# An Update on Oligosaccharides and Their Esters from Traditional Chinese Medicines: Chemical Structures and Biological Activities

Authors: Xiang-Yang Chen; Ru-Feng Wang; Bin Liu
Journal: Evidence-Based Complementary and Alternative Medicine
 (2015)

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## Abstract

A great number of naturally occurring oligosaccharides and oligosaccharide esters have been isolated from traditional Chinese medicinal plants, which are used widely in Asia and show prominent curative effects in the prevention and treatment of kinds of diseases. Numerousin vitro and in vivo experiments have revealed that oligosaccharides and their esters exhibited various activities, including antioxidant, antidepressant, cytotoxic, antineoplastic, anti-inflammatory, neuroprotective, cerebral protective, antidiabetic, plant growth-regulatory, and immunopotentiating activities. This review summarizes the investigations on the distribution, chemical structures, and bioactivities of natural oligosaccharides and their esters from traditional Chinese medicines between 2003 and 2013.


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## Body

## 1. Introduction

Oligosaccharides and their esters, a significant group of phytochemical compounds, are widely distributed in the roots, rhizomes, stems, barks, leaves, aerial, and whole parts of medicinal plants. They not only serve as the energy storage components, but also play a vital role in the treatment of diseases. Before 2003, there have been a number of reviews and reports in respect to the isolation and structure elucidation of oligosaccharides and their esters from Chinese medicinal plants [1–3], but few biological activities such as cancer chemopreventive, and protein kinase C inhibitory activities had been reported [4–6]. With the development of isolation and identification techniques [7–11], a larger number of oligosaccharides and their esters have been endlessly identified from traditional Chinese medicines in the past decades. These compounds have a wide variety of structure types because of the assembly of different monosaccharide units, the combination of various linking styles and the existence of kinds of substituents. And more promising biological activities associated with some of the oligosaccharides and their esters have been discovered.In vitro andin vivo investigations have demonstrated that they displayed antioxidant, antidepressant, anti-inflammatory, neuroprotective, cerebral protective, antidiabetic, cytotoxic, antineoplastic, plant growth-regulatory, and immunopotentiating activities, and so forth. This review aims to provide a systemic summary of the studies on the distribution, chemical structures and biological activities of naturally occurring oligosaccharides and their esters from traditional Chinese medicines in the past decades. Among these compounds, the number of oligosaccharide esters is much greater than that of oligosaccharides, and the disaccharide esters are a very valuable source of active compounds. This information may help readers understand the structure characteristics and therapeutic indications of oligosaccharides and their esters from traditional Chinese medicines and offer clues to the development of new drugs.


## 2. Chemical Structures

Phytochemical investigations of traditional Chinese medicines have shown that many botanical families, including Polygalaceae, Liliaceae, Asteraceae, Polygonaceae, Smilacaceae, Scrophulariaceae, Asclepiadaceae, Arecaceae, Orobanchaceae, Acanthaceae, Rosaceae, Musaceae, Sparganiaceae, Leguminosae, Equisetaceae, Boraginaceae, Iridaceae, Alismataceae, Lamiaceae, Araliaceae, Rubiaceae, Oleaceae, Apocynaceae, Caryophyllaceae, Aspleniaceae and Trilliaceae, are rich in oligosaccharides and their esters. Oligosaccharides show diversified structures because of the type and the number of monosaccharides, as well as the position of glycosidic bonds. And oligosaccharide esters also display distinctive structural diversity largely owing to the number, type, and position ofO-substituent units, including phenylpropanoid groups (e.g., coumaroyl, feruloyl, caffeoyl, sinapoyl, 3,4,5-trimethoxycinnamoyl, and cinnamoyl), benzoyl,p-methoxybenzoyl, andp-hydroxybenzoyl groups (Figure 2). Moreover, the double bonds of phenylpropanoid groups possesstrans andcis isomeric forms, of which thetrans forms widely exist in nature. Hence, according to the number of monosaccharides and the characteristics of chemical structures, these oligosaccharide esters could be categorized into 7 large groups.


### 2.1. Oligosaccharides

All compounds of this group (Table1 and Figure 1) merely consist of various monosaccharides withoutO-substituents. In addition to the well-known sucrose, β-D-glucopyranosyl(1→2)-β-D-glucopyranoside (1) was isolated fromCamptosorus sibiricus[12]. The oligosaccharides of raffinose (3), stachyose (19), and verbascose (21), all of which belong to the Raffinose family, possess one, two or three galactopyranosyl units linked to sucrose and have been found in the rhizomes and roots ofAlisma orientalis [13],Lycopus lucidus [14],Rehmannia glutinosa [15, 16],Salvia miltiorrhiza [17], andScrophularia ningpoensis [18]. Manninotriose (4) and verbascotetraose (5) consisting of galactopyranosyl units and a glucopyranosyl unit have been isolated fromAlisma orientalis [13].Table 1
Oligosaccharides.
No.
Name
R1
R2
R3
R4
R5
R6
Source
Parts
Reference
22
Perifosaccharide A
OH(e)
OCH3(e)
H
OH(e)
OH
A
Periploca forrestii
Roots
[32]
23
Perifosaccharide B
OH(e)
OCH3(a)
H
OH(e)
OH
A
Periploca forrestii
Roots
[32]
24
Perifosaccharide C
OH(e)
OCH3(e)
H
OH(e)
OCH3
A
Periploca forrestii
Roots
[32]
25
Perifosaccharide D
OAc(e)
OCH3(e)
H
OH(e)
OH
A
Periploca forrestii
Roots
[32]
26
Perisaccharide A
OH(a)
OCH3(e)
OAc
OH(e)
OCH3
A
Periploca sepium
Root barks
[33]
27
Perisaccharide B
OAc(e)
OCH3(a)
H
OH(e)
OH
A
Periploca sepium
Periploca calophylla
Root barks
[33, 34]
28
Perisaccharide C
OH(a)
OCH3(e)
OAc
OCH3(a)
OH
A
Periploca sepium
Root barks
[33]
29
Perisaccharide D
OAc(e)
OCH3(a)
H
OH(e)
OCH3
A
Periploca calophylla
Stems
[34]
30
Perisesaccharide B
OH(a)
OCH3(e)
OAc
OH(e)
OCH3
C
Periploca sepium
Root barks
[35]
31
Perisesaccharide C
OH(a)
OCH3(e)
OH
OCH3(a)
OCH3
C
Periploca sepium
Root barks
[35]
32
Perisesaccharide D
OH(a)
OCH3(e)
OH
OCH3(a)
OH
C
Periploca sepium
Root barks
[35]
33
Perisesaccharide E
OH(a)
OCH3(e)
OAc
OH(e)
OH
C
Periploca sepium
Root barks
[35]
34
Cymaropyranurolactone 4-O-β-D-digitalopyranosyl-(1
→
4)-O-β-D-cymaropyranosyl-(1
→
4)-O-β-D-oleandropyranosyl-(1
→
4)-O-β-D-cymaropyranoside
OH(a)
OCH3(e)
OH
OCH3(e)
OCH3
B
Parabarium huaitingii
Barks
[36]
See Scheme1.Scheme 1Figure 1Figure 2Five oligosaccharides comprising 1-kestose (6), nystose (7), 1-β-fructofuranosylnystose (8), hexasaccharide (9), and heptasaccharide (10) consisting of fructofuranose and glucopyranose have been isolated from the aerial parts and roots ofGynura divaricata subsp.formosana [19],Morinda officinalis [20–22],Saussurea lappa [23], andAralia cordata [24]. Two water-soluble oligosaccharides (11,12) composed of two or three types of monosaccharides including glucopyranose, fructopyranose, and fructofuranose have been obtained from the whole plants ofBlumea riparia [25, 26].Besides, malto-oligosaccharides (17, n = 0~8) consisting of α-D-glucopyranosyl residues assembled by (1→4)-linkages and inulo-oligosaccharides (18, n = 1~3) consisting of only fructosyl residues formed by (2→1)-linkages have been found in the roots ofPanax ginseng [27, 28] andMorinda officinalis [20], respectively. Three noteworthy oligosaccharides (2,13,14) formed by α-D-glucopyranosyl units with (1→6)-linkages and a (1→4)-linkage have been found in the roots ofPanax ginseng [28]. And two linear oligosaccharides termed heptasaccharide (15) and octasaccharide (16) consisting of glucose and mannose monomers were identified from the rhizomes ofParis polyphylla var.yunnanensis [29, 30]. A pentasaccharide, stellariose (20) consisting of a raffinose backbone with two galactosyl residues bound to the fructosyl and glucosyl moieties was identified from the stems ofStellaria media [31].Oligosaccharides (Table1) are composed of seven kinds of deoxyhexoses including cymaropyranose, canaropyranose, digitoxopyranose, oleandropyranose, digitalopyranose, cymaropyranurolactone, and oleandronic acid-δ-lactone. Oleandronic acid-δ-lactone exhibits the boat and chair conformations. The hydroxyl, methyl, and acetyl groups are located at the equatorial (e) and axial (a) bonds in the chair conformation of deoxyhexoses. These oligosaccharides were isolated from the traditional Chinese medicines including the roots ofPeriploca forrestii, the root barks ofP. sepium, the stems ofP. calophylla, and the barks ofParabarium huaitingii.


### 2.2. Oligosaccharide Esters

#### 2.2.1. Phenylpropanoid-Derived Disaccharide Esters

Phenylpropanoid-derived disaccharide esters (Table2 and Figure 3) account for a considerable proportion of oligosaccharide esters and mainly possess a core of sucrose carrying a varying number ofO-substituents, including phenylpropanoid groups, acetyl, benzoyl,p-methoxybenzoyl, andp-hydroxybenzoyl groups. Phenylpropanoid substituents are just present at 1′, 3′, 4′, 6′ positions of β-D-fructofuranosyl unit in compounds35–97, whereas they appear at 2, 3, 4, 6 positions of α-D-glucopyranosyl moiety in compounds98–101. Moreover, compounds76–97 are mainly esterified with acetyl groups along with a phenylpropanoid substituent, coumaroyl, feruloyl, or 3,4,5-trimethoxycinnamoyl group. Interestingly, the phenylpropanoid substituents are only attached to the 3′ position of sucrose. The two sugar rings of compounds102–128 both possess phenylpropanoid substituents. These oligosaccharide esters have been found in the roots and rhizomes ofPolygala tricornis,P. tenuifolia,Fagopyrum tataricum,Scrophularia ningpoensis,Cynanchum amplexicaule,Smilax riparia,Paris polyphyllavar.yunnanensis,Smilacis glabrae,Fagopyrum dibotrys, andSparganium stoloniferum, the underground parts ofTrillium kamtschaticum, the stems ofPolygonum sachalinensis,P. cuspidatum,P. hydropiper,Smilax china, andCalamus quiquesetinervius, the aerial parts ofPolygala sibirica,Smilax bracteata,Heterosmilax erythrantha, andMusella lasiocarpa, the leaves ofPersicaria hydropiper andPolygonum hydropiper, the whole plants ofBidens parviflora andPolygala hongkongensis, and the flower buds ofPrunus mume.Table 2
Phenylpropanoid-derived disaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
R7
R8
Source
Parts
Reference
35
Sibiricose A6
H
H
H
H
K
H
H
H
Polygala tricornis
Polygala tenuifolia
Roots  Root barks
[37–40]
36
3′-O-Feruloyl sucrose/Sibiricose A5
H
H
H
H
I
H
H
H
Polygala tenuifolia
Trillium kamtschaticum
Roots Underground parts
[38–42]
37
Glomeratose A
H
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
38
Lapathoside D
H
H
H
H
G
G
H
H
Polygonum sachalinense
Stems
[43]
39
Helonioside A
H
H
H
H
I
I
H
H
Trillium kamtschaticum
Smilax bracteata
Paris polyphylla var. yunnanensis
Undergroundparts  Aerial parts  Roots
[41, 44, 45]
40
Helonioside B
Ac
H
H
H
I
I
H
H
Smilax bracteata
Smilax china
Smilax riparia
Heterosmilax erythrantha
Aerial partsStems Roots and rhizomes
[44, 46–48]
41
Parispolyside F
H
H
H
H
G
I
H
H
Paris Polyphylla var. yunnanensis
Rhizomes
[49, 50]
42
Hydropiperoside
H
H
H
H
G
G
H
G
Polygonum sachalinense
Polygonum cuspidatum
Persicaria hydropiper
StemsLeaves
[43, 51, 52]
43
Tricornose B
D
Ac
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
44
Tenuifoliside A
F
H
H
H
L
H
H
H
Polygala tenuifolia
Polygala hongkongensis
Polygala sibirica
RootsWhole plants     Aerial parts
[38, 40, 42, 53–56]
45
Tatariside A
Ac
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
46
Tatariside E
H
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
47
Tatariside G
H
H
H
H
I
G
H
G
Fagopyrum tataricum
Roots
[57]
48
Smiglaside A
Ac
Ac
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
49
Smiglaside B
Ac
H
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
50
Smiglaside E
Ac
H
H
Ac
I
I
H
G
Smilax china
Stems
[46]
51
Smilaside A
Ac
Ac
H
H
I
I
H
H
Smilax china
Stems
[46]
52
Smilaside B
H
H
H
Ac
I
I
H
H
Smilax china
Stems
[46]
53
Smilaside C
H
H
H
H
I
I
H
G
Smilax china
Stems
[46]
54
Smilaside D
H
H
H
H
I
I
Ac
G
Smilax china
Stems
[46]
55
Smilaside E
Ac
H
H
H
I
I
H
G
Smilax bracteata
Smilax china
Aerial parts  Stems
[44, 46]
56
Smilaside F
Ac
H
H
Ac
G
I
H
G
Smilax china
Stems
[46]
57
Smilaside G
H
H
H
H
G
I
H
G
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
58
Smilaside H
H
H
H
Ac
G
I
H
G
Smilax bracteata
Aerial parts
[44]
59
Smilaside I
Ac
H
H
H
G
I
H
G
Smilax bracteata
Aerial parts
[44]
60
Smilaside J
H
H
H
H
G
I
H
I
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
61
Smilaside K
H
H
H
Ac
I
I
H
G
Smilax bracteata
Aerial parts
[44]
62
Smilaside L
H
H
H
H
I
I
H
I
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
63
Smilaside M
Ac
H
H
Ac
Cis-feruloyl
I
H
H
Smilax riparia
Roots and rhizomes
[59]
64
Smilaside N
Ac
H
H
Ac
I
Cis-feruloyl
H
H
Smilax riparia
Roots and rhizomes
[59]
65
Smilaside P
H
H
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
66
3′,4′,6′-O-Tri-feruloylsucrose
H
H
H
H
I
I
I
H
Smilax riparia
Rhizomes and roots
[60]
67
6′-O-Coumaroylsucrose
H
H
H
H
H
G
H
H
Bidens parviflora
Whole plants
[61]
68
1′-O-Coumaroyl-6′-O-feruloylsucrose
H
H
H
H
H
I
H
G
Smilax bracteata
Aerial parts
[44]
69
4-O-Benzoyl-3′-3,4,5-trimethoxycinnamoylsucrose
H
D
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
70
6-O-Benzoyl-3′-O-3,4,5-trimethoxycinnamoylsucrose
D
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
71
6-O-Benzoyl-3′-O-sinapoylsucrose
D
H
H
H
K
H
H
H
Polygala tricornis
Roots
[37]
72
6-O-p-Methoxybenzoyl-3′-O-3,4,5-trimethoxycinnamoylsucrose
E
H
H
H
L
H
H
H
Polygala tenuifolia
Roots
[56]
73
2,6-Di-acetyl-3′,6′-di-feruloylsucrose
Ac
H
H
Ac
I
I
H
H
Smilax china
Smilax riparia
Heterosmilax erythrantha
StemsRoots and rhizomes   Aerial parts
[46–48, 59]
74
2,6-Di-acetyl-3′-O-cis-feruloy-6′-trans-feruloylsucrose
Ac
H
H
Ac
Cis-feruloy
I
H
H
Smilax riparia
Roots and rhizomes
[59]
75
2,6-Di-acetyl-3′-O-trans-feruloy-6′-cis-feruloylsucrose
Ac
H
H
Ac
I
Cis-feruloyl
H
H
Smilax riparia
Roots and rhizomes
[59]
76
Regaloside A
Ac
H
H
H
I
H
H
H
Trillium kamtschaticum
Underground parts
[41]
77
Tricornose A
Ac
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
78
Mumeose A
H
H
H
Ac
G
H
H
H
Prunus mume
Flower buds
[62, 63]
79
Mumeose B
Ac
H
Ac
H
G
H
H
H
Prunus mume
Flower buds
[62, 63]
80
Mumeose C
Ac
H
Ac
Ac
G
H
H
H
Prunus mume
Flower buds
[62, 63]
81
Mumeose D
Ac
Ac
Ac
Ac
G
H
H
Ac
Prunus mume
Flower buds
[62, 63]
82
Mumeose E
Ac
Ac
Ac
Ac
Cis-coumaroyl
H
H
Ac
Prunus mume
Flower buds
[62, 63]
83
Mumeose F
Ac
Ac
Ac
H
G
H
H
H
Prunus mume
Flower buds
[63]
84
Mumeose G
Ac
H
Ac
H
G
H
Ac
H
Prunus mume
Flower buds
[63]
85
Mumeose H
H
H
Ac
Ac
G
H
Ac
H
Prunus mume
Flower buds
[63]
86
Mumeose I
Ac
Ac
Ac
H
G
Ac
H
H
Prunus mume
Flower buds
[63]
87
Mumeose J
Ac
Ac
Ac
Ac
G
H
Ac
Ac
Prunus mume
Flower buds
[63]
88
Mumeose K
H
H
Ac
Ac
G
H
H
H
Prunus mume
Flower buds
[64]
89
Mumeose L
Ac
H
Ac
Ac
G
H
Ac
H
Prunus mume
Flower buds
[64]
90
Mumeose M
Ac
Ac
Ac
H
G
H
Ac
Ac
Prunus mume
Flower buds
[64]
91
Mumeose N
Ac
Ac
Ac
H
G
Ac
Ac
H
Prunus mume
Flower buds
[64]
92
Mumeose O
Ac
H
Ac
Ac
G
H
Ac
Ac
Prunus mume
Flower buds
[64]
93
1′,2,3,4,6-O-Penta-acetyl-3′-O-trans-coumaroylsucrose
Ac
Ac
Ac
Ac
G
H
H
Ac
Musella lasiocarpa
Aerial parts
[65]
94
1′,2,3,4,6-O-Penta-acetyl-3′-O-cis-coumaroylsucrose
Ac
Ac
Ac
Ac
Cis-coumaroyl
H
H
Ac
Musella lasiocarpa
Aerial parts
[65]
95
1′,2,3,6-O-Tetra-acetyl-3′-O-cis-feruloylsucrose
Ac
H
Ac
Ac
Cis-feruloyl
H
H
Ac
Sparganium stoloniferum
Rhizomes
[66]
96
1′,2,4,6-O-Tetra-acetyl-3′-O-trans-feruloylsucrose
Ac
Ac
H
Ac
I
H
H
Ac
Sparganium stoloniferum
Rhizomes
[66]
97
1′,2,3,6-O-Tetra-acetyl-3′-O-trans-feruloylsucrose
Ac
H
Ac
Ac
I
H
H
Ac
Sparganium stoloniferum
Rhizomes
[67]
98
Sibirioside A
M
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
99
Sibricose A1
K
H
H
H
H
H
H
H
Cynanchum amplexicaule
Roots
[69]
100
6-O-Caffeoylsucrose
J
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
101
Acretoside
I
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
102
Tenuifoliside B
F
H
H
H
K
H
H
H
Polygala tenuifolia
Roots
[42, 56]
103
Tenuifoliside C
K
H
H
H
L
H
H
H
Polygala tricornis
Polygala tenuifolia
Roots
[37, 42, 56]
104
Heterosmilaside
H
H
I
H
H
I
H
H
Heterosmilax erythrantha
Aerial parts
[48]
105
Quiquesetinerviuside A
H
I
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
106
Quiquesetinerviuside B
Ac
I
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
107
Quiquesetinerviuside C
H
I
H
Ac
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
108
Quiquesetinerviuside D
Ac
G
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
109
Quiquesetinerviuside E
H
G
H
Ac
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
110
Vanicoside A
I
H
H
Ac
G
G
H
G
Polygonum sachalinensis
Polygonum cuspidatum
Polygonum hydropiper
StemsLeaves      Rhizomes
[51, 52, 71, 72]
111
Vanicoside B
I
H
H
H
G
G
H
G
Polygonum sachalinensis
Polygonum cuspidatum
Persicaria hydropiper
Stems   Leaves     Rhizomes
[43, 51, 52, 71, 72]
112
Vanicoside D
G
H
H
H
G
G
H
G
Persicaria hydropiper
Leaves
[51]
113
Vanicoside E
I
Ac
H
Ac
G
G
H
G
Polygonum hydropiper
Stems and leaves
[72]
114
Lapathoside A
I
H
H
H
G
G
H
I
Polygonum sachalinensis
Polygonum cuspidatum
Fagopyrum dibotrys
StemsRhizomes
[51, 73]
115
Lapathoside C
I
H
H
H
G
G
H
H
Polygonum sachalinensis
Polygonum cuspidatum
Stems
[43, 52]
116
Diboside A
G
H
H
H
G
I
H
G
Fagopyrum tataricum
Fagopyrum dibotrys
Roots    Rhizomes
[57]
117
Hidropiperoside A
I
H
H
H
H
G
H
G
Polygonum hydropiper
Stems and leaves
[72]
118
Hidropiperoside B
I
H
H
Ac
G
G
H
I
Polygonum hydropiper
Stems and leaves
[72]
119
Tatariside B
I
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
120
Tatariside C
I
Ac
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
121
Tatariside D
G
H
H
Ac
G
I
H
H
Fagopyrum tataricum
Roots
[57]
122
Tatariside F
G
H
H
H
I
I
H
G
Fagopyrum tataricum
Roots
[57]
123
3′,6-O-Di-sinapoylsucrose
K
H
H
H
K
H
H
H
Polygala tricornis
Polygala hongkongensis
Polygala sibirica
Polygala tenuifolia
Cynanchum amplexicaule
Roots  Root barks  Whole plants  Aerial parts
[37–39, 41, 53–56, 69, 74]
124
6,6′-O-Di-coumaroylsucrose
G
H
H
H
H
G
H
H
Bidens parviflora
Whole plants
[61]
125
1′,3′,6′-O-Tri-coumaroyl-6-feruloylsucrose
I
H
H
H
G
G
H
G
Fagopyrum tataricum
Roots
[75, 76]
126
3′,6′-O-Di-coumaroyl-1′,6-O-di-feruloylsucrose
I
H
H
H
G
G
H
I
Fagopyrum tataricum
Roots
[75, 76]
127
3′-O-Coumaroyl-1′,6′,6-O-tri-feruloylsucrose
I
H
H
H
I
G
H
I
Fagopyrum tataricum
Roots
[75, 76]
128
1′,3′,6′,6-O-Tetra-feruloylsucrose
I
H
H
H
I
I
H
I
Fagopyrum tataricum
Roots
[75, 76]
See Scheme 2.Scheme 2Figure 3Cistanoside F (129) has been found in the stems ofCistanche tubulosa [80] andC. sinensis [81], the barks ofPaulownia tomentosavar.tomentosa[82], and the aerial parts ofAcanthus ilicifolius [83]. Cistanoside I (130) has also been isolated from the stems of theCistanche plants [84]. Both of them are composed of glucosyl and rhamnosyl groups connected by a 1→3 glycosidic bond. In addition, 6,6′-sucrose ester of (1α,2α,3β,4β)-3,4-bis(4-hydroxyphenyl)-1,2-cyclobutanedicarboxylic acid (131) with a bis(4-hydroxyphenyl) cyclobutanedicarboxyl group as the acyl unit in the molecule structure was isolated from the whole plants ofBidens parviflora[61].


#### 2.2.2. Fatty Acid-Derived Disaccharide Esters

Eight monosubstituted disaccharide esters (Table3) with a sucrose moiety possess six different types of fatty acid residues which attach to the 6 or 6′ position of sucrose. These fatty acids include linoleic acid, palmitic acid, linolenic acid, myristic acid, hexadeca-7,10,13-trienoic acid, and hexadeca-7,10-dienoic acid. The above sucrose fatty acid esters have been found in the rhizomes ofAstragalus membranaceus and the roots ofEquisetum hiemale.Table 3
Fatty acid-derived disaccharide esters.
Number
Name
R1
R2
Source
Parts
Reference
132
6′-O-Linoleylsucrose
H
O
Astragalus membranaceus
Roots
[77]
133
6′-O-Palmitoylsucrose
H
P
Astragalus membranaceus
Roots
[77]
134
6-O-Palmitoylsucrose
P
H
Astragalus membranaceus
Roots
[77]
135
6′-O-Linolenoylsucrose
H
N
Astragalus membranaceus
Equisetum hiemale
Roots              Aerial parts
[77, 78]
136
6-O-Linoleylsucrose
O
H
Astragalus membranaceus
Roots
[77]
137
6-O-Myristoylsucrose
Q
H
Astragalus membranaceus
Roots
[77]
138
6-O-[(7Z,10Z,13Z)-Hexadeca-7,10,13-trienoyl]sucrose
H
R
Equisetum hiemale
Aerial parts
[78]
139
6-O-[(7Z,10Z)-Hexadeca-7,10-dienoyl]sucrose
H
S
Equisetum hiemale
Aerial parts
[78]
See Scheme3.Scheme 3


#### 2.2.3. Lignan-Derived Disaccharide Esters

Six lignan-derived disaccharide esters (Figure4) contain a sucrose core esterified with different lignan residues covalently linked to the 3′ and 6′ positions of β-D-fructofuranosyl unit and have been isolated from the whole parts ofTrigonotis peduncularis [85] and the aerial parts ofEritrichium rupestre [86].Figure 4


#### 2.2.4. Phenylpropanoid-Derived Trisaccharide Esters

In this group, all oligosaccharide esters consist of three monosaccharides including glucopyranose, fructofuranose, and rhamnopyranose withO-substituents, which comprise feruloyl, sinapoyl, and 3,4,5-trimethoxycinnamoyl groups. Oligosaccharide esters (146–149) listed in Table 4 as well as kankanose (150), cistantubulose A1/A2 (151), cistansinensose A1/A2 (152), and compound153 shown in Figure 5 have been found in the roots ofPolygala tricornis [37], the stems ofCistanche tubulosa [81, 87] andC. sinensis [80], the whole parts ofBoschniakia rossica [88], and the rhizomes ofIris brevicaulis [89].Table 4
Phenylpropanoid-derived trisaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
R7
Source
Parts
Reference
146
Tricornose C
K
H
H
H
H
L
H
Polygala tricornis
Roots
[37]
147
Tricornose D
K
H
H
H
H
K
H
Polygala tricornis
Roots
[37]
148
Tricornose E
K
H
H
H
K
L
H
Polygala tricornis
Roots
[37]
149
Tricornose F
K
H
H
H
I
L
H
Polygala tricornis
Roots
[37]
See Scheme4.Scheme 4Figure 5


#### 2.2.5. Phenylpropanoid-Derived Tetrasaccharide Esters

Phenylpropanoid-derived tetrasaccharide esters (154–159) (Table 5) consisting of three glucopyranosyl units and a fructofuranosyl unit have been identified from the roots ofPolygala tricornis. The nonsugar moieties of these oligosaccharides include coumaroyl, feruloyl, sinapoyl, and 3,4,5-trimethoxycinnamoyl groups.Table 5
Phenylpropanoid-derived tetrasaccharide esters.
Number
Name
R1
R2
R3
Source
Parts
Reference
154
Tricornose G
K
H
K
Polygala tricornis
Roots
[37]
155
Tricornose H
K
K
K
Polygala tricornis
Roots
[37]
156
Tricornose I
K
K
L
Polygala tricornis
Roots
[37]
157
Tricornose J
K
I
L
Polygala tricornis
Roots
[37]
158
Tricornose K
K
I
K
Polygala tricornis
Roots
[37]
159
Tricornose L
K
G
K
Polygala tricornis
Roots
[37]
See Scheme5.Scheme 5


#### 2.2.6. Phenylpropanoid-Derived Pentasaccharide Esters

As shown in Table6, oligosaccharide esters (160-179) possessing a skeleton of five sugar residues have been isolated from the roots ofPolygala tenuifolia. The sugar residues are composed of two types of monosaccharides including fructofuranose and glucopyranose, which are esterified with acetyl, benzoyl, rhamnose-substituted/nonsubstituted coumaroyl, and rhamnose-substituted/nonsubstituted feruloyl groups. Other than that, a structure-complex oligosaccharide polyester shown in Figure 5, polygalajaponicose I (180), consisting of a pentasaccharide backbone esterified with feruloyl, coumaroyl, rhamnosyl-coumaroyl, acetyl, and benzoyl groups has been obtained from the roots ofP. japonica [90].Table 6
Phenylpropanoid-derived pentasaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
Source
Parts
Reference
160
Tenuifoliose A
G
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[38, 42]
161
Tenuifoliose B
G
D
I
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
162
Tenuifoliose C
G
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
163
Tenuifoliose F
G
D
U
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
164
Tenuifoliose G
G
D
U
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
165
Tenuifoliose H
G
D
G
Ac
Ac
Ac
Polygala tenuifolia
Roots
[38, 42, 79]
166
Tenuifoliose I
G
D
G
Ac
H
Ac
Polygala tenuifolia
Roots
[42, 79]
167
Tenuifoliose J
G
D
G
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
168
Tenuifoliose K
G
D
G
H
H
Ac
Polygala tenuifolia
Roots
[42]
169
Tenuifoliose L
G
D
T
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42, 79]
170
Tenuifoliose M
G
D
T
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
171
Tenuifoliose N
I
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
172
Tenuifoliose O
I
D
I
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
173
Tenuifoliose P
I
D
I
H
H
Ac
Polygala tenuifolia
Roots
[42]
174
Tenuifoliose Q
G
D
T
H
Ac
Ac
Polygala tenuifolia
Roots
[79]
175
Tenuifoliose S
G
D
G
H
H
H
Polygala tenuifolia
Roots
[42]
176
Tenuifoliose T
G
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
177
Tenuifoliose V
H
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
178
Tenuifoliose W
I
D
U
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
179
Tenuifoliose X
I
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
See Scheme6.Scheme 6


#### 2.2.7. Others

Polygalatenosides A–C (181–183) (Figure 6) containing a galactosyl unit and a polygolitosyl unit esterified with benzoyl groups at 3, 4 and 6 positions have been found in the roots ofPolygala tenuifolia [91]. Three sucrose esters, including polygalatenoside D (190), telephiose F (191), and 6-O-benzoylsucrose (192), possess one benzoyl group, two benzoyl groups, and ap-methoxybenzoyl group, respectively. They were isolated from the roots ofP. tenuifolia [91], the whole plants ofP. telephioides [92], and the roots ofP. tricornis [37]. Six trisaccharide esters, named telephioses A–E and G (184–189) with substituents of acetyl and benzoyl groups, were isolated from the whole plants ofP. telephioides [92, 93]. Moreover, a trisaccharide ester (193), pubescenside A from the flowers ofSyringa pubescens, possesses a fatty acid residue [94].Figure 6


## 2.1. Oligosaccharides

All compounds of this group (Table1 and Figure 1) merely consist of various monosaccharides withoutO-substituents. In addition to the well-known sucrose, β-D-glucopyranosyl(1→2)-β-D-glucopyranoside (1) was isolated fromCamptosorus sibiricus[12]. The oligosaccharides of raffinose (3), stachyose (19), and verbascose (21), all of which belong to the Raffinose family, possess one, two or three galactopyranosyl units linked to sucrose and have been found in the rhizomes and roots ofAlisma orientalis [13],Lycopus lucidus [14],Rehmannia glutinosa [15, 16],Salvia miltiorrhiza [17], andScrophularia ningpoensis [18]. Manninotriose (4) and verbascotetraose (5) consisting of galactopyranosyl units and a glucopyranosyl unit have been isolated fromAlisma orientalis [13].Table 1
Oligosaccharides.
No.
Name
R1
R2
R3
R4
R5
R6
Source
Parts
Reference
22
Perifosaccharide A
OH(e)
OCH3(e)
H
OH(e)
OH
A
Periploca forrestii
Roots
[32]
23
Perifosaccharide B
OH(e)
OCH3(a)
H
OH(e)
OH
A
Periploca forrestii
Roots
[32]
24
Perifosaccharide C
OH(e)
OCH3(e)
H
OH(e)
OCH3
A
Periploca forrestii
Roots
[32]
25
Perifosaccharide D
OAc(e)
OCH3(e)
H
OH(e)
OH
A
Periploca forrestii
Roots
[32]
26
Perisaccharide A
OH(a)
OCH3(e)
OAc
OH(e)
OCH3
A
Periploca sepium
Root barks
[33]
27
Perisaccharide B
OAc(e)
OCH3(a)
H
OH(e)
OH
A
Periploca sepium
Periploca calophylla
Root barks
[33, 34]
28
Perisaccharide C
OH(a)
OCH3(e)
OAc
OCH3(a)
OH
A
Periploca sepium
Root barks
[33]
29
Perisaccharide D
OAc(e)
OCH3(a)
H
OH(e)
OCH3
A
Periploca calophylla
Stems
[34]
30
Perisesaccharide B
OH(a)
OCH3(e)
OAc
OH(e)
OCH3
C
Periploca sepium
Root barks
[35]
31
Perisesaccharide C
OH(a)
OCH3(e)
OH
OCH3(a)
OCH3
C
Periploca sepium
Root barks
[35]
32
Perisesaccharide D
OH(a)
OCH3(e)
OH
OCH3(a)
OH
C
Periploca sepium
Root barks
[35]
33
Perisesaccharide E
OH(a)
OCH3(e)
OAc
OH(e)
OH
C
Periploca sepium
Root barks
[35]
34
Cymaropyranurolactone 4-O-β-D-digitalopyranosyl-(1
→
4)-O-β-D-cymaropyranosyl-(1
→
4)-O-β-D-oleandropyranosyl-(1
→
4)-O-β-D-cymaropyranoside
OH(a)
OCH3(e)
OH
OCH3(e)
OCH3
B
Parabarium huaitingii
Barks
[36]
See Scheme1.Scheme 1Figure 1Figure 2Five oligosaccharides comprising 1-kestose (6), nystose (7), 1-β-fructofuranosylnystose (8), hexasaccharide (9), and heptasaccharide (10) consisting of fructofuranose and glucopyranose have been isolated from the aerial parts and roots ofGynura divaricata subsp.formosana [19],Morinda officinalis [20–22],Saussurea lappa [23], andAralia cordata [24]. Two water-soluble oligosaccharides (11,12) composed of two or three types of monosaccharides including glucopyranose, fructopyranose, and fructofuranose have been obtained from the whole plants ofBlumea riparia [25, 26].Besides, malto-oligosaccharides (17, n = 0~8) consisting of α-D-glucopyranosyl residues assembled by (1→4)-linkages and inulo-oligosaccharides (18, n = 1~3) consisting of only fructosyl residues formed by (2→1)-linkages have been found in the roots ofPanax ginseng [27, 28] andMorinda officinalis [20], respectively. Three noteworthy oligosaccharides (2,13,14) formed by α-D-glucopyranosyl units with (1→6)-linkages and a (1→4)-linkage have been found in the roots ofPanax ginseng [28]. And two linear oligosaccharides termed heptasaccharide (15) and octasaccharide (16) consisting of glucose and mannose monomers were identified from the rhizomes ofParis polyphylla var.yunnanensis [29, 30]. A pentasaccharide, stellariose (20) consisting of a raffinose backbone with two galactosyl residues bound to the fructosyl and glucosyl moieties was identified from the stems ofStellaria media [31].Oligosaccharides (Table1) are composed of seven kinds of deoxyhexoses including cymaropyranose, canaropyranose, digitoxopyranose, oleandropyranose, digitalopyranose, cymaropyranurolactone, and oleandronic acid-δ-lactone. Oleandronic acid-δ-lactone exhibits the boat and chair conformations. The hydroxyl, methyl, and acetyl groups are located at the equatorial (e) and axial (a) bonds in the chair conformation of deoxyhexoses. These oligosaccharides were isolated from the traditional Chinese medicines including the roots ofPeriploca forrestii, the root barks ofP. sepium, the stems ofP. calophylla, and the barks ofParabarium huaitingii.


## 2.2. Oligosaccharide Esters

### 2.2.1. Phenylpropanoid-Derived Disaccharide Esters

Phenylpropanoid-derived disaccharide esters (Table2 and Figure 3) account for a considerable proportion of oligosaccharide esters and mainly possess a core of sucrose carrying a varying number ofO-substituents, including phenylpropanoid groups, acetyl, benzoyl,p-methoxybenzoyl, andp-hydroxybenzoyl groups. Phenylpropanoid substituents are just present at 1′, 3′, 4′, 6′ positions of β-D-fructofuranosyl unit in compounds35–97, whereas they appear at 2, 3, 4, 6 positions of α-D-glucopyranosyl moiety in compounds98–101. Moreover, compounds76–97 are mainly esterified with acetyl groups along with a phenylpropanoid substituent, coumaroyl, feruloyl, or 3,4,5-trimethoxycinnamoyl group. Interestingly, the phenylpropanoid substituents are only attached to the 3′ position of sucrose. The two sugar rings of compounds102–128 both possess phenylpropanoid substituents. These oligosaccharide esters have been found in the roots and rhizomes ofPolygala tricornis,P. tenuifolia,Fagopyrum tataricum,Scrophularia ningpoensis,Cynanchum amplexicaule,Smilax riparia,Paris polyphyllavar.yunnanensis,Smilacis glabrae,Fagopyrum dibotrys, andSparganium stoloniferum, the underground parts ofTrillium kamtschaticum, the stems ofPolygonum sachalinensis,P. cuspidatum,P. hydropiper,Smilax china, andCalamus quiquesetinervius, the aerial parts ofPolygala sibirica,Smilax bracteata,Heterosmilax erythrantha, andMusella lasiocarpa, the leaves ofPersicaria hydropiper andPolygonum hydropiper, the whole plants ofBidens parviflora andPolygala hongkongensis, and the flower buds ofPrunus mume.Table 2
Phenylpropanoid-derived disaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
R7
R8
Source
Parts
Reference
35
Sibiricose A6
H
H
H
H
K
H
H
H
Polygala tricornis
Polygala tenuifolia
Roots  Root barks
[37–40]
36
3′-O-Feruloyl sucrose/Sibiricose A5
H
H
H
H
I
H
H
H
Polygala tenuifolia
Trillium kamtschaticum
Roots Underground parts
[38–42]
37
Glomeratose A
H
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
38
Lapathoside D
H
H
H
H
G
G
H
H
Polygonum sachalinense
Stems
[43]
39
Helonioside A
H
H
H
H
I
I
H
H
Trillium kamtschaticum
Smilax bracteata
Paris polyphylla var. yunnanensis
Undergroundparts  Aerial parts  Roots
[41, 44, 45]
40
Helonioside B
Ac
H
H
H
I
I
H
H
Smilax bracteata
Smilax china
Smilax riparia
Heterosmilax erythrantha
Aerial partsStems Roots and rhizomes
[44, 46–48]
41
Parispolyside F
H
H
H
H
G
I
H
H
Paris Polyphylla var. yunnanensis
Rhizomes
[49, 50]
42
Hydropiperoside
H
H
H
H
G
G
H
G
Polygonum sachalinense
Polygonum cuspidatum
Persicaria hydropiper
StemsLeaves
[43, 51, 52]
43
Tricornose B
D
Ac
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
44
Tenuifoliside A
F
H
H
H
L
H
H
H
Polygala tenuifolia
Polygala hongkongensis
Polygala sibirica
RootsWhole plants     Aerial parts
[38, 40, 42, 53–56]
45
Tatariside A
Ac
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
46
Tatariside E
H
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
47
Tatariside G
H
H
H
H
I
G
H
G
Fagopyrum tataricum
Roots
[57]
48
Smiglaside A
Ac
Ac
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
49
Smiglaside B
Ac
H
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
50
Smiglaside E
Ac
H
H
Ac
I
I
H
G
Smilax china
Stems
[46]
51
Smilaside A
Ac
Ac
H
H
I
I
H
H
Smilax china
Stems
[46]
52
Smilaside B
H
H
H
Ac
I
I
H
H
Smilax china
Stems
[46]
53
Smilaside C
H
H
H
H
I
I
H
G
Smilax china
Stems
[46]
54
Smilaside D
H
H
H
H
I
I
Ac
G
Smilax china
Stems
[46]
55
Smilaside E
Ac
H
H
H
I
I
H
G
Smilax bracteata
Smilax china
Aerial parts  Stems
[44, 46]
56
Smilaside F
Ac
H
H
Ac
G
I
H
G
Smilax china
Stems
[46]
57
Smilaside G
H
H
H
H
G
I
H
G
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
58
Smilaside H
H
H
H
Ac
G
I
H
G
Smilax bracteata
Aerial parts
[44]
59
Smilaside I
Ac
H
H
H
G
I
H
G
Smilax bracteata
Aerial parts
[44]
60
Smilaside J
H
H
H
H
G
I
H
I
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
61
Smilaside K
H
H
H
Ac
I
I
H
G
Smilax bracteata
Aerial parts
[44]
62
Smilaside L
H
H
H
H
I
I
H
I
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
63
Smilaside M
Ac
H
H
Ac
Cis-feruloyl
I
H
H
Smilax riparia
Roots and rhizomes
[59]
64
Smilaside N
Ac
H
H
Ac
I
Cis-feruloyl
H
H
Smilax riparia
Roots and rhizomes
[59]
65
Smilaside P
H
H
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
66
3′,4′,6′-O-Tri-feruloylsucrose
H
H
H
H
I
I
I
H
Smilax riparia
Rhizomes and roots
[60]
67
6′-O-Coumaroylsucrose
H
H
H
H
H
G
H
H
Bidens parviflora
Whole plants
[61]
68
1′-O-Coumaroyl-6′-O-feruloylsucrose
H
H
H
H
H
I
H
G
Smilax bracteata
Aerial parts
[44]
69
4-O-Benzoyl-3′-3,4,5-trimethoxycinnamoylsucrose
H
D
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
70
6-O-Benzoyl-3′-O-3,4,5-trimethoxycinnamoylsucrose
D
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
71
6-O-Benzoyl-3′-O-sinapoylsucrose
D
H
H
H
K
H
H
H
Polygala tricornis
Roots
[37]
72
6-O-p-Methoxybenzoyl-3′-O-3,4,5-trimethoxycinnamoylsucrose
E
H
H
H
L
H
H
H
Polygala tenuifolia
Roots
[56]
73
2,6-Di-acetyl-3′,6′-di-feruloylsucrose
Ac
H
H
Ac
I
I
H
H
Smilax china
Smilax riparia
Heterosmilax erythrantha
StemsRoots and rhizomes   Aerial parts
[46–48, 59]
74
2,6-Di-acetyl-3′-O-cis-feruloy-6′-trans-feruloylsucrose
Ac
H
H
Ac
Cis-feruloy
I
H
H
Smilax riparia
Roots and rhizomes
[59]
75
2,6-Di-acetyl-3′-O-trans-feruloy-6′-cis-feruloylsucrose
Ac
H
H
Ac
I
Cis-feruloyl
H
H
Smilax riparia
Roots and rhizomes
[59]
76
Regaloside A
Ac
H
H
H
I
H
H
H
Trillium kamtschaticum
Underground parts
[41]
77
Tricornose A
Ac
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
78
Mumeose A
H
H
H
Ac
G
H
H
H
Prunus mume
Flower buds
[62, 63]
79
Mumeose B
Ac
H
Ac
H
G
H
H
H
Prunus mume
Flower buds
[62, 63]
80
Mumeose C
Ac
H
Ac
Ac
G
H
H
H
Prunus mume
Flower buds
[62, 63]
81
Mumeose D
Ac
Ac
Ac
Ac
G
H
H
Ac
Prunus mume
Flower buds
[62, 63]
82
Mumeose E
Ac
Ac
Ac
Ac
Cis-coumaroyl
H
H
Ac
Prunus mume
Flower buds
[62, 63]
83
Mumeose F
Ac
Ac
Ac
H
G
H
H
H
Prunus mume
Flower buds
[63]
84
Mumeose G
Ac
H
Ac
H
G
H
Ac
H
Prunus mume
Flower buds
[63]
85
Mumeose H
H
H
Ac
Ac
G
H
Ac
H
Prunus mume
Flower buds
[63]
86
Mumeose I
Ac
Ac
Ac
H
G
Ac
H
H
Prunus mume
Flower buds
[63]
87
Mumeose J
Ac
Ac
Ac
Ac
G
H
Ac
Ac
Prunus mume
Flower buds
[63]
88
Mumeose K
H
H
Ac
Ac
G
H
H
H
Prunus mume
Flower buds
[64]
89
Mumeose L
Ac
H
Ac
Ac
G
H
Ac
H
Prunus mume
Flower buds
[64]
90
Mumeose M
Ac
Ac
Ac
H
G
H
Ac
Ac
Prunus mume
Flower buds
[64]
91
Mumeose N
Ac
Ac
Ac
H
G
Ac
Ac
H
Prunus mume
Flower buds
[64]
92
Mumeose O
Ac
H
Ac
Ac
G
H
Ac
Ac
Prunus mume
Flower buds
[64]
93
1′,2,3,4,6-O-Penta-acetyl-3′-O-trans-coumaroylsucrose
Ac
Ac
Ac
Ac
G
H
H
Ac
Musella lasiocarpa
Aerial parts
[65]
94
1′,2,3,4,6-O-Penta-acetyl-3′-O-cis-coumaroylsucrose
Ac
Ac
Ac
Ac
Cis-coumaroyl
H
H
Ac
Musella lasiocarpa
Aerial parts
[65]
95
1′,2,3,6-O-Tetra-acetyl-3′-O-cis-feruloylsucrose
Ac
H
Ac
Ac
Cis-feruloyl
H
H
Ac
Sparganium stoloniferum
Rhizomes
[66]
96
1′,2,4,6-O-Tetra-acetyl-3′-O-trans-feruloylsucrose
Ac
Ac
H
Ac
I
H
H
Ac
Sparganium stoloniferum
Rhizomes
[66]
97
1′,2,3,6-O-Tetra-acetyl-3′-O-trans-feruloylsucrose
Ac
H
Ac
Ac
I
H
H
Ac
Sparganium stoloniferum
Rhizomes
[67]
98
Sibirioside A
M
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
99
Sibricose A1
K
H
H
H
H
H
H
H
Cynanchum amplexicaule
Roots
[69]
100
6-O-Caffeoylsucrose
J
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
101
Acretoside
I
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
102
Tenuifoliside B
F
H
H
H
K
H
H
H
Polygala tenuifolia
Roots
[42, 56]
103
Tenuifoliside C
K
H
H
H
L
H
H
H
Polygala tricornis
Polygala tenuifolia
Roots
[37, 42, 56]
104
Heterosmilaside
H
H
I
H
H
I
H
H
Heterosmilax erythrantha
Aerial parts
[48]
105
Quiquesetinerviuside A
H
I
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
106
Quiquesetinerviuside B
Ac
I
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
107
Quiquesetinerviuside C
H
I
H
Ac
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
108
Quiquesetinerviuside D
Ac
G
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
109
Quiquesetinerviuside E
H
G
H
Ac
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
110
Vanicoside A
I
H
H
Ac
G
G
H
G
Polygonum sachalinensis
Polygonum cuspidatum
Polygonum hydropiper
StemsLeaves      Rhizomes
[51, 52, 71, 72]
111
Vanicoside B
I
H
H
H
G
G
H
G
Polygonum sachalinensis
Polygonum cuspidatum
Persicaria hydropiper
Stems   Leaves     Rhizomes
[43, 51, 52, 71, 72]
112
Vanicoside D
G
H
H
H
G
G
H
G
Persicaria hydropiper
Leaves
[51]
113
Vanicoside E
I
Ac
H
Ac
G
G
H
G
Polygonum hydropiper
Stems and leaves
[72]
114
Lapathoside A
I
H
H
H
G
G
H
I
Polygonum sachalinensis
Polygonum cuspidatum
Fagopyrum dibotrys
StemsRhizomes
[51, 73]
115
Lapathoside C
I
H
H
H
G
G
H
H
Polygonum sachalinensis
Polygonum cuspidatum
Stems
[43, 52]
116
Diboside A
G
H
H
H
G
I
H
G
Fagopyrum tataricum
Fagopyrum dibotrys
Roots    Rhizomes
[57]
117
Hidropiperoside A
I
H
H
H
H
G
H
G
Polygonum hydropiper
Stems and leaves
[72]
118
Hidropiperoside B
I
H
H
Ac
G
G
H
I
Polygonum hydropiper
Stems and leaves
[72]
119
Tatariside B
I
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
120
Tatariside C
I
Ac
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
121
Tatariside D
G
H
H
Ac
G
I
H
H
Fagopyrum tataricum
Roots
[57]
122
Tatariside F
G
H
H
H
I
I
H
G
Fagopyrum tataricum
Roots
[57]
123
3′,6-O-Di-sinapoylsucrose
K
H
H
H
K
H
H
H
Polygala tricornis
Polygala hongkongensis
Polygala sibirica
Polygala tenuifolia
Cynanchum amplexicaule
Roots  Root barks  Whole plants  Aerial parts
[37–39, 41, 53–56, 69, 74]
124
6,6′-O-Di-coumaroylsucrose
G
H
H
H
H
G
H
H
Bidens parviflora
Whole plants
[61]
125
1′,3′,6′-O-Tri-coumaroyl-6-feruloylsucrose
I
H
H
H
G
G
H
G
Fagopyrum tataricum
Roots
[75, 76]
126
3′,6′-O-Di-coumaroyl-1′,6-O-di-feruloylsucrose
I
H
H
H
G
G
H
I
Fagopyrum tataricum
Roots
[75, 76]
127
3′-O-Coumaroyl-1′,6′,6-O-tri-feruloylsucrose
I
H
H
H
I
G
H
I
Fagopyrum tataricum
Roots
[75, 76]
128
1′,3′,6′,6-O-Tetra-feruloylsucrose
I
H
H
H
I
I
H
I
Fagopyrum tataricum
Roots
[75, 76]
See Scheme 2.Scheme 2Figure 3Cistanoside F (129) has been found in the stems ofCistanche tubulosa [80] andC. sinensis [81], the barks ofPaulownia tomentosavar.tomentosa[82], and the aerial parts ofAcanthus ilicifolius [83]. Cistanoside I (130) has also been isolated from the stems of theCistanche plants [84]. Both of them are composed of glucosyl and rhamnosyl groups connected by a 1→3 glycosidic bond. In addition, 6,6′-sucrose ester of (1α,2α,3β,4β)-3,4-bis(4-hydroxyphenyl)-1,2-cyclobutanedicarboxylic acid (131) with a bis(4-hydroxyphenyl) cyclobutanedicarboxyl group as the acyl unit in the molecule structure was isolated from the whole plants ofBidens parviflora[61].


### 2.2.2. Fatty Acid-Derived Disaccharide Esters

Eight monosubstituted disaccharide esters (Table3) with a sucrose moiety possess six different types of fatty acid residues which attach to the 6 or 6′ position of sucrose. These fatty acids include linoleic acid, palmitic acid, linolenic acid, myristic acid, hexadeca-7,10,13-trienoic acid, and hexadeca-7,10-dienoic acid. The above sucrose fatty acid esters have been found in the rhizomes ofAstragalus membranaceus and the roots ofEquisetum hiemale.Table 3
Fatty acid-derived disaccharide esters.
Number
Name
R1
R2
Source
Parts
Reference
132
6′-O-Linoleylsucrose
H
O
Astragalus membranaceus
Roots
[77]
133
6′-O-Palmitoylsucrose
H
P
Astragalus membranaceus
Roots
[77]
134
6-O-Palmitoylsucrose
P
H
Astragalus membranaceus
Roots
[77]
135
6′-O-Linolenoylsucrose
H
N
Astragalus membranaceus
Equisetum hiemale
Roots              Aerial parts
[77, 78]
136
6-O-Linoleylsucrose
O
H
Astragalus membranaceus
Roots
[77]
137
6-O-Myristoylsucrose
Q
H
Astragalus membranaceus
Roots
[77]
138
6-O-[(7Z,10Z,13Z)-Hexadeca-7,10,13-trienoyl]sucrose
H
R
Equisetum hiemale
Aerial parts
[78]
139
6-O-[(7Z,10Z)-Hexadeca-7,10-dienoyl]sucrose
H
S
Equisetum hiemale
Aerial parts
[78]
See Scheme3.Scheme 3


### 2.2.3. Lignan-Derived Disaccharide Esters

Six lignan-derived disaccharide esters (Figure4) contain a sucrose core esterified with different lignan residues covalently linked to the 3′ and 6′ positions of β-D-fructofuranosyl unit and have been isolated from the whole parts ofTrigonotis peduncularis [85] and the aerial parts ofEritrichium rupestre [86].Figure 4


### 2.2.4. Phenylpropanoid-Derived Trisaccharide Esters

In this group, all oligosaccharide esters consist of three monosaccharides including glucopyranose, fructofuranose, and rhamnopyranose withO-substituents, which comprise feruloyl, sinapoyl, and 3,4,5-trimethoxycinnamoyl groups. Oligosaccharide esters (146–149) listed in Table 4 as well as kankanose (150), cistantubulose A1/A2 (151), cistansinensose A1/A2 (152), and compound153 shown in Figure 5 have been found in the roots ofPolygala tricornis [37], the stems ofCistanche tubulosa [81, 87] andC. sinensis [80], the whole parts ofBoschniakia rossica [88], and the rhizomes ofIris brevicaulis [89].Table 4
Phenylpropanoid-derived trisaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
R7
Source
Parts
Reference
146
Tricornose C
K
H
H
H
H
L
H
Polygala tricornis
Roots
[37]
147
Tricornose D
K
H
H
H
H
K
H
Polygala tricornis
Roots
[37]
148
Tricornose E
K
H
H
H
K
L
H
Polygala tricornis
Roots
[37]
149
Tricornose F
K
H
H
H
I
L
H
Polygala tricornis
Roots
[37]
See Scheme4.Scheme 4Figure 5


### 2.2.5. Phenylpropanoid-Derived Tetrasaccharide Esters

Phenylpropanoid-derived tetrasaccharide esters (154–159) (Table 5) consisting of three glucopyranosyl units and a fructofuranosyl unit have been identified from the roots ofPolygala tricornis. The nonsugar moieties of these oligosaccharides include coumaroyl, feruloyl, sinapoyl, and 3,4,5-trimethoxycinnamoyl groups.Table 5
Phenylpropanoid-derived tetrasaccharide esters.
Number
Name
R1
R2
R3
Source
Parts
Reference
154
Tricornose G
K
H
K
Polygala tricornis
Roots
[37]
155
Tricornose H
K
K
K
Polygala tricornis
Roots
[37]
156
Tricornose I
K
K
L
Polygala tricornis
Roots
[37]
157
Tricornose J
K
I
L
Polygala tricornis
Roots
[37]
158
Tricornose K
K
I
K
Polygala tricornis
Roots
[37]
159
Tricornose L
K
G
K
Polygala tricornis
Roots
[37]
See Scheme5.Scheme 5


### 2.2.6. Phenylpropanoid-Derived Pentasaccharide Esters

As shown in Table6, oligosaccharide esters (160-179) possessing a skeleton of five sugar residues have been isolated from the roots ofPolygala tenuifolia. The sugar residues are composed of two types of monosaccharides including fructofuranose and glucopyranose, which are esterified with acetyl, benzoyl, rhamnose-substituted/nonsubstituted coumaroyl, and rhamnose-substituted/nonsubstituted feruloyl groups. Other than that, a structure-complex oligosaccharide polyester shown in Figure 5, polygalajaponicose I (180), consisting of a pentasaccharide backbone esterified with feruloyl, coumaroyl, rhamnosyl-coumaroyl, acetyl, and benzoyl groups has been obtained from the roots ofP. japonica [90].Table 6
Phenylpropanoid-derived pentasaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
Source
Parts
Reference
160
Tenuifoliose A
G
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[38, 42]
161
Tenuifoliose B
G
D
I
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
162
Tenuifoliose C
G
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
163
Tenuifoliose F
G
D
U
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
164
Tenuifoliose G
G
D
U
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
165
Tenuifoliose H
G
D
G
Ac
Ac
Ac
Polygala tenuifolia
Roots
[38, 42, 79]
166
Tenuifoliose I
G
D
G
Ac
H
Ac
Polygala tenuifolia
Roots
[42, 79]
167
Tenuifoliose J
G
D
G
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
168
Tenuifoliose K
G
D
G
H
H
Ac
Polygala tenuifolia
Roots
[42]
169
Tenuifoliose L
G
D
T
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42, 79]
170
Tenuifoliose M
G
D
T
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
171
Tenuifoliose N
I
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
172
Tenuifoliose O
I
D
I
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
173
Tenuifoliose P
I
D
I
H
H
Ac
Polygala tenuifolia
Roots
[42]
174
Tenuifoliose Q
G
D
T
H
Ac
Ac
Polygala tenuifolia
Roots
[79]
175
Tenuifoliose S
G
D
G
H
H
H
Polygala tenuifolia
Roots
[42]
176
Tenuifoliose T
G
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
177
Tenuifoliose V
H
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
178
Tenuifoliose W
I
D
U
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
179
Tenuifoliose X
I
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
See Scheme6.Scheme 6


### 2.2.7. Others

Polygalatenosides A–C (181–183) (Figure 6) containing a galactosyl unit and a polygolitosyl unit esterified with benzoyl groups at 3, 4 and 6 positions have been found in the roots ofPolygala tenuifolia [91]. Three sucrose esters, including polygalatenoside D (190), telephiose F (191), and 6-O-benzoylsucrose (192), possess one benzoyl group, two benzoyl groups, and ap-methoxybenzoyl group, respectively. They were isolated from the roots ofP. tenuifolia [91], the whole plants ofP. telephioides [92], and the roots ofP. tricornis [37]. Six trisaccharide esters, named telephioses A–E and G (184–189) with substituents of acetyl and benzoyl groups, were isolated from the whole plants ofP. telephioides [92, 93]. Moreover, a trisaccharide ester (193), pubescenside A from the flowers ofSyringa pubescens, possesses a fatty acid residue [94].Figure 6


## 2.2.1. Phenylpropanoid-Derived Disaccharide Esters

Phenylpropanoid-derived disaccharide esters (Table2 and Figure 3) account for a considerable proportion of oligosaccharide esters and mainly possess a core of sucrose carrying a varying number ofO-substituents, including phenylpropanoid groups, acetyl, benzoyl,p-methoxybenzoyl, andp-hydroxybenzoyl groups. Phenylpropanoid substituents are just present at 1′, 3′, 4′, 6′ positions of β-D-fructofuranosyl unit in compounds35–97, whereas they appear at 2, 3, 4, 6 positions of α-D-glucopyranosyl moiety in compounds98–101. Moreover, compounds76–97 are mainly esterified with acetyl groups along with a phenylpropanoid substituent, coumaroyl, feruloyl, or 3,4,5-trimethoxycinnamoyl group. Interestingly, the phenylpropanoid substituents are only attached to the 3′ position of sucrose. The two sugar rings of compounds102–128 both possess phenylpropanoid substituents. These oligosaccharide esters have been found in the roots and rhizomes ofPolygala tricornis,P. tenuifolia,Fagopyrum tataricum,Scrophularia ningpoensis,Cynanchum amplexicaule,Smilax riparia,Paris polyphyllavar.yunnanensis,Smilacis glabrae,Fagopyrum dibotrys, andSparganium stoloniferum, the underground parts ofTrillium kamtschaticum, the stems ofPolygonum sachalinensis,P. cuspidatum,P. hydropiper,Smilax china, andCalamus quiquesetinervius, the aerial parts ofPolygala sibirica,Smilax bracteata,Heterosmilax erythrantha, andMusella lasiocarpa, the leaves ofPersicaria hydropiper andPolygonum hydropiper, the whole plants ofBidens parviflora andPolygala hongkongensis, and the flower buds ofPrunus mume.Table 2
Phenylpropanoid-derived disaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
R7
R8
Source
Parts
Reference
35
Sibiricose A6
H
H
H
H
K
H
H
H
Polygala tricornis
Polygala tenuifolia
Roots  Root barks
[37–40]
36
3′-O-Feruloyl sucrose/Sibiricose A5
H
H
H
H
I
H
H
H
Polygala tenuifolia
Trillium kamtschaticum
Roots Underground parts
[38–42]
37
Glomeratose A
H
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
38
Lapathoside D
H
H
H
H
G
G
H
H
Polygonum sachalinense
Stems
[43]
39
Helonioside A
H
H
H
H
I
I
H
H
Trillium kamtschaticum
Smilax bracteata
Paris polyphylla var. yunnanensis
Undergroundparts  Aerial parts  Roots
[41, 44, 45]
40
Helonioside B
Ac
H
H
H
I
I
H
H
Smilax bracteata
Smilax china
Smilax riparia
Heterosmilax erythrantha
Aerial partsStems Roots and rhizomes
[44, 46–48]
41
Parispolyside F
H
H
H
H
G
I
H
H
Paris Polyphylla var. yunnanensis
Rhizomes
[49, 50]
42
Hydropiperoside
H
H
H
H
G
G
H
G
Polygonum sachalinense
Polygonum cuspidatum
Persicaria hydropiper
StemsLeaves
[43, 51, 52]
43
Tricornose B
D
Ac
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
44
Tenuifoliside A
F
H
H
H
L
H
H
H
Polygala tenuifolia
Polygala hongkongensis
Polygala sibirica
RootsWhole plants     Aerial parts
[38, 40, 42, 53–56]
45
Tatariside A
Ac
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
46
Tatariside E
H
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
47
Tatariside G
H
H
H
H
I
G
H
G
Fagopyrum tataricum
Roots
[57]
48
Smiglaside A
Ac
Ac
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
49
Smiglaside B
Ac
H
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
50
Smiglaside E
Ac
H
H
Ac
I
I
H
G
Smilax china
Stems
[46]
51
Smilaside A
Ac
Ac
H
H
I
I
H
H
Smilax china
Stems
[46]
52
Smilaside B
H
H
H
Ac
I
I
H
H
Smilax china
Stems
[46]
53
Smilaside C
H
H
H
H
I
I
H
G
Smilax china
Stems
[46]
54
Smilaside D
H
H
H
H
I
I
Ac
G
Smilax china
Stems
[46]
55
Smilaside E
Ac
H
H
H
I
I
H
G
Smilax bracteata
Smilax china
Aerial parts  Stems
[44, 46]
56
Smilaside F
Ac
H
H
Ac
G
I
H
G
Smilax china
Stems
[46]
57
Smilaside G
H
H
H
H
G
I
H
G
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
58
Smilaside H
H
H
H
Ac
G
I
H
G
Smilax bracteata
Aerial parts
[44]
59
Smilaside I
Ac
H
H
H
G
I
H
G
Smilax bracteata
Aerial parts
[44]
60
Smilaside J
H
H
H
H
G
I
H
I
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
61
Smilaside K
H
H
H
Ac
I
I
H
G
Smilax bracteata
Aerial parts
[44]
62
Smilaside L
H
H
H
H
I
I
H
I
Smilax bracteata
Smilacis glabrae
Aerial partsRhizomes
[44, 58]
63
Smilaside M
Ac
H
H
Ac
Cis-feruloyl
I
H
H
Smilax riparia
Roots and rhizomes
[59]
64
Smilaside N
Ac
H
H
Ac
I
Cis-feruloyl
H
H
Smilax riparia
Roots and rhizomes
[59]
65
Smilaside P
H
H
H
Ac
I
I
H
I
Smilax riparia
Roots and rhizomes
[47]
66
3′,4′,6′-O-Tri-feruloylsucrose
H
H
H
H
I
I
I
H
Smilax riparia
Rhizomes and roots
[60]
67
6′-O-Coumaroylsucrose
H
H
H
H
H
G
H
H
Bidens parviflora
Whole plants
[61]
68
1′-O-Coumaroyl-6′-O-feruloylsucrose
H
H
H
H
H
I
H
G
Smilax bracteata
Aerial parts
[44]
69
4-O-Benzoyl-3′-3,4,5-trimethoxycinnamoylsucrose
H
D
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
70
6-O-Benzoyl-3′-O-3,4,5-trimethoxycinnamoylsucrose
D
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
71
6-O-Benzoyl-3′-O-sinapoylsucrose
D
H
H
H
K
H
H
H
Polygala tricornis
Roots
[37]
72
6-O-p-Methoxybenzoyl-3′-O-3,4,5-trimethoxycinnamoylsucrose
E
H
H
H
L
H
H
H
Polygala tenuifolia
Roots
[56]
73
2,6-Di-acetyl-3′,6′-di-feruloylsucrose
Ac
H
H
Ac
I
I
H
H
Smilax china
Smilax riparia
Heterosmilax erythrantha
StemsRoots and rhizomes   Aerial parts
[46–48, 59]
74
2,6-Di-acetyl-3′-O-cis-feruloy-6′-trans-feruloylsucrose
Ac
H
H
Ac
Cis-feruloy
I
H
H
Smilax riparia
Roots and rhizomes
[59]
75
2,6-Di-acetyl-3′-O-trans-feruloy-6′-cis-feruloylsucrose
Ac
H
H
Ac
I
Cis-feruloyl
H
H
Smilax riparia
Roots and rhizomes
[59]
76
Regaloside A
Ac
H
H
H
I
H
H
H
Trillium kamtschaticum
Underground parts
[41]
77
Tricornose A
Ac
H
H
H
L
H
H
H
Polygala tricornis
Roots
[37]
78
Mumeose A
H
H
H
Ac
G
H
H
H
Prunus mume
Flower buds
[62, 63]
79
Mumeose B
Ac
H
Ac
H
G
H
H
H
Prunus mume
Flower buds
[62, 63]
80
Mumeose C
Ac
H
Ac
Ac
G
H
H
H
Prunus mume
Flower buds
[62, 63]
81
Mumeose D
Ac
Ac
Ac
Ac
G
H
H
Ac
Prunus mume
Flower buds
[62, 63]
82
Mumeose E
Ac
Ac
Ac
Ac
Cis-coumaroyl
H
H
Ac
Prunus mume
Flower buds
[62, 63]
83
Mumeose F
Ac
Ac
Ac
H
G
H
H
H
Prunus mume
Flower buds
[63]
84
Mumeose G
Ac
H
Ac
H
G
H
Ac
H
Prunus mume
Flower buds
[63]
85
Mumeose H
H
H
Ac
Ac
G
H
Ac
H
Prunus mume
Flower buds
[63]
86
Mumeose I
Ac
Ac
Ac
H
G
Ac
H
H
Prunus mume
Flower buds
[63]
87
Mumeose J
Ac
Ac
Ac
Ac
G
H
Ac
Ac
Prunus mume
Flower buds
[63]
88
Mumeose K
H
H
Ac
Ac
G
H
H
H
Prunus mume
Flower buds
[64]
89
Mumeose L
Ac
H
Ac
Ac
G
H
Ac
H
Prunus mume
Flower buds
[64]
90
Mumeose M
Ac
Ac
Ac
H
G
H
Ac
Ac
Prunus mume
Flower buds
[64]
91
Mumeose N
Ac
Ac
Ac
H
G
Ac
Ac
H
Prunus mume
Flower buds
[64]
92
Mumeose O
Ac
H
Ac
Ac
G
H
Ac
Ac
Prunus mume
Flower buds
[64]
93
1′,2,3,4,6-O-Penta-acetyl-3′-O-trans-coumaroylsucrose
Ac
Ac
Ac
Ac
G
H
H
Ac
Musella lasiocarpa
Aerial parts
[65]
94
1′,2,3,4,6-O-Penta-acetyl-3′-O-cis-coumaroylsucrose
Ac
Ac
Ac
Ac
Cis-coumaroyl
H
H
Ac
Musella lasiocarpa
Aerial parts
[65]
95
1′,2,3,6-O-Tetra-acetyl-3′-O-cis-feruloylsucrose
Ac
H
Ac
Ac
Cis-feruloyl
H
H
Ac
Sparganium stoloniferum
Rhizomes
[66]
96
1′,2,4,6-O-Tetra-acetyl-3′-O-trans-feruloylsucrose
Ac
Ac
H
Ac
I
H
H
Ac
Sparganium stoloniferum
Rhizomes
[66]
97
1′,2,3,6-O-Tetra-acetyl-3′-O-trans-feruloylsucrose
Ac
H
Ac
Ac
I
H
H
Ac
Sparganium stoloniferum
Rhizomes
[67]
98
Sibirioside A
M
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
99
Sibricose A1
K
H
H
H
H
H
H
H
Cynanchum amplexicaule
Roots
[69]
100
6-O-Caffeoylsucrose
J
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
101
Acretoside
I
H
H
H
H
H
H
H
Scrophularia ningpoensis
Roots
[68]
102
Tenuifoliside B
F
H
H
H
K
H
H
H
Polygala tenuifolia
Roots
[42, 56]
103
Tenuifoliside C
K
H
H
H
L
H
H
H
Polygala tricornis
Polygala tenuifolia
Roots
[37, 42, 56]
104
Heterosmilaside
H
H
I
H
H
I
H
H
Heterosmilax erythrantha
Aerial parts
[48]
105
Quiquesetinerviuside A
H
I
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
106
Quiquesetinerviuside B
Ac
I
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
107
Quiquesetinerviuside C
H
I
H
Ac
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
108
Quiquesetinerviuside D
Ac
G
H
H
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
109
Quiquesetinerviuside E
H
G
H
Ac
I
I
H
H
Calamus quiquesetinervius
Stems
[70]
110
Vanicoside A
I
H
H
Ac
G
G
H
G
Polygonum sachalinensis
Polygonum cuspidatum
Polygonum hydropiper
StemsLeaves      Rhizomes
[51, 52, 71, 72]
111
Vanicoside B
I
H
H
H
G
G
H
G
Polygonum sachalinensis
Polygonum cuspidatum
Persicaria hydropiper
Stems   Leaves     Rhizomes
[43, 51, 52, 71, 72]
112
Vanicoside D
G
H
H
H
G
G
H
G
Persicaria hydropiper
Leaves
[51]
113
Vanicoside E
I
Ac
H
Ac
G
G
H
G
Polygonum hydropiper
Stems and leaves
[72]
114
Lapathoside A
I
H
H
H
G
G
H
I
Polygonum sachalinensis
Polygonum cuspidatum
Fagopyrum dibotrys
StemsRhizomes
[51, 73]
115
Lapathoside C
I
H
H
H
G
G
H
H
Polygonum sachalinensis
Polygonum cuspidatum
Stems
[43, 52]
116
Diboside A
G
H
H
H
G
I
H
G
Fagopyrum tataricum
Fagopyrum dibotrys
Roots    Rhizomes
[57]
117
Hidropiperoside A
I
H
H
H
H
G
H
G
Polygonum hydropiper
Stems and leaves
[72]
118
Hidropiperoside B
I
H
H
Ac
G
G
H
I
Polygonum hydropiper
Stems and leaves
[72]
119
Tatariside B
I
H
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
120
Tatariside C
I
Ac
H
Ac
G
G
H
Ac
Fagopyrum tataricum
Roots
[57]
121
Tatariside D
G
H
H
Ac
G
I
H
H
Fagopyrum tataricum
Roots
[57]
122
Tatariside F
G
H
H
H
I
I
H
G
Fagopyrum tataricum
Roots
[57]
123
3′,6-O-Di-sinapoylsucrose
K
H
H
H
K
H
H
H
Polygala tricornis
Polygala hongkongensis
Polygala sibirica
Polygala tenuifolia
Cynanchum amplexicaule
Roots  Root barks  Whole plants  Aerial parts
[37–39, 41, 53–56, 69, 74]
124
6,6′-O-Di-coumaroylsucrose
G
H
H
H
H
G
H
H
Bidens parviflora
Whole plants
[61]
125
1′,3′,6′-O-Tri-coumaroyl-6-feruloylsucrose
I
H
H
H
G
G
H
G
Fagopyrum tataricum
Roots
[75, 76]
126
3′,6′-O-Di-coumaroyl-1′,6-O-di-feruloylsucrose
I
H
H
H
G
G
H
I
Fagopyrum tataricum
Roots
[75, 76]
127
3′-O-Coumaroyl-1′,6′,6-O-tri-feruloylsucrose
I
H
H
H
I
G
H
I
Fagopyrum tataricum
Roots
[75, 76]
128
1′,3′,6′,6-O-Tetra-feruloylsucrose
I
H
H
H
I
I
H
I
Fagopyrum tataricum
Roots
[75, 76]
See Scheme 2.Scheme 2Figure 3Cistanoside F (129) has been found in the stems ofCistanche tubulosa [80] andC. sinensis [81], the barks ofPaulownia tomentosavar.tomentosa[82], and the aerial parts ofAcanthus ilicifolius [83]. Cistanoside I (130) has also been isolated from the stems of theCistanche plants [84]. Both of them are composed of glucosyl and rhamnosyl groups connected by a 1→3 glycosidic bond. In addition, 6,6′-sucrose ester of (1α,2α,3β,4β)-3,4-bis(4-hydroxyphenyl)-1,2-cyclobutanedicarboxylic acid (131) with a bis(4-hydroxyphenyl) cyclobutanedicarboxyl group as the acyl unit in the molecule structure was isolated from the whole plants ofBidens parviflora[61].


## 2.2.2. Fatty Acid-Derived Disaccharide Esters

Eight monosubstituted disaccharide esters (Table3) with a sucrose moiety possess six different types of fatty acid residues which attach to the 6 or 6′ position of sucrose. These fatty acids include linoleic acid, palmitic acid, linolenic acid, myristic acid, hexadeca-7,10,13-trienoic acid, and hexadeca-7,10-dienoic acid. The above sucrose fatty acid esters have been found in the rhizomes ofAstragalus membranaceus and the roots ofEquisetum hiemale.Table 3
Fatty acid-derived disaccharide esters.
Number
Name
R1
R2
Source
Parts
Reference
132
6′-O-Linoleylsucrose
H
O
Astragalus membranaceus
Roots
[77]
133
6′-O-Palmitoylsucrose
H
P
Astragalus membranaceus
Roots
[77]
134
6-O-Palmitoylsucrose
P
H
Astragalus membranaceus
Roots
[77]
135
6′-O-Linolenoylsucrose
H
N
Astragalus membranaceus
Equisetum hiemale
Roots              Aerial parts
[77, 78]
136
6-O-Linoleylsucrose
O
H
Astragalus membranaceus
Roots
[77]
137
6-O-Myristoylsucrose
Q
H
Astragalus membranaceus
Roots
[77]
138
6-O-[(7Z,10Z,13Z)-Hexadeca-7,10,13-trienoyl]sucrose
H
R
Equisetum hiemale
Aerial parts
[78]
139
6-O-[(7Z,10Z)-Hexadeca-7,10-dienoyl]sucrose
H
S
Equisetum hiemale
Aerial parts
[78]
See Scheme3.Scheme 3


## 2.2.3. Lignan-Derived Disaccharide Esters

Six lignan-derived disaccharide esters (Figure4) contain a sucrose core esterified with different lignan residues covalently linked to the 3′ and 6′ positions of β-D-fructofuranosyl unit and have been isolated from the whole parts ofTrigonotis peduncularis [85] and the aerial parts ofEritrichium rupestre [86].Figure 4


## 2.2.4. Phenylpropanoid-Derived Trisaccharide Esters

In this group, all oligosaccharide esters consist of three monosaccharides including glucopyranose, fructofuranose, and rhamnopyranose withO-substituents, which comprise feruloyl, sinapoyl, and 3,4,5-trimethoxycinnamoyl groups. Oligosaccharide esters (146–149) listed in Table 4 as well as kankanose (150), cistantubulose A1/A2 (151), cistansinensose A1/A2 (152), and compound153 shown in Figure 5 have been found in the roots ofPolygala tricornis [37], the stems ofCistanche tubulosa [81, 87] andC. sinensis [80], the whole parts ofBoschniakia rossica [88], and the rhizomes ofIris brevicaulis [89].Table 4
Phenylpropanoid-derived trisaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
R7
Source
Parts
Reference
146
Tricornose C
K
H
H
H
H
L
H
Polygala tricornis
Roots
[37]
147
Tricornose D
K
H
H
H
H
K
H
Polygala tricornis
Roots
[37]
148
Tricornose E
K
H
H
H
K
L
H
Polygala tricornis
Roots
[37]
149
Tricornose F
K
H
H
H
I
L
H
Polygala tricornis
Roots
[37]
See Scheme4.Scheme 4Figure 5


## 2.2.5. Phenylpropanoid-Derived Tetrasaccharide Esters

Phenylpropanoid-derived tetrasaccharide esters (154–159) (Table 5) consisting of three glucopyranosyl units and a fructofuranosyl unit have been identified from the roots ofPolygala tricornis. The nonsugar moieties of these oligosaccharides include coumaroyl, feruloyl, sinapoyl, and 3,4,5-trimethoxycinnamoyl groups.Table 5
Phenylpropanoid-derived tetrasaccharide esters.
Number
Name
R1
R2
R3
Source
Parts
Reference
154
Tricornose G
K
H
K
Polygala tricornis
Roots
[37]
155
Tricornose H
K
K
K
Polygala tricornis
Roots
[37]
156
Tricornose I
K
K
L
Polygala tricornis
Roots
[37]
157
Tricornose J
K
I
L
Polygala tricornis
Roots
[37]
158
Tricornose K
K
I
K
Polygala tricornis
Roots
[37]
159
Tricornose L
K
G
K
Polygala tricornis
Roots
[37]
See Scheme5.Scheme 5


## 2.2.6. Phenylpropanoid-Derived Pentasaccharide Esters

As shown in Table6, oligosaccharide esters (160-179) possessing a skeleton of five sugar residues have been isolated from the roots ofPolygala tenuifolia. The sugar residues are composed of two types of monosaccharides including fructofuranose and glucopyranose, which are esterified with acetyl, benzoyl, rhamnose-substituted/nonsubstituted coumaroyl, and rhamnose-substituted/nonsubstituted feruloyl groups. Other than that, a structure-complex oligosaccharide polyester shown in Figure 5, polygalajaponicose I (180), consisting of a pentasaccharide backbone esterified with feruloyl, coumaroyl, rhamnosyl-coumaroyl, acetyl, and benzoyl groups has been obtained from the roots ofP. japonica [90].Table 6
Phenylpropanoid-derived pentasaccharide esters.
Number
Name
R1
R2
R3
R4
R5
R6
Source
Parts
Reference
160
Tenuifoliose A
G
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[38, 42]
161
Tenuifoliose B
G
D
I
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
162
Tenuifoliose C
G
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
163
Tenuifoliose F
G
D
U
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
164
Tenuifoliose G
G
D
U
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
165
Tenuifoliose H
G
D
G
Ac
Ac
Ac
Polygala tenuifolia
Roots
[38, 42, 79]
166
Tenuifoliose I
G
D
G
Ac
H
Ac
Polygala tenuifolia
Roots
[42, 79]
167
Tenuifoliose J
G
D
G
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
168
Tenuifoliose K
G
D
G
H
H
Ac
Polygala tenuifolia
Roots
[42]
169
Tenuifoliose L
G
D
T
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42, 79]
170
Tenuifoliose M
G
D
T
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
171
Tenuifoliose N
I
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
172
Tenuifoliose O
I
D
I
H
Ac
Ac
Polygala tenuifolia
Roots
[42]
173
Tenuifoliose P
I
D
I
H
H
Ac
Polygala tenuifolia
Roots
[42]
174
Tenuifoliose Q
G
D
T
H
Ac
Ac
Polygala tenuifolia
Roots
[79]
175
Tenuifoliose S
G
D
G
H
H
H
Polygala tenuifolia
Roots
[42]
176
Tenuifoliose T
G
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
177
Tenuifoliose V
H
D
I
Ac
Ac
Ac
Polygala tenuifolia
Roots
[42]
178
Tenuifoliose W
I
D
U
Ac
H
Ac
Polygala tenuifolia
Roots
[42]
179
Tenuifoliose X
I
D
I
H
H
H
Polygala tenuifolia
Roots
[42]
See Scheme6.Scheme 6


## 2.2.7. Others

Polygalatenosides A–C (181–183) (Figure 6) containing a galactosyl unit and a polygolitosyl unit esterified with benzoyl groups at 3, 4 and 6 positions have been found in the roots ofPolygala tenuifolia [91]. Three sucrose esters, including polygalatenoside D (190), telephiose F (191), and 6-O-benzoylsucrose (192), possess one benzoyl group, two benzoyl groups, and ap-methoxybenzoyl group, respectively. They were isolated from the roots ofP. tenuifolia [91], the whole plants ofP. telephioides [92], and the roots ofP. tricornis [37]. Six trisaccharide esters, named telephioses A–E and G (184–189) with substituents of acetyl and benzoyl groups, were isolated from the whole plants ofP. telephioides [92, 93]. Moreover, a trisaccharide ester (193), pubescenside A from the flowers ofSyringa pubescens, possesses a fatty acid residue [94].Figure 6


## 3. Biological Activities of Oligosaccharides and Their Esters

The oligosaccharides and oligosaccharide esters from Chinese medicinal plants are important products with diversified structures, which have triggered an increasing number of studies carried out on the isolated compounds. And thus diverse pharmacological activities have been proved. Among the isolated compounds, oligosaccharides, phenylpropanoid-derived disaccharide esters and trisaccharide esters, fatty acid-derived disaccharide esters, and others from the families Polygonaceae, Asclepiadaceae, Rubiaceae, Polygalaceae, Liliaceae, Smilacaceae, Arecaceae, Orobanchaceae, Scrophulariaceae, Acanthaceae, Rosaceae, Sparganiaceae, Leguminosae, and Equisetaceae have shown significant pharmacological activities including antioxidant, antidepressant, cytotoxic, antineoplastic, anti-inflammatory, antidiabetic, plant growth-regulatory, neuroprotective, and cerebral protective activities. Lignan-derived disaccharide esters, phenylpropanoid-derived tetrasaccharide esters, and pentasaccharide esters with biological activities have not been reported. Aside from the isolated constituents, oligosaccharide mixtures fromRehmannia glutinosa,Panax ginseng, andScrophularia ningpoensiswere also reported to display diverse pharmacological activities, such as antidiabetic, immunopotentiating, enhanced memory, and antineoplastic activities. These active compounds and mixtures could serve as the valuable candidates to be developed as possible drugs for the treatment and prevention of diseases.


### 3.1. Antioxidant Activity

The adverse effects of oxidative stress proposed to play significant roles in the pathogenesis of cardiovascular diseases, atherosclerosis, hypertension, cancer, diabetes mellitus, neurodegenerative diseases, rheumatoid arthritis, ischemia/reperfusion injury, and ageing have become an inevitable and serious issue [95, 96]. Scientists have thus made great efforts to explore antioxidants from medicinal plants by using different kinds of assay methods, which include DPPH radical scavenging assay, hydroxyl radical scavenging assay, superoxide anion scavenging assay, and ABTS radical scavenging method [96].Lapathosides C and D, hydropiperoside, vanicoside B, hidropiperosides A and B, lapathoside A, and diboside A were isolated from thePolygonum,Persicaria, andFagopyrum genera belonging to the Polygonaceae family. The DPPH test revealed that free radical-scavenging activity of the isolated compounds termed lapathoside C (115), hydropiperoside (42), vanicoside B (111), and lapathoside D (38) increased in turn, and lapathoside D exhibited strongest scavenging ability with an IC50 of 0.088 μM [43]. Hidropiperosides A and B (117,118) were reported to show obvious antioxidant response to DPPH radicals with the SC50 values of 23.4 and 26.7 μg/mL, respectively, while vanicoside E moderately exhibited the same activity with a SC50 value of 49.0 μg/mL [72]. Lapathoside A (114) and diboside A (116) just showed lower antioxidant activities with the SC50 values of 199.48 and 165.52 μM, respectively [73].Smiglasides A and B, smilaside P, 2,6-di-acetyl-3′,6′-di-feruloylsucrose, helonioside B, smilasides G–L, and heterosmilaside were isolated from theHeterosmilax andSmilax genera. Compared with ascorbic acid (IC50 143.52 μM) used as positive control, smiglasides A and B, and smilaside P (48,49,65) (IC50 339.58, 330.66 and 314.49 μM, resp.) showed higher antioxidant activities than 2,6-di-acetyl-3′,6′-di-feruloylsucrose (73) and helonioside B (40) (IC50 631.66 and 518.27 μM, resp.) [47]. Additionally, Nhiem et al. reported that helonioside B, heterosmilaside (104), and 2,6-di-acetyl-3′,6′-di-feruloylsucrose exhibited important DPPH radical scavenging activities with the SC50 values of 9.1, 12.7 and 8.7 μg/mL, respectively [48]. Compared with smilasides G-I (57–59) (ED50 68.5–79.4 μM), smilasides J–L (60–62) showed higher radical scavenging activities with an ED50 value of 26.7–32.7 μM [44].Five quiquesetinerviusides A–E (105–109) isolated from theCalamus genus showed weak DPPH scavenging activities (IC50 60.4–101.8 μM) but exhibited better hydroxyl radical scavenging activities (IC50 3.6–8.4 μM). Moreover, quiquesetinerviuside C showed superoxide anion scavenging activity with an IC50 value of about 184.3 μM [70]. Liu et al. investigated the antioxidant capacity of 3′,6-O-di-sinapoylsucrose (DISS) (123) by using the accelerated senescence-prone, short-lived mice (SAMP)in vivo. The analyses indicated that the activities of antioxidant enzymes of SOD and glutathione peroxidase ascended obviously in SAMP mice when amended with DISS 50 mg/kg. Moreover, DISS could downregulate and even restore the level of malondialdehyde in SAMP model group [97].From the above studies, it can be concluded that oligosaccharide esters with antioxidant activities have been identified in the Polygonaceae, Liliaceae, Smilacaceae, and Arecaceae families. The results of the antioxidant assays show that the increased number of phenolic hydroxyl groups and acetyl groups could produce higher antioxidant activity. Fan et al. indicated that the increased number of phenylpropanoid groups was not beneficial to free radical scavenging activity [43]. Zhang et al. pointed out that oligosaccharide esters with feruloyl groups exhibited better antioxidant activities than those with coumaroyl groups [44].


### 3.2. Antidepressant Activity

The oligosaccharides obtained from theMorinda genus not only show specific antidepressant and antistress activities but also have no suppression or excitatory effects on central nervous system as well. What is more, they can be taken orally with little toxicity [21]. The inulin-type hexasaccharide (IHS) (9) fromMorinda officinalis obviously exhibited cytoprotective activity, which contributed to the antidepressant effect, not only by providing the PC12 with protection against Cort-induced lesion with IHS 0.625 and 1.25 μM, but also by reducing the Cort-induced Ca
2
+
i overloading with IHS 2.5 and 10 μM. IHS 5 and 10 μM upregulated the nerve growth factor mRNA expression in Cort-induced PC12 cells [22]. Polygalatenosides A (181) and B (182) were isolated from thePolygala genus. They significantly inhibited the isotope-labeled RTI-55 binding to norepinephrine transporter protein with the IC50 values of 30.0 and 6.04 μM, respectively [91].DISS and tenuifoliside A were isolated from thePolygala andCynanchum genera. Liu et al. investigated the antidepressant effect of YZ ethanol extract based on the tail suspension test (TST) and forced swimming test (FST), which are the ease-of-use and widely-accepted models for estimating antidepressant activities in mice. The results indicated that YZ-50 fraction at a dose of 200 mg/kg was able to significantly decrease the immobility time in TST. Furthermore, YZ-50 possessed ability to inhibit corticosterone-induced injury of human neuroblastoma SH-SY5Y cells. What is more, DISS (123) and tenuifoliside A (44), two major compounds of YZ-50 fraction, showed effective protective response to the lesion in SY5Y cells [53]. The antidepressant-like effect of DISS at the doses of 5, 10, and 20 mg/kg was also tested in chronically mild stressed rats. DISS was able to exhibit antidepressant activity by upregulating the expression of noradrenergic-regulated plasticity genes including cell adhesion molecule L1, brain-derived neurotrophic factor, laminin, and cAMP response element binding protein factor in hippocampus [98]. DISS improved the reward reaction by increasing sucrose intake and obviously decreased the levels of serum cortisol, adrenocorticotrophic hormone, and corticotropin-releasing factor. Further, DISS played an enhanced role in the expression of mineralocorticoid receptor, together with glucocorticoid receptor mRNA [99].


### 3.3. Cytotoxic and Antineoplastic Activities

Smilasides A–F and P, smiglasides A and B, smilaside P, and helonioside A were isolated from theSmilax,Trillium, andParis genera. Kuo et al. obtained smilasides A–F (51–56) and evaluated their cytotoxicity against human tumor cell lines comprising human oral epithelium carcinoma (KB), human cervical carcinoma (Hela), human colon tumor (DLD-1), human breast adenocarcinoma (MCF-7), human lung carcinoma (A-549), and human medulloblastoma (Med) cells by MTT assay. Experimental data indicated that all but smilaside C showed cytotoxicity against three to six human tumor cell lines (ED50 = 5.1–13.0 μg/mL), and smilasides D–F (ED50 = 2.7–5.0 μg/mL) displayed strong cytotoxic activities against DLD-1 cells [46]. Wang et al. reported the antitumor constituents ofSmilax riparia, including smiglasides A (48) and B (49), 2,6-di-acetyl-3′,6′-di-feruloylsucrose (73), helonioside B (40), and smilaside P (65). Only smiglasides A and B, and smilaside P exhibited cytotoxicity against human tumor cell lines with different inhibitory concentrations comparing with cisplatin and paclitaxel as positive controls [47]. Helonioside A (39) exhibited higher cytotoxicity with the increase of concentration (0.1–100 μg/mL) [45]. Tatarisides A–G (45,119–121,46,122,47) and diboside A (116) from theFagopyrum genus exerted cytotoxic activities against different human cell lines, and the cytotoxicity of tatariside C was the most remarkable with the IC50 values ranging from 6.44 to 7.49 μg/mL [57].1′,2,3,6-O-Tetra-acetyl-3′-O-cis-feruloylsucrose (95) from theSparganium plants exhibited extremely weak cytotoxicity against the growth of mice Lung Adenocarcinoma 795 cell lines with an IC50 value of 116 μg/mL [66]. SnS-2, oligosaccharides mixture, including raffinose (3), stachyose (19), and verbascose (21) from the roots ofScrophularia ningpoensis, had antitumor activity against the growth of Lewis pulmonary carcinoma cells transplanted into mice [18].Disaccharide esters and oligosaccharides mixture from the Liliaceae, Polygonaceae, Sparganiaceae, and Scrpophulariaceae families showed effective cytotoxic and antineoplastic activities. The study results indicated that feruloyl and acetyl groups play an important role in mediating cytotoxicity, which seems to be related to the substitution position of feruloyl groups. The feruloyl groups at C-6 or C-1′ are vital for cytotoxicity. In addition, the increased number of acetyl groups could induce higher tumoricidal activity.


### 3.4. Anti-Inflammatory Activity

Inflammation, an important basic pathological process, is a defense response of biopsy with vascular system to damage stimuli such as pathogens, impaired cells and tissues, and physical and chemical factors. However, if the process of inflammatory response cannot end normally when cell debris and pathogens were cleared, the biological defence response will become causative factor and bring about many diseases, such as diabetes, cardiovascular diseases, metabolic syndrome, and cancer [100, 101].Tenuifoliside A (44) from thePolygala genus exhibited strong anti-inflammatory effect not only by suppressing the production of NO, but also by reducing the production of iNOS, prostaglandin E2, cyclooxygenase-2, and proinflammatory cytokines through the inhibition of the mitogen-activated protein kinases pathway and NF-κB pathway [102]. The anti-inflammatory activities of quiquesetinerviusides D (108) and E (109) from theCalamus genus were evaluated in RAW 264.7 cells. Both of them showed significant inhibitory effects against the production of LPS-stimulated NO with the IC50 values of 9.0–29.5 μM [70].Six disaccharide fatty acid esters (132–137) were isolated from theAstragalus andEquisetum genera. The anti-inflammatory effects of these isolated compounds have also been documented. The activation of NF-κB could upregulate the expression of proinflammatory cytokines inducible nitric oxide synthase (iNOS) and tumor necrosis factor alpha (TNF-α). The NF-κB inhibitory activities of compounds132–137 were tested in HepG2 cells stimulated with TNF-α. All of these compounds could significantly restrain TNF-α-induced NF-κB transcriptional activities with the IC50 values of 4.4–24.7 μM. Li et al. pointed out that olefinic bonds and the length of the fatty acid moieties contributed to the NF-κB inhibitory activity. Furthermore, the inhibition increased significantly with the increase of the number of olefinic bonds on the aliphatic moiety [77]. These results may provide a scientific basis for the development of new anti-inflammatory agents.


### 3.5. Neuroprotective and Cerebral Protective Activities

As we all know, glutamate works as a major excitatory amino acid neurotransmitter in the mammalian central nervous system and plays a crucial role in several physiological processes [103]. However, the accumulation of glutamate induces diverse acute and chronic neurodegenerative diseases, such as epilepsy, ischemic stroke, and Parkinson’s disease, as well as Alzheimer’s disease [104]. DISS (123) isolated from thePolygala genus exhibited neuroprotective effect against glutamate-induced SH-SY5Y neuronal cell damage. Thein vitro test demonstrated that DISS (0.6, 6 and 60 μmol/L) played a critical role in increasing cell viability, controlling lactate dehydrogenase and attenuated apoptosis ranging from 1.95% to 2.58% [105].Tenuifoliside B (102) from thePolygala genus was able to significantly shorten the coma time of KCN-induced anoxia mice at the doses of 3 and 10 mg/kg, and it played an important role in ameliorating the scopolamine-induced impairment of performance in passive avoidance task in rats and enhancing the tremors induced by oxotremorine in mice. These results together demonstrated that tenuifoliside B possessed cognitive improving and cerebral protective effects [56].


### 3.6. Antidiabetic Activity

Diabetes mellitus, a chronic debilitating metabolic disease, is characterized by high blood glucose content and comprises three types termed type I, type II, and gestational diabetes [106]. Stachyose (19) extract (a part) fromRehmannia glutinosa obviously exhibited the activity of downregulating fasting plasma glucose level and partially keeping from hyperglycemia induced by adrenaline and glucose without obvious dose-dependent effect. Other than that,in vivo tests in rats induced by alloxan revealed that stachyose extract at the dose of 200 mg/kg significantly decreased blood-sugar level [15].Diboside A, lapathosides C and D, vanicosides A and B, and hydropiperoside were isolated from theFagopyrum,Polygonum, andPersicaria genera belonging to the Polygonaceae family. Diboside A (116) could potentially inhibit α-amylase activity with an IC50 of 26.9 μM and thus retard the starch digestion rate, which is helpful for diabetic individuals in controlling blood sugar level [107]. Lapathoside D (38) exerted stronger activity of α-glucosidase inhibition with an IC50 value of 0.113 mM than acarbose which was chosen as a positive drug for the treatment of type II diabetes [43]. Vanicoside B (111) was reported to have higher β-glucosidase inhibitory activity with an IC50 of 50.5 μM than vanicoside A (110) with an IC50 of 59.9 μM because of the acetyl moiety of the latter possibly decreasing inhibitory activity of vanicoside A [71].Fujimoto et al. investigated the inhibitory effects of mumeoses F–O (83–92) from thePrunus genus on aldose reductase and discovered that caffeoyl groups are crucial for the inhibitory effect on aldose reductase. And thus, mumeoses F, G, H, J, K, L, M and N (IC50 = 22–77 μM), with a coumaroyl group and acetyl groups, inhibited moderately aldose reductase from reducing glucose to sorbitol, which is associated with the chronic complications of diabetes [63, 64].


### 3.7. Elicitors and Regulators

Oligosaccharides are quite propitious for encoding biological information because of diverse monosaccharide units and complex molecular structures and they are therefore first described as biological signals in plants [108]. Oligosaccharides from the cell wall fragments of plants and fungi are powerful signal molecules, such as the elicitors of plant defence response and the regulators of plant growth, and they are capable of exerting biological activities at exceedingly low concentrations [109]. Heptasaccharide (HS) (15) and octasaccharide (OS) (16) isolated from theParis genus possessed plant growth-regulatory activities [29, 30]. The two oligosaccharides significantly promoted the proliferation ofParis polyphylla var.yunnanensis roots at the doses of 2.5–20 mg/L. The octasaccharide had the most obvious effect on the growth ofPanax japonicus var.major hairy roots at a dose of 30 mg/L, while the other had the most positive effect on saponin accumulation ofPanax japonicus var.majorhairy roots at a dose of 10 mg/L [29]. Similarly, Zhou et al. evaluated the stimulating effects of HS and OS on the root growth and saponin production ofPanax ginseng hairy roots, which were induced from the plant roots infected withAgrobacterium rhizogenes strain A4. The results showed that there was a maximum effect on the hairy roots growth and saponin accumulation on day 10. Compared with control group, the root biomass dry weight was increased by more than 1.7-fold while the total saponin content of roots increased by more than 1-fold when these two oligosaccharides were added to the hairy root at a dose of 30 mg/L [30]. The above data illustrate that HS and OS could serve as the plant growth-regulators not only in their original species but also in others.


### 3.8. Immunopotentiating Activity

Macrophages are important targets of investigations on cytophagy, cellular immunity, and molecular immunology. Therefore, they are deemed to play a vital role in host defense comprising phagocytosis, proteolytic processing, pathogenic agent, apoptosis, cytokines production, and foreign antigens presentation [110]. The water-extracted oligosaccharides fromPanax ginseng (WGOS) exhibited better immunopotentiating activity by increasing phagocytic function of macrophages and promoting NO, TNF-α and reactive oxygen species production [110]. In addition, Wan et al. have obtained malto-oligosaccharides (17, n = 3~8) and three oligosaccharides (2,13,14) from thePanax ginsengroots. Thein vitro bioassay pointed out that WGOS could serve as efficacious stimulators of B and T lymphocytes [28]. These studies provided enlightenment that the mixture of oligosaccharides from Chinese herbal medicine exhibits significant effect on immune system.


### 3.9. Others

Acetylcholinesterase (AChE) inhibitors show good therapeutic effects on myasthenia gravis, glaucoma, and Alzheimer’s disease through reversible enzyme inhibition so as to increase the accumulation of acetylcholine in the synapse and then promote and prolong the function of acetylcholine. Vanicoside B (111) showed AChE inhibitory activity with an IC50 of 0.062 mM, while hydropiperoside (42), and lapathosides C (115) and D (38) just exhibited weak enzyme inhibitory activity [43].Wang et al. has explored low molecular mass carbohydrate polymer fromPanax ginseng roots and obtained 30% ethanol elution (PGO) which included peptides and oligosaccharides (17, n = 0~5) identified as maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, and maltoheptaose. Pharmacological experiments revealed that PGO could significantly enhance the memory in scopolamine-induced memory deficit rats [27].Cistanoside F (129) and kankanose (150) were isolated from theCistanche,Paulownia, andAcanthus genera. Pharmacological experiments showed that cistanoside F and kankanose significantly exhibited vasorelaxant effects on the noradrenaline-induced contraction of thoracic aorta from rats [80].


## 3.1. Antioxidant Activity

The adverse effects of oxidative stress proposed to play significant roles in the pathogenesis of cardiovascular diseases, atherosclerosis, hypertension, cancer, diabetes mellitus, neurodegenerative diseases, rheumatoid arthritis, ischemia/reperfusion injury, and ageing have become an inevitable and serious issue [95, 96]. Scientists have thus made great efforts to explore antioxidants from medicinal plants by using different kinds of assay methods, which include DPPH radical scavenging assay, hydroxyl radical scavenging assay, superoxide anion scavenging assay, and ABTS radical scavenging method [96].Lapathosides C and D, hydropiperoside, vanicoside B, hidropiperosides A and B, lapathoside A, and diboside A were isolated from thePolygonum,Persicaria, andFagopyrum genera belonging to the Polygonaceae family. The DPPH test revealed that free radical-scavenging activity of the isolated compounds termed lapathoside C (115), hydropiperoside (42), vanicoside B (111), and lapathoside D (38) increased in turn, and lapathoside D exhibited strongest scavenging ability with an IC50 of 0.088 μM [43]. Hidropiperosides A and B (117,118) were reported to show obvious antioxidant response to DPPH radicals with the SC50 values of 23.4 and 26.7 μg/mL, respectively, while vanicoside E moderately exhibited the same activity with a SC50 value of 49.0 μg/mL [72]. Lapathoside A (114) and diboside A (116) just showed lower antioxidant activities with the SC50 values of 199.48 and 165.52 μM, respectively [73].Smiglasides A and B, smilaside P, 2,6-di-acetyl-3′,6′-di-feruloylsucrose, helonioside B, smilasides G–L, and heterosmilaside were isolated from theHeterosmilax andSmilax genera. Compared with ascorbic acid (IC50 143.52 μM) used as positive control, smiglasides A and B, and smilaside P (48,49,65) (IC50 339.58, 330.66 and 314.49 μM, resp.) showed higher antioxidant activities than 2,6-di-acetyl-3′,6′-di-feruloylsucrose (73) and helonioside B (40) (IC50 631.66 and 518.27 μM, resp.) [47]. Additionally, Nhiem et al. reported that helonioside B, heterosmilaside (104), and 2,6-di-acetyl-3′,6′-di-feruloylsucrose exhibited important DPPH radical scavenging activities with the SC50 values of 9.1, 12.7 and 8.7 μg/mL, respectively [48]. Compared with smilasides G-I (57–59) (ED50 68.5–79.4 μM), smilasides J–L (60–62) showed higher radical scavenging activities with an ED50 value of 26.7–32.7 μM [44].Five quiquesetinerviusides A–E (105–109) isolated from theCalamus genus showed weak DPPH scavenging activities (IC50 60.4–101.8 μM) but exhibited better hydroxyl radical scavenging activities (IC50 3.6–8.4 μM). Moreover, quiquesetinerviuside C showed superoxide anion scavenging activity with an IC50 value of about 184.3 μM [70]. Liu et al. investigated the antioxidant capacity of 3′,6-O-di-sinapoylsucrose (DISS) (123) by using the accelerated senescence-prone, short-lived mice (SAMP)in vivo. The analyses indicated that the activities of antioxidant enzymes of SOD and glutathione peroxidase ascended obviously in SAMP mice when amended with DISS 50 mg/kg. Moreover, DISS could downregulate and even restore the level of malondialdehyde in SAMP model group [97].From the above studies, it can be concluded that oligosaccharide esters with antioxidant activities have been identified in the Polygonaceae, Liliaceae, Smilacaceae, and Arecaceae families. The results of the antioxidant assays show that the increased number of phenolic hydroxyl groups and acetyl groups could produce higher antioxidant activity. Fan et al. indicated that the increased number of phenylpropanoid groups was not beneficial to free radical scavenging activity [43]. Zhang et al. pointed out that oligosaccharide esters with feruloyl groups exhibited better antioxidant activities than those with coumaroyl groups [44].


## 3.2. Antidepressant Activity

The oligosaccharides obtained from theMorinda genus not only show specific antidepressant and antistress activities but also have no suppression or excitatory effects on central nervous system as well. What is more, they can be taken orally with little toxicity [21]. The inulin-type hexasaccharide (IHS) (9) fromMorinda officinalis obviously exhibited cytoprotective activity, which contributed to the antidepressant effect, not only by providing the PC12 with protection against Cort-induced lesion with IHS 0.625 and 1.25 μM, but also by reducing the Cort-induced Ca
2
+
i overloading with IHS 2.5 and 10 μM. IHS 5 and 10 μM upregulated the nerve growth factor mRNA expression in Cort-induced PC12 cells [22]. Polygalatenosides A (181) and B (182) were isolated from thePolygala genus. They significantly inhibited the isotope-labeled RTI-55 binding to norepinephrine transporter protein with the IC50 values of 30.0 and 6.04 μM, respectively [91].DISS and tenuifoliside A were isolated from thePolygala andCynanchum genera. Liu et al. investigated the antidepressant effect of YZ ethanol extract based on the tail suspension test (TST) and forced swimming test (FST), which are the ease-of-use and widely-accepted models for estimating antidepressant activities in mice. The results indicated that YZ-50 fraction at a dose of 200 mg/kg was able to significantly decrease the immobility time in TST. Furthermore, YZ-50 possessed ability to inhibit corticosterone-induced injury of human neuroblastoma SH-SY5Y cells. What is more, DISS (123) and tenuifoliside A (44), two major compounds of YZ-50 fraction, showed effective protective response to the lesion in SY5Y cells [53]. The antidepressant-like effect of DISS at the doses of 5, 10, and 20 mg/kg was also tested in chronically mild stressed rats. DISS was able to exhibit antidepressant activity by upregulating the expression of noradrenergic-regulated plasticity genes including cell adhesion molecule L1, brain-derived neurotrophic factor, laminin, and cAMP response element binding protein factor in hippocampus [98]. DISS improved the reward reaction by increasing sucrose intake and obviously decreased the levels of serum cortisol, adrenocorticotrophic hormone, and corticotropin-releasing factor. Further, DISS played an enhanced role in the expression of mineralocorticoid receptor, together with glucocorticoid receptor mRNA [99].


## 3.3. Cytotoxic and Antineoplastic Activities

Smilasides A–F and P, smiglasides A and B, smilaside P, and helonioside A were isolated from theSmilax,Trillium, andParis genera. Kuo et al. obtained smilasides A–F (51–56) and evaluated their cytotoxicity against human tumor cell lines comprising human oral epithelium carcinoma (KB), human cervical carcinoma (Hela), human colon tumor (DLD-1), human breast adenocarcinoma (MCF-7), human lung carcinoma (A-549), and human medulloblastoma (Med) cells by MTT assay. Experimental data indicated that all but smilaside C showed cytotoxicity against three to six human tumor cell lines (ED50 = 5.1–13.0 μg/mL), and smilasides D–F (ED50 = 2.7–5.0 μg/mL) displayed strong cytotoxic activities against DLD-1 cells [46]. Wang et al. reported the antitumor constituents ofSmilax riparia, including smiglasides A (48) and B (49), 2,6-di-acetyl-3′,6′-di-feruloylsucrose (73), helonioside B (40), and smilaside P (65). Only smiglasides A and B, and smilaside P exhibited cytotoxicity against human tumor cell lines with different inhibitory concentrations comparing with cisplatin and paclitaxel as positive controls [47]. Helonioside A (39) exhibited higher cytotoxicity with the increase of concentration (0.1–100 μg/mL) [45]. Tatarisides A–G (45,119–121,46,122,47) and diboside A (116) from theFagopyrum genus exerted cytotoxic activities against different human cell lines, and the cytotoxicity of tatariside C was the most remarkable with the IC50 values ranging from 6.44 to 7.49 μg/mL [57].1′,2,3,6-O-Tetra-acetyl-3′-O-cis-feruloylsucrose (95) from theSparganium plants exhibited extremely weak cytotoxicity against the growth of mice Lung Adenocarcinoma 795 cell lines with an IC50 value of 116 μg/mL [66]. SnS-2, oligosaccharides mixture, including raffinose (3), stachyose (19), and verbascose (21) from the roots ofScrophularia ningpoensis, had antitumor activity against the growth of Lewis pulmonary carcinoma cells transplanted into mice [18].Disaccharide esters and oligosaccharides mixture from the Liliaceae, Polygonaceae, Sparganiaceae, and Scrpophulariaceae families showed effective cytotoxic and antineoplastic activities. The study results indicated that feruloyl and acetyl groups play an important role in mediating cytotoxicity, which seems to be related to the substitution position of feruloyl groups. The feruloyl groups at C-6 or C-1′ are vital for cytotoxicity. In addition, the increased number of acetyl groups could induce higher tumoricidal activity.


## 3.4. Anti-Inflammatory Activity

Inflammation, an important basic pathological process, is a defense response of biopsy with vascular system to damage stimuli such as pathogens, impaired cells and tissues, and physical and chemical factors. However, if the process of inflammatory response cannot end normally when cell debris and pathogens were cleared, the biological defence response will become causative factor and bring about many diseases, such as diabetes, cardiovascular diseases, metabolic syndrome, and cancer [100, 101].Tenuifoliside A (44) from thePolygala genus exhibited strong anti-inflammatory effect not only by suppressing the production of NO, but also by reducing the production of iNOS, prostaglandin E2, cyclooxygenase-2, and proinflammatory cytokines through the inhibition of the mitogen-activated protein kinases pathway and NF-κB pathway [102]. The anti-inflammatory activities of quiquesetinerviusides D (108) and E (109) from theCalamus genus were evaluated in RAW 264.7 cells. Both of them showed significant inhibitory effects against the production of LPS-stimulated NO with the IC50 values of 9.0–29.5 μM [70].Six disaccharide fatty acid esters (132–137) were isolated from theAstragalus andEquisetum genera. The anti-inflammatory effects of these isolated compounds have also been documented. The activation of NF-κB could upregulate the expression of proinflammatory cytokines inducible nitric oxide synthase (iNOS) and tumor necrosis factor alpha (TNF-α). The NF-κB inhibitory activities of compounds132–137 were tested in HepG2 cells stimulated with TNF-α. All of these compounds could significantly restrain TNF-α-induced NF-κB transcriptional activities with the IC50 values of 4.4–24.7 μM. Li et al. pointed out that olefinic bonds and the length of the fatty acid moieties contributed to the NF-κB inhibitory activity. Furthermore, the inhibition increased significantly with the increase of the number of olefinic bonds on the aliphatic moiety [77]. These results may provide a scientific basis for the development of new anti-inflammatory agents.


## 3.5. Neuroprotective and Cerebral Protective Activities

As we all know, glutamate works as a major excitatory amino acid neurotransmitter in the mammalian central nervous system and plays a crucial role in several physiological processes [103]. However, the accumulation of glutamate induces diverse acute and chronic neurodegenerative diseases, such as epilepsy, ischemic stroke, and Parkinson’s disease, as well as Alzheimer’s disease [104]. DISS (123) isolated from thePolygala genus exhibited neuroprotective effect against glutamate-induced SH-SY5Y neuronal cell damage. Thein vitro test demonstrated that DISS (0.6, 6 and 60 μmol/L) played a critical role in increasing cell viability, controlling lactate dehydrogenase and attenuated apoptosis ranging from 1.95% to 2.58% [105].Tenuifoliside B (102) from thePolygala genus was able to significantly shorten the coma time of KCN-induced anoxia mice at the doses of 3 and 10 mg/kg, and it played an important role in ameliorating the scopolamine-induced impairment of performance in passive avoidance task in rats and enhancing the tremors induced by oxotremorine in mice. These results together demonstrated that tenuifoliside B possessed cognitive improving and cerebral protective effects [56].


## 3.6. Antidiabetic Activity

Diabetes mellitus, a chronic debilitating metabolic disease, is characterized by high blood glucose content and comprises three types termed type I, type II, and gestational diabetes [106]. Stachyose (19) extract (a part) fromRehmannia glutinosa obviously exhibited the activity of downregulating fasting plasma glucose level and partially keeping from hyperglycemia induced by adrenaline and glucose without obvious dose-dependent effect. Other than that,in vivo tests in rats induced by alloxan revealed that stachyose extract at the dose of 200 mg/kg significantly decreased blood-sugar level [15].Diboside A, lapathosides C and D, vanicosides A and B, and hydropiperoside were isolated from theFagopyrum,Polygonum, andPersicaria genera belonging to the Polygonaceae family. Diboside A (116) could potentially inhibit α-amylase activity with an IC50 of 26.9 μM and thus retard the starch digestion rate, which is helpful for diabetic individuals in controlling blood sugar level [107]. Lapathoside D (38) exerted stronger activity of α-glucosidase inhibition with an IC50 value of 0.113 mM than acarbose which was chosen as a positive drug for the treatment of type II diabetes [43]. Vanicoside B (111) was reported to have higher β-glucosidase inhibitory activity with an IC50 of 50.5 μM than vanicoside A (110) with an IC50 of 59.9 μM because of the acetyl moiety of the latter possibly decreasing inhibitory activity of vanicoside A [71].Fujimoto et al. investigated the inhibitory effects of mumeoses F–O (83–92) from thePrunus genus on aldose reductase and discovered that caffeoyl groups are crucial for the inhibitory effect on aldose reductase. And thus, mumeoses F, G, H, J, K, L, M and N (IC50 = 22–77 μM), with a coumaroyl group and acetyl groups, inhibited moderately aldose reductase from reducing glucose to sorbitol, which is associated with the chronic complications of diabetes [63, 64].


## 3.7. Elicitors and Regulators

Oligosaccharides are quite propitious for encoding biological information because of diverse monosaccharide units and complex molecular structures and they are therefore first described as biological signals in plants [108]. Oligosaccharides from the cell wall fragments of plants and fungi are powerful signal molecules, such as the elicitors of plant defence response and the regulators of plant growth, and they are capable of exerting biological activities at exceedingly low concentrations [109]. Heptasaccharide (HS) (15) and octasaccharide (OS) (16) isolated from theParis genus possessed plant growth-regulatory activities [29, 30]. The two oligosaccharides significantly promoted the proliferation ofParis polyphylla var.yunnanensis roots at the doses of 2.5–20 mg/L. The octasaccharide had the most obvious effect on the growth ofPanax japonicus var.major hairy roots at a dose of 30 mg/L, while the other had the most positive effect on saponin accumulation ofPanax japonicus var.majorhairy roots at a dose of 10 mg/L [29]. Similarly, Zhou et al. evaluated the stimulating effects of HS and OS on the root growth and saponin production ofPanax ginseng hairy roots, which were induced from the plant roots infected withAgrobacterium rhizogenes strain A4. The results showed that there was a maximum effect on the hairy roots growth and saponin accumulation on day 10. Compared with control group, the root biomass dry weight was increased by more than 1.7-fold while the total saponin content of roots increased by more than 1-fold when these two oligosaccharides were added to the hairy root at a dose of 30 mg/L [30]. The above data illustrate that HS and OS could serve as the plant growth-regulators not only in their original species but also in others.


## 3.8. Immunopotentiating Activity

Macrophages are important targets of investigations on cytophagy, cellular immunity, and molecular immunology. Therefore, they are deemed to play a vital role in host defense comprising phagocytosis, proteolytic processing, pathogenic agent, apoptosis, cytokines production, and foreign antigens presentation [110]. The water-extracted oligosaccharides fromPanax ginseng (WGOS) exhibited better immunopotentiating activity by increasing phagocytic function of macrophages and promoting NO, TNF-α and reactive oxygen species production [110]. In addition, Wan et al. have obtained malto-oligosaccharides (17, n = 3~8) and three oligosaccharides (2,13,14) from thePanax ginsengroots. Thein vitro bioassay pointed out that WGOS could serve as efficacious stimulators of B and T lymphocytes [28]. These studies provided enlightenment that the mixture of oligosaccharides from Chinese herbal medicine exhibits significant effect on immune system.


## 3.9. Others

Acetylcholinesterase (AChE) inhibitors show good therapeutic effects on myasthenia gravis, glaucoma, and Alzheimer’s disease through reversible enzyme inhibition so as to increase the accumulation of acetylcholine in the synapse and then promote and prolong the function of acetylcholine. Vanicoside B (111) showed AChE inhibitory activity with an IC50 of 0.062 mM, while hydropiperoside (42), and lapathosides C (115) and D (38) just exhibited weak enzyme inhibitory activity [43].Wang et al. has explored low molecular mass carbohydrate polymer fromPanax ginseng roots and obtained 30% ethanol elution (PGO) which included peptides and oligosaccharides (17, n = 0~5) identified as maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose, and maltoheptaose. Pharmacological experiments revealed that PGO could significantly enhance the memory in scopolamine-induced memory deficit rats [27].Cistanoside F (129) and kankanose (150) were isolated from theCistanche,Paulownia, andAcanthus genera. Pharmacological experiments showed that cistanoside F and kankanose significantly exhibited vasorelaxant effects on the noradrenaline-induced contraction of thoracic aorta from rats [80].


## 4. Conclusion

Traditional Chinese medicine from natural kingdom plays an indelible role in the treatment of human diseases, and it has aroused the attention of those who have engaged in medicinal pharmaceutical chemistry. Therefore, scientists have made great contributions day after day to investigate the valid chemicals from traditional Chinese medicines. In the past decades, about 193 oligosaccharides and their esters have been identified from traditional Chinese medicinal plants. On the one hand, only a few oligosaccharides and their mixtures were investigated and just exhibited antidepressant, antineoplastic, antidiabetic, plant growth-regulatory, immunopotentiating, and enhanced memory activities. More exploratory work is still needed to excavate biological and pharmacological activities of oligosaccharides. On the other hand, oligosaccharide esters exhibited multi-advantageous activities. Bioassays have revealed that antioxidant, cytotoxic, antineoplastic, and anti-inflammatory activities are the most notable bioactivities. Of course, to search for the natural products with these activities is a hotpot in the contemporary drug research. Oligosaccharide esters provide a vast treasure trove for medical researchers. After considering the current studies, it should be taken as future directions to make more mechanism of action studies and clinical trials to further evaluate its potential as new drugs. Moreover, the structure-activity relationships discussed in this review will provide reference information for further exploring their relationships and continually discovering the new bioactive oligosaccharide esters.



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