Chromatographic Fingerprints of Honeys Dr Peter Brooks Daniel
Chromatographic Fingerprints of Honeys Dr Peter Brooks & Daniel Meloncelli USC Honey Research Lab pbrooks@usc. edu. au 61 7 5430 2828
Some Basic Facts 1. Compounds collected from Nectar and Honey Dew by the Bees are responsible for the properties of honey, eg. Taste and Aroma. 2. Compounds unique to one Nectar or Honey Dew, are marker compounds of the honey source. 3. There is no such thing as 100% monofloral Honey. Question? Can chromatography be used to authenticate honey type?
Phenolic fingerprints by HPLC Authenticating Floral Source by RP-HPLC Tasmanian L. scoparium honey Lep New Zealand L. scoparium honey KA 0. 8 min: Kojic acid 4. 3 min Leptosperin 8. 3 min: 4 -methoxyphenyllactic acid 10. 3 min: Methyl syringate Lep MSR KA 4 MPL MSR
Phenolic fingerprints by HPLC NZ L. scoparium honey NZ K. ericoides honey Leptosperin Methyl syringate KA KA Methyl syringate 4 MPL
Phenolic fingerprints by HPLC NZ Pohutukawa honey NZ Rata honey
Phenolic fingerprints by HPLC NZ Clover honey NZ Kamahi honey
Phenolic fingerprints by HPLC NZ Rewarewa honey NZ Blue Borage honey
Phenolic fingerprints by HPLC NZ Thyme honey NZ Tarawi honey
Phenolic fingerprints by HPLC NZ Honey Dew honey NZ Ulmo Chile honey
Phenolic fingerprints by HPLC L. laevigatum honey (Tas. ) L. whitei honey (NSW) Methyl syringate KA Methyl syringate Lep KA Lep
Identifying “Mislabelled” honeys Reverse-Phase High Performance Liquid Chromatography (RP-HPLC-PDA) L. polygalifolium honey Leptosperin Methyl syringate “Fake” L. polygalifolium honey
DHA, MGO and HMF NZ L. scoparium honey NZ K. ericoides honey MGO (547 ppm) DHA (4623 ppm) HMF (5 ppm) HMF (9 ppm) DHA (103 ppm) MGO (25 ppm)
Marker Compounds in Honey ) Mean (SE) concentration of compounds (µg/g, ppm) Honey sample DHA HMF MGO KJA LEP 3 PA 2 MB 4 MPL MSR L. scoparium (TAS) 1169 (83) 4 (1) 237 (31) 125 (17) 1051 (105) 906 (187) 14 (14) 623 (71) 97 (12) L. scoparium (NZ) 2665 (398) 10 (3) 519 (91) 252 (24) 681 (127) 1199 (165) 70 (18) 41 (41) 87 (18) L. polygalifolium 1475 (314) 20 (4) 543 (91) 197 (28) 399 (80) 665 (86) 183 (33) 5 (4) 97 (15) L. whitei 2823 (623) 13 (2) 518 (88) 156 (20) 74 (18) 223 (35) 76 (20) 4 (4) 148 (51) L. liversidgei 824 (165) 35 (16) 451 (89) 213 (47) 175 (29) 306 (55) 48 (37) 13 (4) 61 (11) L. laevigatum 78 (42) 68 (61) 40 (19) 107 (57) 20 (20) 1509 (622) 117 (71) nd 20 (20) Kunzea ericoides 64 (19) 5 (1) 6 (3) 85 (29) 15 (4) 1265 (192) nd 1128 (182) 222 (30) Pohutukawa 36 (13) 30 (14) 2 (2) 38 (38) nd nd nd 7 (7) 3 (3) Rata 40 (6) 17 (4) 4 (4) 54 (10) nd nd nd 20 (11) nd Kamahi 12 (6) 5 (1) nd 11 (11) nd nd nd 9 (9) nd Clover 43 (21) 11 (5) 2 (2) 25 (18) 9 (5) nd nd nd 4 (2) Rewarewa 80 (28) 20 (7) 10 (4) 197 (44) 48 (12) 104 (36) nd 37 (18) 21 (7) Blue Borage *13 -15 *10 -32 nd *70 -108 *7 -13 nd nd *0 -59 *2 -9 Thyme *3 -12 *35 -36 nd nd *0 -4 nd nd Tawari *4 -9 *2 -7 nd nd
Can Manuka purity be fingerprinted? Question ? If a mature high purity Manuka from New Zealand is approx. DHA 2600 ppm; MGO 520 ppm; and Leptosperin 680 ppm, Then is a 50% Manuka approx. DHA > 1200 ppm; MGO > 250 ppm; Leptosperin > 300 ppm ? And is a 20% Manuka; DHA > 500 ppm; MGO > 100 ppm; Leptosperin > 120 ppm ?
GC-MS of Volatiles in L. scoparium and K. ericoides
GC-MS of Volatiles in L. scoparium and K. ericoides L. scoparium Compound in trace Dihydroxyacetone (DHA), bis. TMS ether Mean SD K. ericoides range Mean SD range 162. 3 89. 9 21. 6 -297. 5 1. 3 0 -3. 5 4 -Methoxy-benzaldehyde 0. 0 0 1. 5 0. 9 0. 3 -3. 2 2 -Methoxyacetophenone 6. 6 1. 4 3. 7 -8. 2 0. 0 0 Benzene acetic acid, TMS ester 0. 0 0 2. 6 1. 1 1. 3 -4. 4 2 -Methyl-4 -propylphenol 0. 0 0 11. 6 13. 3 2. 2 -41. 3 2 -Methoxybenzoic acid TMS (STD) 33. 1 27. 5 6. 1 -90. 0 0 Mandelic acid TMS ether TMS ester 0. 0 0 3. 1 0. 7 1. 7 -3. 6 4 -Methoxy-benzoic acid, TMS ester 0. 0 0 7. 0 3. 9 2. 0 -13. 5 3 -(3, 4 -Dimethoxyphenyl)-2 -propenoic acid, methyl ester 0. 0 0 6. 2 3. 5 1. 5 -10. 4 4 -Methoxy-benzeneacetic acid, TMS ester 0. 0 0 5. 4 2. 9 3. 1 -10. 0 Myrtenoic acid, TMS ester 0. 0 0 32. 6 6. 4 24. 2 -40. 8 3, 5 -Dimethoxy-benzoic acid, methyl ester 2. 7 2. 1 0. 9 -7. 4 0. 0 0 3 -Phenyl-3 -TMSoxypropanoic acid TMS ester 7. 0 6. 3 2. 4 -20. 3 0. 0 0 4 -Methoxymandelic acid, TMS ether TMS ester 0. 0 0 31. 1 11. 4 16. 4 -42. 8 3, 4 -Dimethoxy-benzoic acid, TMS ester 3. 3 3. 6 0. 8 -11. 5 0. 0 0 o-Methoxymandelic acid TMS 18. 5 10. 6 11. 0 -38. 8 0. 0 0 3, 4 -Dimethoxymandelic acid, di-TMS 27. 9 17. 4 11. 6 -64. 2 0. 0 0 2. 3 2. 6 0. 4 -8. 2 Caffeic acid (TMS)
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