药学学报

No.	1		2		3		4
1a	3.20 s	67.4		1.52 m	39.2		1.50 m	39.1	1.68 m	40.1
1b			0.77 brt (11.4)		0.71 brt (11.4)		0.94 m
2a		178.2	1.98 m	26.8	1.98 m	26.8	1.85 m	27.4
2b			1.78 m		1.76 m		1.67 m
3	4.82 s	85.1	3.12 dd (11.4, 4.2)	88.7	3.09 dd (11.4, 4.2)	88.7	3.10 dd (12.0, 4.8)	90.0
4		44.2		40.0		40.0		40.6
5	2.17 dd (12.0, 3.0)	57.5	0.63 dd (12.0, 2.4)	56.5	0.61 dd (12.0, 2.4)	56.4	0.74 dd (10.8, 3.0)	57.7
6a	1.62 m	19.4	1.38 m	18.6	1.40 m	18.6	1.58 m	19.1
6b	1.42 m		1.28 m		1.30 m		1.55 m
7a	1.72 dt (12.0, 3.0)	35.2	1.52 m	36.2	1.51 m	36.4	1.54 m	36.9
7b	1.52 dt (3.0, 12.0)		1.35 m		1.38 m		1.47 m
8		42.6		37.7		37.5		38.5
9	2.22 dd (12.6, 2.4)	45.4	0.84 dd (12.6, 3.0)	53.2	0.85 dd (12.6, 3.0)	52.9	0.89 m	54.2
10		49.9		37.4		37.4		38.3
11a	2.07 m	24.4	1.53 m	21.9	1.50 m	21.6	1.65 m	22.5
11b	1.57 m		1.31 m		1.30 m		1.50 m
12a	1.94 dd (12.6, 3.6)	26.5	1.96 m	28.8	2.16 m	26.3	1.86 m	29.2
12b	1.30 dt (3.6, 12.6)		1.80 m		1.81 m		1.68 m
13	2.78 dt (3.6, 12.6)	38.9	2.70 m	38.6	2.76 brd (12.6)	41.9	2.48 m	38.0
14		43.8		53.6		54.5		54.6
15a	2.09 m	31.8	2.22 d (8.4)	40.2	1.81 d (9.0)	40.7	2.06 d (8.4)	37.1
15b	1.33 m		1.91 d (8.4)		1.52 d (9.0)		1.18 d (8.4)
16a	3.06 m	32.2		110.3		108.3		111.4
16b	1.52 m
17		57.3	1.69 d (7.2)	53.9		134.9	1.00 d (7.2)	54.4
18	1.67 t (12.6)	50.2	1.02 s	18.9	1.00 s	19.2	1.14 s	19.2
19	3.33 dt (4.8, 12.6)	47.6	0.71 s	16.7	0.75 s	16.7	0.88 s	16.9
20		151.7		69.2		124.4		69.4
21a	2.04 m	31.2	1.43 s	29.9	1.70 brs	18.9	1.14 s	29.6
21b	1.32 m
22a	2.18 m	37.0	2.14 dd (14.4, 10.8)	47.0	2.25 m	37.3	1.47 dd (11.4, 2.4)	45.4
22b	1.43 m		1.97 dd (14.4, 5.4)		1.98 m		1.38 dd (14.4, 11.4)
23	1.41 s	31.9	5.03 m	69.0	4.44 m	73.5	4.68 m	69.7
24a	1.22 s	20.7	5.43 brd (7.8)	127.2	2.30 dd (14.4, 7.8)	49.3	5.16 brd (8.4)	126.3
24b					1.85 dd (14.4, 3.6)
25	1.39 s	19.2		135.6		69.8		136.7
26	1.36 s	17.7	1.63 s	25.9	1.51 s	30.7	1.72 brs	25.7
27	1.07 s	15.5	1.71 s	18.7	1.48 s	31.4	1.68 brs	18.4
28		175.3	1.14 s	28.4	1.13 s	28.4	1.01 s	28.5
29a	4.82 brs	109.8	1.10 s	17.3	1.11 s	17.3	0.87 s	17.3
29b	4.63 brs
30a	1.61 s	19.8	4.29 brs	66.2	4.20 brs	66.2	4.02 d (7.8)	66.9
30b							3.93 d (7.8)

No.	1		2		3		4
1a	3.20 s	67.4		1.52 m	39.2		1.50 m	39.1	1.68 m	40.1
1b			0.77 brt (11.4)		0.71 brt (11.4)		0.94 m
2a		178.2	1.98 m	26.8	1.98 m	26.8	1.85 m	27.4
2b			1.78 m		1.76 m		1.67 m
3	4.82 s	85.1	3.12 dd (11.4, 4.2)	88.7	3.09 dd (11.4, 4.2)	88.7	3.10 dd (12.0, 4.8)	90.0
4		44.2		40.0		40.0		40.6
5	2.17 dd (12.0, 3.0)	57.5	0.63 dd (12.0, 2.4)	56.5	0.61 dd (12.0, 2.4)	56.4	0.74 dd (10.8, 3.0)	57.7
6a	1.62 m	19.4	1.38 m	18.6	1.40 m	18.6	1.58 m	19.1
6b	1.42 m		1.28 m		1.30 m		1.55 m
7a	1.72 dt (12.0, 3.0)	35.2	1.52 m	36.2	1.51 m	36.4	1.54 m	36.9
7b	1.52 dt (3.0, 12.0)		1.35 m		1.38 m		1.47 m
8		42.6		37.7		37.5		38.5
9	2.22 dd (12.6, 2.4)	45.4	0.84 dd (12.6, 3.0)	53.2	0.85 dd (12.6, 3.0)	52.9	0.89 m	54.2
10		49.9		37.4		37.4		38.3
11a	2.07 m	24.4	1.53 m	21.9	1.50 m	21.6	1.65 m	22.5
11b	1.57 m		1.31 m		1.30 m		1.50 m
12a	1.94 dd (12.6, 3.6)	26.5	1.96 m	28.8	2.16 m	26.3	1.86 m	29.2
12b	1.30 dt (3.6, 12.6)		1.80 m		1.81 m		1.68 m
13	2.78 dt (3.6, 12.6)	38.9	2.70 m	38.6	2.76 brd (12.6)	41.9	2.48 m	38.0
14		43.8		53.6		54.5		54.6
15a	2.09 m	31.8	2.22 d (8.4)	40.2	1.81 d (9.0)	40.7	2.06 d (8.4)	37.1
15b	1.33 m		1.91 d (8.4)		1.52 d (9.0)		1.18 d (8.4)
16a	3.06 m	32.2		110.3		108.3		111.4
16b	1.52 m
17		57.3	1.69 d (7.2)	53.9		134.9	1.00 d (7.2)	54.4
18	1.67 t (12.6)	50.2	1.02 s	18.9	1.00 s	19.2	1.14 s	19.2
19	3.33 dt (4.8, 12.6)	47.6	0.71 s	16.7	0.75 s	16.7	0.88 s	16.9
20		151.7		69.2		124.4		69.4
21a	2.04 m	31.2	1.43 s	29.9	1.70 brs	18.9	1.14 s	29.6
21b	1.32 m
22a	2.18 m	37.0	2.14 dd (14.4, 10.8)	47.0	2.25 m	37.3	1.47 dd (11.4, 2.4)	45.4
22b	1.43 m		1.97 dd (14.4, 5.4)		1.98 m		1.38 dd (14.4, 11.4)
23	1.41 s	31.9	5.03 m	69.0	4.44 m	73.5	4.68 m	69.7
24a	1.22 s	20.7	5.43 brd (7.8)	127.2	2.30 dd (14.4, 7.8)	49.3	5.16 brd (8.4)	126.3
24b					1.85 dd (14.4, 3.6)
25	1.39 s	19.2		135.6		69.8		136.7
26	1.36 s	17.7	1.63 s	25.9	1.51 s	30.7	1.72 brs	25.7
27	1.07 s	15.5	1.71 s	18.7	1.48 s	31.4	1.68 brs	18.4
28		175.3	1.14 s	28.4	1.13 s	28.4	1.01 s	28.5
29a	4.82 brs	109.8	1.10 s	17.3	1.11 s	17.3	0.87 s	17.3
29b	4.63 brs
30a	1.61 s	19.8	4.29 brs	66.2	4.20 brs	66.2	4.02 d (7.8)	66.9
30b							3.93 d (7.8)

No.	1		2		3		4
1′	6.38 d (8.4)	94.5		4.93 d (4.2)	104.4		4.92 d (4.2)	104.4	4.36 d (6.6)	106.1
2′	4.35 dd (9.0, 8.4)	79.8	4.78 dd (9.0, 4.2)	75.4	4.78 dd (9.0, 4.2)	75.5	3.94 dd (8.4, 6.6)	74.3
3′	4.66 t (9.0)	78.6	4.37 dd (9.0, 4.2)	83.3	4.36 dd (9.0, 4.2)	83.4	3.85 dd (8.4, 3.0)	83.5
4′	4.29 t (9.0)	70.3	4.52 m	68.3	4.50 m	68.2	4.02 m	70.3
5′a	4.02 m	79.8	4.36 dd (11.4, 6.6)	63.7	4.35 dd (11.4, 6.6)	63.7	3.83 m	66.1
5′b			3.97 dd (11.4, 3.0)		3.96 dd (11.4, 3.0)		3.52 m
6′a	4.39 dd (12.6, 3.0)	62.2
6′b	4.34 dd (12.6, 2.4)
1′′	5.79 d (7.8)	102.7	5.00 d (7.8)	104.3	4.99 d (7.2)	104.4	4.60 d (7.2)	103.4
2′′	4.20 dd (9.6, 7.8)	85.7	4.14 dd (8.4, 7.8)	83.5	4.14 dd (9.0, 7.2)	84.3	3.58 dd (9.0, 7.2)	81.6
3′′	4.38 dd (9.6, 9.0)	77.4	4.26 dd (9.0, 8.4)	78.6	4.26 dd (9.6, 9.0)	78.6	3.59 t (9.0)	78.6
4′′	4.15 t (9.0)	72.6	3.84 t (9.0)	71.8	3.84 t (9.6)	71.9	3.33 t (9.0)	71.2
5′′	3.97 m	78.3	4.07 m	76.9	4.07 m	77.0	3.31 m	78.1
6′′a	4.62 brd (12.6)	63.7	4.90 dd (10.8, 1.8)	70.7	4.90 dd (10.8, 1.8)	70.7	3.86 dd (12.0, 3.0)	62.4
6′′b	4.32 dd (12.6, 4.8)		3.94 dd (10.8, 7.2)		3.94 dd (10.8, 8.4)		3.67 dd (12.0, 6.0)
1′′′	5.39 d (7.8)	105.9	5.38 d (7.2)	106.8	5.38 d (7.0)	106.9	4.80 d (7.2)	105.1
2′′′	4.10 dd (9.0, 7.8)	76.9	4.20 dd (9.0, 7.2)	76.6	4.20 dd (9.0, 7.0)	76.7	3.35 dd (9.0, 7.2)	75.3
3′′′	4.25 t (9.0)	78.2	4.18 t (9.0)	78.4	4.19 t (9.0)	78.4	3.31 t (9.0)	77.8
4′′′	4.15 t (9.0)	71.9	4.22 m	71.2	4.22 m	71.2	3.53 m	71.0
5′′′a	4.04 m	79.5	4.51 dd (12.0, 5.4)	68.2	4.53 dd (12.0, 5.4)	68.3	3.93 dd (12.0, 5.4)	67.5
5′′′b			3.82 dd (12.0, 10.2)		3.82 dd (12.0, 10.2)		3.22 dd (12.0, 9.6)
6′′′a	4.62 brd (12.0)	63.1
6′′′b	4.28 dd (12.0, 6.6)
1′′′′			5.96 brs	102.0	5.95 brs	102.0	5.41 brd (1.8)	100.7
2′′′′			4.66 brd (3.0)	72.7	4.65 brd (3.6)	72.8	3.82 dd (3.0, 1.8)	72.8
3′′′′			4.55 dd (9.6, 3.0)	72.9	4.55 dd (9.6, 3.6)	72.9	3.83 dd (9.0, 3.0)	73.0
4′′′′			4.32 t (9.6)	74.3	4.31 t (9.6)	74.3	3.53 t (9.0)	81.0
5′′′′			4.54 m	70.4	4.54 m	70.5	4.14 m	68.0
6′′′′			1.66 d (6.0)	19.0	1.66 d (6.6)	18.9	1.23 d (6.6)	17.0
1′′′′′			4.90 d (7.8)	105.6	4.90 d (8.4)	105.6	5.19 brd (1.8)	103.2
2′′′′′			4.07 dd (9.0, 7.8)	75.7	4.07 t (8.4)	75.8	3.95 dd (3.0, 1.8)	72.4
3′′′′′			4.24 t (9.0)	78.4	4.23 dd (9.0, 8.4)	78.4	3.64 dd (9.0, 3.0)	72.4
4′′′′′			4.28 t (9.0)	71.8	4.28 t (9.0)	71.8	3.39 t (9.0)	73.9
5′′′′′			3.91 m	78.8	3.91 m	78.9	3.70 m	70.3
6′′′′′a			4.51 dd (12.0, 2.4)	62.9	4.51 dd (12.0, 3.0)	62.9	1.24 d (6.0)	18.6
6′′′′′b			4.39 dd (12.0, 5.4)		4.38 dd (12.0, 5.4)

No.	1		2		3		4
1′	6.38 d (8.4)	94.5		4.93 d (4.2)	104.4		4.92 d (4.2)	104.4	4.36 d (6.6)	106.1
2′	4.35 dd (9.0, 8.4)	79.8	4.78 dd (9.0, 4.2)	75.4	4.78 dd (9.0, 4.2)	75.5	3.94 dd (8.4, 6.6)	74.3
3′	4.66 t (9.0)	78.6	4.37 dd (9.0, 4.2)	83.3	4.36 dd (9.0, 4.2)	83.4	3.85 dd (8.4, 3.0)	83.5
4′	4.29 t (9.0)	70.3	4.52 m	68.3	4.50 m	68.2	4.02 m	70.3
5′a	4.02 m	79.8	4.36 dd (11.4, 6.6)	63.7	4.35 dd (11.4, 6.6)	63.7	3.83 m	66.1
5′b			3.97 dd (11.4, 3.0)		3.96 dd (11.4, 3.0)		3.52 m
6′a	4.39 dd (12.6, 3.0)	62.2
6′b	4.34 dd (12.6, 2.4)
1′′	5.79 d (7.8)	102.7	5.00 d (7.8)	104.3	4.99 d (7.2)	104.4	4.60 d (7.2)	103.4
2′′	4.20 dd (9.6, 7.8)	85.7	4.14 dd (8.4, 7.8)	83.5	4.14 dd (9.0, 7.2)	84.3	3.58 dd (9.0, 7.2)	81.6
3′′	4.38 dd (9.6, 9.0)	77.4	4.26 dd (9.0, 8.4)	78.6	4.26 dd (9.6, 9.0)	78.6	3.59 t (9.0)	78.6
4′′	4.15 t (9.0)	72.6	3.84 t (9.0)	71.8	3.84 t (9.6)	71.9	3.33 t (9.0)	71.2
5′′	3.97 m	78.3	4.07 m	76.9	4.07 m	77.0	3.31 m	78.1
6′′a	4.62 brd (12.6)	63.7	4.90 dd (10.8, 1.8)	70.7	4.90 dd (10.8, 1.8)	70.7	3.86 dd (12.0, 3.0)	62.4
6′′b	4.32 dd (12.6, 4.8)		3.94 dd (10.8, 7.2)		3.94 dd (10.8, 8.4)		3.67 dd (12.0, 6.0)
1′′′	5.39 d (7.8)	105.9	5.38 d (7.2)	106.8	5.38 d (7.0)	106.9	4.80 d (7.2)	105.1
2′′′	4.10 dd (9.0, 7.8)	76.9	4.20 dd (9.0, 7.2)	76.6	4.20 dd (9.0, 7.0)	76.7	3.35 dd (9.0, 7.2)	75.3
3′′′	4.25 t (9.0)	78.2	4.18 t (9.0)	78.4	4.19 t (9.0)	78.4	3.31 t (9.0)	77.8
4′′′	4.15 t (9.0)	71.9	4.22 m	71.2	4.22 m	71.2	3.53 m	71.0
5′′′a	4.04 m	79.5	4.51 dd (12.0, 5.4)	68.2	4.53 dd (12.0, 5.4)	68.3	3.93 dd (12.0, 5.4)	67.5
5′′′b			3.82 dd (12.0, 10.2)		3.82 dd (12.0, 10.2)		3.22 dd (12.0, 9.6)
6′′′a	4.62 brd (12.0)	63.1
6′′′b	4.28 dd (12.0, 6.6)
1′′′′			5.96 brs	102.0	5.95 brs	102.0	5.41 brd (1.8)	100.7
2′′′′			4.66 brd (3.0)	72.7	4.65 brd (3.6)	72.8	3.82 dd (3.0, 1.8)	72.8
3′′′′			4.55 dd (9.6, 3.0)	72.9	4.55 dd (9.6, 3.6)	72.9	3.83 dd (9.0, 3.0)	73.0
4′′′′			4.32 t (9.6)	74.3	4.31 t (9.6)	74.3	3.53 t (9.0)	81.0
5′′′′			4.54 m	70.4	4.54 m	70.5	4.14 m	68.0
6′′′′			1.66 d (6.0)	19.0	1.66 d (6.6)	18.9	1.23 d (6.6)	17.0
1′′′′′			4.90 d (7.8)	105.6	4.90 d (8.4)	105.6	5.19 brd (1.8)	103.2
2′′′′′			4.07 dd (9.0, 7.8)	75.7	4.07 t (8.4)	75.8	3.95 dd (3.0, 1.8)	72.4
3′′′′′			4.24 t (9.0)	78.4	4.23 dd (9.0, 8.4)	78.4	3.64 dd (9.0, 3.0)	72.4
4′′′′′			4.28 t (9.0)	71.8	4.28 t (9.0)	71.8	3.39 t (9.0)	73.9
5′′′′′			3.91 m	78.8	3.91 m	78.9	3.70 m	70.3
6′′′′′a			4.51 dd (12.0, 2.4)	62.9	4.51 dd (12.0, 3.0)	62.9	1.24 d (6.0)	18.6
6′′′′′b			4.39 dd (12.0, 5.4)		4.38 dd (12.0, 5.4)

No.	5		6		7		8
1a	1.70 m	39.9		1.69 m	40.0		1.70 m	40.0	1.71 m	40.0
1b	0.95 dt (3.0, 13.8)		0.94 dt (3.0, 13.8)		0.94 dt (3.6, 13.8)		0.95 dt (3.0, 13.8)
2a	1.85 m	27.2	1.83 m	27.2	1.83 m	27.3	1.82 m	27.2
2b	1.72 m		1.70 m		1.69 m		1.69 m
3	3.07 dd (11.4, 4.2)	89.8	3.08 dd (11.4, 4.2)	89.7	3.11 dd (11.4, 4.2)	89.7	3.09 dd (11.4, 4.2)	89.7
4		40.6		40.5		40.5		40.5
5	0.75 brd (11.4)	57.5	0.74 brd (10.8)	57.5	0.74 brd (11.4)	57.5	0.75 brd (11.4)	57.5
6a	1.58 m	19.2	1.57 m	19.2	1.58 m	19.1	1.58 m	19.1
6b	1.53 m		1.52 m		1.52 m		1.50 m
7a	1.56 m	36.9	1.55 m	36.9	1.64 m	36.9	1.59 m	36.8
7b	1.48 m		1.47 m		1.49 m		1.48 m
8		38.5		38.5		38.5		38.4
9	0.88 m	54.1	0.88 m	54.1	0.88 m	54.2	0.82 dd (12.6, 3.0)	54.0
10		38.3		38.3		38.3		38.2
11a	1.65 m	22.5	1.64 m	22.5	1.64 m	22.5	1.62 m	22.4
11b	1.50 m		1.50 m		1.49 m		1.47 m
12a	1.86 m	29.2	1.85 m	29.2	1.86 m	29.2	1.90 m	29.1
12b	1.69 m		1.68 m		1.69 m		1.68 m
13	2.49 m	38.0	2.48 m	38.1	2.49 m	38.1	2.36 m	38.4
14		54.6		54.6		54.6		54.0
15a	2.07 d (9.0)	37.1	2.06 d (8.4)	37.1	2.06 d (8.4)	37.1	1.71 d (9.0)	40.2
15b	1.19 d (9.0)		1.18 d (8.4)		1.19 d (8.4)		1.53 d (9.0)
16		111.4		111.4		111.4		111.5
17	1.01 d (7.2)	54.4	1.00 d (6.6)	54.4	1.00 d (7.2)	54.4	1.45 d (7.2)	54.0
18	1.15 s	19.2	1.14 s	19.2	1.14 s	19.2	1.12 s	19.1
19	0.90 s	16.9	0.89 s	16.9	0.85 s	16.8	0.89 s	16.9
20		69.4		69.4		69.4		70.2
21	1.15 s	29.6	1.14 s	29.6	1.14 s	29.6	1.18 s	28.9
22a	1.48 dd (13.8, 1.8)	45.4	1.47 dd (13.8, 1.8)	45.4	1.47 brd (13.8)	45.4	1.77 dd (14.4, 5.4)	46.5
22b	1.39 dd (13.8, 10.4)		1.38 dd (13.8, 10.4)		1.38 dd (13.8, 10.4)		1.68 dd (14.4, 10.4)
23	4.69 m	69.7	4.68 m	69.7	4.68 m	69.7	4.65 m	69.8
24	5.17 brd (8.4)	126.3	5.16 brd (8.4)	126.3	5.22 brd (8.4)	126.3	5.17 brd (8.4)	126.8
25		136.7		136.7		136.7		137.6
26	1.72 s	25.8	1.72 s	25.8	1.72 s	25.8	1.72 s	25.8
27	1.69 s	18.4	1.68 s	18.4	1.69 s	18.4	1.66 s	18.3
28	1.02 s	28.6	1.02 s	28.6	1.01 s	28.5	1.02 s	28.6
29	0.88 s	17.2	0.87 s	17.2	0.88 s	17.1	0.87 s	17.2
30a	4.04 d (7.8)	66.8	4.03 d (7.8)	66.9	4.03 d (7.8)	66.9	4.01 d (7.2)	66.9
30b	3.95 d (7.8)		3.94 d (7.8)		3.94 d (7.8)		3.99 d (7.2)

No.	5		6		7		8
1a	1.70 m	39.9		1.69 m	40.0		1.70 m	40.0	1.71 m	40.0
1b	0.95 dt (3.0, 13.8)		0.94 dt (3.0, 13.8)		0.94 dt (3.6, 13.8)		0.95 dt (3.0, 13.8)
2a	1.85 m	27.2	1.83 m	27.2	1.83 m	27.3	1.82 m	27.2
2b	1.72 m		1.70 m		1.69 m		1.69 m
3	3.07 dd (11.4, 4.2)	89.8	3.08 dd (11.4, 4.2)	89.7	3.11 dd (11.4, 4.2)	89.7	3.09 dd (11.4, 4.2)	89.7
4		40.6		40.5		40.5		40.5
5	0.75 brd (11.4)	57.5	0.74 brd (10.8)	57.5	0.74 brd (11.4)	57.5	0.75 brd (11.4)	57.5
6a	1.58 m	19.2	1.57 m	19.2	1.58 m	19.1	1.58 m	19.1
6b	1.53 m		1.52 m		1.52 m		1.50 m
7a	1.56 m	36.9	1.55 m	36.9	1.64 m	36.9	1.59 m	36.8
7b	1.48 m		1.47 m		1.49 m		1.48 m
8		38.5		38.5		38.5		38.4
9	0.88 m	54.1	0.88 m	54.1	0.88 m	54.2	0.82 dd (12.6, 3.0)	54.0
10		38.3		38.3		38.3		38.2
11a	1.65 m	22.5	1.64 m	22.5	1.64 m	22.5	1.62 m	22.4
11b	1.50 m		1.50 m		1.49 m		1.47 m
12a	1.86 m	29.2	1.85 m	29.2	1.86 m	29.2	1.90 m	29.1
12b	1.69 m		1.68 m		1.69 m		1.68 m
13	2.49 m	38.0	2.48 m	38.1	2.49 m	38.1	2.36 m	38.4
14		54.6		54.6		54.6		54.0
15a	2.07 d (9.0)	37.1	2.06 d (8.4)	37.1	2.06 d (8.4)	37.1	1.71 d (9.0)	40.2
15b	1.19 d (9.0)		1.18 d (8.4)		1.19 d (8.4)		1.53 d (9.0)
16		111.4		111.4		111.4		111.5
17	1.01 d (7.2)	54.4	1.00 d (6.6)	54.4	1.00 d (7.2)	54.4	1.45 d (7.2)	54.0
18	1.15 s	19.2	1.14 s	19.2	1.14 s	19.2	1.12 s	19.1
19	0.90 s	16.9	0.89 s	16.9	0.85 s	16.8	0.89 s	16.9
20		69.4		69.4		69.4		70.2
21	1.15 s	29.6	1.14 s	29.6	1.14 s	29.6	1.18 s	28.9
22a	1.48 dd (13.8, 1.8)	45.4	1.47 dd (13.8, 1.8)	45.4	1.47 brd (13.8)	45.4	1.77 dd (14.4, 5.4)	46.5
22b	1.39 dd (13.8, 10.4)		1.38 dd (13.8, 10.4)		1.38 dd (13.8, 10.4)		1.68 dd (14.4, 10.4)
23	4.69 m	69.7	4.68 m	69.7	4.68 m	69.7	4.65 m	69.8
24	5.17 brd (8.4)	126.3	5.16 brd (8.4)	126.3	5.22 brd (8.4)	126.3	5.17 brd (8.4)	126.8
25		136.7		136.7		136.7		137.6
26	1.72 s	25.8	1.72 s	25.8	1.72 s	25.8	1.72 s	25.8
27	1.69 s	18.4	1.68 s	18.4	1.69 s	18.4	1.66 s	18.3
28	1.02 s	28.6	1.02 s	28.6	1.01 s	28.5	1.02 s	28.6
29	0.88 s	17.2	0.87 s	17.2	0.88 s	17.1	0.87 s	17.2
30a	4.04 d (7.8)	66.8	4.03 d (7.8)	66.9	4.03 d (7.8)	66.9	4.01 d (7.2)	66.9
30b	3.95 d (7.8)		3.94 d (7.8)		3.94 d (7.8)		3.99 d (7.2)

No.	5		6		7		8
1′	4.50 d (4.8)	104.8		4.44 d (5.4)	105.3		4.46 d (5.4)	105.3	4.45 d (5.4)	105.3
2′	3.98 brd (4.8)	76.0	3.96 brd (5.4)	75.9	3.86 brd (5.4)	75.6	3.96 brd (5.4)	75.9
3′	3.95 m	82.3	3.89 m	81.9	3.88 m	82.9	3.90 m	81.8
4′	3.94 m	68.9	3.97 m	69.4	4.05 m	68.7	3.97 m	69.4
5′a	3.85 brd (10.8)	63.8	3.86 dd (12.0, 3.6)	64.8	3.87 brd (12.0)	65.0	3.86 dd (12.0, 2.4)	64.8
5′b	3.51 brd (10.8)		3.48 dd (12.0, 2.4)		3.54 brd (12.0)		3.48 dd (12.0, 2.4)
1′′	4.58 d (7.8)	103.6	4.61 d (7.2)	103.4	4.50 d (7.2)	104.2	4.61 d (7.2)	103.5
2′′	3.54 dd (9.0, 7.8)	82.7	3.54 dd (9.0, 7.2)	82.4	3.31 dd (9.0, 7.2)	75.1	3.54 dd (8.4, 7.2)	82.4
3′′	3.60 t (9.0)	78.1	3.59 t (9.0)	78.4	3.36 t (9.0)	78.0	3.59 t (8.4)	78.4
4′′	3.31 t (9.0)	71.7	3.34 t (9.0)	71.3	3.27 t (9.0)	71.6	3.34 dd (9.0, 8.4)	71.3
5′′	3.55 m	76.8	3.32 m	78.1	3.52 m	77.0	3.32 m	78.2
6′′a	4.22 dd (10.8, 2.4)	70.5	3.87 dd (12.0, 2.4)	62.5	4.16 dd (11.4, 2.4)	70.2	3.87 dd (12.0, 2.4)	62.5
6′′b	3.65 dd (10.8, 8.4)		3.65 dd (12.0, 5.4)		3.73 dd (11.4, 7.8)		3.65 dd (12.0, 5.4)
1′′′	4.69 d (7.2)	105.8	4.73 d (7.2)	105.6	4.35 d (7.8)	104.8	4.73 d (7.8)	105.6
2′′′	3.32 dd (9.0, 7.2)	75.7	3.33 dd (9.0, 7.2)	75.5	3.20 dd (9.0, 7.8)	75.1	3.33 dd (9.0, 7.2)	75.5
3′′′	3.33 t (9.0)	77.6	3.32 t (9.0)	77.7	3.34 t (9.0)	78.0	3.32 t (9.0)	77.7
4′′′	3.54 m	70.9	3.53 m	71.0	3.32 t (9.0)	71.6	3.53 m	71.0
5′′′a	3.93 dd (11.4, 5.4)	67.6	3.93 dd (11.4, 5.4)	67.5	3.26 m	78.0	3.93 dd (11.4, 5.4)	67.5
5′′′b	3.25 t (11.4)		3.22 t (11.4)				3.22 t (11.4)
6′′′a					3.93 dd (12.0, 3.6)	62.7
6′′′b					3.66 dd (12.0, 4.2)
1′′′′	5.15 brs	101.8	5.20 brs	101.8	5.22 brs	102.0	5.20 brs	101.8
2′′′′	3.89 brd (2.4)	72.1	3.90 brd (3.0)	72.1	3.93 brd (2.4)	72.1	3.90 brd (3.0)	72.1
3′′′′	3.68 dd (9.6, 2.4)	72.1	3.68 dd (9.6, 3.0)	72.2	3.72 dd (9.0, 3.6)	72.1	3.68 dd (9.6, 3.0)	72.2
4′′′′	3.41 t (9.6)	73.9	3.40 t (9.6)	73.9	3.39 t (9.0)	73.8	3.40 t (9.6)	73.9
5′′′′	3.84 m	70.2	3.88 m	70.1	3.85 m	70.3	3.88 m	70.1
6′′′′	1.23 d (6.0)	18.0	1.22 d (6.0)	18.0	1.21 d (6.0)	18.0	1.22 d (6.0)	18.0
1′′′′′	4.31 d (7.8)	104.9
2′′′′′	3.22 dd (8.4, 7.8)	75.1
3′′′′′	3.35 dd (9.0, 8.4)	77.8
4′′′′′	3.30 dd (9.0, 8.4)	71.5
5′′′′′	3.28 m	78.0
6′′′′′a	3.87dd (12.0, 2.4)	62.7
6′′′′′b	3.67 dd (12.0, 5.4)

No.	5		6		7		8
1′	4.50 d (4.8)	104.8		4.44 d (5.4)	105.3		4.46 d (5.4)	105.3	4.45 d (5.4)	105.3
2′	3.98 brd (4.8)	76.0	3.96 brd (5.4)	75.9	3.86 brd (5.4)	75.6	3.96 brd (5.4)	75.9
3′	3.95 m	82.3	3.89 m	81.9	3.88 m	82.9	3.90 m	81.8
4′	3.94 m	68.9	3.97 m	69.4	4.05 m	68.7	3.97 m	69.4
5′a	3.85 brd (10.8)	63.8	3.86 dd (12.0, 3.6)	64.8	3.87 brd (12.0)	65.0	3.86 dd (12.0, 2.4)	64.8
5′b	3.51 brd (10.8)		3.48 dd (12.0, 2.4)		3.54 brd (12.0)		3.48 dd (12.0, 2.4)
1′′	4.58 d (7.8)	103.6	4.61 d (7.2)	103.4	4.50 d (7.2)	104.2	4.61 d (7.2)	103.5
2′′	3.54 dd (9.0, 7.8)	82.7	3.54 dd (9.0, 7.2)	82.4	3.31 dd (9.0, 7.2)	75.1	3.54 dd (8.4, 7.2)	82.4
3′′	3.60 t (9.0)	78.1	3.59 t (9.0)	78.4	3.36 t (9.0)	78.0	3.59 t (8.4)	78.4
4′′	3.31 t (9.0)	71.7	3.34 t (9.0)	71.3	3.27 t (9.0)	71.6	3.34 dd (9.0, 8.4)	71.3
5′′	3.55 m	76.8	3.32 m	78.1	3.52 m	77.0	3.32 m	78.2
6′′a	4.22 dd (10.8, 2.4)	70.5	3.87 dd (12.0, 2.4)	62.5	4.16 dd (11.4, 2.4)	70.2	3.87 dd (12.0, 2.4)	62.5
6′′b	3.65 dd (10.8, 8.4)		3.65 dd (12.0, 5.4)		3.73 dd (11.4, 7.8)		3.65 dd (12.0, 5.4)
1′′′	4.69 d (7.2)	105.8	4.73 d (7.2)	105.6	4.35 d (7.8)	104.8	4.73 d (7.8)	105.6
2′′′	3.32 dd (9.0, 7.2)	75.7	3.33 dd (9.0, 7.2)	75.5	3.20 dd (9.0, 7.8)	75.1	3.33 dd (9.0, 7.2)	75.5
3′′′	3.33 t (9.0)	77.6	3.32 t (9.0)	77.7	3.34 t (9.0)	78.0	3.32 t (9.0)	77.7
4′′′	3.54 m	70.9	3.53 m	71.0	3.32 t (9.0)	71.6	3.53 m	71.0
5′′′a	3.93 dd (11.4, 5.4)	67.6	3.93 dd (11.4, 5.4)	67.5	3.26 m	78.0	3.93 dd (11.4, 5.4)	67.5
5′′′b	3.25 t (11.4)		3.22 t (11.4)				3.22 t (11.4)
6′′′a					3.93 dd (12.0, 3.6)	62.7
6′′′b					3.66 dd (12.0, 4.2)
1′′′′	5.15 brs	101.8	5.20 brs	101.8	5.22 brs	102.0	5.20 brs	101.8
2′′′′	3.89 brd (2.4)	72.1	3.90 brd (3.0)	72.1	3.93 brd (2.4)	72.1	3.90 brd (3.0)	72.1
3′′′′	3.68 dd (9.6, 2.4)	72.1	3.68 dd (9.6, 3.0)	72.2	3.72 dd (9.0, 3.6)	72.1	3.68 dd (9.6, 3.0)	72.2
4′′′′	3.41 t (9.6)	73.9	3.40 t (9.6)	73.9	3.39 t (9.0)	73.8	3.40 t (9.6)	73.9
5′′′′	3.84 m	70.2	3.88 m	70.1	3.85 m	70.3	3.88 m	70.1
6′′′′	1.23 d (6.0)	18.0	1.22 d (6.0)	18.0	1.21 d (6.0)	18.0	1.22 d (6.0)	18.0
1′′′′′	4.31 d (7.8)	104.9
2′′′′′	3.22 dd (8.4, 7.8)	75.1
3′′′′′	3.35 dd (9.0, 8.4)	77.8
4′′′′′	3.30 dd (9.0, 8.4)	71.5
5′′′′′	3.28 m	78.0
6′′′′′a	3.87dd (12.0, 2.4)	62.7
6′′′′′b	3.67 dd (12.0, 5.4)

No.	9		10	No.	9		10
1a	2.00 dd (12.0, 5.0)	48.5		1.55 m	38.3	15b	1.17 m			1.08 m
1b	0.84 t (12.0)		0.83 dt (5.0, 12.0)		16a	2.24 brd (12.0)	33.6	2.11 brd (12.0)	33.6
2a	3.61 m	69.8	1.43 m	27.2	16b	1.40 m		1.37 m
2b			1.43 m		17		57.7		55.4
3	2.89 d (9.5)	84.5	2.96 dd (10.0, 6.0)	76.8	18	1.62 t (12.0)	50.6	1.50 t (12.0)	48.6
4		40.7		38.5	19	3.04 m	48.7	2.96 m	46.7
5	0.81 dd (11.5, 2.5)	57.0	0.63 brd (12.0)	54.9	20		152.2		150.4
6a	1.63 m	19.7	1.45 m	18.0	21a	1.94 m	31.9	1.81 m	30.1
6b	1.42 m		1.32 m		21b	1.39 m		1.29 m
7a	1.47 m	35.6	1.31 m	33.9	22a	1.91 m	38.4	1.78 m	36.4
7b	1.41 m		1.31 m		22b	1.45 m		1.41 m
8		42.1		40.3	23	0.99 s	29.3	0.86 s	28.1
9	1.38 m	52.1	1.24 dd (12.0, 2.5)	50.0	24	0.78 s	17.4	0.64 s	15.8
10		39.6		36.7	25	0.92 s	18.1	0.76 s	16.0
11a	1.46 m	22.4	1.37 m	20.5	26	0.97 s	16.8	0.86 s	15.8
11b	1.30 m		1.14 dq (4.5, 12.0)		27	1.01 s	15.2	0.92 s	14.4
12a	1.74 m	27.0	1.62 m	25.1	28		/		177.4
12b	1.07 dq (4.5, 12.0)		0.96 dq (4.5, 12.0)		29a	4.71 brd (2.5)	110.3	4.68 brs	109.7
13	2.33 brt (12.0)	39.7	2.23 brt (12.0)	37.6	29b	4.60 dq (2.5, 1.0)		4.55 brs
14		43.8		42.0	30	1.70 brd (1.0)	19.7	1.64 brs	19.0
15a	1.55 m	31.0	1.37 m	29.2

No.	9		10	No.	9		10
1a	2.00 dd (12.0, 5.0)	48.5		1.55 m	38.3	15b	1.17 m			1.08 m
1b	0.84 t (12.0)		0.83 dt (5.0, 12.0)		16a	2.24 brd (12.0)	33.6	2.11 brd (12.0)	33.6
2a	3.61 m	69.8	1.43 m	27.2	16b	1.40 m		1.37 m
2b			1.43 m		17		57.7		55.4
3	2.89 d (9.5)	84.5	2.96 dd (10.0, 6.0)	76.8	18	1.62 t (12.0)	50.6	1.50 t (12.0)	48.6
4		40.7		38.5	19	3.04 m	48.7	2.96 m	46.7
5	0.81 dd (11.5, 2.5)	57.0	0.63 brd (12.0)	54.9	20		152.2		150.4
6a	1.63 m	19.7	1.45 m	18.0	21a	1.94 m	31.9	1.81 m	30.1
6b	1.42 m		1.32 m		21b	1.39 m		1.29 m
7a	1.47 m	35.6	1.31 m	33.9	22a	1.91 m	38.4	1.78 m	36.4
7b	1.41 m		1.31 m		22b	1.45 m		1.41 m
8		42.1		40.3	23	0.99 s	29.3	0.86 s	28.1
9	1.38 m	52.1	1.24 dd (12.0, 2.5)	50.0	24	0.78 s	17.4	0.64 s	15.8
10		39.6		36.7	25	0.92 s	18.1	0.76 s	16.0
11a	1.46 m	22.4	1.37 m	20.5	26	0.97 s	16.8	0.86 s	15.8
11b	1.30 m		1.14 dq (4.5, 12.0)		27	1.01 s	15.2	0.92 s	14.4
12a	1.74 m	27.0	1.62 m	25.1	28		/		177.4
12b	1.07 dq (4.5, 12.0)		0.96 dq (4.5, 12.0)		29a	4.71 brd (2.5)	110.3	4.68 brs	109.7
13	2.33 brt (12.0)	39.7	2.23 brt (12.0)	37.6	29b	4.60 dq (2.5, 1.0)		4.55 brs
14		43.8		42.0	30	1.70 brd (1.0)	19.7	1.64 brs	19.0
15a	1.55 m	31.0	1.37 m	29.2

酸枣仁水提取物中的三萜类成分

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郝文飒 , 朱承根 , 雷小强 , 徐成博 , 郭庆兰 ^* , 石建功 ^*

药学学报 | 研究论文 2023,58(9): 2734-2745

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药学学报 |研究论文 2023 , 58 (9) : 2734 -2745

酸枣仁水提取物中的三萜类成分

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郝文飒, 朱承根, 雷小强, 徐成博, 郭庆兰^*, 石建功^*

作者信息

中国医学科学院、北京协和医学院药物研究所, 天然药物活性物质与功能国家重点实验室, 北京 100050

通讯作者:

*郭庆兰, Tel: 86-10-83154789, Fax: 86-10-63017757, E-mail: guonina@imm.ac.cn;

石建功, Tel: 86-10-63025166, Fax: 86-10-63017757, E-mail: shijg@imm.ac.cn

Triterpenoids from an aqueous extract of the Ziziphus jujuba var. spinosa seeds

Wen-sa HAO, Cheng-gen ZHU, Xiao-qiang LEI, Cheng-bo XU, Qing-lan GUO^*, Jian-gong SHI^*

Affiliations

Key Laboratory of Bioactive Substance and Function of Natural Medicines, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, China

出版时间: 2023-09-12 doi: 10.16438/j.0513-4870.2023-0026

文章导航

摘要

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通过大孔吸附树脂、MCI树脂、正相硅胶、Sephadex LH-20和Toyopearl HW-40C柱色谱结合制备薄层色谱和反相HPLC等多种色谱分离方法, 从酸枣仁水提取物中分离得到4个新三萜苷类及6个已知三萜类化合物。利用多种波谱学方法, 结合酸水解反应, 确定了它们的结构, 新化合物分别命名为酸枣仁美洲茶酸苷A (1)、23-表酸枣仁皂苷A (2) 及酸枣仁皂苷J和K (3和4), 已知化合物鉴定为酸枣仁皂苷A~C (5~7)、酸枣仁皂苷II (8)、卖珠子酸(9) 和白桦脂酸(10)。其中, 1的结构得到单晶X-射线衍射分析的确证。

关键词

鼠李科 / 枣属 / 酸枣 / 三萜 / 酸枣仁美洲茶酸苷A / 酸枣仁皂苷衍生物

Abstract

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Four new triterpenoids, together with six known analogues, were isolated from an aqueous extract of the Ziziphus jujuba var. spinosa seeds, by multiple column chromatographic separation methods using stationary phases of macroporous adsorption resin, MCI resin, normal phase silica gel, Sephadex LH-20, and Toyopearl HW-40C as well as preparative thin-layer chromatography and reversed-phase HPLC. Their structures were determined by spectroscopic data analysis, the new structures were trivially named jujubaceanothoside A (1), 23-epijujuboside A (2), and jujubosides J and K (3 and 4), while the known analogues were identified as jujubosides A-C (5-7) and II (8), alphitolic acid (9), and betulinic acid (10). The structure of 1 was confirmed by single crystal X-ray diffraction.

Key words

Rhamnaceae / Ziziphus / Ziziphus jujuba var. spinasa / triterpennoid / jujubaceanothoside A / jujuboside derivative

引用本文

郝文飒, 朱承根, 雷小强, 徐成博, 郭庆兰, 石建功. 酸枣仁水提取物中的三萜类成分. 药学学报, 2023 , 58 (9) : 2734 -2745 . DOI: 10.16438/j.0513-4870.2023-0026

Wen-sa HAO, Cheng-gen ZHU, Xiao-qiang LEI, Cheng-bo XU, Qing-lan GUO, Jian-gong SHI. Triterpenoids from an aqueous extract of the Ziziphus jujuba var. spinosa seeds[J]. Acta Pharmaceutica Sinica, 2023 , 58 (9) : 2734 -2745 . DOI: 10.16438/j.0513-4870.2023-0026

正文

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酸枣仁为鼠李科(Rhamnaceae) 枣属(Ziziphus) 植物酸枣Ziziphus jujuba Mill. Var. spinasa (Bunge) Hu ex H.F. Chou的干燥成熟种仁, 也是经典的常用中药之一, 具有养肝、宁心、安神和敛汗, 以及治虚烦不眠、惊悸、怔忡、烦渴和虚汗等功效^[1]。药理学研究反复证明酸枣仁提取物具有催眠、抗惊厥^[1-3]、改善记忆减退^[4]、抗抑郁等多种中枢药理作用^[5-8]。同时, 据报道从酸枣仁中已分离鉴定了包括三萜和黄酮及其苷类, 以及包括环肽的生物碱类和有机酸类等化学成分237个, 但该报道中化合物的数目不但包含了从基原植物酸枣的根、茎、叶和果肉等不同部位中仅用HPLC-MS等方法初步检测鉴定的成分, 也包含了同属植物大枣等中发现的成分^[9]。另外, 从酸枣仁中发现的主要成分环肽生物碱类酸枣仁碱A (sanjoinine A)^[10-16]、三萜苷类酸枣仁皂苷A^[17-22]和黄酮碳苷类斯皮诺素(spinosin)^[23-26]等不同结构类型的若干化合物均显示有中枢抑制等药理作用。但是, 已有的研究几乎全部使用有机溶剂进行提取, 与包括酸枣仁的多数传统中药以水煎为主的用药方式不同。因此, 作为对常用中药化学成分多样性系统研究的内容之一^[27-39], 作者开展了酸枣仁水提取物化学成分的研究, 为进一步深入揭示酸枣仁化学成分的特点奠定基础。本文报道酸枣仁水提取物中10个三萜类化合物(1~10, 图 1) 的分离和结构鉴定。其中, 1~4为新结构化合物, 1的结构得到单晶X-射线衍射分析的确证; 其他均为酸枣仁中已报道成分。

结果和讨论

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化合物1为无色结晶, [α]$ {}_{\mathrm{D}}^{20} $ +2.12 (c 0.38, MeOH)。根据(+)-HR-ESI-MS m/z 995.480 7 [M+Na]⁺ (C₄₈H₇₆O₂₀Na计算值, 995.482 2) 和NMR谱数据(表 1和2) 确定其分子组成为C₄₈H₇₆O₂₀。在吡啶-d₅中, 该化合物的¹H NMR谱显示可归属于3个β-六碳糖基的特征端基氢信号[δ_H 6.38 (d, J = 8.4 Hz, H-1ʹ)、5.79 (d, J = 7.8 Hz, H-1″)和5.39 (d, J = 7.8 Hz, H-1‴)], 1个末端烯键的氢信号[δ_H 4.82 (brs, H-29a) 和4.63 (brs, H-29b)], 6个叔甲基的单峰信号[δ_H 1.07 (H₃-27)、1.22 (H₃-24)、1.36 (H₃-26)、1.39 (H₃-25)、1.41 (H₃-23) 和1.61 (H₃-30)], 以及多个连氧和非连氧亚甲基和次甲基的信号。其¹³C NMR和DEPT谱给出可归属于3个β-六碳糖基的18个碳信号以及可归属于苷元的30个碳信号; 其中, 苷元部分的碳信号包括1个羧基或/和酯基[δ_C 178.2 (C-2) 和175.3 (C-28)]、1个末端烯键[δ_C 151.7 (C-20) 和109.8 (C-29)]、5个sp³杂化季碳、7个sp³杂化次甲基且1个连氧[δ_C 85.1 (C-3)]、8个sp³杂化亚甲基和6个甲基。与酸枣仁中已报道化合物的相关数据比较, 以上波谱数据显示该化合物为一个特殊三萜的三-β-六碳糖苷, 其结构通过2D NMR实验数据分析进行了确定。

借助HSQC数据分析对NMR谱中氢及其相连碳的信号进行了准确归属(表 1和2), 并通过1D TOCSY实验和偶合常数分析推定3个β-六碳糖基均为β-葡萄糖基。根据¹H-¹H COSY谱中H-5/H₂-6/H₂-7和H-9/H₂-11/H₂-12/H-13/H-18/H-19/H₂-21/H₂-22的交叉峰信号, 推定邻位氢依次偶合的结构片段(图 2)。在HMBC谱中, H-1/C-2和C-4, H₃-23和H₃-24/C-3、C-4和C-5, H₃-25/C-1、C-5、C-9和C-10的两键和三键异核远程相关, 结合它们的化学位移, 表明1中存在1-羧基-3-羟基-4, 4, 10-三甲基取代的环戊烷结构单元, 且CH-5和C-10分别与CH₂-6和CH-9连接。由H₃-26与C-7、C-8、C-9和C-14的HMBC相关信号推断季碳C-8与CH₂-7、CH-9、C-14和CH₃-26相连。同时, 根据H₃-27与C-8、C-13、C-14和C-15的HMBC相关信号推定C-8通过C-14与CH-13、CH₂-15和CH₃-27相连接。通过H-16b、H-18和H-22a与C-17和C-28的两键和三键HMBC相关信号, 结合它们的化学位移, 推断季碳C-17与CH₂-16、CH-18、CH₂-22和羧基C-28相连。由H₃-30与C-19、C-20和C-29的HMBC相关信号, 结合它们的化学位移, 推定C-19上有1个异丙烯基取代。另外, 根据HMBC谱中H-1′/C-28、H-1″/C-2′和H-1‴/C-2ʺ的相关信号, 推断1个β-葡萄糖基与苷元的羧基C-28以酯苷键连接, 其余两个β-葡萄糖基依次以苷键连接在C-2′和C-2″上。在1的ROESY谱中(图 3), 交叉峰H-1/H₃-24和H₃-24/H₃-25证明这些氢取向五元环的一侧, 而交叉峰H-3/H₃-23、H-5/H-9、H-5/H₃-23、H-9/H₃-27和H-18/H₃-27表明它们取向环系的另一侧。同时, H-13/H-19和H-13/H₃-26表明这些氢取向环系的同侧。综合以上情况, 确定1的结构和相对构型如图 2所示, 为美洲茶酸(ceanothic acid^{[40, 41]}) 的三β-葡萄糖苷。经酸水解、衍生化和气相色谱分析确证1酸水解后释放出D-葡萄糖。在正己烷-乙醇-水(1:1:2) 溶液中, 1生长出适合X-射线衍射的单晶, 利用铜靶X-射线衍射分析, 进一步确证了其结构和绝对构型, 晶体结构ORTEP图如图 4所示, Flack参数为-0.01 (4)。因此, 化合物1的结构确定为美洲茶酸-28-O-β-D-吡喃葡萄基-(1‴→2ʺ)-O-β-D-吡喃葡萄糖-(1ʺ→2′)-O-β-D-吡喃葡萄糖酯苷, 命名为酸枣仁美洲茶酸苷A (jujubaceanothoside A)。

化合物2为白色粉末, [α]$ {}_{\mathrm{D}}^{20} $ -18.9 (c 0.32, MeOH)。通过(-)-HR-ESI-MS m/z 1 205.592 7 [M-H]^- (C₅₈H₉₃O₂₆, 计算值1 205.596 1) 和NMR谱数据(表 1和2) 确定其分子式为C₅₈H₉₄O₂₆, 且与同时得到的酸枣仁皂苷A (jujuboside A^{[42, 43]}, 5) 为同分异构体。比较2和5在相同溶剂吡啶-d₅中的NMR数据^[44-46], 主要差别是2中苷元部分的H-15a、H-23和H-24及C-15分别被屏蔽位移Δδ_H -0.28、-0.18和-0.18及Δδ_C -3.0, 而H-15b被去屏蔽位移Δδ_H +0.36。以上差别与拥有C-23差向异构苷在吡啶-d₅中NMR数据的差异一致。经酸水解、衍生化和气相色谱分析确证2酸水解后释放出D-葡萄糖、D-木糖、L-阿拉伯糖和L-鼠李糖。由此推断2是酸枣仁皂苷A的C-23差向异构体, 并得到2D NMR实验数据分析的确证(图 2和3)。特别是, 在HMBC谱中, H-1′/C-3、H-1′′′′/C-2′、H-1″/C-3′、H-1‴/C-2″和H-1′′′′/C-6″的异核远程交叉峰确证2中糖链的苷化位置, 以及5个糖基单元之间的连接关系与酸枣仁皂苷A的完全相同。同时, 在2的ROESY谱中, 交叉峰H-17/H-23确证H-23与H-17取向相同。因此, 化合物2的结构得到确定, 命名为23-表酸枣仁皂苷A (23-epijujuboside A)。

化合物3为白色粉末, [α]$ {}_{\mathrm{D}}^{20} $ -40.8 (c 0.44, MeOH), 波谱数据显示其为2和5的又一同分异构体。比较3和2的NMR数据(表 1和2) 显示二者的糖基单元及相互连接关系完全相同。然而, 3苷元部分的1个亚甲基[δ_H 2.30 (dd, J = 14.4和7.8 Hz, H-24a), 1.85 (dd, J = 14.4和3.6 Hz, H-24b); δ_C 49.3 (C-24)] 和1个四取代双键[δ_C 134.9 (C-17) 和124.4 (C-20)] 的信号分别替代了2苷元部分的1个次甲基和三取代双键。同时, 3的H-15a、H-15b、H-23、H₃-26和H₃-27及C-16、C-21和C-22分别向高场位移Δδ_H -0.41、-0.39、-0.59、-0.12和-0.23及Δδ_C -2.0、-11.0和-9.7, 相反H₃-21及C-23、C-26和C-27分别向低场位移Δδ_H +0.27及Δδ_C +4.5、+4.8和+12.7。由此推断3是2的17(20)-烯-25-羟基衍生物, 并得到3的2D NMR实验(图 2和3) 以及酸水解、衍生化和气相色谱数据分析的证实。尤其是3的¹H-¹H COSY谱中H-22a和H-24a与H-23的交叉峰, 以及HMBC谱中H₃-21与C-17、C-20和C-22, H-23与C-16, H₃-26和H₃-27与C-24和C-25的HMBC交叉峰信号, 结合这些氢和碳的化学位移, 确证双键位于C-17和C-20之间, 环氧位于C-16与C-23之间, 羟基取代在C-25上。同时, 在HMBC谱中, H-1′/C-3、H-1′′′′/C-2′、H-1″/C-3′、H-1‴/C-2″和H-1‴″/C-6″的交叉峰确证3中糖的苷化位置及5个糖基单元之间的连接关系与2的完全相同。在3的ROESY谱中, 交叉峰H-13/H-23和H-15b/H-23显示H-23处于母环的β-取向。另外, 经衍生化和气相色谱分析也证明3酸水解后释放出D-葡萄糖、D-木糖、L-阿拉伯糖和L-鼠李糖。因此, 化合物3的结构得到确定为25-羟基-21(17)-脱水-双氢酸枣仁皂苷A, 结合已报道酸枣仁皂苷的命名顺序^{[9, 47]}, 取名为酸枣仁皂苷J (jujuboside J)。

化合物4为白色粉末, [α]$ {}_{\mathrm{D}}^{20} $ -31.2 (c 0.81, MeOH)。由(-)-HR-ESI-MS m/z 1 191.617 7[M+H]⁺ (C₅₈H₉₅O₂₅, 计算值1 191.615 7) 和NMR谱数据(表 1和2) 为C₅₈H₉₄O₂₅, 较2、3和5少1个氧原子。比较4与5的NMR数据, 显示二者拥有完全相同的苷元部分, 差别之处仅在于4中的1个α-吡喃鼠李糖基取代了酸枣仁皂苷A中的1个β-吡喃葡萄糖基。由此推断4是酸枣仁皂苷A中的1个β-吡喃葡萄糖基单元被α-吡喃鼠李糖基取代的衍生物, 并通过4的2D NMR数据分析对其结构进行了确定。通过HSQC、¹H-¹H COSY、TOCSY、HMBC和ROESY谱数据分析(图 2和3), 证明4的苷元部分与5的完全相同。根据¹H-¹H COSY和TOCSY谱中邻位氢依次偶合的交叉峰信号, 结合它们的化学位移和偶合常数, 确认4中含有1个α-吡喃阿拉伯糖基、1个β-吡喃葡萄糖基、1个β-吡喃木糖基和2个α-吡喃鼠李糖基。特别是根据HMBC谱中H-1′/C-3、H-1′′′′/C-2′、H-1″/C-3′、H-1‴/C-2″和H-1‴″/C-4‴的交叉峰, 确证α-吡喃阿拉伯糖基连接在苷元的C-3上, 1个α-吡喃鼠李糖基和β-吡喃葡萄糖基分别连接在α-吡喃阿拉伯糖基的C-2′和C-3′上, β-吡喃木糖基连接在β-吡喃葡萄糖基的C-2″上, 另一个α-吡喃鼠李糖基连接在内侧α-吡喃鼠李糖基的C-4‴上。经酸水解、衍生化和气相色谱分析证明4水解后释放出D-葡萄糖、D-木糖、L-阿拉伯糖和L-鼠李糖。因此, 化合物4的结构得到确定, 命名为酸枣仁皂苷K (jujuboside K)。

通过波谱数据分析(表 3~5), 结合与文献报道数据比较, 已知化合物分别鉴定为酸枣仁皂苷A~C (jujubosides A~C, 5~7)^{[45, 46, 48]}、酸枣仁皂苷II (jujuboside II, 8)^[47]、卖珠子酸(alphitolic acid, 9)^{[40, 49]}和白桦脂酸(10)^{[40, 50]}。以上研究结果证明酸枣仁水提取物中不但包含与已报道有机溶剂提取物相同的成分, 而且存在未发现的三萜衍生物。特别是, 化合物1是从酸枣仁中分离得到第一个美洲茶烷型三萜苷类化合物, 2是第二个具有23S构型的酸枣仁皂苷衍生物, 3是第一个20(17)-脱水的酸枣仁皂苷衍生物。这些结构独特三萜苷类的药理活性及其对酸枣仁临床应用相关功效的贡献, 尚需累积样品后进行探究。

实验部分

收起

AUTOPOL V型旋光测定仪(美国Rudolph公司), Nicolet impact 5700型傅立叶变换红外光谱仪(美国Thermo Electron Corporation公司), JASCO V-650型紫外光谱仪、JASCO J-815型CD测定仪(日本JASCO公司), Bruker 500和Bruker 700型核磁共振仪(德国Bruker公司) 或SYS-600型核磁共振仪(美国Varian公司), Q Exactive Focus型质谱仪(美国Thermo Fisher Scientific公司), XtaLAB Synergy型单晶衍射仪(日本Rigaku公司), SSI-1500型高效液相色谱仪(美国Scientific Systems公司)。Sephadex LH-20 (瑞典Amersham Pharmacia公司), Toyopearl HW-40C和HW-40F凝胶树脂(日本TOSOH公司), HP-20型大孔吸附树脂(日本Mitsubishi Chemical公司), CHP 20P型MCI树脂(日本Mitsubishi Chemical公司), MGII C18半制备色谱柱(日本大曹株式会社), 柱色谱硅胶(200~300目) 及薄层色谱用硅胶GF₂₅₄ (青岛海洋化工厂生产)。色谱甲醇和色谱乙腈(美国Honeywell公司), 其他试剂若无特别说明, 均购自北京市通广精细化工公司, 级别为分析纯或色谱纯。

酸枣仁购于河北安国药材市场, 于2016年8月从河北省内丘县采集, 由中国医学科学院药物研究所马林副研究员鉴定为酸枣Ziziphus jujuba var. spinosa的种子, 生药样本保存于中国医学科学院药物研究所药用植物标本室(标本号: ID-S-2752)。

1 提取与分离

将干燥的酸枣仁(97 kg) 粉碎以后, 用水煎煮30 min (3×300 L), 将水提物过滤、合并, 减压浓缩至120 L。浓缩液用HP-20大孔吸附树脂柱色谱分离, 依次用水、50%乙醇和95%乙醇洗脱。洗脱液分别减压浓缩溶剂得到相应的流分A~C。50%乙醇洗脱部分即组分B (1.6 kg) 再用CHP 20P型MCI树脂柱色谱分离, 依次用水、30%乙醇、50%乙醇和95%乙醇洗脱, 得到组分B1~B4。其中, B3 (110 g) 经Sephadex LH-20凝胶柱色谱分离, 以甲醇和水为洗脱剂, 梯度洗脱, 经薄层色谱检测, 合并成分相同流分, 浓缩溶剂后, 得到子流分B3-1~B3-23。B3-5 (4.82 g) 用Toyopearl HW-40C凝胶柱色谱分离, 依次用50%甲醇和95%乙醇洗脱, 得到B3-5-1~B3-5-12。B3-5-2 (160.2 mg) 用Sephadex LH-20凝胶柱色谱, 以甲醇和水为洗脱剂, 梯度洗脱, 得到B3-5-2-1~B3-5-2-10; 其中, B3-5-2-5 (54 mg) 经制备薄层色谱(乙酸乙酯-乙醇-水4:2:1) 分离得到B3-5-2-5-1~B3-5-2-5-4。B3-5-2-5-3经反相半制备HPLC分离(MGII C18色谱柱, 55%甲醇, 2.0 mL·min^-1) 得到1 (t_R = 30.3 min, 3.8 mg)。B3-5-2-6 (84 mg) 经制备薄层色谱(乙酸乙酯-乙醇-水8:2:1) 分离得到B3-5-2-6-1~B3-5-2-6-6; 其中, B3-5-2-6-2经反相半制备HPLC (MGII C18色谱柱, 55%甲醇, 2.0 mL·min^-1) 分离得到2 (t_R = 35.6 min, 3.2 mg), B3-5-2-6-3经反相半制备HPLC (MGII C18色谱柱, 55%甲醇, 2.0 mL·min^-1) 分离得到5 (t_R = 45.1 min, 7.7 mg)。B3-7 (2.5 g) 经Toyopearl HW-40F凝胶柱色谱分离, 依次用50%甲醇和95%乙醇洗脱, 得到B3-7-1~B3-7-12, B3-7-11 (416 mg) 用Sephadex LH-20凝胶柱色谱, 以甲醇和水为洗脱剂梯度洗脱, 得到B3-7-11-1~B3-7-11-13, 其中B3-7-11-12 (64.7 mg) 经反相半制备HPLC (MGII C18色谱柱, 50%甲醇, 2.0 mL·min^-1) 分离得到3 (t_R = 56.3 min, 4.4 mg)。组分C (112 g) 经硅胶柱色谱分离, 用石油醚-二氯甲烷-甲醇(1:1:0~0:0:1) 洗脱, 得到C1~C10。其中, C4 (24 g)经硅胶柱色谱分离, 用二氯甲烷-甲醇梯度洗脱, 根据薄层色谱检测, 合并相同组分, 得到亚组分C4-1~C4-4。C4-3 (4.0 g) 经Sephadex LH-20凝胶柱色谱分离, 以石油醚-二氯甲烷-甲醇(5:5:1) 为洗脱剂, 得到C4-3-1~C4-3-15; C4-3-9 (44.8 mg) 经制备薄层色谱(石油醚-乙酸乙酯, 2:1), 得到C4-3-9-1~C4-3-9-3; 其中, C4-3-9-1 (16.7 mg) 经反相半制备HPLC (MGII C18色谱柱, 90%甲醇, 2.0 mL·min^-1) 分离得到10 (t_R = 30.4 min, 7.9 mg); C4-3-11 (93.5 mg) 经制备薄层色谱(二氯甲烷-丙酮3:1) 得到C4-3-11-1和C4-3-11-2, C4-3-11-1 (6.7 mg) 再经反相半制备HPLC (MGII C18色谱柱, 80%甲醇, 2.0 mL·min^-1) 分离得到9 (t_R = 25.2 min, 3.7 mg)。C8 (8.0 g) 经硅胶柱色谱分离, 用二氯甲烷-甲醇-水(20:10:1) 洗脱, 得到C8-1~C8-5。C8-4经反相半制备HPLC (MGII C18色谱柱, 60%甲醇, 2.0 mL·min^-1) 分离得到4 (t_R = 25.2 min, 8.1 mg)、6 (t_R = 31.2 min, 18.8 mg)、7 (t_R = 55.2 min, 7.4 mg) 和8 (t_R = 65.7 min, 7.8 mg)。

2 结构鉴定

化合物1: 无色结晶, mp 245.6~248.3 ℃; [α]$ {}_{\mathrm{D}}^{20} $ +2.12 (c 0.38, MeOH); UV (MeOH) λ_max (log ε) 203 (3.10), 254.4 (2.44) nm; CD (MeOH): 200 (Δε +11.16) nm; IR ν_max 3 365, 2 943, 2 873, 1 747, 1 695, 1 645, 1 544, 1 455, 1 377, 1 262, 1 077, 1 031, 888, 802 cm^-1; ¹H NMR (pyridine-d₅, 600 MHz)、¹³C NMR (pyridine-d₅, 175 MHz) 数据见表 1和2。(+)-HR-ESI-MS m/z 995.480 7 [M+Na]⁺ (C₄₈H₇₆O₂₀Na计算值, 995.482 2)。单晶X-射线衍射数据: C₄₈H₇₆O₂₀, 单斜晶系(monoclinic), a =14.532 6 (2) Å, b = 12.122 5 (10) Å, c = 16.760 5 (2) Å, α = 90°, β = 111°, γ = 90°, V = 2 754.76 (6) Å³, ρ = 1.258 g·cm^-3, space group P2₁, T = 293 (2) K, Z = 2, μ(Cu Kα) = 0.847 mm^-1, Cu Kα(λ = 1.541 84)。收集55 528个衍射数据(reflections collected), 其中11 317个独立衍射数据(independent reflections); R₁ = 0.044 [I > 2σ(I)], wR₂ = 0.123 9 [I > 2σ(I)]; R₁ = 0.045 8 (all data), wR₂ = 0.126 1 (all data); F² = 1.032, Flack parameter = -0.01 (4)。CCDC: 2234256。

化合物2: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -18.9 (c 0.32, MeOH); UV (MeOH) λ_max (log ε) 203.6 (3.33), 267.6 (2.26) nm; CD (MeOH): 200.0 (Δε +6.64) nm; IR ν_max 3 338, 2 961, 2 924, 2 854, 1 456, 1 374, 1 260, 1 075, 1 033, 991, 801 cm^-1; ¹H NMR (pyridine-d₅, 600 MHz)、¹³C NMR (pyridine-d₅, 175 MHz) 数据见表 1和2。(-)-HR-ESI-MS m/z 1 205.592 7 [M-H]^- (C₅₈H₉₃O₂₆计算值, 1 205.596 1)。

化合物3: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -40.8 (c 0.44, MeOH); UV (MeOH) λ_max (log ε) 205.8 (4.21), 254.8 (3.03) nm; CD (MeOH): 211.0 (Δε -1.83) nm; IR ν_max 3 384, 2 932, 1 675, 1 459, 1 376, 1 306, 1 205, 1 134, 1 071, 1 042, 987, 909 cm^-1; ¹H NMR (pyridine-d₅, 600 MHz)、¹³C NMR (pyridine-d₅, 175 MHz) 数据见表 1和2。(+)-HR-ESI-MS m/z 1 207.610 4 [M+H]⁺ (C₅₈H₉₅O₂₆计算值, 1 207.610 6)。

化合物4: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -31.2 (c 0.81, MeOH); UV (MeOH) λ_max (log ε) 203.6 (3.83), 275.4(2.54) nm; CD (MeOH): 203.5 (Δε -0.78) nm; IR ν_max 3 369, 2 941, 2 858, 1 644, 1 568, 1 452, 1 421, 1 374, 1 288, 1 262, 1 213, 1 136, 1 077, 1 043, 1 030, 980 cm^-1; ¹H NMR (methanol-d₄, 600 MHz) 数据见表 1和2; ¹³C NMR (methanol-d₄, 150 MHz) 数据见表 1和2。(+)-HR-ESI-MS m/z 1 191.617 7 [M+H]⁺ (C₅₈H₉₅O₂₅计算值, 1 191.615 7)。

化合物5: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -33.1 (c 0.77, MeOH); UV (MeOH) λ_max (log ε) 203.0 (3.06), 254.6 (2.03) nm; CD (MeOH): 200.0 (Δε -6.76) nm; IR ν_max 3 370, 2 945, 2 915, 2 834, 1 647, 1 449, 1 374, 1 288, 1 212, 1 077, 1 029, 981 cm^-1; ¹H NMR (methanol-d₄, 600 MHz)、¹³C NMR (methanol-d₄, 150 MHz)数据见表 3和4。(-)-HR-ESI-MS m/z 1 205.592 7 [M-H]^- (C₅₈H₉₃O₂₆计算值, 1 205.596 1)。

化合物6: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -43.4 (c 1.88, MeOH); UV (MeOH) λ_max (log ε) 202.6 (3.93) nm; CD (MeOH): 200.0 (Δε -2.57) nm; IR ν_max 3 387, 2 943, 2 907, 2 866, 1 641, 1 566, 1 449, 1 390, 1 374, 1 288, 1 260, 1 212, 1 138, 1 075, 1 039, 980, 837, 788 cm^-1; ¹H NMR (methanol-d₄, 600 MHz)、¹³C NMR (methanol-d₄, 150 MHz) 数据见表 3和4。(+)-HR-ESI-MS m/z 1 045.558 0 [M+H]⁺ (C₅₂H₈₅O₂₁计算值, 1 045.557 8)。

化合物7: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -36.8 (c 0.74, MeOH); UV (MeOH) λ_max (log ε) 203.2 (3.72), 270.8 (2.66) nm; CD (MeOH): 200.0 (Δε -0.53) nm; IR ν_max 3 384, 2 943, 2 913, 1 636, 1 448, 1 389, 1 374, 1 288, 1 260, 1 213, 1 136, 1 073, 1 044, 1 027, 981, 785 cm^-1; ¹H NMR (methanol-d₄, 600 MHz)、¹³C NMR (methanol-d₄, 150 MHz) 数据见表 3和4。(+)-HRESIMS m/z 1 075.569 1 [M+H]⁺ (C₅₃H₈₇O₂₂计算值, 1 075.568 4)。

化合物8: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -16.6 (c 0.78, MeOH); UV (MeOH) λ_max (log ε) 203.4 (3.14), 269.4 (2.31) nm; IR ν_max 3 386, 2 963, 2 926, 2 858, 1 450, 1 369, 1 300, 1 261, 1 214, 1 073, 1 040, 987, 802 cm^-1; ¹H NMR (methanol-d₄, 600 MHz)、¹³C NMR (methanol-d₄, 150 MHz) 数据见表 3和4。(-)-HR-ESI-MS m/z 1 043.540 9 [M-H]^- (C₂₃H₃₃O₅计算值, 1 043.542 1)。

化合物9: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ -2.74 (c 0.16, MeOH); UV (MeOH) λ_max (log ε) 203.6 (3.33) nm; CD (MeOH): 200 (Δε +5.75) nm; IR ν_max 2 942, 2 869, 1 686, 1 639, 1 450, 1 388, 1 236, 1 193, 1 138, 1 107, 1 044, 1 010, 984, 945, 883, 793 cm^-1; ¹H NMR (methanol-d₄, 500 MHz)、¹³C NMR (methanol-d₄, 125 MHz) 数据见表 5。(+)-HR-ESI-MS m/z 473.362 8 [M+H]⁺ (C₃₀H₄₉O₄计算值, 473.362 5)。

化合物10: 白色粉末; [α]$ {}_{\mathrm{D}}^{20} $ +0.18 (c 0.94, MeOH); UV (MeOH) λ_max (log ε) 203.8 (3.26) nm; CD (MeOH): 200.0 (Δε +5.75) nm; IR ν_max 2 940, 2 868, 1 686, 1 640, 1 448, 1 376, 1 237, 1 136, 1 044, 883, 797 cm^-1; ¹H NMR (DMSO-d₆, 500 MHz)、¹³C NMR (DMSO-d₆, 125 MHz)数据见表 5。(-)-HR-ESI-MS m/z 455.352 9 [M-H]^- (C₃₀H₄₇O₃计算值, 455.353 1)。

3 化合物1~4的水解

分别取化合物1~4 (约3.0~5.0 mg) 与5 mol·L^-1盐酸水溶液(各2.0 mL) 在90 ℃下加热水解3 h。减压蒸干溶剂后将反应物溶解在1 mL水中, 用等体积乙酸乙酯萃取3次, 浓缩水层得到糖部分。将1~4各自水解得到的糖与对照品(L-阿拉伯糖、D-木糖、L-鼠李糖和D-葡萄糖) 共薄层比对, 展开剂为异丙醇-水-氨水(60:30:2.4), 结果显示1的水解物质中只含有与D-葡萄糖对照品R_f值一致的成分, 而2~4的水解物中均含有与L-阿拉伯糖、D-木糖、L-鼠李糖和D-葡萄糖对照品R_f值一致的糖。另外, 将1~4分别水解得到的糖部分以及对照品D-和L-型阿拉伯糖、木糖、鼠李糖和葡萄糖(各2 mg) 溶解在无水吡啶(1.2 mL) 中, 加入4.0 mg L-半胱氨酸甲酯盐酸盐, 加热到60 ℃, 持续2 h。将反应混合物蒸干至无吡啶味, 加入1.0 mL N-三甲基硅咪唑, 并再加热至60 ℃持续2 h。向反应混合物加入2 mL水并用等体积正己烷萃取3次, 合并萃取液浓缩得到糖的噻唑三甲基硅醚化衍生物。再用1 mL正己烷溶解后, 进行气相色谱分析。分析条件: FID检测器温度300 ℃, 起始温度200 ℃, 以10 ℃·min^-1的速率程序升温至280 ℃, 并且维持35 min; 载气: N₂。结果显示, 1水解得到糖衍生物的保留时间与D-葡萄糖衍生物的一致, 2~4水解得到糖衍生物的保留时间均与L-阿拉伯糖、D-木糖、L-鼠李糖和D-葡萄糖衍生物的一致。

作者贡献: 石建功负责实验设计、数据分析及稿件修订; 朱承根和郭庆兰负责实验指导、数据核实及稿件修改; 郝文飒负责实验实施及初稿撰写; 雷小强和徐成博协助实施部分实验。

利益冲突: 作者声明无利益冲突。

基金

收起

国家自然科学基金资助项目(82293681)
国家自然科学基金资助项目(82293685)
国家自然科学基金资助项目(82293680)
中国医学科学院医学与健康科技创新工程项目(2022-I2M-JB-011)
中国医学科学院医学与健康科技创新工程项目(2021-I2M-1-028)

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2023年第58卷第9期

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doi: 10.16438/j.0513-4870.2023-0026

接收时间：2023-01-10
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出版时间：2023-09-12

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收稿日期：2023-01-10
修回日期：2023-02-06

基金

国家自然科学基金资助项目(82293681)

国家自然科学基金资助项目(82293685)

国家自然科学基金资助项目(82293680)

中国医学科学院医学与健康科技创新工程项目(2022-I2M-JB-011)

中国医学科学院医学与健康科技创新工程项目(2021-I2M-1-028)

作者信息

中国医学科学院、北京协和医学院药物研究所, 天然药物活性物质与功能国家重点实验室, 北京 100050

通讯作者:

*郭庆兰, Tel: 86-10-83154789, Fax: 86-10-63017757, E-mail: guonina@imm.ac.cn;

石建功, Tel: 86-10-63025166, Fax: 86-10-63017757, E-mail: shijg@imm.ac.cn

参考文献

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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No.	1		2		3		4
1a	3.20 s	67.4		1.52 m	39.2		1.50 m	39.1	1.68 m	40.1
1b			0.77 brt (11.4)		0.71 brt (11.4)		0.94 m
2a		178.2	1.98 m	26.8	1.98 m	26.8	1.85 m	27.4
2b			1.78 m		1.76 m		1.67 m
3	4.82 s	85.1	3.12 dd (11.4, 4.2)	88.7	3.09 dd (11.4, 4.2)	88.7	3.10 dd (12.0, 4.8)	90.0
4		44.2		40.0		40.0		40.6
5	2.17 dd (12.0, 3.0)	57.5	0.63 dd (12.0, 2.4)	56.5	0.61 dd (12.0, 2.4)	56.4	0.74 dd (10.8, 3.0)	57.7
6a	1.62 m	19.4	1.38 m	18.6	1.40 m	18.6	1.58 m	19.1
6b	1.42 m		1.28 m		1.30 m		1.55 m
7a	1.72 dt (12.0, 3.0)	35.2	1.52 m	36.2	1.51 m	36.4	1.54 m	36.9
7b	1.52 dt (3.0, 12.0)		1.35 m		1.38 m		1.47 m
8		42.6		37.7		37.5		38.5
9	2.22 dd (12.6, 2.4)	45.4	0.84 dd (12.6, 3.0)	53.2	0.85 dd (12.6, 3.0)	52.9	0.89 m	54.2
10		49.9		37.4		37.4		38.3
11a	2.07 m	24.4	1.53 m	21.9	1.50 m	21.6	1.65 m	22.5
11b	1.57 m		1.31 m		1.30 m		1.50 m
12a	1.94 dd (12.6, 3.6)	26.5	1.96 m	28.8	2.16 m	26.3	1.86 m	29.2
12b	1.30 dt (3.6, 12.6)		1.80 m		1.81 m		1.68 m
13	2.78 dt (3.6, 12.6)	38.9	2.70 m	38.6	2.76 brd (12.6)	41.9	2.48 m	38.0
14		43.8		53.6		54.5		54.6
15a	2.09 m	31.8	2.22 d (8.4)	40.2	1.81 d (9.0)	40.7	2.06 d (8.4)	37.1
15b	1.33 m		1.91 d (8.4)		1.52 d (9.0)		1.18 d (8.4)
16a	3.06 m	32.2		110.3		108.3		111.4
16b	1.52 m
17		57.3	1.69 d (7.2)	53.9		134.9	1.00 d (7.2)	54.4
18	1.67 t (12.6)	50.2	1.02 s	18.9	1.00 s	19.2	1.14 s	19.2
19	3.33 dt (4.8, 12.6)	47.6	0.71 s	16.7	0.75 s	16.7	0.88 s	16.9
20		151.7		69.2		124.4		69.4
21a	2.04 m	31.2	1.43 s	29.9	1.70 brs	18.9	1.14 s	29.6
21b	1.32 m
22a	2.18 m	37.0	2.14 dd (14.4, 10.8)	47.0	2.25 m	37.3	1.47 dd (11.4, 2.4)	45.4
22b	1.43 m		1.97 dd (14.4, 5.4)		1.98 m		1.38 dd (14.4, 11.4)
23	1.41 s	31.9	5.03 m	69.0	4.44 m	73.5	4.68 m	69.7
24a	1.22 s	20.7	5.43 brd (7.8)	127.2	2.30 dd (14.4, 7.8)	49.3	5.16 brd (8.4)	126.3
24b					1.85 dd (14.4, 3.6)
25	1.39 s	19.2		135.6		69.8		136.7
26	1.36 s	17.7	1.63 s	25.9	1.51 s	30.7	1.72 brs	25.7
27	1.07 s	15.5	1.71 s	18.7	1.48 s	31.4	1.68 brs	18.4
28		175.3	1.14 s	28.4	1.13 s	28.4	1.01 s	28.5
29a	4.82 brs	109.8	1.10 s	17.3	1.11 s	17.3	0.87 s	17.3
29b	4.63 brs
30a	1.61 s	19.8	4.29 brs	66.2	4.20 brs	66.2	4.02 d (7.8)	66.9
30b							3.93 d (7.8)

No.

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

3.20 s

67.4

1.52 m

39.2

1.50 m

39.1

1.68 m

40.1

0.77 brt (11.4)

0.71 brt (11.4)

0.94 m

178.2

1.98 m

26.8

1.98 m

26.8

1.85 m

27.4

1.78 m

1.76 m

1.67 m

4.82 s

85.1

3.12 dd (11.4, 4.2)

88.7

3.09 dd (11.4, 4.2)

88.7

3.10 dd (12.0, 4.8)

90.0

44.2

40.0

40.6

2.17 dd (12.0, 3.0)

57.5

0.63 dd (12.0, 2.4)

56.5

0.61 dd (12.0, 2.4)

56.4

0.74 dd (10.8, 3.0)

57.7

1.62 m

19.4

1.38 m

18.6

1.40 m

18.6

1.58 m

19.1

1.42 m

1.28 m

1.30 m

1.55 m

1.72 dt (12.0, 3.0)

35.2

1.52 m

36.2

1.51 m

36.4

1.54 m

36.9

1.52 dt (3.0, 12.0)

1.35 m

1.38 m

1.47 m

42.6

37.7

37.5

38.5

2.22 dd (12.6, 2.4)

45.4

0.84 dd (12.6, 3.0)

53.2

0.85 dd (12.6, 3.0)

52.9

0.89 m

54.2

49.9

37.4

38.3

11a

2.07 m

24.4

1.53 m

21.9

1.50 m

21.6

1.65 m

22.5

11b

1.57 m

1.31 m

1.30 m

1.50 m

12a

1.94 dd (12.6, 3.6)

26.5

1.96 m

28.8

2.16 m

26.3

1.86 m

29.2

12b

1.30 dt (3.6, 12.6)

1.80 m

1.81 m

1.68 m

2.78 dt (3.6, 12.6)

38.9

2.70 m

38.6

2.76 brd (12.6)

41.9

2.48 m

38.0

43.8

53.6

54.5

54.6

15a

2.09 m

31.8

2.22 d (8.4)

40.2

1.81 d (9.0)

40.7

2.06 d (8.4)

37.1

15b

1.33 m

1.91 d (8.4)

1.52 d (9.0)

1.18 d (8.4)

16a

3.06 m

32.2

110.3

108.3

111.4

16b

1.52 m

57.3

1.69 d (7.2)

53.9

134.9

1.00 d (7.2)

54.4

1.67 t (12.6)

50.2

1.02 s

18.9

1.00 s

19.2

1.14 s

19.2

3.33 dt (4.8, 12.6)

47.6

0.71 s

16.7

0.75 s

16.7

0.88 s

16.9

151.7

69.2

124.4

69.4

21a

2.04 m

31.2

1.43 s

29.9

1.70 brs

18.9

1.14 s

29.6

21b

1.32 m

22a

2.18 m

37.0

2.14 dd (14.4, 10.8)

47.0

2.25 m

37.3

1.47 dd (11.4, 2.4)

45.4

22b

1.43 m

1.97 dd (14.4, 5.4)

1.98 m

1.38 dd (14.4, 11.4)

1.41 s

31.9

5.03 m

69.0

4.44 m

73.5

4.68 m

69.7

24a

1.22 s

20.7

5.43 brd (7.8)

127.2

2.30 dd (14.4, 7.8)

49.3

5.16 brd (8.4)

126.3

24b

1.85 dd (14.4, 3.6)

1.39 s

19.2

135.6

69.8

136.7

1.36 s

17.7

1.63 s

25.9

1.51 s

30.7

1.72 brs

25.7

1.07 s

15.5

1.71 s

18.7

1.48 s

31.4

1.68 brs

18.4

175.3

1.14 s

28.4

1.13 s

28.4

1.01 s

28.5

29a

4.82 brs

109.8

1.10 s

17.3

1.11 s

17.3

0.87 s

17.3

29b

4.63 brs

30a

1.61 s

19.8

4.29 brs

66.2

4.20 brs

66.2

4.02 d (7.8)

66.9

30b

3.93 d (7.8)

No.	1		2		3		4
1′	6.38 d (8.4)	94.5		4.93 d (4.2)	104.4		4.92 d (4.2)	104.4	4.36 d (6.6)	106.1
2′	4.35 dd (9.0, 8.4)	79.8	4.78 dd (9.0, 4.2)	75.4	4.78 dd (9.0, 4.2)	75.5	3.94 dd (8.4, 6.6)	74.3
3′	4.66 t (9.0)	78.6	4.37 dd (9.0, 4.2)	83.3	4.36 dd (9.0, 4.2)	83.4	3.85 dd (8.4, 3.0)	83.5
4′	4.29 t (9.0)	70.3	4.52 m	68.3	4.50 m	68.2	4.02 m	70.3
5′a	4.02 m	79.8	4.36 dd (11.4, 6.6)	63.7	4.35 dd (11.4, 6.6)	63.7	3.83 m	66.1
5′b			3.97 dd (11.4, 3.0)		3.96 dd (11.4, 3.0)		3.52 m
6′a	4.39 dd (12.6, 3.0)	62.2
6′b	4.34 dd (12.6, 2.4)
1′′	5.79 d (7.8)	102.7	5.00 d (7.8)	104.3	4.99 d (7.2)	104.4	4.60 d (7.2)	103.4
2′′	4.20 dd (9.6, 7.8)	85.7	4.14 dd (8.4, 7.8)	83.5	4.14 dd (9.0, 7.2)	84.3	3.58 dd (9.0, 7.2)	81.6
3′′	4.38 dd (9.6, 9.0)	77.4	4.26 dd (9.0, 8.4)	78.6	4.26 dd (9.6, 9.0)	78.6	3.59 t (9.0)	78.6
4′′	4.15 t (9.0)	72.6	3.84 t (9.0)	71.8	3.84 t (9.6)	71.9	3.33 t (9.0)	71.2
5′′	3.97 m	78.3	4.07 m	76.9	4.07 m	77.0	3.31 m	78.1
6′′a	4.62 brd (12.6)	63.7	4.90 dd (10.8, 1.8)	70.7	4.90 dd (10.8, 1.8)	70.7	3.86 dd (12.0, 3.0)	62.4
6′′b	4.32 dd (12.6, 4.8)		3.94 dd (10.8, 7.2)		3.94 dd (10.8, 8.4)		3.67 dd (12.0, 6.0)
1′′′	5.39 d (7.8)	105.9	5.38 d (7.2)	106.8	5.38 d (7.0)	106.9	4.80 d (7.2)	105.1
2′′′	4.10 dd (9.0, 7.8)	76.9	4.20 dd (9.0, 7.2)	76.6	4.20 dd (9.0, 7.0)	76.7	3.35 dd (9.0, 7.2)	75.3
3′′′	4.25 t (9.0)	78.2	4.18 t (9.0)	78.4	4.19 t (9.0)	78.4	3.31 t (9.0)	77.8
4′′′	4.15 t (9.0)	71.9	4.22 m	71.2	4.22 m	71.2	3.53 m	71.0
5′′′a	4.04 m	79.5	4.51 dd (12.0, 5.4)	68.2	4.53 dd (12.0, 5.4)	68.3	3.93 dd (12.0, 5.4)	67.5
5′′′b			3.82 dd (12.0, 10.2)		3.82 dd (12.0, 10.2)		3.22 dd (12.0, 9.6)
6′′′a	4.62 brd (12.0)	63.1
6′′′b	4.28 dd (12.0, 6.6)
1′′′′			5.96 brs	102.0	5.95 brs	102.0	5.41 brd (1.8)	100.7
2′′′′			4.66 brd (3.0)	72.7	4.65 brd (3.6)	72.8	3.82 dd (3.0, 1.8)	72.8
3′′′′			4.55 dd (9.6, 3.0)	72.9	4.55 dd (9.6, 3.6)	72.9	3.83 dd (9.0, 3.0)	73.0
4′′′′			4.32 t (9.6)	74.3	4.31 t (9.6)	74.3	3.53 t (9.0)	81.0
5′′′′			4.54 m	70.4	4.54 m	70.5	4.14 m	68.0
6′′′′			1.66 d (6.0)	19.0	1.66 d (6.6)	18.9	1.23 d (6.6)	17.0
1′′′′′			4.90 d (7.8)	105.6	4.90 d (8.4)	105.6	5.19 brd (1.8)	103.2
2′′′′′			4.07 dd (9.0, 7.8)	75.7	4.07 t (8.4)	75.8	3.95 dd (3.0, 1.8)	72.4
3′′′′′			4.24 t (9.0)	78.4	4.23 dd (9.0, 8.4)	78.4	3.64 dd (9.0, 3.0)	72.4
4′′′′′			4.28 t (9.0)	71.8	4.28 t (9.0)	71.8	3.39 t (9.0)	73.9
5′′′′′			3.91 m	78.8	3.91 m	78.9	3.70 m	70.3
6′′′′′a			4.51 dd (12.0, 2.4)	62.9	4.51 dd (12.0, 3.0)	62.9	1.24 d (6.0)	18.6
6′′′′′b			4.39 dd (12.0, 5.4)		4.38 dd (12.0, 5.4)

No.

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

1′

6.38 d (8.4)

94.5

4.93 d (4.2)

104.4

4.92 d (4.2)

104.4

4.36 d (6.6)

106.1

2′

4.35 dd (9.0, 8.4)

79.8

4.78 dd (9.0, 4.2)

75.4

4.78 dd (9.0, 4.2)

75.5

3.94 dd (8.4, 6.6)

74.3

3′

4.66 t (9.0)

78.6

4.37 dd (9.0, 4.2)

83.3

4.36 dd (9.0, 4.2)

83.4

3.85 dd (8.4, 3.0)

83.5

4′

4.29 t (9.0)

70.3

4.52 m

68.3

4.50 m

68.2

4.02 m

70.3

5′a

4.02 m

79.8

4.36 dd (11.4, 6.6)

63.7

4.35 dd (11.4, 6.6)

63.7

3.83 m

66.1

5′b

3.97 dd (11.4, 3.0)

3.96 dd (11.4, 3.0)

3.52 m

6′a

4.39 dd (12.6, 3.0)

62.2

6′b

4.34 dd (12.6, 2.4)

1′′

5.79 d (7.8)

102.7

5.00 d (7.8)

104.3

4.99 d (7.2)

104.4

4.60 d (7.2)

103.4

2′′

4.20 dd (9.6, 7.8)

85.7

4.14 dd (8.4, 7.8)

83.5

4.14 dd (9.0, 7.2)

84.3

3.58 dd (9.0, 7.2)

81.6

3′′

4.38 dd (9.6, 9.0)

77.4

4.26 dd (9.0, 8.4)

78.6

4.26 dd (9.6, 9.0)

78.6

3.59 t (9.0)

78.6

4′′

4.15 t (9.0)

72.6

3.84 t (9.0)

71.8

3.84 t (9.6)

71.9

3.33 t (9.0)

71.2

5′′

3.97 m

78.3

4.07 m

76.9

4.07 m

77.0

3.31 m

78.1

6′′a

4.62 brd (12.6)

63.7

4.90 dd (10.8, 1.8)

70.7

4.90 dd (10.8, 1.8)

70.7

3.86 dd (12.0, 3.0)

62.4

6′′b

4.32 dd (12.6, 4.8)

3.94 dd (10.8, 7.2)

3.94 dd (10.8, 8.4)

3.67 dd (12.0, 6.0)

1′′′

5.39 d (7.8)

105.9

5.38 d (7.2)

106.8

5.38 d (7.0)

106.9

4.80 d (7.2)

105.1

2′′′

4.10 dd (9.0, 7.8)

76.9

4.20 dd (9.0, 7.2)

76.6

4.20 dd (9.0, 7.0)

76.7

3.35 dd (9.0, 7.2)

75.3

3′′′

4.25 t (9.0)

78.2

4.18 t (9.0)

78.4

4.19 t (9.0)

78.4

3.31 t (9.0)

77.8

4′′′

4.15 t (9.0)

71.9

4.22 m

71.2

4.22 m

71.2

3.53 m

71.0

5′′′a

4.04 m

79.5

4.51 dd (12.0, 5.4)

68.2

4.53 dd (12.0, 5.4)

68.3

3.93 dd (12.0, 5.4)

67.5

5′′′b

3.82 dd (12.0, 10.2)

3.22 dd (12.0, 9.6)

6′′′a

4.62 brd (12.0)

63.1

6′′′b

4.28 dd (12.0, 6.6)

1′′′′

5.96 brs

102.0

5.95 brs

102.0

5.41 brd (1.8)

100.7

2′′′′

4.66 brd (3.0)

72.7

4.65 brd (3.6)

72.8

3.82 dd (3.0, 1.8)

72.8

3′′′′

4.55 dd (9.6, 3.0)

72.9

4.55 dd (9.6, 3.6)

72.9

3.83 dd (9.0, 3.0)

73.0

4′′′′

4.32 t (9.6)

74.3

4.31 t (9.6)

74.3

3.53 t (9.0)

81.0

5′′′′

4.54 m

70.4

4.54 m

70.5

4.14 m

68.0

6′′′′

1.66 d (6.0)

19.0

1.66 d (6.6)

18.9

1.23 d (6.6)

17.0

1′′′′′

4.90 d (7.8)

105.6

4.90 d (8.4)

105.6

5.19 brd (1.8)

103.2

2′′′′′

4.07 dd (9.0, 7.8)

75.7

4.07 t (8.4)

75.8

3.95 dd (3.0, 1.8)

72.4

3′′′′′

4.24 t (9.0)

78.4

4.23 dd (9.0, 8.4)

78.4

3.64 dd (9.0, 3.0)

72.4

4′′′′′

4.28 t (9.0)

71.8

4.28 t (9.0)

71.8

3.39 t (9.0)

73.9

5′′′′′

3.91 m

78.8

3.91 m

78.9

3.70 m

70.3

6′′′′′a

4.51 dd (12.0, 2.4)

62.9

4.51 dd (12.0, 3.0)

62.9

1.24 d (6.0)

18.6

6′′′′′b

4.39 dd (12.0, 5.4)

4.38 dd (12.0, 5.4)

No.	5		6		7		8
1a	1.70 m	39.9		1.69 m	40.0		1.70 m	40.0	1.71 m	40.0
1b	0.95 dt (3.0, 13.8)		0.94 dt (3.0, 13.8)		0.94 dt (3.6, 13.8)		0.95 dt (3.0, 13.8)
2a	1.85 m	27.2	1.83 m	27.2	1.83 m	27.3	1.82 m	27.2
2b	1.72 m		1.70 m		1.69 m		1.69 m
3	3.07 dd (11.4, 4.2)	89.8	3.08 dd (11.4, 4.2)	89.7	3.11 dd (11.4, 4.2)	89.7	3.09 dd (11.4, 4.2)	89.7
4		40.6		40.5		40.5		40.5
5	0.75 brd (11.4)	57.5	0.74 brd (10.8)	57.5	0.74 brd (11.4)	57.5	0.75 brd (11.4)	57.5
6a	1.58 m	19.2	1.57 m	19.2	1.58 m	19.1	1.58 m	19.1
6b	1.53 m		1.52 m		1.52 m		1.50 m
7a	1.56 m	36.9	1.55 m	36.9	1.64 m	36.9	1.59 m	36.8
7b	1.48 m		1.47 m		1.49 m		1.48 m
8		38.5		38.5		38.5		38.4
9	0.88 m	54.1	0.88 m	54.1	0.88 m	54.2	0.82 dd (12.6, 3.0)	54.0
10		38.3		38.3		38.3		38.2
11a	1.65 m	22.5	1.64 m	22.5	1.64 m	22.5	1.62 m	22.4
11b	1.50 m		1.50 m		1.49 m		1.47 m
12a	1.86 m	29.2	1.85 m	29.2	1.86 m	29.2	1.90 m	29.1
12b	1.69 m		1.68 m		1.69 m		1.68 m
13	2.49 m	38.0	2.48 m	38.1	2.49 m	38.1	2.36 m	38.4
14		54.6		54.6		54.6		54.0
15a	2.07 d (9.0)	37.1	2.06 d (8.4)	37.1	2.06 d (8.4)	37.1	1.71 d (9.0)	40.2
15b	1.19 d (9.0)		1.18 d (8.4)		1.19 d (8.4)		1.53 d (9.0)
16		111.4		111.4		111.4		111.5
17	1.01 d (7.2)	54.4	1.00 d (6.6)	54.4	1.00 d (7.2)	54.4	1.45 d (7.2)	54.0
18	1.15 s	19.2	1.14 s	19.2	1.14 s	19.2	1.12 s	19.1
19	0.90 s	16.9	0.89 s	16.9	0.85 s	16.8	0.89 s	16.9
20		69.4		69.4		69.4		70.2
21	1.15 s	29.6	1.14 s	29.6	1.14 s	29.6	1.18 s	28.9
22a	1.48 dd (13.8, 1.8)	45.4	1.47 dd (13.8, 1.8)	45.4	1.47 brd (13.8)	45.4	1.77 dd (14.4, 5.4)	46.5
22b	1.39 dd (13.8, 10.4)		1.38 dd (13.8, 10.4)		1.38 dd (13.8, 10.4)		1.68 dd (14.4, 10.4)
23	4.69 m	69.7	4.68 m	69.7	4.68 m	69.7	4.65 m	69.8
24	5.17 brd (8.4)	126.3	5.16 brd (8.4)	126.3	5.22 brd (8.4)	126.3	5.17 brd (8.4)	126.8
25		136.7		136.7		136.7		137.6
26	1.72 s	25.8	1.72 s	25.8	1.72 s	25.8	1.72 s	25.8
27	1.69 s	18.4	1.68 s	18.4	1.69 s	18.4	1.66 s	18.3
28	1.02 s	28.6	1.02 s	28.6	1.01 s	28.5	1.02 s	28.6
29	0.88 s	17.2	0.87 s	17.2	0.88 s	17.1	0.87 s	17.2
30a	4.04 d (7.8)	66.8	4.03 d (7.8)	66.9	4.03 d (7.8)	66.9	4.01 d (7.2)	66.9
30b	3.95 d (7.8)		3.94 d (7.8)		3.94 d (7.8)		3.99 d (7.2)

No.

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

1.70 m

39.9

1.69 m

40.0

1.70 m

40.0

1.71 m

40.0

0.95 dt (3.0, 13.8)

0.94 dt (3.0, 13.8)

0.94 dt (3.6, 13.8)

0.95 dt (3.0, 13.8)

1.85 m

27.2

1.83 m

27.2

1.83 m

27.3

1.82 m

27.2

1.72 m

1.70 m

1.69 m

3.07 dd (11.4, 4.2)

89.8

3.08 dd (11.4, 4.2)

89.7

3.11 dd (11.4, 4.2)

89.7

3.09 dd (11.4, 4.2)

89.7

40.6

40.5

0.75 brd (11.4)

57.5

0.74 brd (10.8)

57.5

0.74 brd (11.4)

57.5

0.75 brd (11.4)

57.5

1.58 m

19.2

1.57 m

19.2

1.58 m

19.1

1.58 m

19.1

1.53 m

1.52 m

1.50 m

1.56 m

36.9

1.55 m

36.9

1.64 m

36.9

1.59 m

36.8

1.48 m

1.47 m

1.49 m

1.48 m

38.5

38.4

0.88 m

54.1

0.88 m

54.1

0.88 m

54.2

0.82 dd (12.6, 3.0)

54.0

38.3

38.2

11a

1.65 m

22.5

1.64 m

22.5

1.64 m

22.5

1.62 m

22.4

11b

1.50 m

1.49 m

1.47 m

12a

1.86 m

29.2

1.85 m

29.2

1.86 m

29.2

1.90 m

29.1

12b

1.69 m

1.68 m

1.69 m

1.68 m

2.49 m

38.0

2.48 m

38.1

2.49 m

38.1

2.36 m

38.4

54.6

54.0

15a

2.07 d (9.0)

37.1

2.06 d (8.4)

37.1

2.06 d (8.4)

37.1

1.71 d (9.0)

40.2

15b

1.19 d (9.0)

1.18 d (8.4)

1.19 d (8.4)

1.53 d (9.0)

111.4

111.5

1.01 d (7.2)

54.4

1.00 d (6.6)

54.4

1.00 d (7.2)

54.4

1.45 d (7.2)

54.0

1.15 s

19.2

1.14 s

19.2

1.14 s

19.2

1.12 s

19.1

0.90 s

16.9

0.89 s

16.9

0.85 s

16.8

0.89 s

16.9

69.4

70.2

1.15 s

29.6

1.14 s

29.6

1.14 s

29.6

1.18 s

28.9

22a

1.48 dd (13.8, 1.8)

45.4

1.47 dd (13.8, 1.8)

45.4

1.47 brd (13.8)

45.4

1.77 dd (14.4, 5.4)

46.5

22b

1.39 dd (13.8, 10.4)

1.38 dd (13.8, 10.4)

1.68 dd (14.4, 10.4)

4.69 m

69.7

4.68 m

69.7

4.68 m

69.7

4.65 m

69.8

5.17 brd (8.4)

126.3

5.16 brd (8.4)

126.3

5.22 brd (8.4)

126.3

5.17 brd (8.4)

126.8

136.7

137.6

1.72 s

25.8

1.72 s

25.8

1.72 s

25.8

1.72 s

25.8

1.69 s

18.4

1.68 s

18.4

1.69 s

18.4

1.66 s

18.3

1.02 s

28.6

1.02 s

28.6

1.01 s

28.5

1.02 s

28.6

0.88 s

17.2

0.87 s

17.2

0.88 s

17.1

0.87 s

17.2

30a

4.04 d (7.8)

66.8

4.03 d (7.8)

66.9

4.03 d (7.8)

66.9

4.01 d (7.2)

66.9

30b

3.95 d (7.8)

3.94 d (7.8)

3.99 d (7.2)

No.	5		6		7		8
1′	4.50 d (4.8)	104.8		4.44 d (5.4)	105.3		4.46 d (5.4)	105.3	4.45 d (5.4)	105.3
2′	3.98 brd (4.8)	76.0	3.96 brd (5.4)	75.9	3.86 brd (5.4)	75.6	3.96 brd (5.4)	75.9
3′	3.95 m	82.3	3.89 m	81.9	3.88 m	82.9	3.90 m	81.8
4′	3.94 m	68.9	3.97 m	69.4	4.05 m	68.7	3.97 m	69.4
5′a	3.85 brd (10.8)	63.8	3.86 dd (12.0, 3.6)	64.8	3.87 brd (12.0)	65.0	3.86 dd (12.0, 2.4)	64.8
5′b	3.51 brd (10.8)		3.48 dd (12.0, 2.4)		3.54 brd (12.0)		3.48 dd (12.0, 2.4)
1′′	4.58 d (7.8)	103.6	4.61 d (7.2)	103.4	4.50 d (7.2)	104.2	4.61 d (7.2)	103.5
2′′	3.54 dd (9.0, 7.8)	82.7	3.54 dd (9.0, 7.2)	82.4	3.31 dd (9.0, 7.2)	75.1	3.54 dd (8.4, 7.2)	82.4
3′′	3.60 t (9.0)	78.1	3.59 t (9.0)	78.4	3.36 t (9.0)	78.0	3.59 t (8.4)	78.4
4′′	3.31 t (9.0)	71.7	3.34 t (9.0)	71.3	3.27 t (9.0)	71.6	3.34 dd (9.0, 8.4)	71.3
5′′	3.55 m	76.8	3.32 m	78.1	3.52 m	77.0	3.32 m	78.2
6′′a	4.22 dd (10.8, 2.4)	70.5	3.87 dd (12.0, 2.4)	62.5	4.16 dd (11.4, 2.4)	70.2	3.87 dd (12.0, 2.4)	62.5
6′′b	3.65 dd (10.8, 8.4)		3.65 dd (12.0, 5.4)		3.73 dd (11.4, 7.8)		3.65 dd (12.0, 5.4)
1′′′	4.69 d (7.2)	105.8	4.73 d (7.2)	105.6	4.35 d (7.8)	104.8	4.73 d (7.8)	105.6
2′′′	3.32 dd (9.0, 7.2)	75.7	3.33 dd (9.0, 7.2)	75.5	3.20 dd (9.0, 7.8)	75.1	3.33 dd (9.0, 7.2)	75.5
3′′′	3.33 t (9.0)	77.6	3.32 t (9.0)	77.7	3.34 t (9.0)	78.0	3.32 t (9.0)	77.7
4′′′	3.54 m	70.9	3.53 m	71.0	3.32 t (9.0)	71.6	3.53 m	71.0
5′′′a	3.93 dd (11.4, 5.4)	67.6	3.93 dd (11.4, 5.4)	67.5	3.26 m	78.0	3.93 dd (11.4, 5.4)	67.5
5′′′b	3.25 t (11.4)		3.22 t (11.4)				3.22 t (11.4)
6′′′a					3.93 dd (12.0, 3.6)	62.7
6′′′b					3.66 dd (12.0, 4.2)
1′′′′	5.15 brs	101.8	5.20 brs	101.8	5.22 brs	102.0	5.20 brs	101.8
2′′′′	3.89 brd (2.4)	72.1	3.90 brd (3.0)	72.1	3.93 brd (2.4)	72.1	3.90 brd (3.0)	72.1
3′′′′	3.68 dd (9.6, 2.4)	72.1	3.68 dd (9.6, 3.0)	72.2	3.72 dd (9.0, 3.6)	72.1	3.68 dd (9.6, 3.0)	72.2
4′′′′	3.41 t (9.6)	73.9	3.40 t (9.6)	73.9	3.39 t (9.0)	73.8	3.40 t (9.6)	73.9
5′′′′	3.84 m	70.2	3.88 m	70.1	3.85 m	70.3	3.88 m	70.1
6′′′′	1.23 d (6.0)	18.0	1.22 d (6.0)	18.0	1.21 d (6.0)	18.0	1.22 d (6.0)	18.0
1′′′′′	4.31 d (7.8)	104.9
2′′′′′	3.22 dd (8.4, 7.8)	75.1
3′′′′′	3.35 dd (9.0, 8.4)	77.8
4′′′′′	3.30 dd (9.0, 8.4)	71.5
5′′′′′	3.28 m	78.0
6′′′′′a	3.87dd (12.0, 2.4)	62.7
6′′′′′b	3.67 dd (12.0, 5.4)

No.

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

1′

4.50 d (4.8)

104.8

4.44 d (5.4)

105.3

4.46 d (5.4)

105.3

4.45 d (5.4)

105.3

2′

3.98 brd (4.8)

76.0

3.96 brd (5.4)

75.9

3.86 brd (5.4)

75.6

3.96 brd (5.4)

75.9

3′

3.95 m

82.3

3.89 m

81.9

3.88 m

82.9

3.90 m

81.8

4′

3.94 m

68.9

3.97 m

69.4

4.05 m

68.7

3.97 m

69.4

5′a

3.85 brd (10.8)

63.8

3.86 dd (12.0, 3.6)

64.8

3.87 brd (12.0)

65.0

3.86 dd (12.0, 2.4)

64.8

5′b

3.51 brd (10.8)

3.48 dd (12.0, 2.4)

3.54 brd (12.0)

3.48 dd (12.0, 2.4)

1′′

4.58 d (7.8)

103.6

4.61 d (7.2)

103.4

4.50 d (7.2)

104.2

4.61 d (7.2)

103.5

2′′

3.54 dd (9.0, 7.8)

82.7

3.54 dd (9.0, 7.2)

82.4

3.31 dd (9.0, 7.2)

75.1

3.54 dd (8.4, 7.2)

82.4

3′′

3.60 t (9.0)

78.1

3.59 t (9.0)

78.4

3.36 t (9.0)

78.0

3.59 t (8.4)

78.4

4′′

3.31 t (9.0)

71.7

3.34 t (9.0)

71.3

3.27 t (9.0)

71.6

3.34 dd (9.0, 8.4)

71.3

5′′

3.55 m

76.8

3.32 m

78.1

3.52 m

77.0

3.32 m

78.2

6′′a

4.22 dd (10.8, 2.4)

70.5

3.87 dd (12.0, 2.4)

62.5

4.16 dd (11.4, 2.4)

70.2

3.87 dd (12.0, 2.4)

62.5

6′′b

3.65 dd (10.8, 8.4)

3.65 dd (12.0, 5.4)

3.73 dd (11.4, 7.8)

3.65 dd (12.0, 5.4)

1′′′

4.69 d (7.2)

105.8

4.73 d (7.2)

105.6

4.35 d (7.8)

104.8

4.73 d (7.8)

105.6

2′′′

3.32 dd (9.0, 7.2)

75.7

3.33 dd (9.0, 7.2)

75.5

3.20 dd (9.0, 7.8)

75.1

3.33 dd (9.0, 7.2)

75.5

3′′′

3.33 t (9.0)

77.6

3.32 t (9.0)

77.7

3.34 t (9.0)

78.0

3.32 t (9.0)

77.7

4′′′

3.54 m

70.9

3.53 m

71.0

3.32 t (9.0)

71.6

3.53 m

71.0

5′′′a

3.93 dd (11.4, 5.4)

67.6

3.93 dd (11.4, 5.4)

67.5

3.26 m

78.0

3.93 dd (11.4, 5.4)

67.5

5′′′b

3.25 t (11.4)

3.22 t (11.4)

6′′′a

3.93 dd (12.0, 3.6)

62.7

6′′′b

3.66 dd (12.0, 4.2)

1′′′′

5.15 brs

101.8

5.20 brs

101.8

5.22 brs

102.0

5.20 brs

101.8

2′′′′

3.89 brd (2.4)

72.1

3.90 brd (3.0)

72.1

3.93 brd (2.4)

72.1

3.90 brd (3.0)

72.1

3′′′′

3.68 dd (9.6, 2.4)

72.1

3.68 dd (9.6, 3.0)

72.2

3.72 dd (9.0, 3.6)

72.1

3.68 dd (9.6, 3.0)

72.2

4′′′′

3.41 t (9.6)

73.9

3.40 t (9.6)

73.9

3.39 t (9.0)

73.8

3.40 t (9.6)

73.9

5′′′′

3.84 m

70.2

3.88 m

70.1

3.85 m

70.3

3.88 m

70.1

6′′′′

1.23 d (6.0)

18.0

1.22 d (6.0)

18.0

1.21 d (6.0)

18.0

1.22 d (6.0)

18.0

1′′′′′

4.31 d (7.8)

104.9

2′′′′′

3.22 dd (8.4, 7.8)

75.1

3′′′′′

3.35 dd (9.0, 8.4)

77.8

4′′′′′

3.30 dd (9.0, 8.4)

71.5

5′′′′′

3.28 m

78.0

6′′′′′a

3.87dd (12.0, 2.4)

62.7

6′′′′′b

3.67 dd (12.0, 5.4)

No.	9		10	No.	9		10
1a	2.00 dd (12.0, 5.0)	48.5		1.55 m	38.3	15b	1.17 m			1.08 m
1b	0.84 t (12.0)		0.83 dt (5.0, 12.0)		16a	2.24 brd (12.0)	33.6	2.11 brd (12.0)	33.6
2a	3.61 m	69.8	1.43 m	27.2	16b	1.40 m		1.37 m
2b			1.43 m		17		57.7		55.4
3	2.89 d (9.5)	84.5	2.96 dd (10.0, 6.0)	76.8	18	1.62 t (12.0)	50.6	1.50 t (12.0)	48.6
4		40.7		38.5	19	3.04 m	48.7	2.96 m	46.7
5	0.81 dd (11.5, 2.5)	57.0	0.63 brd (12.0)	54.9	20		152.2		150.4
6a	1.63 m	19.7	1.45 m	18.0	21a	1.94 m	31.9	1.81 m	30.1
6b	1.42 m		1.32 m		21b	1.39 m		1.29 m
7a	1.47 m	35.6	1.31 m	33.9	22a	1.91 m	38.4	1.78 m	36.4
7b	1.41 m		1.31 m		22b	1.45 m		1.41 m
8		42.1		40.3	23	0.99 s	29.3	0.86 s	28.1
9	1.38 m	52.1	1.24 dd (12.0, 2.5)	50.0	24	0.78 s	17.4	0.64 s	15.8
10		39.6		36.7	25	0.92 s	18.1	0.76 s	16.0
11a	1.46 m	22.4	1.37 m	20.5	26	0.97 s	16.8	0.86 s	15.8
11b	1.30 m		1.14 dq (4.5, 12.0)		27	1.01 s	15.2	0.92 s	14.4
12a	1.74 m	27.0	1.62 m	25.1	28		/		177.4
12b	1.07 dq (4.5, 12.0)		0.96 dq (4.5, 12.0)		29a	4.71 brd (2.5)	110.3	4.68 brs	109.7
13	2.33 brt (12.0)	39.7	2.23 brt (12.0)	37.6	29b	4.60 dq (2.5, 1.0)		4.55 brs
14		43.8		42.0	30	1.70 brd (1.0)	19.7	1.64 brs	19.0
15a	1.55 m	31.0	1.37 m	29.2

No.

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

δ_H

δ_C

2.00 dd (12.0, 5.0)

48.5

1.55 m

38.3

15b

1.17 m

1.08 m

0.84 t (12.0)

0.83 dt (5.0, 12.0)

16a

2.24 brd (12.0)

33.6

2.11 brd (12.0)

33.6

3.61 m

69.8

1.43 m

27.2

16b

1.40 m

1.37 m

1.43 m

57.7

55.4

2.89 d (9.5)

84.5

2.96 dd (10.0, 6.0)

76.8

1.62 t (12.0)

50.6

1.50 t (12.0)

48.6

40.7

38.5

3.04 m

48.7

2.96 m

46.7

0.81 dd (11.5, 2.5)

57.0

0.63 brd (12.0)

54.9

152.2

150.4

1.63 m

19.7

1.45 m

18.0

21a

1.94 m

31.9

1.81 m

30.1

1.42 m

1.32 m

21b

1.39 m

1.29 m

1.47 m

35.6

1.31 m

33.9

22a

1.91 m

38.4

1.78 m

36.4

1.41 m

1.31 m

22b

1.45 m

1.41 m

42.1

40.3

0.99 s

29.3

0.86 s

28.1

1.38 m

52.1

1.24 dd (12.0, 2.5)

50.0

0.78 s

17.4

0.64 s

15.8

39.6

36.7

0.92 s

18.1

0.76 s

16.0

11a

1.46 m

22.4

1.37 m

20.5

0.97 s

16.8

0.86 s

15.8

11b

1.30 m

1.14 dq (4.5, 12.0)

1.01 s

15.2

0.92 s

14.4

12a

1.74 m

27.0

1.62 m

25.1

177.4

12b

1.07 dq (4.5, 12.0)

0.96 dq (4.5, 12.0)

29a

4.71 brd (2.5)

110.3

4.68 brs

109.7

2.33 brt (12.0)

39.7

2.23 brt (12.0)

37.6

29b

4.60 dq (2.5, 1.0)

4.55 brs

43.8

42.0

1.70 brd (1.0)

19.7

1.64 brs

19.0

15a

1.55 m

31.0

1.37 m

29.2