Post on 24-May-2018
Kangaroo Island Propolis Types and Their Distribution
Colin Duke, Faculty of Pharmacy Rujee Duke, Faculty of Medicine Van Tran, Faculty of Pharmacy
Abdallah Abu-Mellal, Faculty of Pharmacy Douglas King, Faculty of Pharmacy
Tran VH, Duke RK, Abu-Mellal A and Duke CC. (2012) Propolis with high flavonoid content collected by honey bees from Acacia paradoxa.
Phytochemistry 81, 126-132.
Kangaroo thorn, Acacia paradoxa
Abu-Mellal A, Koolaji N, Duke RK, Tran VH and Duke CC. (2012) Prenylated cinnamate and stilbenes from Kangaroo Island propolis and their antioxidant activity.
Phytochemistry 77, 251-259.
Lepidosperma sp. ( Cyperaceae)
OCH3
O
OOH
OCH3
O
OO
OH
methyl (E)-4-(4'-hydroxy-3'-methylbut-(E)-2'-enyloxy)cinnamate
methyl (E)-4-(3'-carboxybut-(E)-2'-enyloxy)cinnamate
Sedge Type 1 Propolis
OH
OHOH
OH
OHO
OH
OH
OH
OHOH
OH
OH
O
OH
OH
OH
O
OH
O
OH
OHOH
O
OH
OOH
O
cinnamates
O-prenylstilbenes
C-prenylstilbenes
Hive S25, 4 December 20091/13/2010 2:14:24 PM
P-082_Proton_02
13.5 13.0 12.5 12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
12.274
86
7.6724
6 7.4581
07.2
6038
7.0166
56.8
5613
6.6314
9
6.3265
9
5.6693
15.5
0046 4.5
0599
3.9519
8
3.4072
6 2.0780
3
1.7579
6
0.8799
6
0.0000
0
Hive S22, 4 December 20091/20/2010 11:07:34 AM
P-080_Proton_01
13.5 13.0 12.5 12.0 11.5 11.0 10.5 10.0 9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
13.544
88 13.199
84
11.501
1011.
36652
7.8868
2 7.6107
97.4
3216
7.2608
7
6.5590
6 6.2037
46.0
1336
5.7921
5
5.3487
5
3.9294
6
2.0241
9 0.8804
50.7
5614
0.0000
0
Kangaroo thorn propolis Proton NMR spectrum
Sedge type 1 propolis Proton NMR spectrum
2/26/2010 4:19:15 PM
dcl3_Proton_01
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
7.6249
9 7.4566
37.3
0002
7.0499
3
6.8463
4
6.5908
7 6.3510
6
5.7716
0 5.4999
7
5.2861
05.1
6718
4.6219
84.4
8886
3.9446
33.7
7775
3.3896
4 2.0447
5
1.7990
71.7
5110
1.6850
3
1.2538
6
0.8799
6
0.0000
0
100222-31 Lepidosperma sp.
Type 1
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
7.6279
2 7.4556
5
7.27
6.8996
8 6.8497
6
6.5752
1
6.3471
4
5.7706
2 5.4994
9
4.6332
34.5
0696
3.9446
33.8
2424
3.3955
2
2.3002
2
1.7985
8 1.7496
4
0.8799
6
0.00
P-129 Sedge type 1 propolis w w
s
s
Lepidosperma sp. Type 2
2/26/2010 4:10:11 PM
100222_03_cdcl3_Proton_01
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
8.20
787
8.16
872 7.71
210
7.67
197
7.40
084
6.47
977
5.35
560
5.18
088
3.74
691
3.42
733
3.34
853
1.81
326
1.69
238
1.19
269
1.15
207
0.00
000
100222-03
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
8.1912
38.1
5208 7.7
1308
7.6729
57.5
0557
7.3959
4
6.9373
76.8
9724
6.6833
6
6.4787
96.4
3866
6.0138
5 5.3472
8
4.1301
2 4.0537
7
3.4121
6
3.1982
9 2.2845
62.2
1311
2.0452
41.8
1375
1.7007
01.6
1652
0.8
0.0000
0
P-042
s
w
w w
s
Sedge type 2 propolis
5/24/2010 2:27:21 PM
100501-01_Proton_01
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
7.62890
7.45369
7.27359
6.84928
6.59380
6.34763
5.77453
5.48236
5.28806
5.16669
5.10355 4.634
21 4.48935
4.08558
3.94317
3.82375
3.41167
1.82011
1.74866 1.254
35
0.88045
0.00000
5/28/2010 6:17:08 PM
P-250_Proton_01
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
7.6670
8 7.4576
1
7.2789
8
6.8987
1
6.5918
5
6.3598
7
5.7750
2 5.5024
2
4.6214
9 4.4962
0
4.0831
43.9
4757
3.8242
4
3.4106
9
2.5860
4
1.7990
7 1.7501
3
1.4266
31.2
5435
0.8799
60.7
1356
0.0000
0
5/28/2010 6:51:16 PM
P-260_Proton_01
7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0Chemical Shift (ppm)
7.66
854
7.45
565
7.26
919
6.86
151
6.62
757
6.36
378
5.77
062
5.50
536
4.63
519
4.49
571
4.08
852
3.94
512
3.82
375
3.41
118 2.21
360
1.79
956
1.74
964
1.25
387
0.87
996
0.00
000PLANT RESIN
BEE HIND LEGS
PROPOLIS FROM HIVE
F S2 S1 K C S1 P
Propolis from 64 Apiary Sites Analysed by 1H-NMR
Propolis Type # Sites Purity # Samples %TOTAL
Sedge Type 1 33 80-100% 157 48.3
70 to 90% 25 7.7
Sedge Type 2 2 80-100% 1 0.3
70 to 90% 1 0.3
Kangaroo Thorn 8 80-100% 16 4.9
70 to 90% 3 0.9
"Flavanone" 8 80-100% 9 2.8
70 to 90% 4 1.2
"C-Prenyl" 3 80-100% 6 1.8
70 to 90% 1 0.3
"Purple spot" 2 80-100% 2 0.6
70 to 90% 1 0.3
Mixed propolis 43 99 30.5
TOTAL 325 100.0
Distribution of 6 Main Types of Propolis
K
K
K K
K K
F F
N
20 km Sedge type 1 propolis
Kangaroo thorn propolis
“Flavanone” propolis
S2 Sedge type 2 propolis
S1
K
F
“C-prenyl” propolis C
“Purple spot” propolis
S1 S1 S1
S1 S1 S1
S1 S1 S1 S1
S1
S1 S1 S1
S1
S1 S1 S1
S1 S2
P
P P C
C K
K
S1
S1
S1
S1 S1 S1
S1
S2
Further Research on Propolis
Statistical Evaluation of NMR profiles • Clustering or scoring of match from comparison of
NMR spectra of propolis using computer software • Statistical evaluation for propolis types based on
cluster/match with selected NMR spectral profiles
Quantitative HPLC Analyses • Major and minor constituent profiles • Accurate and precise determination of amounts of
key constituents • Statistical evaluation for defining single plant source
propolis types based on specific constituents and their quantities
Botanical characterisation of the Lepidosperma sp. Sedge Type 1 and Sedge Type 2 through collaboration • George Plunkett and Jeremy Bruhl, University of New
England, NSW, AUSTRALIA • Karen Wilson, Royal Botanic Gardens, Sydney, NSW,
AUSTRALIA
Medicinal evaluation of extracts and constituents • Indigenous medicinal use of Lepidosperma species • In vitro and in vivo biological testing • Antioxidant assays
Betty McAdam for collection of propolis samples and ongoing research collaboration (JH & E McAdam, Hog Bay Apiary, Penneshaw, Kangaroo Island) Provision of propolis samples for research from beekeepers, on Kangaroo Island, in particular Graham Carmichael Major funding support from a National Health and Medical Research Council Complementary and Alternative Medicine Grant, 2008-2011
ACKNOWLEDGEMENTS
.