Supplementary Information LC-MS-guided isolation of anti-inflammatory 2-(2-phenylethyl)chromone dimers from Chinese agarwood (Aquilaria sinensis) Hui-Xia Huo #, Yu-Fan Gu #, Zhi-Xiang Zhu, Yun-Feng Zhang, Xiao-Nan Chen, Peng-Wei Guan, She-Po Shi, Yue-Lin Song, Yun-Fang Zhao, Peng-Fei Tu*, Jun Li** a Modern Research Center for Traditional Chinese Medicine, School of Chinese Materia Medica, Beijing University of Chinese Medicine, Beijing 100029, People s Republic of China *Corresponding authors. **Corresponding authors. E-mail addresses: drlj666@163.com (J. Li), pengfeitu@163.com (P.F. Tu). # These two authors contribute equally.
Contents: 2 pages: Figure S1. HRESIMS spectrum of compound 1... 5 Figure S2. UV spectrum of compound 1... 5 Figure S3. IR spectrum of compound 1... 6 Figure S4. 1 H NMR spectrum of compound 1 in DMS-d 6... 6 Figure S5. 13 C NMR spectrum of compound 1 in DMS-d 6... 7 Figure S6. ghsqc spectrum of compound 1 in DMS-d 6... 7 Figure S7. ghmbc spectrum of compound 1 in DMS-d 6... 8 Figure S8. 1 H- 1 H CSY spectrum of compound 1 in DMS-d 6... 8 Figure S9. RESY spectrum of compound 1 in DMS-d 6... 9 Figure S10. HRESIMS spectrum of compound 2... 9 Figure S11. UV spectrum of compound 2... 10 Figure S12. IR spectrum of compound 2... 10 Figure S13. 1 H NMR spectrum of compound 2 in DMS-d 6... 11 Figure S14. 13 C NMR spectrum of compound 2 in DMS-d 6... 11 Figure S15. ghsqc spectrum of compound 2 in DMS-d 6... 12 Figure S16. ghmbc spectrum of compound 2 in DMS-d 6... 12 Figure S17. 1 H- 1 H CSY spectrum of compound 2 in DMS-d 6... 13 Figure S18. RESY spectrum of compound 2 in DMS-d 6... 13 Figure S19. HRESIMS spectrum of compound 3... 14 Figure S20. UV spectrum of compound 3... 14 Figure S21. IR spectrum of compound 3... 15 Figure S22. 1 H NMR spectrum of compound 3 in DMS-d 6... 15 Figure S23. 13 C NMR spectrum of compound 3 in DMS-d 6... 16 Figure S24. ghsqc spectrum of compound 3 in DMS-d 6... 16 Figure S25. ghmbc spectrum of compound 3 in DMS-d 6... 17 Figure S26. 1 H- 1 H CSY spectrum of compound 3 in DMS-d 6... 17 Figure S27. RESY spectrum of compound 3 in DMS-d 6... 18 Figure S28. HRESIMS spectrum of compound 4... 18 Figure S29. UV spectrum of compound 4... 19 Figure S30. IR spectrum of compound 4... 19 Figure S31. 1 H NMR spectrum of compound 4 in DMS-d 6... 20 Figure S32. 13 C NMR spectrum of compound 4 in DMS-d 6... 20 Figure S33. ghsqc spectrum of compound 4 in DMS-d 6... 21 Figure S34. ghmbc spectrum of compound 4 in DMS-d 6... 21 Figure S35. 1 H- 1 H CSY spectrum of compound 4 in DMS-d 6... 22 Figure S36. RESY spectrum of compound 4 in DMS-d 6... 22 Figure S37. HRESIMS spectrum of compound 5... 23 Figure S38. UV spectrum of compound 5... 23 Figure S39. IR spectrum of compound 5... 24 Figure S40. 1 H NMR spectrum of compound 5 in DMS-d 6... 24 Figure S41. 13 C NMR spectrum of compound 5 in DMS-d 6... 25 Figure S42. ghsqc spectrum of compound 5 in DMS-d 6... 25 Figure S43. ghmbc spectrum of compound 5 in DMS-d 6... 26 Figure S44. 1 H- 1 H CSY spectrum of compound 5 in DMS-d 6... 26 Figure S45. RESY spectrum of compound 5 in DMS-d 6... 27
Figure S46. HRESIMS spectrum of compound 6... 27 Figure S47. UV spectrum of compound 6... 28 Figure S48. IR spectrum of compound 6... 28 Figure S49. 1 H NMR spectrum of compound 6 in DMS-d 6... 29 Figure S50. 13 C NMR spectrum of compound 6 in DMS-d 6... 29 Figure S51. ghsqc spectrum of compound 6 in DMS-d 6... 30 Figure S52. ghmbc spectrum of compound 6 in DMS-d 6... 30 Figure S53. 1 H- 1 H CSY spectrum of compound 6 in DMS-d 6... 31 Figure S54. RESY spectrum of compound 6 in DMS-d 6... 31 Figure S55. HRESIMS spectrum of compound 7... 32 Figure S56. UV spectrum of compound 7... 32 Figure S57. IR spectrum of compound 7... 33 Figure S58. 1 H NMR spectrum of compound 7 in CD 3 D... 33 Figure S59. 13 C NMR spectrum of compound 7 in CD 3 D... 34 Figure S60. ghsqc spectrum of compound 7 in CD 3 D... 34 Figure S61. ghmbc spectrum of compound 7 in CD 3 D... 35 Figure S62. 1 H- 1 H CSY spectrum of compound 7 in CD 3 D... 35 Figure S63. RESY spectrum of compound 7 in CD 3 D... 36 Figure S64. HRESIMS spectrum of compound 8... 36 Figure S65. UV spectrum of compound 8... 37 Figure S66. IR spectrum of compound 8... 37 Figure S67. 1 H NMR spectrum of compound 8 in CD 3 D... 38 Figure S68. 13 C NMR spectrum of compound 8 in CD 3 D... 38 Figure S69. ghsqc spectrum of compound 8 in CD 3 D... 39 Figure S70. ghmbc spectrum of compound 8 in CD 3 D... 39 Figure S71. 1 H- 1 H CSY spectrum of compound 8 in CD 3 D... 40 Figure S72. RESY spectrum of compound 8 in CD 3 D... 40 Figure S73. HRESIMS spectrum of compound 9... 41 Figure S74. UV spectrum of compound 9... 41 Figure S75. IR spectrum of compound 9... 42 Figure S76. 1 H NMR spectrum of compound 9 in CD 3 D... 42 Figure S77. 13 C NMR spectrum of compound 9 in CD 3 D... 43 Figure S78. ghsqc spectrum of compound 9 in CD 3 D... 43 Figure S79. ghmbc spectrum of compound 9 in CD 3 D... 44 Figure S80. 1 H- 1 H CSY spectrum of compound 9 in CD 3 D... 44 Figure S81. RESY spectrum of compound 9 in CD 3 D... 45 Figure S82. HRESIMS spectrum of compound 10... 45 Figure S83. UV spectrum of compound 10... 46 Figure S84. IR spectrum of compound 10... 46 Figure S85. 1 H NMR spectrum of compound 10 in CD 3 D... 47 Figure S86. 13 C NMR spectrum of compound 10 in CD 3 D... 47 Figure S87. ghsqc spectrum of compound 10 in CD 3 D... 48 Figure S88. ghmbc spectrum of compound 10 in CD 3 D... 48 Figure S89. 1 H- 1 H CSY spectrum of compound 10 in CD 3 D... 49 Figure S90. RESY spectrum of compound 10 in CD 3 D... 49 Figure S91. HRESIMS spectrum of compound 11... 50 3
Figure S92. UV spectrum of compound 11... 50 Figure S93. IR spectrum of compound 11... 51 Figure S94. 1 H NMR spectrum of compound 11 in DMS-d... 51 Figure S95. 13 C NMR spectrum of compound 11 in DMS-d 6... 52 Figure S96. ghsqc spectrum of compound 11 in DMS-d 6... 52 Figure S97. ghmbc spectrum of compound 11 in DMS-d 6... 53 Figure S98. 1 H- 1 H CSY spectrum of compound 11 in DMS-d 6... 53 Figure S99. RESY spectrum of compound 11 in DMS-d 6... 54 Figure S100. HRESIMS spectrum of compound 12... 54 Figure S101. UV spectrum of compound 12... 55 Figure S102. IR spectrum of compound 12... 55 Figure S103. 1 H NMR spectrum of compound 12 in CD 3 D... 56 Figure S104. 13 C NMR spectrum of compound 12 in CD 3 D... 56 Figure S105. ghsqc spectrum of compound 12 in CD 3 D... 57 Figure S106. ghmbc spectrum of compound 12 in CD 3 D... 57 Figure S107. 1 H- 1 H CSY spectrum of compound 12 in CD 3 D... 58 Figure S108. RESY spectrum of compound 12 in CD 3 D... 58 Figure S109. HRESIMS spectrum of compound 13... 59 Figure S110. UV spectrum of compound 13... 59 Figure S111. IR spectrum of compound 13... 60 Figure S112. 1 H NMR spectrum of compound 13 in CD 3 D... 60 Figure S113. 13 C NMR spectrum of compound 13 in CD 3 D... 61 Figure S114. ghsqc spectrum of compound 13 in CD 3 D... 61 Figure S115. ghmbc spectrum of compound 13 in CD 3 D... 62 Figure S116. 1 H- 1 H CSY spectrum of compound 13 in CD 3 D... 62 Figure S117. RESY spectrum of compound 13 in CD 3 D... 63 Figure S118. HRESIMS spectrum of compound 14... 63 Figure S119. UV spectrum of compound 14... 64 Figure S120. IR spectrum of compound 14... 64 Figure S121. 1 H NMR spectrum of compound 14 in DMS-d... 65 Figure S122. 13 C NMR spectrum of compound 14 in DMS-d 6... 65 Figure S123. ghsqc spectrum of compound 14 in DMS-d 6... 66 Figure S124. ghmbc spectrum of compound 14 in DMS-d 6... 66 Figure S125. RESY spectrum of compound 14 in DMS-d 6... 67 Figure S126. HRESIMS spectrum of compound 15... 67 Figure S127. UV spectrum of compound 15... 68 Figure S128. IR spectrum of compound 15... 68 Figure S129. 1 H NMR spectrum of compound 15 in CD 3 D... 69 Figure S130. 13 C NMR spectrum of compound 15 in CD 3 D... 69 Figure S131. ghsqc spectrum of compound 15 in CD 3 D... 70 Figure S132. ghmbc spectrum of compound 15 in CD 3 D... 70 Figure S133. RESY spectrum of compound 15 in CD 3 D... 71 4
Figure S1. HRESIMS spectrum of compound 1 Figure S2. UV spectrum of compound 1 5
Figure S3. IR spectrum of compound 1 H CH 3 Figure S4. 1 H NMR spectrum of compound 1 in DMS-d 6 6
H CH 3 Figure S5. 13 C NMR spectrum of compound 1 in DMS-d 6 Figure S6. ghsqc spectrum of compound 1 in DMS-d 6 7
H CH 3 Figure S7. ghmbc spectrum of compound 1 in DMS-d 6 H CH 3 Figure S8. 1 H- 1 H CSY spectrum of compound 1 in DMS-d 6 8
6'' 7'' 6 7 8 5 Figure S9. RESY spectrum of compound 1 in DMS-d 6 Figure S10. HRESIMS spectrum of compound 2 9
Figure S11. UV spectrum of compound 2 Figure S12. IR spectrum of compound 2 10
CH 3 H CH 3 Figure S13. 1 H NMR spectrum of compound 2 in DMS-d 6 CH 3 H CH 3 Figure S14. 13 C NMR spectrum of compound 2 in DMS-d 6 11
Figure S15. ghsqc spectrum of compound 2 in DMS-d 6 CH 3 H CH 3 Figure S16. ghmbc spectrum of compound 2 in DMS-d 6 12
CH 3 H CH 3 Figure S17. 1 H- 1 H CSY spectrum of compound 2 in DMS-d 6 6'' 7'' 6 7 8 5 3' 4' 5' Figure S18. RESY spectrum of compound 2 in DMS-d 6 13
Figure S19. HRESIMS spectrum of compound 3 Figure S20. UV spectrum of compound 3 14
Figure S21. IR spectrum of compound 3 H Figure S22. 1 H NMR spectrum of compound 3 in DMS-d 6 15
H Figure S23. 13 C NMR spectrum of compound 3 in DMS-d 6 Figure S24. ghsqc spectrum of compound 3 in DMS-d 6 16
H Figure S25. ghmbc spectrum of compound 3 in DMS-d 6 H Figure S26. 1 H- 1 H CSY spectrum of compound 3 in DMS-d 6 17
6 5 7 8 Figure S27. RESY spectrum of compound 3 in DMS-d 6 Figure S28. HRESIMS spectrum of compound 4 18
Figure S29. UV spectrum of compound 4 Figure S30. IR spectrum of compound 4 19
H CH 3 Figure S31. 1 H NMR spectrum of compound 4 in DMS-d 6 H CH 3 Figure S32. 13 C NMR spectrum of compound 4 in DMS-d 6 20
Figure S33. ghsqc spectrum of compound 4 in DMS-d 6 H CH 3 Figure S34. ghmbc spectrum of compound 4 in DMS-d 6 21
H CH 3 Figure S35. 1 H- 1 H CSY spectrum of compound 4 in DMS-d 6 5'' 6 5 7 8 8'' 7'' Figure S36. RESY spectrum of compound 4 in DMS-d 6 22
Figure S37. HRESIMS spectrum of compound 5 Figure S38. UV spectrum of compound 5 23
Figure S39. IR spectrum of compound 5 CH 3 H CH 3 Figure S40. 1 H NMR spectrum of compound 5 in DMS-d 6 24
CH 3 H CH 3 Figure S41. 13 C NMR spectrum of compound 5 in DMS-d 6 Figure S42. ghsqc spectrum of compound 5 in DMS-d 6 25
CH 3 H CH 3 Figure S43. ghmbc spectrum of compound 5 in DMS-d 6 CH 3 H CH 3 Figure S44. 1 H- 1 H CSY spectrum of compound 5 in DMS-d 6 26
8'' 7'' 5'' 6 7 5 8 Figure S45. RESY spectrum of compound 5 in DMS-d 6 Figure S46. HRESIMS spectrum of compound 6 27
Figure S47. UV spectrum of compound 6 Figure S48. IR spectrum of compound 6 28
CH 3 H CH 3 H 3 C Figure S49. 1 H NMR spectrum of compound 6 in DMS-d 6 CH 3 H CH 3 H 3 C Figure S50. 13 C NMR spectrum of compound 6 in DMS-d 6 29
Figure S51. ghsqc spectrum of compound 6 in DMS-d 6 CH 3 H CH 3 H 3 C Figure S52. ghmbc spectrum of compound 6 in DMS-d 6 30
CH 3 H CH 3 H 3 C Figure S53. 1 H- 1 H CSY spectrum of compound 6 in DMS-d 6 5'' 6 5 7 8 4''' 3''' 5''' 8'' 7'' 5' 3' 4' Figure S54. RESY spectrum of compound 6 in DMS-d 6 31
Figure S55. HRESIMS spectrum of compound 7 Figure S56. UV spectrum of compound 7 32
Figure S57. IR spectrum of compound 7 H H 3 C CH 3 Figure S58. 1 H NMR spectrum of compound 7 in CD 3 D 33
H H 3 C CH 3 Figure S59. 13 C NMR spectrum of compound 7 in CD 3 D Figure S60. ghsqc spectrum of compound 7 in CD 3 D 34
H H 3 C CH 3 Figure S61. ghmbc spectrum of compound 7 in CD 3 D H H 3 C CH 3 Figure S62. 1 H- 1 H CSY spectrum of compound 7 in CD 3 D 35
7 8 6 5''' 5 2''' 3''' 6'' 7'' 8'' Figure S63. RESY spectrum of compound 7 in CD 3 D Figure S64. HRESIMS spectrum of compound 8 36
Figure S65. UV spectrum of compound 8 Figure S66. IR spectrum of compound 8 37
CH 3 H H 3 C CH 3 Figure S67. 1 H NMR spectrum of compound 8 in CD 3 D CH 3 H H 3 C CH 3 Figure S68. 13 C NMR spectrum of compound 8 in CD 3 D 38
Figure S69. ghsqc spectrum of compound 8 in CD 3 D CH 3 H H 3 C CH 3 Figure S70. ghmbc spectrum of compound 8 in CD 3 D 39
CH 3 H H 3 C CH 3 Figure S71. 1 H- 1 H CSY spectrum of compound 8 in CD 3 D 7 8 3' 5' 4' 6 5''' 3''' 2''' 5 6'' 7'' 8'' Figure S72. RESY spectrum of compound 8 in CD 3 D 40
Figure S73. HRESIMS spectrum of compound 9 Figure S74. UV spectrum of compound 9 41
Figure S75. IR spectrum of compound 9 H H Figure S76. 1 H NMR spectrum of compound 9 in CD 3 D 42
H H Figure S77. 13 C NMR spectrum of compound 9 in CD 3 D Figure S78. ghsqc spectrum of compound 9 in CD 3 D 43
H H Figure S79. ghmbc spectrum of compound 9 in CD 3 D H H Figure S80. 1 H- 1 H CSY spectrum of compound 9 in CD 3 D 44
6 7 8'' 7'' 6'' 5'' 5 8 Figure S81. RESY spectrum of compound 9 in CD 3 D Figure S82. HRESIMS spectrum of compound 10 45
Figure S83. UV spectrum of compound 10 Figure S84. IR spectrum of compound 10 46
CH 3 H H H 3 C Figure S85. 1 H NMR spectrum of compound 10 in CD 3 D CH 3 H H H 3 C Figure S86. 13 C NMR spectrum of compound 10 in CD 3 D 47
Figure S87. ghsqc spectrum of compound 10 in CD 3 D CH 3 H H H 3 C Figure S88. ghmbc spectrum of compound 10 in CD 3 D 48
CH 3 H H H 3 C Figure S89. 1 H- 1 H CSY spectrum of compound 10 in CD 3 D 6 7 7'' 6'' 5 8 8'' 5'' Figure S90. RESY spectrum of compound 10 in CD 3 D 49
Figure S91. HRESIMS spectrum of compound 11 Figure S92. UV spectrum of compound 11 50
Figure S93. IR spectrum of compound 11 H Cl H Figure S94. 1 H NMR spectrum of compound 11 in DMS-d 6 51
H Cl H Figure S95. 13 C NMR spectrum of compound 11 in DMS-d 6 Figure S96. ghsqc spectrum of compound 11 in DMS-d 6 52
H Cl H Figure S97. ghmbc spectrum of compound 11 in DMS-d 6 H Cl H Figure S98. 1 H- 1 H CSY spectrum of compound 11 in DMS-d 6 53
7 8 6 7'' 5 5'' Figure S99. RESY spectrum of compound 11 in DMS-d 6 Figure S100. HRESIMS spectrum of compound 12 54
Figure S101. UV spectrum of compound 12 Figure S102. IR spectrum of compound 12 55
CH 3 H H 3 C H H H CH 3 Figure S103. 1 H NMR spectrum of compound 12 in CD 3 D CH 3 H H 3 C H H H CH 3 Figure S104. 13 C NMR spectrum of compound 12 in CD 3 D 56
Figure S105. ghsqc spectrum of compound 12 in CD 3 D CH 3 H H 3 C H CH 3 H H Figure S106. ghmbc spectrum of compound 12 in CD 3 D 57
CH 3 H H 3 C H H H CH 3 Figure S107. 1 H- 1 H CSY spectrum of compound 12 in CD 3 D 4''' 5''' 8'' 5' 4' 3' 5'' 6'' 8 7 6 5 Figure S108. RESY spectrum of compound 12 in CD 3 D 58
Figure S109. HRESIMS spectrum of compound 13 Figure S110. UV spectrum of compound 13 59
Figure S111. IR spectrum of compound 13 H 3 C H CH 3 H CH 3 H H Figure S112. 1 H NMR spectrum of compound 13 in CD 3 D 60
H 3 C H CH 3 H CH 3 H H Figure S113. 13 C NMR spectrum of compound 13 in CD 3 D Figure S114. ghsqc spectrum of compound 13 in CD 3 D 61
H 3 C H CH 3 H CH 3 H H H 3 C Figure S115. ghmbc spectrum of compound 13 in CD 3 D H CH 3 H CH 3 H H Figure S116. 1 H- 1 H CSY spectrum of compound 13 in CD 3 D 62
4''' 5''' 8'' 5'' 7'' 5' 4' 7 8 3' 6 5 Figure S117. RESY spectrum of compound 13 in CD 3 D Figure S118. HRESIMS spectrum of compound 14 63
Figure S119. UV spectrum of compound 14 Figure S120. IR spectrum of compound 14 64
H H 3 C H Figure S121. 1 H NMR spectrum of compound 14 in DMS-d H H 3 C H Figure S122. 13 C NMR spectrum of compound 14 in DMS-d 6 65
Figure S123. ghsqc spectrum of compound 14 in DMS-d 6 H H 3 C H Figure S124. ghmbc spectrum of compound 14 in DMS-d 6 66
7 6 5''' 4''' 3''' Figure S125. RESY spectrum of compound 14 in DMS-d 6 Figure S126. HRESIMS spectrum of compound 15 67
Figure S127. UV spectrum of compound 15 Figure S128. IR spectrum of compound 15 68
CH 3 H 3 C H H 3 C H Figure S129. 1 H NMR spectrum of compound 15 in CD 3 D CH 3 H 3 C H H 3 C H Figure S130. 13 C NMR spectrum of compound 15 in CD 3 D 69
Figure S131. ghsqc spectrum of compound 15 in CD 3 D CH 3 H 3 C H H 3 C H Figure S132. ghmbc spectrum of compound 15 in CD 3 D 70
7 8 5' 3' 4' 5''' 4''' 3''' Figure S133. RESY spectrum of compound 15 in CD 3 D 71