2014, 19, 19610-19632; doi: 10. 3390/molecules191219610 molecules
Table 2. Terpenes identified in propolis since 2000. No
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- 9. The Chemical Categories Reported in Propolis
- Table 4.
- Figure 3.
- 11. The Geographical Origins of Propolis
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Table 2. Terpenes identified in propolis since 2000. No. Chemical Name Geographical Location Reference Monoterpenes 112
[54]
113 Linalool Brazil
[52] 114 Camphor Iran [55]
Sesquiterpenes 115 Junipene Greece [54]
116 γ-Elemene Brazil [52]
Molecules 2014, 19 19618
Sesquiterpenes 117 α-Ylangene Brazil [52] 118 Valencene Brazil [52]
119 8-βH-Cedran-8-ol Turkey [53]
120 4-βH,5α-Eremophil-1(10)-ene Turkey [53]
121 α-Bisabolol Turkey [23] 122
α-Eudesmol Turkey [23]
123 α-Cadinol Turkey [23] 124 Patchoulene Indonesia [56]
Diterpenes 125 Manoyl oxide Greece
[57] 126 Ferruginol Greece [57]
127 Ferruginolone Greece
[57] 128 2-Hydroxyferruginol Greece [57]
129 6/7-Hydroxyferruginol Greece
[57] 130 Sempervirol Greece [57]
131 Abietic acid
Greece [57]
132 18-Succinyloxyabietadiene Greece
[57] 133 18-Succinyloxyhydroxyabietatriene Greece [57] 134 18-Hydroxyabieta-8,11,13-triene Greece [57] 135 Imbricataloic acid Greece
[57] 136 Imbricatoloic acid Greece
[57] 137 Diterpenic acid Greece
[57] 138 Neoabietic acid Greece
[57] 139 Labda-8(17),12,13-triene Greece [57]
140 Hydroxydehydroabietic acid
Greece [57]
141 Dihydroxyabieta-8,11,13-triene Greece
[57] 142 13(14)-Dehydrojunicedric acid Greece
[57] 143 Dehydroabietic acid Greece
[57] 144 18-Hydroxyabieta-8,11,13-triene Greece [57] 145 Junicedric acid Greece
[29] 146 14,15-Dinor-13-oxo-8(17)-labden-19-oic acid Greece
[29] 147
tran-Communal Greece [29]
148 Palmitoyl isocupressic acid Greece [29]
149 Oleoyl isocupressic acid Greece
[29] 150 13-Hydroxy-8(17),14-labdadien-19-oic acid Greece
[29] 151 15-Oxolabda-8(17),13(E)-dien-19-oic acid Greece [29]
152 Pimaric acid
Greece [29]
153 Totarolone Greece
[29] Triterpenes 154 Lupeol alkanoates Brazil [58]
155 Lupeol Brazil
[58] 156 Lupeol acetate Cuba
[59] 157 Lanosterol acetate Egypt
[35] Molecules 2014, 19 19619
Triterpenes 158 Lanosterol Cuba
[59] 159 Germanicol acetate Cuba
[59] 160 Germanicol Cuba [59]
161 β-Amyrin acetate Cuba [59]
162 β-Amyrone Cuba [59] 163
α-Amyrin acetate Cuba
[59] 164
α-Amyrone Cuba [59]
165 24-Methylene-9,19-ciclolanostan-3β-ol Brazil [58]
166 (22Z,24E)-3-Oxocycloart-22,24-dien-26-oic acid Burma
[60] 167 (24E)-3-Oxo-27,28-dihydroxycycloart-24-en-26-oic acid Burma [60]
168 3,4-seco-Cycloart-12-hydroxy-4(28),24-dien-3-oicacid Greece [29] 169 Cycloart-3,7-dihydroxy-24-en-28-oic acid Greece [29]
170 3-Oxo-triterpenic acid methyl ester Egypt [61]
5. Phenolics Brazilian green propolis is rich in phenylpropanoids including cinnamic acid, p-coumaric acid, caffeic acid, ferulic acid and their derivatives. Among these substances, prenylated cinnamic acids turn out to be a salient chemical feature and have a consanguineous bearing on antimicrobial activity of green propolis. In recent years, researchers identified a series of phenylpropanoid derivatives 171–180 in Brazilian propolis. Meanwhile, some caffeic acid derivatives 182–183 and isoferulic acid derivative 184 were also identified in poplar propolis by GC-MS. Chlorogenic acid is abundant in Brazilian propolis of floral origin from Citrus spp. [62]. Three quinic acid derivatives 185–187 were identified in this type of propolis. Another class of phenolics, stilbenes, are not very common in plants. In 2010, Petrova et al. identified two geranylstilbenes; schweinfurthin A (188) and schweinfurthin B (189) in propolis produced in Kenya. Macaranga schweinfurthii is the only plant source of these two geranylstilbenes to this date [37]. In 2012, another stilbene, 5-farnesyl-3'-hydroxyresveratrol (190) was identified in Solomon Island propolis, which is also present in Macaranga plants [31]. These results suggest that Macaranga is probably the plant source of the propolis from Kenya and Solomon Island. However, many stilbenes
makes this type of propolis a stronger scavenging activity towards DPPH free radical than Brazilian propolis [63], suggesting the source of stilbenes is not limited to only a few plants. Lignans as main chemical compounds in tropical propolis have attracted a worldwide research interest. In the past 12 years, researchers identified three lignans 206–208 in Kenyan and Brazilian propolis. As shown in the Table 3, other phenolic compounds and derivatives were identified in propolis from Brazil (209–219), Indonesia (220–229), France (230), Iran (231–239) and Malta (240–241). Among these chemicals, nemorosone (215) is the exclusive and principal component of Clusia rosea floral resins, indicating that Clusia spp. is the plant origin of the brown propolis [64]. Tschimgin (232), tschimganin (233), ferutinin (236), tefernin (237) identified in Iranian propolis are the characteristic compositions of the Ferula species, which is considered as another plant source of Iranian propolis besides poplar.
Molecules 2014, 19 19620
No. Chemical Name Geographical Location Reference Phenylpropanoids 171
Brazil
[65] 172
trans-3-Methoxy-4-hydroxycinnamic acid Brazil
[65] 173
3-Prenyl cinnamic acid allyl ester Brazil
[66] 174
p-Methoxycinnamic acid Brazil
[66] 175 Dihydrocinnamic acid Brazil
[66] 176 3-Prenyl-4-hydroxycinnamic acid Brazil
[67] 177 3,5-Diprenyl-4-hydroxycinnamic acid Brazil [67] 178 3-Methyl-2-butenyl isoferulate Brazil [66]
179 3-Methyl-3-butenyl caffeate Brazil [66]
180 Hexadecyl caffeate Brazil [66]
181 Methyl(E)-4-(4'-hydroxy-3'-methylbut- (E)-2'-enyloxy) cinnamate Australia [63] 182 Tetradecenyl caffeate (isomer) Egypt [35]
183 Tetradecenyl caffeate Egypt [35]
184 2-Methyl-2-butenyl ferulate Uruguay [68]
Chlorogenic acids 185
4-Feruoyl quinic acid Brazil
[62] 186
5-Ferruoyl quinic acid Brazil
[33] 187 3,4,5-tri-O-Caffeoylquinic acid Brazil [69]
Stilbenes 188 Schweinfurthin A Kenya
[37] 189 Schweinfurthin B Kenya
[37] 190 5'-Farnesyl-3'-hydroxyresveratrol Solomon Island
[31] 191 5,4'-Dihydroxy-3'-methoxy-3-prenyloxy-E-stilbene. Australia [63] 192 3,5,3',4'-Tetrahydroxy-2-prenyl-E-stilbene Australia [63] 193 3,5,4'-Trihydroxy-3'-methoxy-2-prenyl-E-stilbene Australia [63] 194 5,3',4'-Trihydroxy-3-methoxy-2-prenyl-E-stilbene Australia [63] 195 5,4'-Dihydroxy-3,3'-dimethoxy-2-prenyl-E-stilbene Australia [63] 196 5,4'-Dihydroxy-3-prenyloxy-E-stilbene Australia [63] 197 3',4'-Dihydroxy-E-stilbene Australia [63] 198 3',4'-Dihydroxy-3,5-dimethoxy-E-stilbene Australia [63] 199 Diprenylated dihydrostilbene Australia [63] 200 3,5-Dihydroxy-2-prenyl-E-stilbene Australia [63] 201 4-Prenyldihydroresveratrol Australia [63]
202 3-Prenylresveratrol Australia [63] 203
(+)-Pinoresinol dimethyl ether Brazil
[44] 204 (+)-Pinoresinol Brazil [44]
205 (+)-Syringaresinol Brazil
[44] Lignans
206 Tetrahydrojusticidin B Kenya [37] 207 6-Methoxydiphyllin Kenya
208 Phyllam ricin C Kenya [37]
Molecules 2014, 19 19621
No. Chemical Name Geographical Location Reference Other phenolics 209 8-(Methyl-butanechromane)-6-propenoic acid
Brazil [70]
210 3-Hydroxy-2,2-dimethyl-8-prenylchromane-6-propenoic acid Brazil
[70] 211 2,2-Dimethyl-8-prenylchromene-6-propenoic acid Brazil
[70] 212 2,2-Dimethylchromene-6-propenoic acid Brazil [70] 213 2,2-Dimethyl-6-carboxyethnyl-2H-1-benzopyran Brazil [70]
214 2,2-Dimethyl-6-carboxyethenyl-8-prenyl-2H-1-benzopyran Brazil [70] 215 Nemorosone Brazil [9]
216 7-epi-clusianone Brazil
[9] 217 Xanthochymol Brazil [9]
218 Gambogenone Brazil
[9] 219 Hyperibone A Brazil
[71] 220 5-Pentadecylresorcinol Indonesia [72]
221 5-(8'Z,11'Z-Heptadecadienyl)-resorcinol Indonesia [72]
222 5-(11'Z-Heptadecenyl)-resorcinol Indonesia [72]
223 5-Heptadecylresorcinol Indonesia [72] 224 1,3-Bis(trimethylsilylloxy)-5,5-proylbenzene Indonesia [56] 225 3,4-Dimethylthioquinoline Indonesia [56]
226 4-Oxo-2-thioxo-3-thiazolidinepropionic acid
Indonesia [56] 227
D -glucofuranuronic acid Indonesia [56]
228 Dofuranuronic acid
Indonesia [56]
229 3-Quinolinecarboxamine Indonesia [56] 230 Baccharin France [73]
231 Suberosin Iran
[55] 232 Tschimgin Iran [55]
233 Tschimganin Iran
[55] 234 Bornyl p-hydroxybenzoate Iran [55]
235 Bornyl vanillate Iran [55]
236 Ferutinin Iran
[55] 237 Tefernin Iran [55]
238 Ferutinol p-hydroxybenzoate Iran [55]
239 Ferutinol vanillate Iran [55]
240 2-Acetoxy-6-p-methoxybenzoyl jaeschkeanadiol Malta
[74] 241 2-Acetoxy-6-p-hydroxybenzoyl jaeschkeanadiol Malta [74]
6. Sugars The question about the origin of sugars in propolis has not been solved yet. Nectar and honey are thought to be the sources of glucose, fructose and sucrose. Others suggest that they come from hydrolyzed flavonoid glycosides in propolis. In addition, mucilages containing numerous sugars, sugar alcohols and acids were listed among potential propolis sugar sources by Crane [75]. In the propolis originated from the Canary Islands and Malta, many sugars, sugar alcohols and uronic acids were identified, supporting the claim that plant mucilages were the source of these compounds [74]. In Egyptian propolis, many sugars, sugar alcohols and uronic acids were identified by GC-MS. Among Molecules 2014, 19 19622
these substances, galactitol, gluconic acid, galacturonic acid and 2-O-glycerylgalactose were identified in propolis for the first time [61]. 7. Hydrocarbons Hydrocarbons are other basic components of propolis. In recent years, alkanes, alkenes, alkadienes, monoesters, diesters, aromatic esters, fatty acids and steroids have been identified in many types of propolis such as Egyptian propolis [35], Brazilian propolis [65] and Anatolian propolis [76]. Comparing the compositions of Brazilian propolis waxes and comb waxes which were produced by the same colony, no difference was found to allow a distinction, suggesting a common origin for both wax sources [77]. This result not only illustrates that propolis waxes are secreted by bees [78], but also indicates that the composition of propolis waxes and comb waxes is only dependent on genetic factors of the bees, not plant sources.
Trace elements (Ca, K, Mg, Na, Al, B, Ba, Cr, Fe, Mn, Ni, Sr and Zn) and toxic elements (As, Cd, Hg and Pb) were discovered by atomic emission/absorption spectrometry in propolis samples collected from different Croatian regions [79]. Br, Co, Cr, Fe, Rb, Sb, Sm and Zn were identified in different Argentinean propolis by neutron activation analysis. These studies show that the trace element profiles can be useful for propolis identification according to their location [80]. 9. The Chemical Categories Reported in Propolis The chemical categories reported in propolis during 2000 and 2012 are summarized in Figure 3 and Table 4, indicating consistency with the categories reported previously (Figure 1). It is well recognized that the chemical composition of herbal medicines are affected by many environmental factors while maintaining their genetic characteristics [81]. Similar effects to propolis can be expected from environmental factors. However, bee species needs to be considered together with geographical factors and plant sources.
Flavonoids Luteolin Australia, Brazil, Burma, Canada, Chinese, Cuba, Egypt, Greece, Japan, Kenya, Mexico, Nepal, Poland, Portugal, Solomon Island, Taiwan
[26,31,34,36–39, 41–47,61] Prenylated flavanones 7-O-prenylpino- cembrin Greece, Japan
[39,42]
Neo-flavonoids Cearoin Nepal
Dalbergia Apis mellifera [50]
Molecules 2014, 19 19623
Chemical Category Example Compound Geographical Origin Plant Source Bee Species References Monoterpenes Sesquiterpenes Diterpenes Linalool abietic acid Brazil, Greece, Indonesia, Iran, Malta, Turkey
[37,52,53,55,56,74] Triterpenes Lupeol acetate
Burma, Brazil, Cuba, Egypt, Greece
Apis mellifera [29,35,58–60] Phenylpropanoid s and esters p-Methoxycinnamic acid
Australia, Brazil, Egypt, Uruguay
Citrus Apis mellifera [61,63,66,68] Prenylated phenylpropanoids 3-Prenyl-4- hydroxycinnamic acid Brazilian Green propolis Baccharies Africanized Apis mellifera [67]
Stilbenes and prenylated stilbenes 3-Prenylresveratrol Australia, Brazil, Greece, Indonesia, Kenya Macaranga Apis mellifera [31,37,44,63,72] Lignans 6-Methoxydiphyllin Kenya
Apis mellifera [37]
Coumarins Prenylated coumarin suberosin Iran
Apis mellifera [55]
Figure 3. Representative chemical components identified in propolis since 2000.
Molecules 2014, 19 19624
We propose that species, subspecies and varieties of bees have a major impact on the chemical components and quality of propolis. The genus Apis contains 10 generally recognized species. Honeybee, A. mellifera, is widely spread in Europe, Ural Mountains, Africa, and Asia. All other recognised Apis species are of Asian distribution. About 25 subspecies have been recognized for A. mellifera, based on morphometry, behaviour and biogeography [82], belonging to three or four major subspecies groups [83]. The most popular species of honeybee is the European honeybee, Apies mellifera. It has been shown that varieties of bee affect the antibacterial activity of propolis collected from the same apiary; A. mellifera carnica hives showed weaker antibacterial activity than that of A. mellifera anatolica and A. mellifera caucasica. The three honeybee races used neither the same nor the single plant source [23]. In another type of propolis, geopropolis, produced by stingless bee species, Melipona scutellaris, benzophenones, but no flavonoids, have been identified as the major compounds [84]; However, geopropolis produced by Melipona fasciculate contains high concentrations of polyphenols, flavonoids, triterpenoids, saponins, and even tannins [85]. Although different species of honeybee prefer different plants, the chemical profile of propolis that is produced by the same species is not always same. Brazilian green and red propolis both originate from Africanized A. mellifera [65,86], but these propolis are rich in prenylated phenylpropanoids and isoflavonoids respectively. The differences are due to the plants, namely B. dracunculifolia and
bees (Tetragonula carbonaria), C-methylated flavanones, terpenic acids and phenolic acids, such as gallic acid, diterpenic acids of pimaric and abietic type are the predominant chemicals, but it lacks the characteristic flavonoids and prenylated phenolics found in propolis from honeybees species in Australia [87,88]. Therefore, the variant chemical composition of propolis depends on the bees’ preferences of botanical sources and the species and varieties of bees [89–91]. 11. The Geographical Origins of Propolis Propolis collected from many countries have demonstrated chemical profiles similar to the poplar type propolis: China [92], Korea, Croatia [93], different regions of Taiwan [43,94,95], New Zealand [96] and Africa [35]. Poplar tree (Populus nigra L. and P. alba L) is common in Europe, and is used to name the common type of propolis that is rich in flavonoids and phenylpropanoids. However, flavonoids are not restricted to poplar; furthermore, in areas where poplars are not native plants, such as Australia and equatorial regions of South America, bees will seek other plants to produce propolis, which contain the flavonoids of the poplar type propolis [36]. Propolis from the tropical zone, Brazilian green and red propolis, are respectively rich in prenylated derivatives of p-coumaric acid, and some isoflavonoids that are different from the ones found in poplar type propolis [3,97]. In addition, propolis from Solomon Island, Burma, Greek, Japan are characterized by the geranylated and prenylated flavonoids (Table 1). |