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Scientia Horticulturae 142 (2012) 158165

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Scientia Horticulturae
journal homepage: www.elsevier.com/locate/scihorti

Identication of oral fragrances in tree peony cultivars by gas


chromatographymass spectrometry
Shanshan Li a,b , Liguang Chen c , Yanjun Xu d , Lijin Wang a,b , Liangsheng Wang a,
a
Beijing Botanical Garden/Key Laboratory of Plant Resources, Institute of Botany, Chinese Academy of Sciences, 20 Nanxincun, Xiangshan, Beijing 100093, China
b
Graduate University of Chinese Academy of Sciences, Beijing 100049, China
c
The Institute of Forest Protection, Chinese Academy of Forestry, Beijing 100091, China
d
Department of Applied Chemistry, China Agricultural University, Beijing 100094, China

a r t i c l e i n f o a b s t r a c t

Article history: Volatile organic components in petals of thirty tree peony cultivars were analyzed using a headspace
Received 10 December 2011 solid-phase microextraction technique (HS-SPME) coupled with GCMS. 146 volatile organic compo-
Received in revised form 28 April 2012 nents were detected, in which 81 of them were scent components. The major scent components were
Accepted 20 May 2012
terpenes, alcohols, arenes and alkanes. According to major fragrances and the results of sensory evalu-
ation, thirty cultivars were classied into ve fragrance patterns: a woody scent, a rose scent, a lily of
Keywords:
the valley scent, a phenolic scent and an unidentied scent, in which cis-ocimene, d-citronellol, linalool,
Paeonia
1,3,5-trimethoxybenzene (TMB) and pentadecane were their major oral fragrances, respectively. Seven
Tree peony
Floral fragrance
cultivars were evaluated for their potential in the development and utilization of tree peony owers: Tian
GCMS Xiang, Lan Bao Shi, Dian Jiang Feng Dan, Bai He Zhan Chi, Chun Xue, Hu Die Bao Chun and High
SPME Noon. In particular, High Noon has signicant high fragrance content for breeding fragrant peonies.
2012 Elsevier B.V. All rights reserved.

1. Introduction that a fundamental research on fragrance of tree peony owers is


urgently needed.
Tree peony (Paeonia suffruticosa), known as one of the famous Extraction of the volatile compounds is an essential step for fur-
traditional owers with excellent ornamental characteristics, orig- ther analytical identication. The following methods are used in
inates in China since the Eastern Jin Dynasty and has been common for this purpose: purge and trap, liquidliquid extraction,
subsequently introduced to Japan, America and Europe from Tang solid-phase extraction (SPE), simultaneous distillation extraction
Dynasty (Li, 1998). So far, tree peony has been cultivated as a com- (SDE), steam distillation (SD), solid-phase microextraction (SPME)
mercial plant worldwide due to their high ornamental value and and supercritical-uid extraction (SFE). Among them, SPME in
various cultivars. Producers and researchers have been devoted headspace mode (HS) has an excellent performance for the anal-
to breeding showy cultivars with various colors and petals as the ysis of volatile compounds (Augusto et al., 2003; Martinez-Vidal
major trait patterns (Li et al., 2009; Wang et al., 2001; Zhang et al., et al., 1997). It is an ideal sample preparation technique because it
2007). Recently, researchers showed intensive interests in their is fast, solvent-free and cost-effective.
functions for human health. It has been found that peony ow- So far, in order to breed fragrant cultivars, researchers have
ers are good natural antioxidant resources and their extract can done a lot of work on the analysis of oral fragrances and genetic
protect DNA from being damaged by OH (Li et al., 2009; Wang resources in some important ornamentals, such as Hybrid Tea roses
et al., 2004). Numerous aromatic products in tree peony owers (Cherri-Martin et al., 2007), Osmanthus fragrans varieties (Hu et al.,
have been developed, such as peony pollen-yam yoghurt (Zhao, 2009), herbaceous peonies (Huang et al., 2010), Cyclamen owers
2008), nutritious peony wine (Zhao, 2006), peony scented tea and and their hybrids (Ishizaka et al., 2002) and Petunia hybrida culti-
peony essential oil (You et al., 2011). In addition, the planting area of vars (Nakamura et al., 2006). However, there are only two reports
tree peony in China has been expanded to more than seven thou- on the study of the essential oils and volatile compounds in tree
sand hectares and therefore the comprehensive development of peony. Liu et al. (1999) detected 52 essential oil components from
peony owers is believed to be of great potential. All these imply a mixture of several tree peony cultivars with steam distillation
approach. Additionally, Zhou et al. (2008) analyzed volatile com-
pounds in ten tree peony cultivars by using headspace solid-phase
microextraction technique (HS-SPME). In their study, 34 volatile
Corresponding author. Tel.: +86 10 6283 6654; fax: +86 10 6259 0348. compounds were identied. Both studies revealed that there were
E-mail address: wanglsh@ibcas.ac.cn (L. Wang). abundant natural avoring substances in tree peony petals, such as

0304-4238/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.scienta.2012.05.015
S. Li et al. / Scientia Horticulturae 142 (2012) 158165 159

citronellol, geraniol and phenylethanol. However, tree peony cul- were desorbed by exposing the ber in the GC injector port for 3 min
tivars were classied into six cultivar-groups, namely Zhongyuan with a splitless injection. Helium was used as a carrier gas at a ow
(Central Plain), Xibei (Northwest), Jiangnan (the Lower Reaches of rate of 1.0 mL min1 . The initial oven temperature was maintained
the Yangtze River of China), Xinan (Southwest), Japanese, European at 55 C for 3 min and then raised to 210 C at the rate of 3 C min1
and American cultivar-group (Wang, 2001). It has to be noted that which was held isothermal for 1 min. The temperature of the injec-
the number of both the cultivars analyzed and the compounds iden- tor, transfer line, ion source and quadrupole were 250, 260, 230
tied have not covered the six cultivar-groups of the entire tree and 150 C, respectively. The ionization potential of mass selective
peony cultivars. Meanwhile, the scented fragrances differing from detector was 70 eV and the scan range was 30600 amu. The iden-
volatile compounds need to be claried in tree peony at global level tication of the compounds was based on comparison of their mass
(Liu et al., 1999; Zhou et al., 2008). spectra with a NIST05 database through a G1701DA ChemStation
In this study, we analyze volatile components in thirty tree (Agilent, USA).
peony cultivars covering six cultivar-groups and the scented fra-
grances are differentiated from volatile compounds for the rst 3. Results and discussion
time. Thirty cultivars are classied into ve groups by using hier-
archical cluster analysis. On this basis, we rst propose the concept 3.1. Floral fragrance
of the fragrance pattern in tree peony cultivars. Furthermore, this
study will also provide some valuable information for elucidation According to the total ionic chromatogram (Fig. 1), 146 volatile
of the chemical mechanism of ower fragrance formation in tree organic components were identied by comparison with known
peony. libraries, in which 81 compounds were identied as scent compo-
nents in thirty tree peony cultivars (Chemical Book, 2011; Huang
2. Materials and methods et al., 2010; Liang et al., 2010; Wei et al., 2010). We reported
more than 34 or 51 compounds compared with previous studies
2.1. Plant materials (Liu et al., 1999; Zhou et al., 2008). Simultaneously, the fragrance
collected with HS-SPME matched well was more corresponded to
Thirty Paeonia suffruticosa cultivars from six cultivar-groups the fragrance of the entire ower (Ishizaka et al., 2002). Table 2
were used in this study (Table 1). The plants were grown in Bei- shows that the main scent components were terpenes, alcohols,
jing Botanical Garden, Institute of Botany, the Chinese Academy of arenes and alkanes. In addition, a small amount of esters, alde-
Science (IBCAS), Beijing, China. hydes and other components were detected. The relative areas of
scent components covered a broad range from 43.22 to 98.28%.
2.2. Volatile collections Among the thirty cultivars, Shima Nishiki, Bai He Zhan Chi and
Tian Xiang possess the highest peak areas of scent components
All full-blown ower petals (three or four days after owering) over 97.17%, which is in agreement with their heavy olfactory
were collected from each cultivar in the morning between ve and fragrance. The results revealed the differences in scent compo-
seven oclock and immediately processed, in May, 2010. Two grams nents and concentrations which can guide the application in avors
of the ower petals, chosen at random from an entire ower, was and fragrances, scented teas and oral breeding systems in tree
placed in a brown glass vial (40 mL) enclosed with a plastic cap peony.
having a polytetrauoroethylene septum. These and subsequent
procedures were repeated three times for each cultivar. 3.2. Fragrance pattern
Volatile compounds were extracted by headspace SPME using a
100 m polydimethyl-siloxane coated ber attached to a manual Relative contents of 81 aromatic compounds were used as
SPME holder (Supelco, Bellefonte, PA, USA). The ber was exposed variables to establish a hierarchical cluster analysis by using the
to each sample manually penetrating the septum for 30 min at room cluster program SPSS 11.5 (Zhang and Dong, 2004). The methods
temperature and then was injected into the injection port of the of between-groups linkage, Wards method and centroid cluster-
GC, which was set at 250 C. Besides, the ber was conditioned in ing were used to obtain consistent cluster results. In each case,
the GC injection port for 30 min at 250 C before the rst volatile the squared Euclidean distance between clusters was chosen as a
collection. proximity measurement. The results were printed in the form of a
The analysis was carried out by using a gas chromatograph-mass dendrogram (Fig. 2). Taking comprehensive consideration of clus-
spectrometer (GC6890N/MS5973, Agilent) tted with an HP-5MS ter results, major fragrances and the results of sensory evaluation
capillary column (5% phenyl methyl siloxane, 30 m 0.25 mm i.d., (unpublished data), thirty tree peony cultivars were nally classi-
0.25 m lm thickness, Agilent). Volatile compounds on the ber ed into ve groups. We dened ve fragrance patterns: a woody

Table 1
Thirty samples of tree peony cultivars.

Cultivar-group Cultivar (Paeonia suffruticosa cv.)

Zhongyuan Tian Xiang (1), Tao Yuan Xian Jing (2), Yin Hong Qiao Dui (3), Hong Xing (5), Man Tian Xing
(7), Lan Bao Shi (8), Chu E Huang (9), Bai He Zhan Chi (10), Shu N Zhuang (12), Hu Die Bao
Chun (13), Jin Yun Hong (14), Hei Hai Sa Jin (16), Chun Xue (21), Hu Lan (22), Tao Hong Liu L
(29), Zi Luo Lan (30).

Northwest Xue Lian (11), Ju Hua Lan (15), Ju Yuan Shao N (18), Xin Xing (19), Diao Chan Bai Yue (17).

Southwest Chang Kang Le (4).

Jiangnan Feng Dan (20), Dian Jiang Feng Dan (6).

Japanese Shima Daijin (24), Shima Nishiki (25), Taiyoh (26), Mure Garasu (27), Shichi Fukujin (28).
European and American High Noon (23).

Numbers in parentheses indicate the number of tree peony in Tables 2 and 3.


160 S. Li et al. / Scientia Horticulturae 142 (2012) 158165

Fig. 1. Total ionic chromatogram of volatile components of Shima Daijin.

scent (cluster I, major fragrance, cis-ocimene), a rose scent (clus- 3.2.1. A woody scent
ter II, d-citronellol), a lily of the valley scent (cluster III, linalool), Cultivars falling into the woody scent were Tian Xiang, Tao
a phenolic scent (cluster IV, 1,3,5-trimethoxybenzene, TMB), and Yuan Xian Jing, Yin Hong Qiao Dui, Dian Jiang Feng Dan, Lan
an unidentied scent (cluster V, pentadecane). In addition, similar- Bao Shi, Feng Dan and Shima Nishiki, in which cis-ocimene
ity rates of fragrance pattern of thirty cultivars (Wang et al., 1991) was their major scent component. As shown in Table 2, these
were calculated to examine the clustering algorithms precision and seven cultivars also produced detectable amounts of all or some of
the results indicated that classication approach was efcient and the following: [s-(E,E)]-1-methyl-5-methylene-8-(1-methylethyl)-
reliable (Table 3). 1,6-cyclodecadiene, geraniol, pentadecane and d-citronellol. The

Fig. 2. Hierarchical cluster dendritic diagram of thirty tree peony cultivars.


Table 2
Types and proportions of oral fragrances in thirty tree peony cultivars petals.

Compounds RT (min) Relative contents (%)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
1,4-Cyclohexadiene, 1-methyl-4-(1-methylethyl)- 4.18 0.00 0.00 1.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3-Hexen-1-ol, (Z)- 5.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.29 0.00 0.00 0.00 0.00 0.00 0.00 0.00
-Pinene 6.71 0.00 0.00 0.00 0.00 1.78 0.00 0.00 0.40 0.52 0.00 0.00 1.42 0.46 0.42 0.00
-Myrcene 8.83 0.44 0.00 0.00 0.00 0.00 0.52 0.00 0.78 0.00 0.00 0.00 0.95 0.00 0.00 0.50
d-Limonene 10.29 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.35 0.15 0.00 0.00 0.62 0.00 0.00 0.00
1,3,6-Octatriene, 3,7-dimethyl-, (E)- 10.68 0.84 0.79 0.79 0.00 0.00 0.94 0.00 0.85 0.33 0.36 0.00 0.00 0.34 0.00 0.00
cis-Ocimene 11.16 75.13 35.54 32.82 0.68 0.00 58.85 0.00 63.35 12.58 18.24 6.77 0.48 22.21 0.00 0.23
Bicyclo[3.1.0]hexane, 6-isopropylidene-1-methyl- 12.77 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.15 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzenemethanol, 4-(1-methylethyl)- 13.26 0.00 0.00 0.00 0.00 0.00 0.31 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2H-Pyran, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)- 13.84 0.00 2.35 0.00 0.00 0.00 0.00 0.00 0.15 1.33 0.68 1.82 0.67 0.34 0.00 0.00
Phenylethyl alcohol 14.32 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9.39 0.00 0.00 0.00 1.48
2H-Pyran, 3,6-dihydro-4-methyl-2-(2-methyl-1-propenyl)- 15.78 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.08 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3-Nonen-1-ol, (Z)- 16.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.40 0.00 0.00
Benzene, 1,4-dimethoxy- 16.39 0.57 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.33 0.26 0.00 1.48 0.00 0.00 1.06
Benzoic acid, ethyl ester 16.63 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.14 0.00 0.27 0.00 0.00 0.00 0.00 0.00
Anisole, p-allyl- 17.79 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.79 0.00 0.00
2-Octen-1-ol, 3,7-dimethyl- 18.85 0.00 0.00 0.00 0.00 0.00 0.00 8.13 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Nerol 19.33 0.00 0.00 0.00 1.96 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.73 3.09

S. Li et al. / Scientia Horticulturae 142 (2012) 158165


d-Citronellol 19.35 5.18 25.91 10.07 0.00 1.36 8.40 11.47 8.34 11.03 62.99 31.17 27.86 45.15 0.00 0.00
2,6-Octadienal, 3,7-dimethyl-, (Z)- 19.68 0.00 0.00 0.00 0.00 0.00 2.54 0.00 1.53 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Geraniol 20.54 5.18 0.00 0.00 0.52 0.00 5.05 0.00 5.30 0.00 0.00 0.00 7.69 0.00 0.63 7.46
(E)-Citral 21.02 0.62 0.00 0.00 0.00 0.00 3.38 0.00 1.59 0.00 0.00 0.00 0.63 0.00 0.00 0.40
Tridecane 22.16 0.61 0.00 2.58 1.26 5.05 0.99 2.07 0.85 3.06 2.84 2.54 1.19 0.74 0.95 1.82
2,6-Octadienoic acid, 3,7-dimethyl-, methyl ester 23.31 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.29 0.00 0.00 0.00 0.00 0.63 0.00 0.00
1,5,5-Trimethyl-6-methylene-cyclohexene 23.69 0.00 0.00 0.00 0.22 0.00 0.00 0.00 0.00 0.16 0.00 0.00 0.00 0.00 0.00 0.00
-Cubebene 24.21 0.07 0.00 1.17 0.28 0.16 0.00 0.00 0.10 0.31 0.00 0.00 0.00 0.14 0.36 0.37
2,6-Octadiene, 2,6-dimethyl- 24.57 0.42 0.00 0.00 0.17 0.00 0.00 3.80 0.07 0.28 4.19 0.53 0.65 2.70 0.00 0.20
2,6-Octadien-1-ol, 3,7-dimethyl-, acetate, (Z)- 25.05 0.25 0.00 0.00 0.22 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.38 0.00 0.22 0.08
Copaene 25.30 0.00 0.00 0.00 0.22 0.00 0.00 0.00 0.00 0.13 0.00 0.00 0.00 0.00 0.14 0.09
Geranyl acetate 25.87 0.83 0.00 0.00 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.47 0.00 0.44 1.02
3-Tetradecene, (E)- 26.06 0.00 0.00 0.00 0.00 0.31 0.00 0.00 0.00 0.00 0.25 0.00 0.19 0.00 0.32 0.00
Benzene, 1,2-dimethoxy-4-(2-propenyl)- 26.89 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.23 0.00 0.00
Benzene, 1,3,5-trimethoxy- 27.09 0.00 14.21 0.00 20.09 0.00 5.15 5.73 7.32 11.89 1.59 0.00 0.00 14.09 35.61 1.10
Caryophyllene 27.11 3.67 0.00 0.00 0.00 0.00 0.00 5.85 0.00 0.00 0.00 0.00 5.27 0.00 0.00 0.00
Bicyclo[4.4.0]dec-1-ene, 2-isopropyl-5-methyl-9-methylene- 27.50 0.00 0.00 2.25 0.74 0.56 0.00 0.00 0.14 0.12 0.00 0.00 0.00 0.00 0.64 0.12
(+)--Cedrene 28.14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.10
Epizonarene 28.44 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00
-Caryophyllene 28.49 0.27 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.21 0.00 0.31 0.00 0.55 0.00
1H-Cycloprop[e]azulene, decahydro-1,1,7-trimethyl-4-methylene-, 28.53 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.55 0.00 0.00 0.00 0.00 0.00 0.00
[1aR-(1a,4a,7,7a,7b)]-
(+)-Epi-bicyclosesquiphellandrene 28.92 0.00 0.00 0.00 0.26 0.00 0.00 0.00 0.00 0.11 0.00 0.00 0.00 0.00 0.17 0.00
Isoledene 29.38 0.00 0.00 1.16 0.00 0.00 0.00 0.00 0.00 0.33 0.00 0.00 0.00 0.00 0.27 0.00
1,6-Cyclodecadiene, 1-methyl-5-methylene-8-(1-methylethyl)-, [s-(E,E)]- 29.64 0.78 0.00 27.66 12.02 3.05 1.29 0.00 1.43 8.15 1.59 0.00 0.00 0.67 0.00 3.23
Cyclohexene, 6-ethenyl-6-methyl-1-(1-methylethyl)-3-(1-methylethylidene)-, (S)- 30.16 0.00 0.00 0.00 0.47 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Pentadecane 30.52 1.52 11.97 4.63 25.38 35.02 4.84 26.44 1.96 19.43 2.72 21.01 20.24 3.93 25.83 47.27
-Farnesene 30.86 0.66 0.00 1.25 0.47 0.00 0.17 0.00 0.14 0.00 1.26 1.12 0.86 0.20 0.00 0.00
-Muurolene 30.97 0.00 0.00 0.85 0.47 0.00 0.00 0.00 0.15 0.41 0.00 0.00 0.00 0.00 0.17 0.10
Delta-Cadinene 31.38 0.06 0.00 1.30 0.97 0.27 0.10 0.00 0.12 0.45 0.12 0.00 0.00 0.00 0.00 0.19
Naphthalene, 1,2,3,4,4a,7-hexahydro-1,6-dimethyl-4-(1-methylethyl)- 31.72 0.00 0.00 0.00 0.11 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ethanol, 2-(9,12-octadecadienyloxy)-, (Z,Z)- 33.38 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.27
Rhodinyl acetate 33.49 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00 0.00
7-Hexadecene, (Z)- 33.50 0.00 0.00 0.00 0.00 0.63 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.15 0.21
3-Hexadecene, (Z)- 33.64 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.15 0.00 0.00 0.00 0.00 0.00 0.09
2,6-Bis(1,1-dimethylethyl)-4-(1-oxopropyl)phenol 35.80 0.10 0.00 0.00 0.00 0.19 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Bicyclo[5.3.0]decane 36.87 0.00 0.00 0.00 0.00 0.00 1.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
6,9-Heptadecadiene 36.93 0.00 0.00 0.00 0.00 0.00 0.00 1.95 0.00 0.00 0.10 0.00 3.74 0.64 0.00 0.00
3-Octadecene, (E)- 40.62 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.13
Octadecane, 2-methyl- 43.58 0.00 0.00 0.00 0.10 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.19 0.00
9-Nonadecene 43.92 0.00 0.00 0.00 0.00 0.00 0.33 0.00 0.00 0.11 0.00 0.00 0.00 0.00 0.75 0.00

161
Z-5-Nonadecene 43.94 0.00 0.00 0.00 0.94 0.32 0.00 0.00 0.00 0.00 0.00 0.52 0.68 0.07 0.00 0.32
162
Table 2 (Continued )
Compounds RT (min) Relative contents (%)

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
-Pinene 6.71 0.39 7.56 0.00 0.00 0.00 0.00 0.97 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
-Myrcene 8.83 0.00 0.53 0.00 0.00 0.38 0.00 0.16 0.68 1.45 0.00 0.64 0.00 1.24 0.00 0.00
-Phellandrene 9.27 0.00 0.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Acetic acid, hexyl ester 9.76 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.58 0.00 0.00
d-Limonene 10.29 0.00 0.31 0.00 0.00 0.19 0.00 0.21 0.11 0.44 0.00 0.74 0.09 0.52 0.00 0.00
1,3,6-Octatriene, 3,7-dimethyl-, (E)- 10.68 0.00 0.00 0.00 0.00 0.86 0.00 0.00 0.52 0.24 0.00 0.00 0.00 0.68 0.47 0.00
cis-Ocimene 11.16 0.51 0.13 0.00 0.13 44.24 0.48 0.00 0.86 0.44 2.23 0.00 0.00 38.76 32.37 0.00
Cyclohexene, 1-methyl-4-(1-methylethylidene)- 12.81 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.11 0.17 0.00 0.00
-Methyl--[4-methyl-3-pentenyl]oxiranemethanol 12.87 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.46 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzenemethanol, 4-(1-methylethyl)- 13.26 0.00 0.00 0.00 0.00 0.56 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.67 0.00 0.00
Linalool 13.51 0.00 0.00 0.00 0.00 0.00 0.00 0.00 74.16 0.00 0.00 0.00 0.00 0.88 0.00 0.00
2H-Pyran, tetrahydro-4-methyl-2-(2-methyl-1-propenyl)- 13.84 0.54 0.00 0.00 0.00 0.00 0.44 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.28 3.01
Phenylethyl alcohol 14.32 0.00 3.02 0.00 0.00 0.00 7.35 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Rhodinal 15.77 0.00 0.00 0.00 0.00 0.00 0.34 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
3-Nonen-1-ol, (Z)- 16.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.27 0.00 0.00
Benzene, 1,4-dimethoxy- 16.39 0.00 0.00 0.00 0.00 0.00 1.27 2.79 0.00 0.00 0.00 0.00 0.00 0.00 0.26 26.38
Benzoic acid, ethyl ester 16.63 0.31 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.11 0.00 0.32 0.00
Nerol 19.33 0.00 0.70 0.00 0.00 0.00 0.00 6.46 0.00 9.68 11.36 9.78 0.45 0.00 0.00 0.00
19.35 4.24 0.00 0.00 1.76 9.12 45.69 0.00 0.00 0.00 0.00 0.00 0.00 28.19 4.53 24.68

S. Li et al. / Scientia Horticulturae 142 (2012) 158165


d-Citronellol
Benzenepropanol 19.58 0.00 0.00 0.00 0.00 0.73 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,6-Octadienal, 3,7-dimethyl-, (Z)- 19.68 0.00 0.00 0.00 0.00 1.77 0.00 0.00 0.00 1.44 0.00 0.00 0.00 1.88 0.00 0.00
Geraniol 20.54 0.00 3.24 0.00 0.35 3.70 0.00 1.32 3.46 9.49 4.80 4.45 0.21 17.01 0.57 0.00
(E)-Citral 21.02 0.00 0.26 0.00 0.00 1.39 0.00 0.18 0.20 1.83 0.00 0.00 0.00 2.07 0.17 0.00
Tridecane 22.16 1.98 0.63 2.17 2.34 0.79 1.70 0.71 0.37 4.26 18.73 10.68 0.87 1.13 1.97 2.71
2-Propen-1-ol, 3-phenyl- 23.20 0.00 0.00 0.00 0.00 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
2,6-Octadienoic acid, 3,7-dimethyl-, methyl ester 23.31 0.00 0.00 0.00 2.02 0.80 0.00 0.31 0.00 0.81 0.00 1.11 0.00 0.10 0.10 0.00
Eudesma-4(14),11-diene 23.42 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.13 0.00 0.00 0.00
1,5,5-Trimethyl-6-methylene-cyclohexene 23.69 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.22 0.00 0.00 0.00 0.57 0.00 0.00 0.00
-Cubebene 24.21 0.41 0.00 0.00 0.09 0.00 0.00 0.00 0.18 0.00 0.00 0.00 2.97 0.00 0.00 0.38
2,6-Octadiene, 2,6-dimethyl- 24.57 0.12 0.00 0.00 0.00 0.11 0.33 0.08 0.00 0.24 0.00 0.00 0.00 0.63 0.09 0.38
2,6-Octadien-1-ol, 3,7-dimethyl-, acetate, (Z)- 25.05 0.00 0.00 0.00 0.00 0.00 0.00 0.11 0.00 0.73 0.00 0.00 0.00 0.60 0.00 0.00
Ylangene 25.13 0.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.27 0.00 0.00 0.00
Copaene 25.30 0.18 0.00 0.00 0.00 0.00 0.00 0.00 0.11 0.00 0.00 0.00 0.76 0.00 0.00 0.00
8,11-Octadecadienoic acid, methyl ester 25.59 0.00 0.00 0.00 0.06 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Geranyl acetate 25.87 0.00 0.06 0.00 0.00 0.10 0.00 0.09 0.00 2.02 0.00 0.00 0.00 0.94 0.00 0.00
Cyclohexane, 1-ethenyl-1-methyl-2,4-bis(1-methylethenyl)-, [1S-(1,2,4)]- 26.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.23 0.00 0.00 0.00 0.77 0.00 0.00 0.00
3-Tetradecene, (E)- 26.06 0.29 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
()--Gurjunene 26.70 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.11 0.00 0.00 0.00
Benzene, 1,2-dimethoxy-4-(2-propenyl)- 26.89 0.00 0.00 0.00 0.00 0.00 0.09 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Benzene, 1,3,5-trimethoxy- 27.09 0.00 0.00 1.40 0.02 8.48 0.00 22.17 0.00 28.88 27.85 44.41 19.17 0.20 4.34 14.95
Caryophyllene 27.11 14.48 0.00 0.00 17.32 0.00 3.21 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Bicyclo[4.4.0]dec-1-ene, 2-isopropyl-5-methyl-9-methylene- 27.50 0.15 0.00 0.00 0.06 0.00 0.00 0.00 0.15 0.00 0.00 0.00 0.66 0.00 0.00 1.10
Epizonarene 28.44 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.16 0.00 0.00 0.00
-Caryophyllene 28.49 1.22 0.00 0.00 0.77 0.00 0.26 0.00 0.76 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,4,7-Cycloundecatriene, 1,5,9,9-tetramethyl-, Z,Z,Z- 28.50 0.00 0.00 0.00 0.00 0.00 0.00 0.63 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Isocaryophillene 28.79 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.00 0.00 0.00 0.00
(+)-Epi-bicyclosesquiphellandrene 28.92 0.20 0.00 0.00 0.00 0.00 0.00 0.00 0.18 0.00 0.00 0.00 0.99 0.00 0.00 0.00
Isoledene 29.38 0.17 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.12 0.00 0.00 0.00
9-Octadecyne 29.48 0.00 0.14 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
1,6-Cyclodecadiene,1-methyl-5-methylene-8-(1-methylethyl)-, [s-(E,E)]- 29.64 0.35 0.00 0.36 0.07 1.17 0.79 0.00 8.39 0.00 0.00 2.45 1.10 0.11 0.74 7.13
Bicyclo[2.2.1]heptane, 2-cyclopropylidene-1,7,7-trimethyl- 30.15 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.28 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Pentadecane 30.52 35.24 30.48 54.29 50.10 10.36 24.78 45.89 2.15 18.96 15.78 0.85 8.77 1.39 38.64 3.95
-Farnesene 30.86 0.51 0.00 0.00 0.00 0.18 0.10 0.06 0.00 0.22 0.00 0.00 0.30 0.00 0.31 0.33
-Muurolene 30.97 0.55 0.00 0.00 0.09 0.00 0.16 0.00 0.51 0.00 0.00 0.00 1.79 0.00 0.00 0.25
Delta-Cadinene 31.38 0.41 0.00 0.00 0.00 0.06 0.00 0.00 0.00 0.00 0.00 0.00 1.35 0.00 0.00 0.37
1,6,10-Dodecatrien-3-ol, 3,7,11-trimethyl- 33.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.14 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Ethanol, 2-(9,12-octadecadienyloxy)-, (Z,Z)- 33.38 0.00 0.26 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
7-Hexadecene, (Z)- 33.50 0.00 0.62 0.00 0.05 0.07 0.14 0.00 0.00 0.12 0.00 0.00 0.00 0.00 0.00 0.00
3-Hexadecene, (Z)- 33.64 0.33 0.00 0.27 0.00 0.00 0.00 0.09 0.00 0.00 0.00 0.00 0.04 0.00 0.00 0.00
Geranyl butrate 34.73 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.15 0.00 0.00
S. Li et al. / Scientia Horticulturae 142 (2012) 158165 163

owers of all the seven cultivars produced an almost solid fragrance

0.13
0.00
0.00
0.00
0.00
0.00
0.00
0.00
by day, which is consistent with the similarity rates of fragrance

30
pattern more than 0.69. Among them, Tian Xiang, Lan Bao Shi and
Shima Nishiki led a heavy olfactory fragrance and they were useful

0.38
0.00
0.00

0.00
0.00
0.00
0.00
0.00
for the development of peony products and fragrant cultivars.

29
cis-Ocimene gave a typical woody scent (Shu, 2004), which con-
tributed a lot to the oral fragrance of above-mentioned peonies
and it was widely applied in essence. Therefore, Tian Xiang, Lan

0.12
0.00

0.00
0.00
0.00
0.00
0.00
0.00
28
Bao Shi and Dian Jiang Feng Dan were potential materials for pro-
ducing this scented fragrance due to their high content detected on
the gas chromatogram (Table 2).

1.23
0.08
0.05
0.00
0.00
0.00

0.00
0.00
27

3.2.2. A rose scent


In this study, Bai He Zhan Chi, Hu Die Bao Chun, Chun Xue,
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00 Xue Lian, Shu N Zhuang and Zi Luo Lan were described as rose-
26

like fragrances. As shown in Table 2, d-citronellol was detected


as their major aromatic compound, whereas the minor fragrances
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00

were all or parts of cis-ocimene, phenylethyl alcohol, pen-


25

tadecane, 1,3,5-trimethoxybenzene and 1,4-dimethoxy-benzene.


Corresponding to the similarity rates of fragrance pattern, Zi Luo
Lan was different from others because of its high level of 1,4-
4.42

1.41
0.00
0.00
0.00
0.00
0.00
0.00

dimethoxy-benzene, which contributed to its characteristic note


24

blended with d-citronellol. Similarly, Bai He Zhan Chi and Hu


Die Bao Chun emitted a special scent through the agency of cis-
0.14
0.00

0.00
0.00
0.00
0.00
0.00
0.00

ocimene and d-citronellol. In addition, Chun Xue, Xue Lian and


23

Shu N Zhuang, with a delicate aroma, contained relatively high


concentrations of alkanes.
9.24
0.83

0.12
0.00

0.00
0.00
0.00
0.00

Ishizaka et al. (2002) reported that citronellol emitted a rose-like


22

scent and it could be applied to improve the fragrance of owers


and produce perfumes, food avors and fragrances. Since the peak
areas of d-citronellol detected from Bai He Zhan Chi, Hu Die Bao
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
21

Chun and Chun Xue were more than 45.15%, the underlying value
as important fragrance materials would be developed in the future.
1.78

0.64
0.00
0.00
0.00
0.00
0.00
0.00

3.2.3. A lily of the valley scent


20

High Noon differed signicantly from Chinese and Japanese


tree peony cultivars and it was grouped into a category alone due
9.57

0.22
0.08
0.00

0.00
0.00
0.00

0.00

to its unique oral scent. According to our data, linalool was only
19

detected in High Noon (high concentration, 74.16%) and Shima


Nishiki (low concentration, 0.88%) and was believed to be a char-
0.19

0.53
0.00
0.00
0.00
0.00
0.00

0.00

acteristic compound described as a fragrance resembling lily of


18

the valley. Besides, pentadecane, geraniol and [s-(E,E)]-1-methyl-5-


methylene-8-(1-methylethyl)-1,6-cyclodecadiene were identied
Relative contents (%)

as secondary scented compounds in High Noon.


36.49

0.12
0.00

0.00
0.00
0.00
0.00

0.00

The similarity rates of oral pattern with High Noon were less
17

Numbers from one to thirty indicate the number of tree peony in Table 1.

than 0.08 in consistent with the classication result proved to be


effective again. Linalool led a lily of the valley avor (Sun and Hao,
0.11
0.00
0.00
0.00
0.00
0.00
0.00

0.00

2009) and was used to produce essential oils and other avors. Con-
16

sequently, High Noon had a signicant value for breeding fragrant


peonies because of its characteristic aroma composition, pleas-
RT (min)

ant scent, far genetic distance with other tree peony cultivars and
36.87
36.93

43.58
43.71
43.92
43.94
37.09
40.60

unique yellow color.

3.2.4. A phenolic scent


9,12-Octadecadienoic acid, methyl ester

The cultivars that strongly emitted abundant 1,3,5-


trimethoxybenzene were limited to a specic group, which
cis,cis,cis-7,10,13-Hexadecatrienal

had a phenolic avor, including Jin Yun Hong, Shima Daijin,


Chang Kang Le, Chu E Huang, Shima Nishiki, Taiyoh and Mure
Garasu. Pentadecane, geraniol, [s-(E,E)]-1-methyl-5-methylene-
Octadecane, 2-methyl-

8-(1-methylethyl)-1,6-cyclodecadiene, nerol, tridecane and


Bicyclo[5.3.0]decane
6,9-Heptadecadiene
Table 2 (Continued )

cis-ocimene together constituted minor components of these


Z-5-Nonadecene
E-7-Octadecene

9-Nonadecene

seven cultivars, in which pentadecane was the major compound in


Compounds

Chang Kang Le and Chu E Huang. Chang Kang Le, Chu E Huang
and Shima Nishiki emitted lighter avors than others due to
the high concentrations of alkanes. Among these seven cultivars,
Shima Daijin and Taiyoh gave the relatively rich avors, whereas
164
Table 3
Similarity rates of fragrance pattern in thirty tree peony cultivars.

Cultivars 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30
1 1.00 0.78 0.76 0.04 0.02 0.99 0.05 0.99 0.46 0.34 0.24 0.10 0.48 0.01 0.04 0.06 0.02 0.02 0.04 0.95 0.08 0.02 0.02 0.04 0.08 0.01 0.01 0.82 0.66 0.05
2 1.00 0.70 0.37 0.27 0.85 0.46 0.84 0.80 0.74 0.69 0.57 0.88 0.39 0.26 0.30 0.16 0.26 0.25 0.91 0.60 0.35 0.02 0.36 0.35 0.29 0.37 0.87 0.74 0.47
3 1.00 0.31 0.17 0.77 0.17 0.77 0.64 0.44 0.36 0.25 0.52 0.06 0.15 0.14 0.07 0.11 0.11 0.77 0.26 0.09 0.08 0.07 0.11 0.05 0.09 0.69 0.58 0.27
4 1.00 0.76 0.14 0.72 0.12 0.82 0.06 0.40 0.42 0.22 0.90 0.76 0.68 0.46 0.75 0.68 0.29 0.35 0.90 0.06 0.83 0.74 0.60 0.84 0.04 0.62 0.35

S. Li et al. / Scientia Horticulturae 142 (2012) 158165


5 1.00 0.09 0.85 0.04 0.70 0.09 0.56 0.59 0.11 0.58 0.98 0.92 0.63 0.99 0.92 0.23 0.50 0.87 0.04 0.51 0.46 0.05 0.41 0.05 0.76 0.15
6 1.00 0.14 1.00 0.56 0.41 0.32 0.19 0.56 0.12 0.10 0.10 0.06 0.08 0.08 0.98 0.17 0.11 0.02 0.15 0.17 0.10 0.11 0.85 0.70 0.13
7 1.00 0.09 0.77 0.40 0.74 0.79 0.43 0.64 0.83 0.89 0.58 0.85 0.87 0.29 0.73 0.83 0.02 0.57 0.50 0.20 0.51 0.23 0.69 0.38
8 1.00 0.54 0.40 0.29 0.15 0.56 0.11 0.05 0.06 0.03 0.03 0.04 0.98 0.14 0.08 0.02 0.14 0.16 0.12 0.12 0.85 0.67 0.13
9 1.00 0.52 0.72 0.67 0.66 0.71 0.68 0.66 0.42 0.67 0.63 0.69 0.64 0.75 0.06 0.65 0.62 0.43 0.65 0.55 0.84 0.51
10 1.00 0.83 0.77 0.95 0.04 0.05 0.15 0.03 0.04 0.07 0.46 0.85 0.05 0.01 0.05 0.07 0.03 0.04 0.74 0.30 0.61
11 1.00 0.92 0.79 0.31 0.53 0.58 0.35 0.53 0.52 0.43 0.97 0.47 0.02 0.28 0.26 0.02 0.22 0.58 0.59 0.55
12 1.00 0.72 0.33 0.59 0.66 0.45 0.56 0.62 0.30 0.95 0.52 0.03 0.34 0.27 0.04 0.23 0.53 0.51 0.56
13 1.00 0.26 0.08 0.17 0.06 0.08 0.10 0.63 0.79 0.18 0.01 0.25 0.25 0.26 0.27 0.80 0.43 0.64
14 1.00 0.60 0.54 0.37 0.61 0.55 0.27 0.28 0.86 0.02 0.92 0.83 0.78 0.96 0.02 0.52 0.36
15 1.00 0.90 0.63 0.98 0.91 0.24 0.47 0.88 0.04 0.57 0.47 0.08 0.43 0.08 0.76 0.13
16 1.00 0.58 0.92 0.98 0.24 0.55 0.81 0.03 0.47 0.40 0.03 0.38 0.10 0.72 0.16
17 1.00 0.63 0.72 0.15 0.31 0.69 0.02 0.34 0.27 0.02 0.26 0.04 0.48 0.06
18 1.00 0.93 0.22 0.47 0.89 0.03 0.53 0.44 0.05 0.43 0.03 0.76 0.11
19 1.00 0.21 0.49 0.85 0.03 0.47 0.40 0.03 0.38 0.05 0.71 0.11
20 1.00 0.28 0.27 0.02 0.29 0.29 0.19 0.25 0.85 0.79 0.21
21 1.00 0.41 0.02 0.24 0.21 0.02 0.19 0.50 0.44 0.60
22 1.00 0.03 0.80 0.70 0.45 0.74 0.03 0.70 0.28
23 1.00 0.03 0.02 0.01 0.02 0.04 0.03 0.02
24 1.00 0.90 0.83 0.90 0.12 0.46 0.34
25 1.00 0.86 0.82 0.11 0.42 0.34
26 1.00 0.86 0.04 0.11 0.38
27 1.00 0.02 0.39 0.39
28 1.00 0.56 0.35
29 1.00 0.17
30 1.00
Numbers from one to thirty indicate the number of tree peony in Table 1.
S. Li et al. / Scientia Horticulturae 142 (2012) 158165 165

Mure Garasu held a very delicate fragrance as a consequence of in GCMS analysis, and Professor Yongzhen Pang (Institute of
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istry, China Agricultural University, Beijing, China) for assistance

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