2014, 19, 19610-19632; doi: 10. 3390/molecules191219610 molecules
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- Bu səhifədəki naviqasiya:
- Recent Advances in the Chemical Composition of Propolis Shuai Huang 1 , Cui-Ping Zhang 1
- Keywords
- OPEN ACCESS Molecules 2014
- 2. Chemical Compounds in Propolis
- Figure 2.
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www.mdpi.com/journal/molecules Review Recent Advances in the Chemical Composition of Propolis Shuai Huang 1 , Cui-Ping Zhang 1 , Kai Wang 1 , George Q. Li 2, * and Fu-Liang Hu 1, * 1 College of Animal Sciences, Zhejiang University, Hangzhou 310058, China; E-Mails: asmallcaths@163.com (S.H.); lgzcplyx@aliyun.com (C.-P.Z.); kaiwang628@gmail.com (K.W.) 2 Faculty of Pharmacy, University of Sydney, Sydney, NSW 2006, Australia * Authors to whom correspondence should be addressed; E-Mails: george.li@sydney.edu.au (G.Q.L.); flhu@zju.edu.cn (F.-L.H.); Tel./Fax: +61-2-9351-4435 (G.Q.L.); +86-571-8898-2952 or +86-571-8898-2840 (F.-L.H.). External Editor: Marcello Iriti Received: 10 October 2014; in revised form: 13 November 2014 / Accepted: 20 November 2014 / Published: 26 November 2014
describes that propolis is collected from plant resins. From a systematic database search, 241 compounds were identified in propolis for the first time between 2000 and 2012; and they belong to such diverse chemical classes as flavonoids, phenylpropanoids, terpenenes, stilbenes, lignans, coumarins, and their prenylated derivatives, showing a pattern consistent with around 300 previously reported compounds. The chemical characteristics of propolis are linked to the diversity of geographical location, plant sources and bee species. Keywords: propolis; honeybee; flavonoids; phenypropanoids; terpenenes; plant origin
Propolis is a honeybee product with a broad spectrum of biological properties [1]. As a resinous substance, propolis is prepared by the honeybees to seal the cracks, smooth walls, and to keep moisture and temperature stable in the hive all year around. Raw propolis is typically composed of 50% plant resins, 30% waxes, 10% essential and aromatic oils, 5% pollens and 5% other organic substances. It has been reported that propolis is collected from resins of poplars, conifers, birch, pine, alder, willow, palm,
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Propolis is widely used to prevent and treat colds, wounds and ulcers, rheumatism, sprains, heart disease, diabetes [5–8] and dental caries [9] due to its diverse biological properties such as anti-inflammatory [8,10–12], antimicrobial, antioxidant, antitumor [3], antiulcer and anti-HIV activities [13]. The wide application of propolis in modern medicine has drawn growing attention to its chemical composition. Many studies have revealed that the observed effects might be the result of synergistic action of its complex constituents [14–16]. Previous reviews [3,17,18] have covered the knowledge about the chemical composition and botanical origin of propolis throughout 20th century. Until 2000, over 300 chemical components belonging to the flavonoids, terpenes, and phenolics have been identified in propolis. Some representative chemical compounds are summarized in Figure 1.
The characteristic constituents in temperate region propolis are flavonoids without B-ring substituents, such as chrysin, galangin, pinocembrin, pinobanksin. Caffeic acid phenethyl ester (CAPE) is a major constituent of temperate propolis with broad biological activities, including inhibition of nuclear factor κ-B; inhibition of cell proliferation; induction of cell cycle arrest and apoptosis. In tropical region propolis, especially Brazilian green propolis, the dominating chemical components are prenylated Molecules 2014, 19 19612
phenylpropanoids (e.g., artepillin C) and diterpenes. For propolis produced in the Pacific region, geranyl flavanones are the characteristic compounds which are also found in propolis from the African region [19]. The chemical composition of propolis is susceptible to the geographical location, botanical origin [20–23], and bee species [23]. In order to provide a theoretical basis for studying the chemical composition and pharmacological activity of propolis and plant sources, and controlling the quality, chemical components that were isolated for the first time from propolis between 2000 and 2012 were scouted and summarized from databases including BioMed Central, Biosis Citation Index, Medline, and PubMed.
With the development of separation and purification techniques such as high performance liquid chromatography (HPLC), thin layer chromatography [24], gas chromatography (GC), as well as identification techniques, such as mass spectroscopy (MS) [25], nuclear magnetic resonance (NMR), gas chromatography and mass spectroscopy (GC-MS) [26], more compounds have been identified in propolis for the first time; including flavonoids, terpenes, phenolics and their esters, sugars, hydrocarbons and mineral elements. In contrast, relatively common phytochemicals such as alkaloids, and iridoids have not been reported. Two hundred and forty one (241) compounds have been reported for the first time from propolis between 2000 and 2012. Their chemical category, geographical locations, and possible plant source, are summarized below. 3. Flavonoids As the major constituents of propolis, flavonoids contribute greatly to the pharmacological activities of propolis. The quantity of flavonoids is used as a criterion to evaluate the quality of temperate propolis [27]. Flavonoids have a broad spectrum of biological properties, such as antibacterial, antiviral and anti-inflammatory effects [16,28]. According to the chemical structure, flavonoids in propolis are classified into flavones, flavonols, flavanones, flavanonols, chalcones, dihydrochalcones, isoflavones, isodihydroflavones, flavans, isoflavans and neoflavonoids. From 2000 to 2012, 112 flavonoids were identified in different type of propolis for the first time (Table 1). In addition, flavonoid glycosides that are very rare in propolis were identified; they are isorhamnetin-3-O-rutinoside [29] and flavone
Five flavones 1–5 were identified in Chinese, Polish, Egyptian and Mexican propolis. According to the geographical origin and the typical chemical compounds, the botanical origins of these propolis samples are assumed to be the genus Populus. In samples from the Solomon Islands and Kenya, researchers identified four flavonols 6–9 and confirmed that these compounds exhibited potent antibacterial activity [31]. The majority of the identified compounds were also found in the plants Macaranga, suggesting that the genus Macaranga is the likely plant source. In Pacific propolis, scientists identified many prenylated flavanones 21–31 which exhibited strong antimicrobial activity because the lipophilic prenyl group could rapidly damage the membrane and cell wall function [32]. Some flavanones 11, 13, 14, 17–19 were also identified in poplar propolis. Sherstha et al. identified three flavanonols 42–44 in Nepalese propolis, Portuguese propolis and Australian propolis, respectively.
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No. Chemical Name Geographical Location Reference Flavones 1 Luteolin China
[33] 2 6-Cinnamylchrysin China [34]
3 3',5-Dihydroxy-4',7-dimenthoxy flavone
Poland [26]
4 Hexamethoxy flavone
Egypt [35]
5 (7''R)-8-[1-(4'-Hydroxy-3'-methoxyphenyl) prop-2-en-1-yl]chrysin Mexico
[36] Flavonols 6 2'-(8"-Hydroxy-3",8"-dimethyl-oct-2"-enyl)-quercetin Solomon Island
[31] 7 8-(8"-Hydroxy-3",8"-dimethyl-oct-2"-enyl)-quercetin Solomon Island [31]
8 2'-Geranylquercetin Solomon Island
[31] 9 Macarangin Kenya [37]
10 (7"R)-8-[1-(4'-Hydroxy-3'-methoxyphenyl)prop-2-en-1-yl]-galangin Mexico [36] Flavanones 11 3-O-[(S)-2-Methylbutyroyl]pinobanksin China [34]
12 (2S)-5,7-Dihydroxy-4'-methoxy-8-prenylflavanone Solomon Island
[31] 13 Hesperitin-5,7-dimethyl ether Portugal [38] 14 Pinobanksin-5-methyl-ether-3-O-pentanoate Portugal [38] 15 7-O-Prenylstrobopinin Greek [39] 16 7-O-Prenylpinocembrin Greek [39] 17
(2R,3R)-3,5-Dihydroxy-7-methoxyflavanone 3-(2-methyl)-butyrate Mexico [36] 18
(2R,3R)-6[1-(4'-Hydroxy-3'-methoxyphenyl) prop-2en-1-yl] pinobanksin Mexico [40] 19
(2R,3R)-6[1-(4'-Hydroxy-3'-methoxyphenyl) prop-2en-1-yl]-pinobanksin-3-acetate Mexico [40] 20 3',4',6-Trihydroxy-7-methoxy flavanone Nepal
[41] 21 5,7,3',4'-Tetrahydroxy-5'-C-geranylflavanone Japan [42] 22 5,7,3',4'-Tetrahydroxy-6-C-geranylflavanone Japan [42] 23 5,7,3',4'-Tetrahydroxy-2'-C-geranylflavanone Japan [42] 24 5,7,3',4'-Tetrahydroxy-2'-C-geranyl-6-prenlyflavanone Japan [42] 25 Propolin A Taiwan
[43] 26 Propolin B Taiwan
[43] 27 Propolin E Taiwan
[43] 28 Sigmoidin B Taiwan
[43] 29 Bonannione A Taiwan
[31] 30
Solophenol A Solomon Island [31] 31
Sophoraflavanone A Solomon Island [31] 32 (2S)-7-Hydroxyflavanone Brazil [44] 33 (2S)-Liquiritigenin Brazil [44] 34 (2S)-7-Hydroxy-6-methoxyflavanone Brazil [44] 35 (2S)-Naringenin Brazil [44] 36 (2S)-Dihydrobaicalein Brazil [44] 37 (2S)-Dihydrooroxylin A Brazil [44]
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No. Chemical Name Geographical Location Reference Flavanones 38 (2R,3R)-3,7-Dihydroxyflavanone Brazil [44]
39 Garbanzol Brazil
[44] 40 (2R,3R)-3,7-Dihydroxy-6-methoxyflavanone Brazil [44] 41 Alnustinol Brazil [44]
42 (2R, 3R)-3,6,7-Trihydroxyflavanone Nepal [41]
43 5-Methoxy-3-hidroxyflavanone Portugal [38] 44 5,7-Dihydroxy-6-methoxy-2,3-Dihydroflavonol-3-acetate Australia [45] Isoflavones 45 Odoratin Nepal [41]
46 7,3',4'-Trihydroxy-5'-methoxyisoflavonoid Nepal
[41] 47 6,7,3'-Trihydroxy-4'-methoxyisoflavonoid Nepal [41]
48 7,3'-Dihydroxy-6,5'- methoxyisoflavonoid Nepal [41]
49 7-Hydroxy-4'-methoxyisoflavonoid Cuba
[46] 50 5,7-Dihydroxy-4'-methoxyisoflavonoid Cuba [46]
51 Calycosin Brazil
[44] 52 7,4'-Dihydroxyisoflavone Brazil [24]
53 Homopterocarpin Brazil
[24] 54 Medicarpin Brazil [24]
55 4',7-Dimethoxy-2'-isoflavonol Brazil
[24] Isodihydroflavones 56 Daidzein Brazil
[44] 57 Formononetin Brazil [44]
58 Xenognosin B Brazil [44] 59 Biochanin A Brazil
[44] 60 Pratensein Brazil [44]
61 2'-Hydroxybiochanin A Brazil [44] 62 (3S)-Vestitone- Brazil [44] 63 (3S)-Violanone Brazil [44] 64 (3S)-Ferreirin Brazil [44] 65 (3R)-4'-Methoxy-2',3,7-trihydroxyisoflavanone Brazil [44] 66 Biochanin Cuba [25]
Chalcones 67 3,4,2',3'-Tetrahydroxychalcone Brazil [30]
68 Isoliquiritigenin Brazil
[44] 69 4,4'-Dihydroxy-2'-methoxychalcone Brazil [44]
Dihydrochalcones 70 (αS)-α,2',4,4'-Tetrahydroxydihydrochalcone Brazil [44] 71 2',4'-Dihydroxychalcone Brazil [44]
72 2',6'-Dihydroxy-4',4-dimethoxydihydrochalcone Canada [47]
73 2',4',6'-Trihydroxy-4-methoxydihydrochalcone Canada
[47] 74 2',6',4-Tryhydroxy-4'-methoxydihydrochalcone Canada [47]
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No. Chemical Name Geographical Location Reference Flavans
75 8-[(E)-4-Phenylprop-2-en-1-one]-(2R,3S)-2-(3,5-dihydroxyphenyl)- 3,4-dihydro-2H-2-be-nzopyran-5-methoxyl-3,7-diol, China [48] 76 8-[(E)-4-Phenylprop-2-en-1-one]-(2S,3R)-2-(3,5-dihydroxyphenyl)- 3,4-dihydro-2H-2-benzopyran-5-methoxyl-3,7-diol China [48] 77 8-[(E)-4-Phenylprop-2-en-1-one]-(2R,3S)-2-(3-methoxyl-4-hydroxy phenyl)-3,4-dihydro-2H-2-benzopyran-5-methoxyl-3,7-diol China [48] 78 3-Hydroxy-5,6-dimethoxyflavan Mexico
[49] Isoflavans 79 (3S)-Vestitol Brazil [44]
80 (3S)-Isovestitol Brazil [44]
81 (3S)-7-O-Methylvestitol Brazil [44]
82 (3S)-Mucronulatol Brazil [44]
83 7,4'-Dihydroxy-2'-methoxyisoflavone Cuba
[46] 84 Neovestitol Cuba [25]
Pterocarpins (a type of neoflavonoid) 85 Medicarpin Cuba [46]
86 4-Hydroxymedicarpin - [46] 87 Homopterocarpin Cuba
[46] 88 4'-Methoxy-5'hydroxyvesticarpan - [46]
89 3,8-Dihydroxy-9-methoxypterocarpan Cuba
[46] 90 3-Hydroxy-8,9-dimethoxypterocarpan Cuba [46]
91 3,4-Dihydroxy-9-methoxypterocarpan Cuba
[46] 92 3,10-Dihydroxy-9-methoxypterocarpan Brazil [44]
93 6a-Ethoxymedicarpin Brazil
[44] 94 (6aR,11aR)-4-Methoxymedicarpin Brazil [44] Open-chain neoflavonoids 95 Neoflavonoid 1 Nepal [50] 96 Neoflavonoid 2 Nepal
[50] 97 Neoflavonoid 3 Nepal
[50] 98 Neoflavonoid 4 Nepal
[50] 99 Neoflavonoid 5 Nepal
[50] 100 Neoflavonoid 6 Nepal
[50] 101 Neoflavonoid 7 Nepal
[50] 102 Neoflavonoid 8 Nepal
[50] 103 Neoflavonoid 9 Nepal
[50] 104 Neoflavonoid 10 Nepal
[50] 105 (S)-3'-hydroxy-4-methoxydalbergione Nepal [51] 106 (S)-3',4'-dihydroxy-4-methoxydalbergione Nepal [51] 107 (S)-4-methoxydalbergione Nepal [51]
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No. Chemical Name Geographical Location Reference Other flavonoids 108 2,6-Dihydroxy-2-[(4-hydroxyphenyl)methyl]-3-benzofuranone Brazil [44] 109 2-(2',4'-Dihydroxyphenyl)-3-methyl-6-methoxybenzofuran Brazil [44] 110 1-(3',4'-Dihydroxy-2'-methoxyphenyl)-3-(phenyl)propane Mexico [49] 111 (Z)-1-(2'-Methoxy-4',5'dihydroxyphenyl)-2-(3-phenyl)propene Mexico [49] Red Brazilian propolis is a new type of propolis that has attracted wide attention. Researchers identified many compounds typically found in resinous exudates of leguminous plant (Dalbergia
three chalcones 67–69, two dihydrochalcones 70–71. Three dihydrochalcones 72–74 that are considered to be characteristic for the bud exudates of Tacamahaca poplars were found in Canadian samples for the first time. Sha et al. and Lotti et al. identified some flavans 75–78 with high cytotoxic activity in Chinese and Mexican propolis [48,49]. Piccinelli et al. identified two isoflavones: 7-hydroxy-4'-methoxyisoflavonoid and 5,7-dihydroxy- 4'-methoxy isoflavonoids in red Cuban propolis, although their plant source has not been confirmed. They presumably originated from Leguminous plants, which is the same botanical origin of red Brazilian propolis [46]. At the same time, isoflavanes 79–84 and pterocarpins 85–94 were also found in the two types of red propolis. In samples from Nepal, 14 unique open-chain neoflavonoids 95–107 (Figure 2) were identified, which are used as markers of the plant source of this type of propolis.
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Among the compounds isolated from Nepalese propolis, (S)-4-methoxydalbergione and obtusaquinol were reported as constituents of Dalbergia and Machaerium woods, but some neoflavonoids such as cearoin and 9-hydroxy-6,7-dimethoxydalbergiquinol were identified only in Dalbergia species [50]. Other flavonoids 108–111 found in Brazilian and Mexican propolis, respectively, are listed in Table 1.
Although volatiles only represent 10% of the propolis constituents, they account for the characteristic resinous odor and contribute to the pharmacological effects of propolis. As the major compounds among the volatile substances, terpenoids play an important role in distinguishing premium propolis from inferior or fake propolis and they exhibit antioxidant, antimicrobial, and other biological activities. Monoterpenes isolated from propolis include acyclic, monocyclic, dicyclic monoterpenes and their derivatives. The primary acyclic and monocyclic monoterpenes are myrcenes, p-menthanes and cineoles, respectively. The dicyclic monoterpenes in propolis are classified into five groups: thujanes, caranes, pinanes, fenchanes and camphenes. Sesquiterpenes are the most abundant chemical components in propolis. According to the number of the rings, sesquiterpenes fall into four categories: acyclic, monocyclic, dicyclic and tricyclic. The main acyclic sesquiterpenes in propolis are the derivatives of farnesane. There are four types of monocyclic sesquiterpenes, five types of dicyclic sesquiterpenes and ten types of tricyclic sesquiterpenes in propolis. Cembrane, labdane, abietane, pimarane, and totarane are reported to be the major diterpenes in propolis, and some of these are proven to have a broad spectrum of pharmacological properties. The tetracyclic triterpenes in propolis are lanostanes and cycloartane and the pentacyclic triterpenes are oleanane, ursane and lupane. One monoterpene (trans-β-terpineol) and three sesquiterpenes (γ-elemene, α-ylangene, valencene) with valuable biological activities were identified in Brazilian propolis [52]. In Turkish propolis, a few sesquiterpenes 119–123 were identified; and there was no direct evidence to determine the correct plant source of the each type of Turkish propolis [53]. Popova et al. identified the usual “Mediterranean” diterpenes in samples from Greece, together with some diterpenes (Table 2) that are deemed as characteristic oleoresin components of different Coniferae (mainly Pinaceae and Cupressaceae) plants [29], although their plant source was considered to be the Cupressaceae because Greek propolis contained ferruginol, totarol, oxygenated ferruginol and totarol derivatives, and sempervirol, which are typically found in Cupressaceae plant, but not in Pinaceae. Some triterpenes belonging to the lupane (154–156), lanostane (157–158), oleanane (159–161), ursane (162–164) and other types (165–170) were found in Brazilian, Cuban, Greek, Burmese and Egyptian propolis for the first time.
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