Molecules 2012, 17, 8351-8358; doi:10.3390/molecules17078351 OPEN ACCESS
molecules ISSN 1420-3049 www.mdpi.com/journal/molecules Communication
Electrospray Ionization Mass Spectrometric Analysis of Highly Reactive Glycosyl Halides Attila Bokros 1, Annamária Bánfi 1, Zoltán Kupihár 1,*, Zoltán Kele 1, Tünde Zita Illyés 2, János Szolomájer 1 and Lajos Kovács 1,* 1
2
Department of Medicinal Chemistry, Faculty of Medicine, University of Szeged, Dóm tér 8, H-6720 Szeged, Hungary; E-Mails:
[email protected] (A.B.);
[email protected] (A.B.);
[email protected] (Z.K.);
[email protected] (J.S.) Department of Organic Chemistry, Faculty of Science and Technology, University of Debrecen, Egyetem tér 1, H-4010 Debrecen, Hungary; E-Mail:
[email protected]
* Authors to whom correspondence should be addressed; E-Mails:
[email protected] (Z.K.);
[email protected] (L.K.); Tel.: +36-62-545-145; Fax: +36-62-545-971. Received: 18 May 2012; in revised form: 21 June 2012 / Accepted: 25 June 2012 / Published: 10 July 2012
Supplementary Information Unidentified peaks designated by asterisks * and ** have been used as a kind of internal standards to compare the signal intensities of lithium, sodium, potassium and ammonium adduct ions; Identified peaks have labelled in red; The desired molecular ion adducts [M+cation]+ are shown in blue circles .
Molecules 2012, 17
S2
Spectrum 1. Analyte 2 in acetonitrile without any adduct forming agent. CH3
Chemical F ormu la: C 14H19 BrO9
O
Exact Mass: 410.0212 ( 79 Br)
O O
120607 _1_00 21 ( 0.388) Cm (18:25) 354.29 100 343.27
*
367.02
T OF MS ES+ 528
Br
O H3C
O O
O
O CH3
CH3
O
678.51
[M+C F 3COOLi+Li]+ 537.04
[M +Li] +
383.00
722.38
%
417.04 419.04
668.62 540.55
429.76
722.89
397.30
430.25
471.26
312.37 313.98
484.47 496.42
463.28
340
360
380
400
420
440
4 60
541.55
568.57
500
750.91
663.45
513.51
520
610.59
584.48
779.03 680.50
626.86
596.57
536.04
480
750.40
636.45
487.02
435.01 400.38
320
636.48
433.02
337.30
0 300
696.67
638.61 512.50
641.60
560
580
600
6 20
640
660
751.42
696.59 716.56
654.60
5 40
723.38 697.65 732.55
760.61
680
7 00
720
740
760
793.02 799.99
7 80
800
m/z
Molecules 2012, 17
S3
Spectrum 2. Analyte 2 in acetonitrile with 2% formic acid.
120607_1_0 28 (0.517) Cm (23:36) 354.28
TOF MS ES+ 2.05e3
*
%
100
355.29
[M+Na]+
**
359.25
433.02 453.79
375.22 384.31 387.18
331.10
0 300
320
340
360
380
400
415.22
420
440
460
480
500
638.61
553.02 569.01
500.32
520
540
560
580
600
620
640
663.45 668.64
660
680
696.67
700
720
740
760
780
800
m/z
Molecules 2012, 17
S4
Spectrum 3. Analyte 2 in acetonitrile with LiCl. [M+CF3COOLi+Li]+
LiCl 120607_1_1 24 (0.443) Cm (23:29)
TOF MS ES+ 3.50e3
537.04
100
343.26
[M+Li]+
777.04
%
417.04
344.28
*
536.05
354.29 337.11
540.05
776.04 780.06
463.28 420.04
367.02 373.29 397.30
435.01 461.03
701.03
553.02
0 300
320
340
360
380
400
420
440
460
480
795.03
657.06
475.13
500
520
540
560
580
600
620
640
660
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S5
Spectrum 4. Analyte 2 in acetonitrile with NaCl.
NaCl 120607_1_2 25 (0.461) Cm (24:29)
TOF MS ES+ 1.74e3
354.28
100
*
**
%
359.24
343.27
[M+CF3COOLi+Li]+
[M+Na]+
375.22
[M+Li]+
539.05
[M+CF3COOLi+Na]+
433.02
417.04 384.31 337.27
0 300
320
340
389.27 415.22
360
380
553.03
400
451.00
420
440
460
536.04
475.14
480
500
520
540
601.21 612.24
560
580
600
617.19
620
640
654.23
660
676.13
680
779.05
700
720
740
760
780
793.02
800
m/z
Molecules 2012, 17
S6
Spectrum 5. Analyte 2 in acetonitrile with KCl.
KCl 120607_1_3 28 (0.517) Cm (27:35) 354.29
100
TOF MS ES+ 2.27e3
*
**
%
359.24
375.22
[M+CF3COOLi+Li]+
343.27
[M+Na]+ 435.03 384.30 337.27
0 300
320
340
389.26
[M+CF3COOLi+Na]+
[M+K]+
415.23
537.05
553.03 612.23 617.19
451.00
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
654.24
660
676.14
681.11
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S7
Spectrum 6. Analyte 2 in acetonitrile with LiNO3.
gli br + LiNO3 poz 120611_05 26 (0.480) Cm (23:39)
TOF MS ES+ 5.67e3
343.27
100
[M+Li]+
[M+LiNO3+Li]+ 488.04
%
419.04 417.03
[M+CF3COOLi+Li]+
367.02 316.02 337.11
344.27
334.03 366.01
435.01 454.03 436.02
355.12
333.03
320
485.04
397.30
*
340
360
380
489.05
420.04
385.03
315.02
0 300
539.04
400
420
440
472.04
460
480
504.02 505.02
500
520
555.04 574.02 592.04
540
560
580
608.04 625.04 643.02 661.04
600
620
640
660
677.04
680
728.04 744.05 693.04
712.04
700
720
762.03
740
760
779.03 797.04
780
800
m/z
Molecules 2012, 17
S8
Spectrum 7. Analyte 2 in acetonitrile with NaNO3.
NaNO3 120607_2_2 25 (0.461) Cm (25:32) 359.24
100
TOF MS ES+ 3.41e3
**
%
*
354.29
[M+Na]+ 435.01
360.25
375.23
343.26
0 300
320
340
437.20
389.26
353.09
409.17
360
380
400
415.22
420
440
460
555.02
519.99
451.00
480
500
520
540
570.99
560
617.18
580
600
620
659.20 679.11
640
660
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S9
Spectrum 8. Analyte 2 in acetonitrile with KNO3. KNO3 120607_2_3 23 (0.424) Cm (22:31)
TOF MS ES+ 3.00e3
375.21
100
*
354.29
** %
359.25
[M+K]+
376.23
450.99 377.23 387.07 343.28
0 300
320
340
[M+Na]+
433.03
405.23
676.14
425.15
360
380
400
420
675.16 695.06
633.15
453.18 570.99
440
460
480
500
520
540
560
580
655.05
612.22
600
620
640
660
739.08
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S10
Spectrum 9. Analyte 2 in acetonitrile with LiClO4.
[M+Li]+ gli br + LiClO4 poz 120611_06 27 (0.498) Cm (23:33)
TOF MS ES+ 3.03e3
417.04
100
[M+LiClO4+Li]+ 525.01
%
523.01
736.94 337.11 324.91 738.93 644.80 646.80
527.00
420.04
734.94 750.77
432.88 323.91
343.27
*
0 300
320
340
360
522.01
434.87
355.12 313.11
641.80 556.84
398.31
380
400
642.80
540.84
397.29
420
440
460
480
500
520
540
560
648.80
662.81
768.77 772.79
733.94
630.97
580
600
620
640
660
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S11
Spectrum 10. Analyte 2 in acetonitrile with NaClO4.
[M+Na]+
NaClO4 120607_3_2 25 (0.463) Cm (24:40)
TOF MS ES+ 2.38e3
433.02 435.02
100
**
359.25
512.75
510.75
388.81 756.63
%
390.82
514.74 758.62 532.88
634.69
[M+NaClO4+Na]+ 556.96
754.63
491.87
554.96
343.28
*
392.81
760.62
516.75 413.28 402.85
360
380
400
420
558.95
638.69
534.89 477.82
437.02
371.09
340
798.85
509.87
331.11
320
800.84
636.69
360.25 436.02
0 300
632.69
440
460
480
762.62
492.87
500
625.18
536.90
520
540
560
580
600
620
751.69
640
660
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S12
Spectrum 11. Analyte 2 in acetonitrile with KClO4.
KClO4 120607_3_3 26 (0.480) Cm (26:35)
TOF MS ES+ 4.69e3
359.24
100
%
**
[M+K]+
450.99 449.00
360.25
[M+Na]+ 433.03
375.23
532.88
*
343.27
0 300
320
340
360
389.26
452.00
491.86 572.93
509.87
380
400
420
440
460
480
500
520
540
560
588.91
580
600
620
640
660
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S13
Spectrum 12. Analyte 2 in acetonitrile with NH4Cl.
NH4Cl 120607_1_4 26 (0.480) Cm (25:34) 359.24
100
TOF MS ES+ 4.13e3
**
[M+Na]+
%
435.01
*
353.09
360.25
371.11
[M+NH4]+
375.23
[M+K]+
436.02
413.28
331.11
0 300
320
340
570.99
451.00
556.95 532.88
491.87
360
380
400
420
440
460
480
500
520
540
617.19
560
580
600
620
659.20 679.10
640
660
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S14
Spectrum 13. Analyte 2 in acetonitrile with NH4NO3.
NH4NO3 120607_2_4 25 (0.461) Cm (24:34) 359.24
100
TOF MS ES+ 2.73e3
**
*
%
354.29
[M+Na]+ 435.01 375.22
[M+NH4]+
[M+K]+ 450.99
353.10 389.26
331.11
413.27 430.06 518.00
453.19
0 300
320
340
360
380
400
420
440
460
480
500
520
571.00 532.89
540
612.22
560
580
600
617.18
620
654.24
640
659.19 676.14 681.11
660
680
697.07
700
720
740
760
780
800
m/z
Molecules 2012, 17
S15
Spectrum 14. Analyte 2 in acetonitrile with NH4OOCCH3.
NH4oac 120607_4_5 25 (0.461) Cm (24:33) 359.24
100
TOF MS ES+ 2.80e3
**
*
%
354.29
[M+Na]+
375.23
435.02
[M+NH4]+ 389.27
353.09 331.11
0 300
320
340
413.11
360
380
400
420
450.99 532.88
491.87
440
460
480
500
520
540
571.00
560
580
612.24
600
659.20
617.19 654.24 633.15
620
640
660
676.14
681.10
680
697.07
700
720
740
760
780
800
m/z
Molecules 2012, 17
S16
Spectrum 15. Analyte 2 in acetonitrile with NH4OOCH.
NH4form 120607_4_6 30 (0.556) Cm (28:39) 354.29
100
TOF MS ES+ 3.00e3
* **
%
359.24
375.23
[M+NH4]+ 389.27
[M+Na]+ 433.03
612.23
337.27
0 300
320
340
617.19
659.20
633.15 654.24
676.15 681.09 697.06
532.89
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
660
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S17
Spectrum 16. Analyte 2 in acetonitrile with NH4HCO3. NH4HCO3 120607_4_7 22 (0.406) Cm (22:32) 354.29
100
*
TOF MS ES+ 2.91e3
**
%
359.25
375.22
[M+NH4]+
389.26
0 300
320
340
435.03 415.21
337.27
360
380
400
[M+Na]+
420
612.23
437.20
440
460
480
500
520
540
560
580
600
617.18
659.20 681.10
633.16
620
640
660
680
697.06
700
720
740
760
780
800
m/z
Molecules 2012, 17
S18
Spectrum 17. Analyte 2 in acetonitrile with LiBr.
[M+Li]+ gli br + LiBr poz 120611_04 35 (0.646) Cm (32:44)
TOF MS ES+ 4.25e3
417.04
100
[M+LiBr+Li]+
%
504.97
502.97 506.97 678.83
337.11 343.27
676.84 680.84
420.04
397.30
355.12 300.88 336.11
0 300
320
340
501.98
356.76
360
442.69
398.29
380
400
528.62 539.05
675.84 682.84
507.97
592.91
420
440
460
480
500
520
540
560
580
600
614.55
620
764.77
694.82
640
660
680
700
720
740
760
780
800
m/z
Molecules 2012, 17
S19
Spectrum 18. Analyte 2 in acetonitrile with LiI.
[M+Li]+ gli br + LiI poz 120611_03 36 (0.664) Cm (34:44)
TOF MS ES+ 2.79e3
417.03
100
[M+LiI+Li]+
%
550.96
337.11 408.79
420.04 549.95 553.96 343.27
320
340
424.75
393.85
336.12
0 300
397.29 394.86
360
380
539.04 465.02
400
420
440
676.63
460
489.04
480
500
675.61 686.88
528.78
520
540
560
580
600
620
640
660
680
694.63
700
720
740
760
780
800
m/z
Molecules 2012, 17
S20
Spectrum 19. Analyte 2 in acetonitrile with LiF (negative ion mode).
120612_BRGLI_NAF_NEG 29 (0.535) Cm (24:36) 113.00
100
TOF MS ES550
[CF3COO]-
[Br] 78.93
[2CF3COOLi+CF3COO]352.99
%
353.01
[CF3COOLi+CF3COO]233.00
[3CF3COOLi+CF3COO]675.12
473.01
694.99
631.09 351.99
265.16
737.03
106.04 131.05
69.00
0
75
100
125
213.10
150
175
200
232.00 248.97
225
250
293.16
275
300
319.17
325
368.99
350
380.98
375
400
430.99
425
466.22
450
480.97
475
500
530.98 549.16
525
550
594.99
575
629.16
600
625
697.04
653.04
650
739.05 758.94
675
700
725
750
775
m/z
Molecules 2012, 17
S21
Spectrum 20. Analyte 2 in acetonitrile with LiCl (negative ion mode).
[2CF3COOLi+CF3COO]-
120516_qp_brgli_neg 18 (0.442) Cm (17:24)
1: TOF MS ES404
352.99
100
352.98
[3CF3COOLi+CF3COO]473.00
[3CF3
COOLi+Cl]-
[4CF3COOLi+CF3COO]-
473.03
593.04
%
394.99
[CF3COOLi+CF3COO]-
[5CF3COOLi+CF3COO]-
232.97 232.99 316.95 318.96
358.94
515.01 397.00
154.97 COO]-
[CF3 76.94
0
75
112.98 122.89
100
125
156.96 204.90 231.99
150
175
200
225
238.94
282.93 315.96
352.00
393.99 362.93
712.07
438.97
513.99 517.02
436.00
324.92
275
300
325
350
375
400
425
592.02
472.02
480.94
406.90 452.91
250
713.04
[4CF3COOLi+Cl]-
450
475
500
594.03 557.00 635.00 700.88 542.84 558.98 662.91
525
550
575
600
625
650
675
700
714.05 734.84 777.91
725
750
775
m/z 800
Molecules 2012, 17
S22
Spectrum 21. Analyte 2 in acetonitrile with LiBr (negative ion mode).
[4LiBr+Br]-
gli br + LiBr neg 120611_01 28 (0.517) Cm (22:46) 100
TOF MS ES4.01e3
426.6642
[LiBr+Br]166.8597
428.6602
[CF3COOLi+3LiBr+Br][5LiBr+Br]460.7229
[CF3COOLi+2LiBr+Br]-
514.5970
[2CF3COOLi+CF3COO]-
%
164.8624
424.6654
[CF3COOLi+CF3COO]-
374.7906
168.8595
[2LiBr+Br]- [3LiBr+Br]254.7945
[CF3
COOLi+Br]-
512.5934 462.7335
406.8642
352.9876 492.7963
[CF3COOLi+LiBr+Br]-
198.9274
516.5963
430.6609
340.7210 404.8679 232.9957
338.7315
286.8565
0
60
80
592.9951
318.9206
558.9345
284.8634 288.8566
[Br]-
163.8611
100
120
140
160
200
403.8752
314.7437
197.9310
180
546.6702
376.7974
256.7858
220
240
260
280
300
320
340
360
380
400
420
440
460
480
500
520
540
560
580
600
m/z
Molecules 2012, 17
S23
Spectrum 22. Analyte 2 in acetonitrile with LiBr (negative ion mode).
gli br + LiI neg
[4LiI+I]-
120611_02 40 (0.738) Cm (38:52)
TOF MS ES1.03e4
662.59
100
[2LiI+I]394.75
[CF3COOLi+LiI+I]-
[3LiI+I]-
380.71
%
528.67
[5LiI+I]-
661.60
[CF3COOLi+3LiI+I]-
796.51
648.68
[CF3COOLi+2LiI+I]514.76
[3LiI+NaI+I]795.51
[2CF3COOLi+LiI+I]-
360.73
[3CF3COOLi+I]-
[2CF3
500.83
[CF3COOLi+4LiI+I]-
647.68
COOLi+2LiI+I]-
[2CF3COOLi+3LiI+I]-
634.76
781.60
678.59
768.66
486.92
0 300
320
340
360
380
400
420
440
460
480
500
520
540
560
580
600
620
640
660
680
782.61
700
720
740
760
780
800
m/z
Molecules 2012, 17
S24
Spectrum 23. Analyte 2 in acetonitrile with NH4OOCCH3 (negative ion mode).
120612_BRGLI_NH4OAC_NEG 109 (2.010) Cm (106:117) 100
80.92
TOF MS ES1.15e3
[Br] -
%
78.93
[2CF3COOLi+CF3COO]352.99
[CF3COOLi+CF3COO][CF3COO]-
673.11
233.00
112.99
633.10
[3CF3COOLi+CF3
652.99
0
75
100
125
150
175
200
225
250
275
489.13 507.14
385.04
300
325
350
375
400
425
450
475
737.03
697.01
473.00 352.00 265.16
695.01
COO]-
500
525
549.14
550
715.14
589.08 615.09
575
600
625
650
675
700
725
739.02 758.93
750
775
m/z
Molecules 2012, 17
S25
Spectrum 24. Accurate mass analysis of analyte 1 in acetonitrile with LiCl. LiCl MeCN 120612_qp_clgli_poshrms 134 (3.292) AM (Cen,4, 80.00, Ht,8600.0,785.84,0.70,LS 5); Sm (SG, 3x5.00); Sb (15,10.00 ); Cm (133:138)
1: TOF MS ES+ 1.64e3
395.1256
100
%
[M(35Cl)+Li]+
397.1238
396.1290 397.2961
394.1273
391.1763 391.0958
0
390
391
398.1271 398.3002
393.1601 391.3189 392.1799
392
393.7252
393
394
394.7955
395
396.2980
395.2881
396
397
398
401.1345
399.1435
400.1420
399
400
402.1410
401
402
403.2907
403
m/z
Molecules 2012, 17
Table 25. Report of accurate mass analysis of analyte 1 in acetonitrile with LiCl.
•
Elemental Composition Report
• • • •
Single Mass Analysis Tolerance = 10.0 PPM / DBE: min = -1.5, max = 50.0 Element prediction: Off Number of isotope peaks used for i-FIT = 3
• • • • • • •
Monoisotopic Mass, Even Electron Ions 65 formula(e) evaluated with 1 results within limits (all results (up to 1000) for each mass) Elements Used: C: 0-500 H: 0-1000 7Li: 1-1 O: 0-20 35Cl: 1-1 Minimum: -1.5 Maximum: 5.0 10.0 50.0 Mass Calc. Mass mDa PPM DBE i-FIT i-FIT (Norm) Formula 395.1256 395.1238 1.8 4.6 10.5 97.5 0.0 C21 H21 7Li O5 35Cl
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S26
Molecules 2012, 17
S27
Spectrum 26. CID spectrum of peaks 537/539 of analyte 2 in acetonitrile-LiCl at low collision energy.
pljusz 120615_GLIBR_LICL_537 34 (0.627) Cm (32:34)
TOF MSMS 537.02ES+ 537.04 139 + [M+CF3COOLi+Li]
100
%
539.04
[M+Li]+ 417.05
536.03 540.04
419.04 419.06 420.04
0
60
80
100
120
140
160
180
200
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240
260
280
300
320
340
360
380
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420
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540
m/z
Molecules 2012, 17
S28
Spectrum 27. CID spectrum of peaks 417/419 and 537/539 of analyte 2 in acetonitrile-LiCl at high collision energy.
pljusz 120615_GLIBR_LICL_417 23 (0.424) Cm (21:27) 337.12
100
TOF MSMS 417.02ES+ 3.32e3
[M-HBr+Li]+
[M+Li]+
%
109.03
235.08
169.05 175.06
211.07
277.09
236.09
417.04 336.11
278.09
338.12 420.04
0 120615_GLIBR_LICL_537 42 (0.775) Cm (38:50) 337.12
100
TOF MSMS 537.02ES+ 2.44e3
[M-HBr+Li]+
%
[M+Li]+
175.06
0
60
80
100
120
235.08
169.05
109.03
140
160
180
211.06
200
220
236.08
240
419.04
277.10 336.12
278.11
260
280
[M+CF3COOLi+Li]+
338.12
300
320
340
420.06
360
380
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420
440
537.04
460
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520
540
m/z
