Table 1.
Relative concentrations of components of tested propolis samples.
| Component | RT | UV λ Max (nm) | [M-H]- | PLS1 | PLS2 | PLS3 | PLU | UK1 | UK2 | UK3 | UT | KZ | GP |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| * Caffeoyl-glycerol | 1.88 | 324, 298sh, 242 | 253 | tr | tr | tr | tr | tr | tr | tr | tr | tr | tr |
| p-Hydroxy benzoic acid | 2.13 | 256 | 137 | tr | tr | tr | tr | tr | tr | tr | tr | tr | tr |
| Caffeic acid | 2.17 | 324, 298sh, 242 | 179 | + | + | + | tr | + | + | + | + | + | + |
| * p-Coumaroylglycerol | 2.63 | 310, 300sh, 229 | 237 | tr | tr | tr | tr | - | - | - | - | tr | - |
| p-Coumaric acid | 3.25 | 310, 300sh, 229 | 163 | ++ | +++ | ++ | ++ | + | + | + | + | + | tr |
| Metoxybenzaldehyd | 3.31 | 276 | 135 | tr | tr | tr | - | - | - | - | - | - | - |
| Vanillin | 3.42 | 310,280, 231 | 151 | tr | + | tr | + | tr | tr | tr | - | tr | - |
| Ferulic acid | 3.70 | 324, 298sh, 236 | 193 | ++ | ++ | + | + | + | + | + | tr | + | tr |
| Isoferulic acid | 4.11 | 323, 295sh, 221 | 193 | + | tr | + | tr | + | tr | + | tr | tr | tr |
| Benzoic acid | 5.97 | 281sh, 274sh, 236 | 121 | + | + | tr | + | + | + | + | tr | + | tr |
| * Ferulic acid derivate | 6.82 | 326, 298sh, 236 | 389 | - | - | - | tr | tr | tr | tr | tr | tr | - |
| Acetyl-p-coumraoylglycerol | 7.40 | 311 | 279 | tr | tr | tr | tr | tr | tr | tr | - | tr | - |
| 3,4-Dimethylcaffeic acid (DMCA) | 8.07 | 322, 294sh, 236 | 207 | + | + | + | tr | tr | tr | tr | tr | tr | + |
| * Apigenin-O-glucoside | 8.52 | 315sh, 265 | 431 | tr | tr | tr | - | tr | tr | tr | tr | tr | tr |
| Luteolin | 11.30 | 345, 254 | 285 | tr | tr | tr | - | tr | tr | tr | tr | tr | tr |
| Quercetin | 11.43 | 368, 270sh, 256 | 301 | tr | tr | tr | tr | tr | tr | tr | + | tr | tr |
| Pinobanksin-5-methyl ether | 12.32 | 322sh, 288, 228 | 285 | tr | tr | + | tr | + | + | + | + | tr | + |
| Cinnamic acid | 12.94 | 277 | 147 | tr | + | tr | tr | tr | tr | tr | - | - | - |
| Quercetin-3-methyl ether | 13.68 | 355, 293sh, 255 | 315 | tr | tr | tr | tr | tr | tr | tr | tr | tr | + |
| * 1-Caffeoyl-3-p-coumaroyl glycerol | 15.23 | 315, 298sh, 235 | 399 | tr | tr | - | tr | - | - | - | - | tr | - |
| Naringenine | 15.83 | 330sh, 290, 230 | 271 | tr | tr | tr | tr | tr | tr | tr | tr | tr | tr |
| Pinobanksin | 16.30 | 332sh, 292, 229 | 271 | + | tr | + | tr | + | + | + | + | + | + |
| Apigenin | 16.40 | 338, 290sh, 268 | 269 | + | tr | + | + | + | + | + | tr | + | tr |
| Caffeoyl-feruloylglycerol | 16.12 | 326, 298sh, 240 | 429 | - | - | - | - | - | - | - | - | tr | - |
| Chrysin-5-met ether | 16.80 | 314sh, 264, 247sh | 267 | - | - | tr | tr | tr | tr | tr | tr | tr | tr |
| Kempferolhyl | 17.48 | 366, 322sh, 295sh, 266 | 285 | tr | + | + | + | + | + | + | + | + | tr |
| Isorhamnetin | 19.11 | 371, 298sh, 268sh, 255 | 315 | tr | tr | tr | tr | tr | tr | tr | tr | + | tr |
| Quercetin-methyl ether | 19.57 | 371, 298sh, 268sh, 255 | 315 | - | - | - | - | tr | tr | tr | - | tr | tr |
| Luteolin-5-methyl ether | 20.15 | 350, 298sh, 266, 232sh | 299 | tr | tr | + | tr | + | + | + | tr | + | + |
| ** 1,3-Di-p-coumaroylglycerol | 20.25 | 310, 300sh, 233 | 383 | tr | tr | tr | tr | tr | tr | tr | tr | + | - |
| Quer-5,7-dimethyl ether | 20.71 | 356, 296sh, 269sh, 255 | 329 | tr | tr | tr | tr | tr | tr | tr | tr | + | + |
| p-Coumaroyl-feruloylglycerol | 21.37 | 316, 298sh, 233 | 413 | tr | tr | - | - | - | - | - | tr | tr | - |
| Di-feruloiloglicerol | 21.95 | 323, 298sh | 443 | tr | tr | - | - | tr | tr | tr | - | tr | - |
| 2-Acetyl-1,3-di-caffeoylglycerol | 22.57 | 328, 298sh, 244 | 457 | tr | tr | - | tr | tr | tr | tr | tr | tr | - |
| β-styrylacrilic acid | 23.82 | 311, 240sh | 173 | tr | tr | tr | tr | tr | tr | tr | tr | - | tr |
| Galangin-5-methyl ether | 25.42 | 352, 300sh, 261, 240sh | 283 | tr | tr | tr | - | tr | tr | tr | tr | tr | tr |
| Pinobanksin-5-methyl-ether-3-O-acetate | 25.60 | 289 | 327 | tr | tr | tr | - | tr | tr | tr | tr | tr | tr |
| * Caffeic acid buteniccetin or isobutenic ester | 24.73 | 326, 298sh, 248 | 233 | - | - | - | - | - | - | - | - | tr | tr |
| Rhamnetin | 25.92 | 354, 298sh, 268sh, 255 | 315 | tr | tr | tr | tr | tr | tr | tr | + | tr | - |
| Quercetin-dimethyl ether | 27.22 | 356, 292sh, 268sh, 256 | 329 | tr | tr | tr | tr | - | - | - | tr | tr | + |
| 2-Acetyl-1-caffeoyl-3-p-coumaroylglycerol | 29.23 | 316, 299sh 235 | 441 | + | + | tr | tr | tr | tr | tr | tr | tr | - |
| Quercetin-dimethyl ether | 29.46 | 356, 268sh, 256 | 329 | tr | tr | tr | tr | tr | tr | tr | tr | tr | + |
| Caffeic acid butyl or isobutyl ester | 30.20 | 326, 298sh, 242 | 235 | - | - | - | - | - | - | - | - | tr | tr |
| 2-Acetyl-3-caffeoyl-1-feruloylglycerol | 30.28 | 328, 300sh, 244 | 471 | + | tr | tr | tr | tr | tr | tr | - | tr | - |
| Quercetin-trimethyl ether | 30.63 | 353, 266sh, 254 | 343 | - | - | - | - | - | - | - | tr | - | tr |
| Caffeic acid prenyl ester 1 | 31.92 | 326, 298sh, 246 | 247 | + | tr | + | tr | tr | + | + | + | tr | tr |
| Chrysin | 32.11 | 314sh, 268, | 253 | + | + | +++ | + | +++ | +++ | +++ | +++ | + | +++ |
| Pinobanksin-7-methyl ether | 33.62 | 291, 247sh | 285 | - | - | re | - | tr | tr | tr | - | - | tr |
| Pinocembrin | 33.68 | 330sh, 290, | 255 | ++ | ++ | ++ | ++ | +++ | +++ | +++ | +++ | ++ | + |
| Acacetin | 34.08 | 335, 299sh, 268 | 283 | tr | tr | tr | + | - | - | - | - | +++ | - |
| Caffeic acid prenyl ester 2 | 34.10 | 326, 298sh, 246 | 247 | - | - | - | - | tr | tr | tr | - | tr | + |
| Pinocembrin chalcone | 34.14 | 345 | 255 | - | - | - | - | - | - | - | - | - | + |
| * Caffeic acid prenyl ester 3 | 34.21 | 326, 298sh, 246 | 247 | + | + | + | - | tr | tr | tr | + | tr | ++ |
| * Caffeic acid benzyl ester | 34.62 | 328, 298sh, 244 | 269 | ++ | + | ++ | tr | + | + | + | ++ | tr | tr |
| Caffeic acid prenyl ester 4 | 34.58 | 326, 298sh, 246 | 247 | tr | tr | tr | tr | tr | tr | tr | - | tr | tr |
| Sakuranetin | 35.16 | 290 | 285 | tr | tr | tr | ++ | + | + | + | + | +++ | + |
| Genkwanin | 35.64 | 337, 267, 242sh | 283 | tr | tr | tr | + | - | - | - | tr | + | tr |
| Galangin | 36.07 | 360, 290sh, 266, | 269 | ++ | + | +++ | + | +++ | +++ | +++ | +++ | + | ++ |
| Kaempheride | 37.31 | 366, 292sh, 266, | 299 | + | + | tr | ++ | tr | tr | tr | tr | ++ | tr |
| 2-Acetyl-1,3-di-p-coumaroylglycerol (lasiocarpin A) |
37.55 | 360sh, 312, 232 | 425 | + | ++ | tr | + | tr | tr | tr | tr | ++ | - |
| Pinobanksin-3O-acetate | 37.82 | 332sh, 294, 238 | 313 | + | + | ++ | + | +++ | +++ | +++ | ++ | + | ++ |
| Quercetin-dimethyl | 38.33 | 370, 268sh, 255 | 329 | - | - | - | + | - | - | - | - | + | tr |
| ** 2-Acetyl-3-p-coumaroyl-1-feruloylglycerol | 38.96 | 318, 299sh 235 | 455 | + | + | - | + | tr | tr | tr | tr | + | - |
| Metoxychrysin | 39.27 | 340sh, 310sh, 266 | 283 | tr | - | + | - | + | + | + | + | tr | + |
| 3-Acetyl-1,2-di-p-coumaroylglycerol | 40.09 | 312, 300sh, 238 | 425 | tr | + | - | tr | tr | tr | tr | - | tr | + |
| Caffeic acid phenethyl ester (CAPE) | 40.15 | 326, 298sh, 264 | 283 | + | tr | + | - | + | + | + | + | + | + |
| 2-Acetyl-1,3-di-feruloylglycerol | 40.37 | 328, 298sh, 243 | 485 | + | + | tr | tr | tr | + | tr | - | tr | - |
| Dimethyl luteolin | 41.05 | 348, 267, 246sh | 313 | - | - | - | + | tr | tr | tr | tr | ++ | - |
| Caffeic acid pentyl or isopentyl ester | 41.90 | 326, 298sh, 247 | 249 | - | - | - | - | - | - | - | - | - | - |
| Flavonoid dimethyl ether | 42.53 | 343, 271, 248sh | 343 | - | - | - | - | tr | tr | tr | - | + | - |
| p-Coumaric acid prenyl ester 1 | 45.42 | 311, 299sh, 245sh | 231 | - | - | tr | - | tr | tr | tr | tr | - | - |
| p-Coumaric acid prenyl ester 2 | 45.42 | 311, 299sh, 245sh | 231 | + | + | tr | + | tr | tr | tr | tr | - | tr |
| p-Coumaric acid benzyl ester | 45.80 | 312, 298sh, 244sh | 253 | + | ++ | + | ++ | + | + | + | + | + | tr |
| * Ferulic or isoferulic acid benzyl ester | 47.13 | 326, 298sh | 283 | + | + | + | + | + | + | + | + | + | + |
| Caffeic acid cinnamic ester | 48.04 | 326, 300sh, 243 | 295 | tr | tr | tr | tr | + | + | tr | tr | tr | tr |
| Pinobanksin-3-O-propanoate | 48.58 | 329sh, 294, 234 | 327 | tr | tr | tr | - | tr | tr | tr | tr | tr | + |
| p-Coumaric acid phenethyl ester | 49.21 | 312, 300sh, | 267 | + | + | tr | tr | - | tr | tr | - | - | tr |
| Pinostrobin chalcone | 49.67 | 345, 309sh, 267 | 269 | - | - | - | + | - | tr | tr | tr | tr | + |
| Tectochrysin (chrysin-7-methyl ether) | 51.23 | 310sh, 268 | 267 | tr | - | + | - | + | + | tr | + | - | + |
| Pinostrobin (pinocembrin-5-methyl ether) | 51.40 | 328sh, 290, | 269 | tr | - | tr | + | tr | + | tr | tr | + | + |
| Pinobanksin-3-O-butanoate or isonutanoate | 51.65 | 329sh, 294, 234 | 341 | tr | tr | + | tr | + | tr | + | + | + | + |
| Galangin-7-methyl ether | 52.21 | 353, 268 | 283 | tr | - | tr | tr | + | + | tr | tr | + | + |
| Pinobanksin-3-O-pentanoate or isopentanoate | 53.07 | 332sh, 293, 242 | 355 | tr | - | tr | - | tr | tr | tr | + | tr | + |
| Pinobanksin-3-O-pentenoate or isopentenoate | 53.24 | 332sh, 293, 242 | 353 | - | - | tr | - | tr | tr | tr | tr | ++ | + |
| Pinobanksin-3-O-hexanoate or isohexanoate | 54.09 | 282 | 369 | - | - | - | - | tr | tr | tr | tr | tr | - |
| Metoxycinnamic acid cinnamyl ester | 54.26 | 280 | 293 | tr | tr | tr | tr | tr | tr | tr | tr | tr | tr |
Table legend: “-“—component absent; tr—component presented as trace (ions); +—component present in relatively low concentrations; ++—component present in relatively average concentration; +++—component present in relatively high concentration; *—component tenatively identified; **—subtitution positioning of glycerol was tenatively identified; GP—Greece, Parga; KZ—Kazakhstan, Almastka Oblast; PLS1—Poland, Lower Silesia Region 1; PLS2—Poland, Lower Silesia Region 2; PLS3—Poland, Lower Silesia Region3; PLU—Poland, Lubelszczyzna Region; UK1—Ukraine, Khmelnitsky 1; UK2—Ukraine, Khmelnitsky 2; UK3—Ukraine, Khmelnitsky 3; UT—Ukraine, Tarnopol.