 294–297.
Lacaille-Dubois, M.-A., Hanquet, B., Cui, Z.-H., Lou, Z.-C., Wagner, H., 1997. Jenis-
seensosides C and D, biologically active acylated triterpene saponins from Silene
jenisseensis. Phytochemistry 45, 985–990.
Lacaille-Dubois, M.-A., Hanquet, B., Cui, Z.-H., Lou, Z.-C., Wagner, H., 1999. A new
biologically active acylated triterpene saponin from Silene fortunei. Journal of
Natural Products 62, 133–136.
Larhsinia, M., Marstonb, A., Hostettmann, K., 2003. Triterpenoid saponins from the
roots of Silene cucubalus. Fitoterapia 74, 237–241.
Liu, J., Qin, M.-J., 2007. Chemical constituents from the roots of Arenaria juncea.
Chinese Journal of Natural Medicines 5, 235–236.
Luchanskaya, V.N., Kondratenko, E.S., Gorovits, T.T., Abubakirov, N.K., 1971. Triter-
penoid glycosides from Gypsophylla trichotoma. II. Structure of trichoside A.
Chemistry of Natural Compounds 7, 142–144.
Luo, J.-G., Kong, L.-Y., 2006. A pair of new nortriterpene saponin epimers from the
roots of Gypsophila oldhamiana. Helvetica Chimica Acta 89, 947–953.
Luo, J.-G., Ma, L., Kong, L.-Y., 2008. New triterpenoid saponins with strong [alpha]-
glucosidase inhibitory activity from the roots of Gypsophila oldhamiana. Bioor-
ganic & Medicinal Chemistry 16, 2912–2920.
Luo, J.-G., Zhang, J., Kong, L.-Y., 2006. Studies on triterpenes from Gypsophila
oldhamiana. Zhongguo Zhongyao Zazhi 31, 1640–1641.
68 S. Böttger, M.F. Melzig / Phytochemistry Letters 4 (2011) 59–68
Ma, L., Gu, Y.-C., Luo, J.-G., Wang, J.-S., Huang, X.-F., Kong, L.-Y., 2009. Triterpenoid
saponins from Dianthus versicolor. Journal of Natural Products 72, 640–644.
Marston, A., Gafner, F., Dossaji, S.F., Hostettmann, K., 1988. Fungicidal and mollus-
cicidal saponins from Dolichos kilimandscharicus. Phytochemistry 27, 1325–
1326.
Mathews, F.P., 1933. Toxicity of Drymaria pachyphylla for cattle, sheep and goats.
Journal of the American Veterinary Medical Association 36, 255–260.
Mbark, A.N, Charrouf, Z., Wieruszeski, J.M., Leroy, Y., Kol, O., 1995. Herniaria saponin
A, a novel saponin from Herniaria fontanesii. Natural Product Letters 6, 233–240.
Mbark, A.N., Charrouf, Z., Wray, V., Nimtz, M., Schöpke, T., 2000. Monodesmosidic
saponins from Herniaria hirsuta. Pharmazie 55, 690–692.
Meselhy, M.R., Aboutabi, E.A., 1997. Hopane-type saponins from Polycarpon succu-
lentum growing in Egypt. Phytochemistry 44, 925–929.
Messeguer, J., Marcozzi, G., Spano, L., 1999. In vitro production of dianthin from
crown gall lines of carnation (Dianthus caryophyllus). Plant Cell Reports 18, 451–
455.
MOBOT, 2010. http://www.mobot.org/MOBOT/Research/APWeb/genera/caryo-
phyllaceaegen.html (2010-02-18).
Mostada, H.B., Doehl, J., 1987. Separation and characterization of oleanene-type
pentacyclic triterpenes from Gypsophila arrostii by liquid chromatography-mass
spectrometry. Journal of Chromatography 396, 157–168.
Nie, W., Luo, J.-G., Kong, L.-Y., 2010. New triterpenoid saponins from the roots of
Gypsophila pacifica Kom. Carbohydrate Research 345, 68–73.
Oshima, Y., Ohsawa, T., Oikawa, K., Konno, C., Hikino, H., 1984. Structures of
dianosides A and B, analgesic principles of Dianthus superbus var. longicalycinus
Herbs. Planta Medica 50, 40–43.
Pauthe-Dayde, D., Rochd, M., Henry, M., 1990. Triterpenoid saponin production in
callus and multiple shoot cultures of Gypsophila spp. Phytochemistry 29, 483–
487.
Peng, A., Xiong, H., Yan, Y., 2006. Study on determination of total saponins content in
Pseudostellaria heterophylla. Ziran Kexueban 29, 743–746.
Prestle, J., Hornung, E., Schoenfelder, M., Mundry, K.W., 1992. Mechanism and site of
action of ribosome-inactivating protein type 1 from Dianthus barbatus which
inactivates Escherichia coli ribosomes. FEBS Letters 297, 250–252.
Putieva, Z.M., Mzhel’skaya, L.G., Kondratenko, E.S., Abubakirov, N.K., 1970. Triter-
pene glycosides of Acanthophyllum gypsophiloides. Chemistry of Natural Com-
pounds 6, 506–507.
Qin, J., Li, Q.-Z., Gao, X.-J., 2008. Effect of main components from semen vaccariae on
multiplication and expression of beta-casein of mouse mammary epithelial cell
in vitro. Zhongguo Nongye Kexue 41, 2442–2447.
Rajasekaran, M., Nair, A.G.R., Hellstrom, W.J.G., Sikka, S.C., 1993. Spermicidal
activity of an antifungal saponin obtained from the tropical herb Mollugo
pentaphylla. Contraception 47, 401–412.
Rhiouani, H., Lyoussi, B., Sattaf, A., Cherrah, Y., Hassar, M., 2001. Antihypertensive
effect of Herniaria glabra saponins in the spontaneously hypertensive rat.
Annales Pharmaceutiques Françaises 59, 211–214.
Rudnicki, J., Olszewski, R., Jagiello, R., Linkiewicz, K., Maldachowska, E., Wierzbicka,
J., Gaik, C., 1990. Hair shampoo containing natural saponins. Warszawskie
Zaklady Zielarskie 6.
Sezik, E., Turkoz, S., 1987. Separation of some triterpenic saponins by column
chromatography. Acta Pharmaceutica Turcica 29, 87–93.
Siepmann, C., Bader, G., Hiller, K., Wray, V., Domke, T., Nimtz, M., 1998. New
saponins from the seeds of Agrostemma githago var. githago. Planta Medica
64, 159–164.
Simões, C.M.O., Amoros, M., Girre, L., 1999. Mechanism of antiviral activity of
triterpenoid saponins. Phytotherapy Research 13, 323–328.
Sokol’skaya, A.M., Magzumov, A., 1958. The isolation of saponin from catchfly.
Uchenye Zapiski Kazakhstan University 44, 99–104.
Soliman, H.S.M., Elgamal, M.H., Simon, A., Tóth, G., Horvath, G., Duddeck, H., 1999. A
new gypsogenin saponin from Arenaria filicaulis. Journal of Natural Products 62,
885–888.
Soliman, H.S.M., Simon, A., Tóth, G., Duddeck, H., 2001. Identification and structure
determination of four triterpene saponins from some Middle-East plants.
Magnetic Resonance in Chemistry 39, 567–576.
Strzalka, M., Sendra, J., 1979. Cucubalus baccifer saponosides. Part I. Isolation of the
saponoside fraction and identification of gypsogenin and gypsogenin glucur-
onoside. Herba Polonica 25, 277–284.
Sun, X., 2008. Chinese medical nasal smelling powder for treating pain. Faming
Zhuanli Shenqing Gongkai Shuomingshu 10.
Tagiev, S.A., Ismailov, A.I., 1978. Study of sapogenins of Gypsophila bicolor roots.
Chemistry of Natural Compounds 14, 113.
Tamas, M., Hodisan, V., Grecu, L., Fagarasan, E., Baciu, M., Muica, I., 1978. Studies on
triterpenoid saponins in indigenous medicinal plants. Studii si Cercetari de
Biochimie 21, 89–94.
Tan, N.-H., Zhou, J., Zhao, S.-X., Chen, C.-X., 1996. Rubicunosides B, C, D—three new
triterpenoid saponins with acetylated saccharides from Silene rubicunda.
Huaxue Xuebao 54, 722–728.
Tegisbaev, E.T., Chumbalov, T.K., Abubakirov, N.K., 1965. Triterpenoid glycoside-
silenoside obtained from the roots of Silene latifolia. Rastenievudni Resursy 1,
102–106.
Todorov, T., Todorov, M., 1995. Investigation of the productivity and of the chemical
composition of some species of the genus Gypsophyla L. Rastenievudni Nauki 35,
33–35.
Tschesche, R., Schulze, H., 1974. Über das Hauptsaponin der Kornrade (Agrostemma
githago L.). Chemische Berichte 107, 2710–2719.
Tu, P., Cai, S., Ma, Z., Li, Y., Jiang, Y., Chen, J., Xue, J., 2007. New formulations of
traditional Chinese medicine for treating respiratory diseases. Faming Zhuanli
Shenqing Gongkai Shuomingshu 13.
Vetter, J., Haraszti, E., 1987. Hemolytic saponin content of herbage. Acta Botanica
Hungarica 33, 431–436.
Vincken, J.-P., Heng, L., de Groot, A., Gruppen, H., 2007. Saponins, classification and
occurrence in the plant kingdom. Phytochemistry 68, 275–297.
Weng, A., Bachran, C., Fuchs, H., Krause, E., Stephanowitz, H., Melzig, M.F., 2009.
Enhancement of saporin cytotoxicity by Gypsophila saponins—more than stim-
ulation of endocytosis. Chemico-Biological Interactions 181, 424–429.
Weng, A., Bachran, C., Fuchs, H., Melzig, M.F., 2008. Soapwort saponins trigger
clathrin-mediated endocytosis of saporin, a type I ribosome-inactivating pro-
tein. Chemico-Biological Interactions 176, 204–211.
Williams, M.C., 1978. Toxicity of saponins in Alfombrilla (Drymaria arenarioides).
Journal of Range Management 31, 182–184.
Williams, M.C., Fierro, L.C., 1980. Seasonal concentration and toxicity of saponins in
Alfombrilla. Journal of Range Management 33, 157–158.
Woo, E.H., Woo, W.S., Chmurny, G.N., Hilton, B.D., 1992. Melandrioside A, a Saponin
from Melandrium firmum. Journal of Natural Products 55, 786–794.
Xu, Q, Huang, Y., Peng, G., 2009. Optimization of extraction technology of total
saponins from Arenaria kansuensis maxim by mathematical model. Shipin-
kexue 30, 69–73.
Yang, D., Xie, C., Yang, H., Dai, Y., Li, X., Ji, D., 2009. Cosmetics shampoo composition
containing tea saponins. Faming Zhuanli Shenqing Gongkai Shuomingshu 6.
Yang, X., Rong, H., Bao, Z., Ding, Z., 2003. Study on chemical constituents from
Drymaria diandra BL. Yunnan Daxue Xuebao. Ziran Kexueban 25, 358–360.
Yoshinari, S., Koresawa, S., Yokota, S., Sawamoto, H., Tamura, M., Endo, Y., 1997.
Gypsophilin, a new type 1 ribosome-inactivating protein from Gypsophila
elegans: purification, enzymic characterization, and subcellular localization.
Bioscience, Biotechnology and Biochemistry 61, 324–331.
Yu, D., Li, W., Zhu, H., Jia, J., 2008. Chinese medical formulation for treating
arrhythmia and its preparation. Faming Zhuanli Shenqing Gongkai Shuoming-
shu 11.
Zheng, J., Wu, Y., Cui, X., Sun, H., 2007a. A Chinese medicine for treating osteoporo-
sis. Faming Zhuanli Shenqing Gongkai Shuomingshu 8.
Zheng, Q., Li, W., Han, L., Koike, K., 2007b. Pancreatic lipase-inhibiting triterpenoid
saponins from Gypsophila oldhamiana. Chemical & Pharmaceutical Bulletin 55,
646–650.
Zhou, Y., Xu, Q., Gong, S., Feng, M., 2009. Application of Arenaria brevipetala saponins
in manufacturing analgesics. Faming Zhuanli Shenqing Gongkai Shuomingshu
1–5.
Zou, C., Jiang, J.X., Chen, C.X., Zhou, J., Zhao, Q., 1999. Diacylated Triterpenoid
Saponin from Silene szechuensis. Chinese Chemical Letters 10, 33–36.