Chrysomycins A-C, antileukemic naphthocoumarins from ... · 1 ELECTRONIC SUPPORTING INFORMATION...
Transcript of Chrysomycins A-C, antileukemic naphthocoumarins from ... · 1 ELECTRONIC SUPPORTING INFORMATION...
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ELECTRONIC SUPPORTING INFORMATION (ESI)
Chrysomycins A-C, antileukemic naphthocoumarins from Streptomyces
sporoverrucosus
Shreyans K. Jain,ab Anup S. Pathania,c Rajinder Parshad,d Chandji Raina,d Asif Ali,ab Ajai P. Gupta,e
Manoj Kushwaha,e Subrayashastry Aravinda,f Shashi Bhushan,bc Sandip B. Bharate,bf* Ram A.
Vishwakarmaabf*
aNatural Products Chemistry Division, Indian Institute of Integrative Medicine (CSIR), Canal Road, Jammu-180001,
India.
bAcademy of Scientific and Innovative Research (AcSIR), Anusandhan Bhawan, 2 Rafi Marg, New Delhi-110001, India
cCancer Pharmacology Division, Indian Institute of Integrative Medicine (CSIR), Canal Road, Jammu-180001, India
dFermentation Division, Indian Institute of Integrative Medicine (CSIR), Canal Road, Jammu-180001, India.
eQuality control and quality assurance division, Indian Institute of Integrative Medicine (CSIR), Canal Road, Jammu-
180001, India.
fMedicinal Chemistry Division, Indian Institute of Integrative Medicine (CSIR), Canal Road, Jammu-180001, India
*E-mail: [email protected]; [email protected]
¤ IIIM Publication number IIIM/1556/2013
Fax: +91-191-2569333; Tel: +91-191-2569111
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CONTENTS
S1 . 1H -NMR Spectrum of chrysomycin A (1) in CD3OD
S2. HRMS Spectrum of chrysomycin A (1)
S3. 1H -NMR Spectrum of chrysomycin B (2) in CD3OD
S4. HRMS Spectrum of chrysomycin B (1)
S5. 1H -NMR Spectrum of chrysomycin C (3) in CD3OD
S6. 13C-NMR Spectrum of chrysomycin C (3) in CD3OD
S7. DEPT 135 Spectrum of chrysomycin C (3) in CD3OD
S8. COSY Spectrum of chrysomycin C (3) in CD3OD
S9. HSQC Spectrum of chrysomycin C (3) in CD3OD
S10. HMBC spectrum of chrysomycin C (3) in CD3OD
S11. HRMS of chrysomycin C (3)
S12. HRMS of chrysomycin D (4)
S13. LCMS of active fraction
S14. Screenshot of DNP database search during dereplication
S15. Screenshot of DNP substructure search using basic naphthocoumarin skeleton
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S1 1H -NMR Spectrum of chrysomycin A (1) in CD3OD
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
0
500
1000
1500
2000
2500
3000
3500
4000
4500
500029-jul-shreyan-h1SS-Peak-II
2.49
2.91
1.62
1.21
5.01
0.92
2.48
0.52
1.03
1.03
0.77
0.94
0.77
1.02
0.26
0.43
0.53
1.02
1.00
1.20
1.21
1.22
1.26
1.28
1.29
1.29
1.30
1.31
1.45
3.30
3.30
3.31
3.31
3.31
3.37
3.93
3.94
3.95
3.96
3.97
3.98
4.72
4.74
4.91
5.37
5.39
5.89
5.93
6.21
6.22
6.23
6.24
6.71
6.91
6.92
6.93
6.94
7.17
7.29
7.82
7.89
7.89
7.90
7.91
8.17
8.23
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S2. HRMS Spectrum of chrysomycin A (1)
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S3 1H -NMR Spectrum of chrysomycin B (2) in CD3OD
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
29-jul-shreyan-h1SS-Peak-I
3.18
3.04
3.01
1.11
3.05
0.95
1.14
1.07
0.98
1.23
1.00
1.10
1.12
1.18
1.35
2.29
3.27
3.89
6.11
6.13
6.83
6.84
7.02
7.53
7.80
7.81
8.12
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S4. HRMS Spectrum of chrysomycin B (2)
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S5 1H -NMR Spectrum of chrysomycin C(3) in CD3OD
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.5f1 (ppm)
-500
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
5500
Jul22-2013SS-P-III
2.8
93.4
52.6
2
1.9
5
0.8
5
5.8
6
1.0
2
0.9
2
0.9
6
1.0
1
0.9
5
1.0
0
1.0
0
1.2
01.2
11.2
71.4
5
2.6
82.7
0
3.3
03.3
03.3
13.3
13.3
13.3
7
3.9
23.9
33.9
4
4.7
24.7
3
6.2
26.2
4
6.9
06.9
27.0
9
7.6
3
7.8
87.9
08.1
5
1.11.21.31.41.51.6f1 (ppm)
0
1000
2000
3000
4000
5000
Jul22-2013SS-P-III 1
.20
1.2
1
1.2
7
1.4
5
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S6. 13C NMR Spectrum of chrysomycin C (3) in CD3OD
0102030405060708090100110120130140150160170f1 (ppm)
-2000
0
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
22000
24000
26000
28000
30000Jul22-2013SS-P-III
15.2
217.2
5
24.1
0
29.6
4
56.6
356.6
956.8
356.8
6
73.0
674.6
575.1
276.6
577.7
8
102.9
8
113.0
7115.3
2116.5
3118.4
2121.0
5122.9
1126.8
4128.3
1130.5
3
143.5
9
147.8
0
153.2
7155.4
2158.6
2162.5
5
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S7. DEPT 135 Spectrum of chrysomycin C (3) in CD3OD
0102030405060708090100110120130140f1 (ppm)
-40000
-35000
-30000
-25000
-20000
-15000
-10000
-5000
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
50000Jul22-2013SS-P-III
-0.0
0
15.2
217.2
7
24.1
1
29.6
4
56.6
656.8
4
73.0
674.6
076.6
677.7
9
102.9
4
113.0
6
118.3
7
121.0
2
130.5
3
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S8. COSY Spectrum of chrysomycin C (3) in CD3OD
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f2 (ppm)
0
1
2
3
4
5
6
7
8
9
10
f1 (
ppm
)
Jul22-2013SS-P-III
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S9. HSQC Spectrum of chrysomycin C (3) in CD3OD
-10123456789f2 (ppm)
-20
-10
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
f1 (
ppm
)
Jul22-2013SS-P-III
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S10. HMBC spectrum of chrysomycin C (3) in CD3OD
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f2 (ppm)
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
f1 (
ppm
)
Jul22-2013SS-P-III
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S11. HRMS of chrysomycin C (3)
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S12. HRMS of chrysomycin D (4)
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13. LCMS of active fraction 13.1 LC chromatogram at 280 nm
AU
0.00
0.10
0.20
0.30
0.40
Minutes0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00 70.00 75.00
13.2. LCMS chromatogram in TIC mode
5x10
0
0
0
0
0
0
0
0
0
0
1
1
1
1
1
1
+/-ESI BPC Scan Frag=135.0V SP0004.d Smooth
CH
RY
SO
MY
CIN
-D
CH
RY
SO
MY
CIN
-E CH
RY
SO
MY
CIN
-B
CH
RY
SO
MY
CIN
-A
CH
RY
SO
MY
CIN
-C
Counts vs. Acquisition Time (min)
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60 62 64 66 68 70 72 74
13.3. MS spectras of chrysomycins A-E
3x10
0
2
-ESI Scan:2 (53.3 min) Frag=135.0V SP0004.d
525.0
480.9592.9510.8 560.9 651 0 684 8
3x10
0
5
+ESI Scan:1 (53.3 min) Frag=135.0V SP0004.d
549.0
509.0409.1
527.0465.0425.2352.8 564 9 615 0 658 3 694 9 737 9
Counts vs. Mass-to-Charge (m/z)360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760
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3x10
0
0
1
-ESI Scan:2 (58.8 min) Frag=135.0V SP0004.d
523.0
590.8558.8
3x10
0
2
4
+ESI Scan:1 (58.8 min) Frag=135.0V SP0004.d
547.0
407.0 507.1599.0377.0 432 7 568 9 710 3633 3 679 3 743 1
Counts vs. Mass-to-Charge (m/z)360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760
4x10
0
0
1
-ESI Scan:2 (64.9 min) Frag=135.0V SP0004.d
495.0
563 0376 7 990 7606 94x10
0
2
4
+ESI Scan:1 (64.9 min) Frag=135.0V SP0004.d
379.0
479.1
519.0 764.2434.9 993 1563 1
Counts vs. Mass-to-Charge (m/z)400 450 500 550 600 650 700 750 800 850 900 950 1000
3x10
0
5
-ESI Scan:2 (70.8 min) Frag=135.0V SP0004.d
507.0
574 9174 8 257 0 642 74x10
0
1
2
+ESI Scan:1 (70.7 min) Frag=135.0V SP0004.d
391.0491.0
531.0361.0 782.6447.0273.9141 0 593 0213 0 710 5
0.0
Counts vs. Mass-to-Charge (m/z)100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
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S14. Screenshots of DNP database search during dereplication
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S15. Screenshots of DNP substructure search using basic naphthocoumarin skeleton
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