Transmission Mode Ion/Ion Reactions in the Q0 cell of a Hybrid Triple Quadrupole/Linear Ion Trap Ins...
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Transmission Mode Ion/Ion Reactions in the Q0 cell of a Hybrid Triple Quadrupole/Linear Ion Trap Instrument. Joshua F. Emory and Scott A. McLuckey Department of Chemistry, Purdue University, West Lafayette, IN 47907. Overview.

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Transmission Mode Ion/Ion Reactions in the Q0 cell of a Hybrid Triple Quadrupole/Linear Ion Trap Instrument

Joshua F. Emory and Scott A. McLuckey

Department of Chemistry, Purdue University, West Lafayette, IN 47907


Overview
Overview Hybrid Triple Quadrupole/Linear Ion Trap Instrument

  • The possibility of performing transmission mode ion/ion reactions in the higher pressure RF only Q0 quadrupole is being investigated.

  • The ability to perform these proton transfer charge reduction or charge inversion reactions in Q0 would enable multiple ion/ion reactions to be performed in separate regions of the instrument, perhaps by doing a preparatory reaction in Q0 and a second reaction in Q2.

  • The drawback to performing ion/ion reactions in the Q0 cell is that neither the analyte nor the reagent ion can be isolated prior to introduction into the Q0 quadrupole and the subsequent ion/ion reaction.


Introduction
Introduction Hybrid Triple Quadrupole/Linear Ion Trap Instrument

  • Proton transfer ion/ion reactions have been used for protein charge reduction, to concentrate the charge envelope of proteins as well as to invert the polarity of peptides within the mass spectrometer.

  • These reactions can be performed by storing the reagent in the Q0 cell and passing the analyte through the Q0 cell or by storing the analyte in the Q0 cell and passing the reagent through the Q0 cell.


Experimental
Experimental Hybrid Triple Quadrupole/Linear Ion Trap Instrument

  • Perfluoro-1-octanol (PFO), the charge reduction reagent, solution consisted of a aqueous solution of ~200 to 400 µM of reagent in (48.5:48.5:3) methanol, water, and ammonium hydroxide.

  • Protein electrospray solutions were diluted to ~10 to 20 µM in (49:49:2) water, methanol, and acetic acid.

  • The charge inversion reagents, polypropylenimine diamino-butane (DAB) dendrimers and polyamidoamine (PAMAM) dendrimers were made in aqueous ~1-2% acetic acid and in aqueous ~1-2% ammonium hydroxide, respectively.

  • Bradykinin electrospray solutions consisted of an aqueous solution of ~10 µM concentration of peptide in (49:49:2) methanol, water, and ammonium hydroxide.


Modified Q-Trap 2000/4000 Hybrid Triple Quadrupole/Linear Ion Trap Instrument

Transmission mode reactions in Q0 can be performed by:

By storing the reagent ion in Q0, and transferring the desired analyte ion through the Q0 cell.

By storing the desired analyte ion in Q0, and transferring the reagent ion through the Q0 cell.

Q0

Q1

Q2

Q3

Auxiliary RF applied

for ion parking

Dual ESI sources

N2 CAD Gas

Aux AC

RF

Exit lens

Orifice

Skimmer

IQ1

ST

IQ2

IQ3

Deflector

Triggered +HV

Triggered

-HV

Ion/Ion Reaction

Detector


Mutual Storage Mode Ion/Ion Reactions in a LIT Hybrid Triple Quadrupole/Linear Ion Trap Instrument

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end lens

end lens

LIT

Trapping Anions

Trapping Cations

RF

  • Mutual storage of oppositely charged ions requires application of

    auxiliary RF to the end lenses of the quadrupole.

Transmission Mode Ion/Ion Reactions in a LIT

Passing

Anions

TrappingCations

DC

Passing Cations

Trapping

Anions

DC

  • Does not require application of auxiliary RF to end lenses.

  • Performing ion/ion reactions in Q0 allows further ion/ion reactions

    or CID to be performed in the Q2 or Q3 cell of the instrument.


Transmission mode charge inversion
Transmission Mode Charge Inversion Hybrid Triple Quadrupole/Linear Ion Trap Instrument

  • Involves transfer of multiple protons to an analyte or the removal of multiple protons from an analyte.

  • Charge inversion of an analyte species separates the ionization polarity of the analyte from analysis polarity.

  • Separation of ionization polarity from analysis polarity allows interrogation of an analyte in both polarities, increasing the amount of information that can be obtained from the analyte via dissociation methods such as CID and ETD.


Charge inversion process multiple proton transfer

m+ Hybrid Triple Quadrupole/Linear Ion Trap Instrument

n-

+

-

-

2+

+ H

- H

- H

+ 2H

Charge Inversion Process: Multiple Proton Transfer

Polyamidoamine (PAMAM) Dendrimer

Peptide Ion

(Bradykinin)

1,4-Diaminobutane (DAB) Dendrimer


Charge inversion of bradykinin 1 in q0
Charge Inversion of Bradykinin -1 in Q0 Hybrid Triple Quadrupole/Linear Ion Trap Instrument

100

100

Bradykinin -1

Gen 4

DAB +6

+

50

50

900

1100

300

700

500

700

800

900

1000

1100

1e+7

Passing bradykinin -1

through Q0 for 200 ms

Bradykinin +2

Bradykinin +1

5e+6

DAB +6

DAB +5

DAB +3

DAB +4

700

1100

1300

1500

300

500

900

m/z


Charge inversion of bradykinin 1 in q01
Charge Inversion of Bradykinin +1 in Q0 Hybrid Triple Quadrupole/Linear Ion Trap Instrument

100

100

+

PAMAM

50

50

Bradykinin +2

Bradykinin +1

500

2000

300

500

700

900

1100

0

1000

1500

8e+6

Passing bradykinin +2/+1

through Q0 for 1 s

Bradykinin -1

PAMAM -4

PAMAM -5

4e+6

PAMAM -6

Bradykinin -1

1200

800

1000

400

600

m/z


Ion parking in q0

Quadrupole Rod Hybrid Triple Quadrupole/Linear Ion Trap Instrument

A.

Ion Parking in Q0

  • Application of a Dipolar AC frequency to one pair of rods in a quadrupole

  • Analogous to low amplitude CID

  • Parking has previously been performed in 3D ion traps and in the Q2 cell of 2D traps.


Types of ion parking
Types of Ion Parking Hybrid Triple Quadrupole/Linear Ion Trap Instrument

Quadrupole Rod

A) SFOR ion parking where a single-frequency, on resonance, low amplitude ac signal is applied to an opposing quadrupole rod set.

B) HALF parallel ion parking where a high-amplitude, low-frequency ac signal is applied to an opposing quadrupole rod set.

A.

f0,z (21/2/ro2 Ω)(zV/m) = c(zV/m)

B.

ωz

Ω


Ion/Ion Reaction of Insulin with PFO in Q0 Hybrid Triple Quadrupole/Linear Ion Trap Instrument

Insulin +2

Insulin +3

Insulin +4

100

100

+5

Insulin

-1

PFO

perfluoro-1-octanol

+

+6

50

50

CF3(CF2)6CH2OH

+4

500

700

900

1100

1300

1500

1700

300

400

500

600

200

2e6

No Ion Parking

1e6

4e7

Insulin +4

SFOR Ion Parking of Insulin +4

f = 32.633 kHz, 4 Vp-p

2e7

Insulin +3

3000

1000

1400

1800

2200

2600

3400

m/z


Parallel ion parking of a protein mixture in q0

1000 Hybrid Triple Quadrupole/Linear Ion Trap Instrument

ESI of Protein Mixture:

Insulin, Bovine Cyt. C

Equine Cyt. C, Ubiquitin

Myoglobin, Lysozyme

x3

500

600

1000

1400

Parallel Ion Parking of a Protein Mixture in Q0

150

U+2

100

50

I+2

*

*

*

600

U+3

Insulin = I

Ubiquitin = U

Equine Cyt. C = E

Bovine Cyt. C = B

Myoglobin = M

Lysozyme = L

B+4

I+2

400

M+6

L+5

M+5

E+4

200

E+3

L+4

B+5

E+5

B+3

I+3

U+2

U+4

0

2000

2400

2800

3600

4400

3200

4000

m/z


Results
Results Hybrid Triple Quadrupole/Linear Ion Trap Instrument

  • Charge reduction by proton transfer with or without ion parking of the desired charge state can be performed in the Q0 cell.

  • Charge inversion of bradykinin -1 to +2/+1 and charge inversion of bradykinin +2/+1 to bradykinin -1 can also be performed in the Q0 RF only quadrupole.

  • The use of Q0 as a reaction cell enables two reactions to be performed in rapid succession in separate regions of the instrument. For example, two ion/ion reactions could be performed on an analyte using transmission mode experiments, eliminating the need for auxiliary RF on the end lenses of the Q0 or the Q2 quadrupoles.


Conclusions
Conclusions Hybrid Triple Quadrupole/Linear Ion Trap Instrument

  • Transmission mode proton transfer charge reduction reactions can be performed in the Q0 quadrupole, eliminating the need for application of auxiliary RF on the end lense of the Q0 quadrupole.

  • Charge inversion of bradykinin from negative to positive and from positive to negative in the RF only Q0 cell has been demonstrated.

    • Separates analysis polarity from ionization polarity

  • Performing ion/ion reactions in Q0 allow further ion/ion reactions to be performed in the Q2 and/or Q3 cell of a hybrid linear ion trap.

  • HALF and SFOR methods of ion parking have been successfully demonstrated in the RF only Q0 cell.


References
References Hybrid Triple Quadrupole/Linear Ion Trap Instrument

  • M. He, J.F. Emory, S.A. McLuckey, Anal. Chem., 77 (2005) 3173-3182.

  • M. He, S.A. McLuckey, J. Am. Chem. Soc., 125 (2003) 7756-7757.

  • P. A. Chrisman, S. J. Pitteri, S. A. McLuckey, Anal. Chem., 78 (2006) 310-316.

  • P.A. Chrisman, S.J. Pitteri, S.A. McLuckey, Anal. Chem., 77 (2005) 3411-3414.


Acknowledgments

MDS SCIEX Hybrid Triple Quadrupole/Linear Ion Trap Instrument

NIH GM 43572

McLuckey Group

Acknowledgments


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