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Jul 10, 2012 - Electrospray Ionization Mass Spectrometric Analysis of Highly Reactive Glycosyl Halides. Attila Bokros 1, Annamária Bánfi 1, Zoltán Kupihár 1,* ...

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]d.hu (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

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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



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

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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

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235.08

169.05

109.03

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211.06

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236.08

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419.04

277.10 336.12

278.11

260

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[M+CF3COOLi+Li]+

338.12

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420.06

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537.04

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m/z