Pulsed-DeIayed Extraction for Resolution Enhancement of Linear Time-of-Flight Mass Spectrometer in Surface-Assisted Laser

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.Journdoj’tknwnk Chmihl S’0(ic,ry 2000. V(IL 44, A?).4

Printcti in the Republic oi Korea

Pulsed-DeIayed Extraction for Resolution Enhancement of Linear Time-of-Flight Mass Spectrometer in Surface-Assisted Laser

Resorption/Ionization of Polypropyleneglycol

Junghwan Kim and Weekyung Kang*

Deparfrmwtqf(%ernistty Soongsii University, Stwul 156-743, Koret]

(Received March 14. 2003)

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(a) Resorption and ionization

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GO=Va Gl=Va G2=GND GND

(b) Delayed extraction

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GO= Va+Vp Gl=Va High voltage pulse

(c) Flight

to

^detector

L

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GO= Ve G1 =Ve

Fig. 1.Schematic of a puked-cleltyd exmaction.

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ectrum

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Fi<y.2. Block diagrdm of laser dcso~liotilonizati<)r] time-of-flight mass spectrornewr.

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Initial velocity (mk3) Delay time (IIS)

Mass (mkl

Fig, 3. Numerically predicted broadening of TOF. (a) and (b) m=z~ according^IO variation of initial velocity and delay time, respectively; (c) comparison or continuous (V,=20 kV) and PDE mode^(’t^d=z.ss ^w). ^The imtrumen~al con~uons ar’c as follows.A=2.2 cm. 0=2.6 cm, 1F 100cm, V,=8kV, VF=2kV.

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332 Wm. “+%wik

~1],11Ho-(-cH,CH(CH,)-),-oHNa+ (a) Td=l.Ops

I

P?G5000

20 30 40 50 60 70

TOF (ILS)

Fig. 4. Effect of wrying delay time on tie SALDI TOF spw- Wd ut’ amixture of PPG 2000 and PPC 5003in ME mcde.

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1600

15CUI

2000 2500 3C Mass (amu)

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Fig. 5. Mass spectra of (t) PPC 2000 and (c) PPG 5000 obtained at optimized condition in PDE mode. (lJ) and (d) show the expanded ion signal profiles of (a) and (.c), respectively. Spectra are obtained at PDE condition 01 (a) V,=6 kV.

V,=2 kV and %,=1.7,US;and (c) V,+ kV, 17,=2kV and 1=3.6 I.IS.

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‘m ~:~<:::.:;:’: ,,.,.<”’..:-,:“- ... “’ -....

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~ ~=,z,....:?’: s.------- . ............--

: 1QC3 20C0 3000 4W0 WJO 6fJIX 7030 SQCo WCC

Maas [J?VZ)

Fig. 6,Cakukd mass msohnion as o function of mass:

(dash dotted Iinc) tit given dcluy time in ideal PDE mode;

and (solid line) by instnrmcrurdbroadening. Dashed k rep- resent the minimum rwohnion required for isotopical sepam- tion. The instrumental conti[tions are the same as in Fig. S(a).

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:3.- :

e~

*.-: : f!

l~oo 20C0 3200 4000 50C0 6300 7000

Maas (m/z)

Fig. 7.Comparison of SALD1 mass specma of PPG SO(M) obrainedIron] (a)PDE and (b) continuous extraction al same laser fluence of (L4[ MW/cm~.

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(a) Fragmentation pattern for B and Cseries

~o_xn_ocH_~ ^‘1 , ’5

2 ,j i,,> ~y(CH3)-X.-0-OH H3C 0-CH2

c ! a

o

~H3

HWWI–0 CH2–C—C H3 ~ H2 + CH2=C–X n–O–O H

sommaddud 5en+37 Scdiurn awduct 58n+61

(b) Homolytic cleavage for (B+H) and (C+H) series

CH3 CH3

Rf-Xn-0CH2CSt\– O- CH2CH—X n-O– R2

B+++ { \

% O~H3 C+H

Rj–X n–0 CH2–C W-CH3 H2C– CS--Xn–O -R2

Scdum addd: 58Q+62 .%dium addw 5Sn+9B

F-ig. 8.Possible mechanisms to explain the origin of’the 1iag- ment ions ubscrvcd in Fi,q.5: (a) for B and C series, see the refe~nces formore details; ( tr)homolytic cleavage for (B+H) and (C+H) series,

1. Karas,M: Hillenkasnp, F. And, Chem. 1988, 60, 2299.

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IS.Kovroun, S, V.J?apd (Yommun. Mass Speclrvm. 1997.

11, 810.

16. Ioanoviciu, D. h. J. Mass Specrronr. ]on Processes 1994, 4.3, 13).

17. Yefchak. G. E.; Enke. C. G.: Holland, J. F. fnt. J. Mass Spectrorn. ion Prore.sses 1989, 87, 313.

IX. Erickson. E. D.: Yefchak. G. E.; Enkc. C. G.; Holland, J. F. Im. J. Mass .Ypectrom. km Processes 1990, 97,87 19. .Iuhasz, D; Vestal M. L.; Martin S. A. J. Am. SOC.Maw

Spectrom. 1997, & 209.

20. Kim, J. H.; Kang. iv, K. Bull. Kwwr~ Chem. Sot. 2000, 21.401.

21. Mowat, [. A.; Donovan, R. J.; Mahx, R. R. J.: Rapid C.xmnun. Musx .Ypertrom. 1997. 1[. 89.

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Pulsed-DeIayed Extraction for Resolution Enhancement of Linear Time-of-Flight Mass Spectrometer in Surface-Assisted Laser