ICR Mass Spectrometer

2
Jürgen H. Gross Jürgen H. Gross 1 1 , H. Bernhard Linden , H. Bernhard Linden 2 2 1 Institute of Organic Chemistry, Heidelberg University, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany. 2 Linden CMS, Auf dem Berge 25, 28844 Leeste, Germany. Combined ESI/LIFDI Combined ESI/LIFDI - - Ion Source for a FT Ion Source for a FT - - ICR Mass Spectrometer ICR Mass Spectrometer Concept of the Bruker Dual Source MTP The Dual Source MTP™ available with Bruker ApexQe FT-ICR mass spectrometers simultaneously handles ions entering via the electrospray interface and ions emerging from the (MA)LDI target. ESI ions are deflected into an ion funnel while those from MALDI are traveling on-axis. Other ionization sources may be attached after removal of the MALDI assembly from the ion source housing. 59 th ASMS Conference on Mass Spectrometry, Denver, CO, June 5-9, 2011 TP 056 Advantages of LIFDI In LIFDI the sample transfer capillary delivers the analyte in solution directly onto the emitter positioned in the high vacuum of the ion source. The capillary is fed through a drilled hole in the glass insulator bearing the emitter-holding metal pins. The liquid bridges the narrow gap between the end of the capillary and the activated emitter, and thus, prevents it from mechanical damage. The photograph shows solvent wetting the emitter. Activated Emitter Emitter Pins Sample Transfer Capillary Liquid Wetting the Emitter Glass Insulator with Drilled Hole Upper photograph: Standard configuration of the Dual Source MTP. The rear panel with the entire MALDI unit is replaced by the LIFDI unit. Both cable connections are extended to avoid errors of the data system. Lower photograph: Open source housing with the LIFDI unit attached. After closing the rear panel the LIFDI probe can further be inserted until the tip is located between the first electrodes of the ion funnel. The emitter is illuminated by a white LED light to enable observation of sample transfer by a video camera. Mounting of a LIFDI Unit The Dual Source MTP of the Bruker ApexQe FT-ICR mass spectrometer in our lab is capable of simultaneously collecting ions from both ESI interface and MALDI sample plate. This is achieved by an ion funnel operated under rough vacuum of 1.8 mbar. After removal of the housing’s rear panel this position is open to accept any other ion source. The prototype LIFDI unit attached to the ApexQe replaces the rear panel of the the ion source housing. The LIFDI probe is aligned as to position the emitter axially into the ion funnel entrance. After closing the entrance of the ESI transfer capillary with a septum the pressure inside the ion source housing drops to about 8 x10 -3 mbar by the action of the rotary pump alone. Adding a turbomolecular pump (260 l s -1 ) to the housing delivers high vacuum of 3 x 10 -5 mbar. a d c ESI Interface Entrance of the ESI transfer capillary Rear panel bearing the MALDI sample stage Rear panel bearing LIFDI unit and turbo pump on its outside ESI transfer capillary Feed through and guide for LIFDI probe Ion funnel Emitter Liquid injection field desorption/ionization (LIFDI) ideally complements ESI to ionize nonpolar analytes. Additionally, LIFDI handles compounds sensitive to oxidation or hydrolysis by providing sample supply under inert conditions [1,2]. As LIFDI has proven capabilities on our sector instrument and on FT-ICR instrumentation elsewhere [3,4], it appeared promising to adapt a LIFDI source to a hybrid quadrupole-FT-ICR instrument such as the Bruker ApexQe. Acknowledgment The Deutsche Forschungsgemeinschaft (DFG) and SFB 623 are acknowledged for funding the FT-ICR instrument and Deutscher Akademischer Austausch- dienst (DAAD) for a travel grant to J. H. G. We are indebted to Prof. W. Krätschmer for a sample of C 60 , to Prof. U. Bunz for 3,4,5-tridodecyloxy- benzaldehyde, to Dr. S. Weidner for polystyrenes, and to N. Nieth for measuring reference spectra on our JMS 700 sector instrument. We thank Bruker Daltonik, Bremen, for assistance with parts of the ion source housing and helpful discussions. Illustration of the working principle of the Dual Source MTP accepting ions from two different points of origin at the same time. Scheme courtesy of Bruker Daltonik, Bremen. Construction and Operation of the ESI/LIFDI Combination Source The new ESI/LIFDI combination ion source can readily be switched to ESI operation. To do so, the turbomolecular pump is switched off, the LIFDI probe is retracted by 1 cm and the entrance of the ESI transfer capillary is opened. ESI spectra may then be acquired after about 2 min vacuum adjustment time. The electrostatic charging of the focusing electrodes at the LIFDI probe’s tip serves to deflect ions into the ion funnel and thereby replaces the standard deflection electrode. Switching between positive-ion and negative-ion mode requires about 15 s due to the time required for proper charging of these electrodes. Besides that, there is no noteworthy difference between ESI operation with the LIFDI unit mounted and ESI with the standard configuration of the Dual Source MTP. This is the first ESI/LIFDI combination ion source: a prototype developed for a Bruker ApexQe instruments featuring an ion funnel. Schematic of the LIFDI unit mounted to the ion source housing of the ApexQe instrument. The emitter is positioned in the high vacuum of the ion source housing between the first electrodes of the ion funnel. The additional turbomolecular pump is mounted to the rear panel and evacuates the ion source housing. Sealing of the ESI transfer capillary is achieved by a septum on its entrance (inserted photograph). White LED light Handouts for Download Handouts of this poster in PDF format can be downloaded after this ASMS conference at http://www.linden-cms.de and at http://www.rzuser.uni-heidelberg.de/~bl5

Transcript of ICR Mass Spectrometer

Page 1: ICR Mass Spectrometer

Jürg

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ss

Jürg

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, H. B

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Conc

ept o

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Bru

ker

Dua

l Sou

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MTP

The

Dua

l Sou

rce

MTP

™ a

vaila

ble

with

Bru

ker

Apex

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FT-I

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mas

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ectr

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sim

ulta

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ions

ent

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ospr

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ace

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ions

em

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ons

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defle

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an

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hile

th

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re tr

avel

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on-a

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er io

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sour

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may

be

atta

ched

aft

er r

emov

al o

f the

MAL

DI

asse

mbl

y fr

om th

e io

n so

urce

hou

sing

.

59th

ASM

S Co

nfer

ence

on

Mas

s Sp

ectr

omet

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enve

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O, J

une

5-9,

201

1

TP 0

56

Adva

ntag

es o

f LIF

DI

In L

IFD

I the

sam

ple

tran

sfer

cap

illar

y de

liver

s th

e an

alyt

e in

sol

utio

n di

rect

ly

onto

the

emitt

er p

ositi

oned

in th

e hi

gh v

acuu

m o

f the

ion

sour

ce. T

he

capi

llary

is fe

d th

roug

h a

drill

ed h

ole

in th

e gl

ass

insu

lato

r be

arin

g th

e em

itter

-hol

ding

met

al p

ins.

The

liqu

id b

ridge

s th

e na

rrow

gap

bet

wee

n th

e en

d of

the

capi

llary

and

the

activ

ated

em

itter

, and

thus

, pre

vent

s it

from

m

echa

nica

l dam

age.

The

pho

togr

aph

show

s so

lven

t wet

ting

the

emitt

er.

Act

ivat

ed E

mitt

erEm

itter

Pin

s

Sam

ple

Tran

sfer

C

apill

ary

Liqu

id

Wet

ting

the

Emitt

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ss In

sula

tor w

ithD

rille

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Uppe

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otog

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nfig

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of th

e D

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rear

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s re

plac

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e LI

FDI

unit.

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h ca

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conn

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ns a

re e

xten

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to a

void

err

ors

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eda

ta

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Low

er p

hoto

grap

h: O

pen

sour

ce h

ousi

ng w

ith th

e LI

FDI u

nit

atta

ched

. Aft

er c

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ar p

anel

the

LIFD

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be c

an fu

rthe

r be

in

sert

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ntil

the

tip is

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betw

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the

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nnel

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em

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lum

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whi

te L

ED li

ght t

o en

able

ob

serv

atio

n of

sam

ple

tran

sfer

by

a vi

deo

cam

era.

Mou

ntin

g of

a L

IFD

I Uni

t

The

Dua

l Sou

rce

MTP

of t

he B

ruke

r Ap

exQ

e FT

-ICR

m

ass

spec

trom

eter

in o

ur la

b is

cap

able

of

sim

ulta

neou

sly

colle

ctin

g io

ns fr

om b

oth

ESI

inte

rfac

e an

d M

ALD

I sam

ple

plat

e. T

his

is a

chie

ved

by a

n io

n fu

nnel

ope

rate

d un

der

roug

h va

cuum

of

1.8

mba

r. A

fter

rem

oval

of t

he h

ousi

ng’s

rea

r pa

nel t

his

posi

tion

is o

pen

to a

ccep

t any

oth

er io

n so

urce

. The

pro

toty

pe L

IFD

I uni

t att

ache

d to

the

Apex

Qe

repl

aces

the

rear

pan

el o

f the

the

ion

sour

ce h

ousi

ng. T

he L

IFD

I pro

be is

alig

ned

as to

po

sitio

n th

e em

itter

axi

ally

into

the

ion

funn

el

entr

ance

. Af

ter

clos

ing

the

entr

ance

of t

he E

SI tr

ansf

er

capi

llary

with

a s

eptu

m th

e pr

essu

re in

side

the

ion

sour

ce h

ousi

ng d

rops

to a

bout

8 x

10-3

mba

r by

th

e ac

tion

of th

e ro

tary

pum

p al

one.

Add

ing

a tu

rbom

olec

ular

pum

p (2

60 l

s-1 )

to th

e ho

usin

g de

liver

s hi

gh v

acuu

m o

f 3 x

10-

5m

bar.

a

d

c

ESI I

nter

face

Entr

ance

of t

he E

SI

tran

sfer

cap

illar

y

Rea

r pan

el b

earin

g th

e M

ALD

I sam

ple

stag

e

Rea

r pan

el

bear

ing

LIFD

I uni

t an

d tu

rbo

pum

p on

its

outs

ide

ESI t

rans

fer

capi

llary

Feed

thro

ugh

and

guid

e fo

r LIF

DI p

robe

Ion

funn

elEm

itter

Liqu

id in

ject

ion

field

des

orpt

ion/

ioni

zatio

n (L

IFD

I) id

eally

com

plem

ents

ESI

to io

nize

non

pola

r an

alyt

es.

Addi

tiona

lly, L

IFD

I han

dles

com

poun

ds s

ensi

tive

to

oxid

atio

n or

hyd

roly

sis

by p

rovi

ding

sam

ple

supp

ly

unde

r in

ert c

ondi

tions

[1,2

]. As

LIF

DI h

as p

rove

n ca

pabi

litie

s on

our

sec

tor

inst

rum

ent a

nd o

n FT

-ICR

inst

rum

enta

tion

else

whe

re

[3,4

], it

appe

ared

pro

mis

ing

to a

dapt

a L

IFD

I sou

rce

to a

hy

brid

qua

drup

ole-

FT-I

CR in

stru

men

t suc

h as

the

Bruk

er A

pexQ

e.

Ackn

owle

dgm

ent

The

Deu

tsch

e Fo

rsch

ungs

gem

eins

chaf

t (D

FG) a

nd

SFB

623

are

ackn

owle

dged

for

fund

ing

the

FT-I

CR

inst

rum

ent a

nd D

euts

cher

Aka

dem

isch

er A

usta

usch

-di

enst

(DAA

D) f

or a

trav

el g

rant

to J.

H. G

. W

e ar

e in

debt

ed to

Pro

f. W

. Krä

tsch

mer

for

a sa

mpl

e of

C 6

0, to

Pro

f. U.

Bun

z fo

r 3,

4,5-

trid

odec

ylox

y-be

nzal

dehy

de, t

o D

r. S

. Wei

dner

for

poly

styr

enes

, and

to

N. N

ieth

for

mea

surin

g re

fere

nce

spec

tra

on o

ur JM

S 70

0 se

ctor

inst

rum

ent.

We

than

k Br

uker

Dal

toni

k, B

rem

en, f

or a

ssis

tanc

e w

ith

part

s of

the

ion

sour

ce h

ousi

ng a

nd h

elpf

ul d

iscu

ssio

ns.

Illus

trat

ion

of th

e w

orki

ng p

rinci

ple

of th

e D

ual S

ourc

e M

TP a

ccep

ting

ions

from

tw

o di

ffer

ent p

oint

s of

orig

in a

t the

sam

e tim

e. S

chem

e co

urte

syof

Bru

ker

Dal

toni

k, B

rem

en.

Cons

truc

tion

and

Ope

ratio

n of

the

ESI/

LIFD

I Com

bina

tion

Sour

ceTh

e ne

w E

SI/L

IFD

I com

bina

tion

ion

sour

ce c

an r

eadi

ly b

e sw

itche

dto

ESI

ope

ratio

n. T

o do

so

, the

turb

omol

ecul

ar p

ump

is s

witc

hed

off,

the

LIFD

I pro

be is

ret

ract

ed b

y 1

cm a

nd th

e en

tran

ce o

f the

ESI

tran

sfer

cap

illar

y is

ope

ned.

ESI

spe

ctra

may

then

be

acqu

ired

afte

r ab

out 2

min

vac

uum

adj

ustm

ent t

ime.

The

ele

ctro

stat

ic c

harg

ing

of th

e fo

cusi

ng e

lect

rode

s at

the

LIFD

I pro

be’s

tip

serv

es to

def

lect

ions

into

the

ion

funn

el a

nd th

ereb

y re

plac

es th

e st

anda

rd d

efle

ctio

n el

ectr

ode.

Sw

itchi

ng b

etw

een

posi

tive-

ion

and

nega

tive-

ion

mod

e re

quire

s ab

out 1

5s

due

to th

e tim

e re

quire

d fo

r pr

oper

cha

rgin

g of

thes

e el

ectr

odes

. Be

side

s th

at, t

here

is n

o no

tew

orth

y di

ffer

ence

bet

wee

n ES

I ope

ratio

n w

ith th

e LI

FDI u

nit

mou

nted

and

ESI

with

the

stan

dard

con

figur

atio

n of

the

Dua

l Sou

rce

MTP

.

This

is th

e fir

st E

SI/L

IFD

I co

mbi

natio

n io

n so

urce

: a

prot

otyp

e de

velo

ped

for

a Br

uker

Ape

xQe

inst

rum

ents

feat

urin

g an

ion

funn

el.

Sche

mat

ic o

f the

LIF

DI u

nit m

ount

ed to

the

ion

sour

ce h

ousi

ng

of th

e Ap

exQ

e in

stru

men

t. Th

e em

itter

is p

ositi

oned

in th

e hi

gh v

acuu

m o

f the

ion

sour

ce h

ousi

ng b

etw

een

the

first

el

ectr

odes

of t

he io

n fu

nnel

. The

add

ition

al tu

rbom

olec

ular

pu

mp

is m

ount

ed to

the

rear

pan

el a

nd e

vacu

ates

the

ion

sour

ce h

ousi

ng.

Seal

ing

of th

e ES

I tra

nsfe

r cap

illar

y is

ach

ieve

d by

a s

eptu

m o

nits

ent

ranc

e (in

sert

ed p

hoto

grap

h).

Whi

te L

ED li

ght

Han

dout

s fo

r D

ownl

oad

Han

dout

s of

this

pos

ter

in P

DF

form

at c

an b

e do

wnl

oade

d af

ter

this

ASM

S co

nfer

ence

at

http

://w

ww

.lind

en-c

ms.

dean

d at

ht

tp:/

/ww

w.r

zuse

r.un

i-he

idel

berg

.de/

~bl5

Page 2: ICR Mass Spectrometer

Expe

rimen

tal

Expe

rimen

ts a

re p

erfo

rmed

on

a 9.

4T

Bruk

er A

pexQ

e FT

-ICR

(Qh-

ICR

hybr

id) i

nstr

umen

t with

Dua

l Sou

rce

MTP

(ESI

-to-

MAL

DI s

witc

habl

e). T

he

stan

dard

MAL

DI s

ampl

e st

age

and

the

defle

ctio

n el

ectr

ode

at th

e en

tran

ce o

f th

e io

n fu

nnel

are

rep

lace

d by

the

LIFD

I uni

t com

pris

ing

vacu

um lo

ck, p

robe

, tu

rbom

olec

ular

pum

p, o

bser

vatio

n op

tics,

and

vac

uum

gau

ge. F

or E

SI

oper

atio

n, th

e LI

FDI p

robe

is r

etra

cted

and

its

focu

sing

ele

ctro

des

are

used

to

defle

ct io

ns in

to th

e fu

nnel

. In

LIFD

I mod

e, th

e ES

I tra

nsfe

r ca

pilla

ry is

sea

led

by a

sep

tum

to a

chie

ve <

10–5

mba

r. L

IFD

I spe

ctra

are

acq

uire

d at

em

issi

on-c

ontr

olle

d io

n cu

rren

ts o

f 4×

10–8

mA.

Typi

cally

, ion

s ar

e ac

cum

ulat

ed fo

r 1–

5s

per

tran

sien

t and

then

tran

sfer

red

into

the

ICR

cell.

16–

64 tr

ansi

ents

with

1M

dat

a po

ints

are

acq

uire

d in

po

sitiv

e-io

n br

oadb

and

mod

e.Th

e tim

e-do

mai

n da

ta a

re z

ero-

fille

d an

d ap

odiz

ed b

y a

sine

-bel

l fun

ctio

n pr

ior

to F

ourie

r tr

ansf

orm

atio

n to

del

iver

a

mag

nitu

de s

pect

rum

.

Acqu

isiti

on is

con

trol

led

by B

ruke

r Ap

exCo

ntro

l 3.0

.0 s

oftw

are,

dat

a an

alys

is

is p

erfo

rmed

usi

ng th

e Br

uker

Dat

aAna

lysi

s 4.

0 so

ftw

are.

Tuni

ng o

f the

LIF

DI s

ourc

e is

ach

ieve

d us

ing

the

pers

iste

nt c

atio

n si

gnal

of

trih

exyl

(tetr

adec

yl)­p

hosp

honi

um tr

is(p

enta

fluor

oeth

yl)­t

riflu

orop

hosp

hate

,an

ioni

c liq

uid

[5].

Thus

, the

pot

entia

ls fo

r io

n tr

ansf

er fr

om th

e fie

ld e

mitt

er

thro

ugh

the

ion

funn

el in

to th

e hQ

h-in

terf

ace

are

adju

sted

. Pol

yeth

ylen

e gl

ycol

600

(bel

ow) a

nd P

EG15

00 a

re u

sed

for

exte

rnal

mas

s ca

libra

tion

to

assu

re m

ass

accu

raci

es o

f 1pp

m in

ESI

and

LIF

DI m

odes

of o

pera

tion.

LIFD

I spe

ctru

m o

f PEG

60

0 af

ter

exte

rnal

ca

libra

tion.

Rel

evan

t pa

ram

eter

s ar

e lis

ted

in th

e he

ader

.

Appl

icat

ions

of t

he N

ew E

SI/L

IFD

I Com

bina

tion

Sour

ce

OH

O

O

OC

12H

25

C12

H25

H25

C12

OH

O

O

OH

C12

H25

H25

C12

McL

-C12

H24

+.

+.

m/z

490

,401

6

m/z

658

,589

7

LIFD

I spe

ctru

m o

f 3,

4,5-

trid

odec

ylox

y-be

nzal

dehy

de

LIFD

I spe

ctra

of

[60]

fulle

rene

un

der

diff

eren

t tr

appi

ng

cond

ition

s

Qh

gas

1.0

l/s

Trap

ping

15

V

Inte

nsity

4 x

105

coun

ts

Qh

gas

1.35

l/s

Trap

ping

17

V

Inte

nsity

8 x

105

coun

ts

Qh

gas

1.2

l/s

Trap

ping

15

V

Inte

nsity

6 x

105

coun

ts

LIFD

I spe

ctra

of d

iffer

ent c

ompo

unds

are

obt

aine

d ex

hibi

ting

good

in

tens

ity w

hen

clos

ed-s

hell

ions

suc

h as

[cat

ion]

+, [

M+

H]+

or [M

+N

a]+

are

form

ed. A

s us

ual i

n FD

-MS,

non

pola

r an

alyt

es p

refe

rabl

y de

liver

op

en-s

hell

mol

ecul

ar io

ns, M

+• ,

mor

e re

adily

und

ergo

ing

radi

cal-

indu

ced

diss

ocia

tions

. The

refo

re, s

pect

ra o

f non

pola

r co

mpo

unds

are

stil

l so

mew

hat u

nsat

isfa

ctor

y du

e to

red

uced

ion

abun

danc

e an

d in

crea

sed

frag

men

tatio

n. P

resu

mab

ly, t

he p

ecul

iarit

ies

of th

e io

n op

tics

and

its

spec

ific

pres

sure

reg

imes

are

cau

sing

thes

e m

olec

ular

ion

loss

es. W

hile

th

e ov

eral

l tra

nsm

issi

on in

crea

ses

at h

ighe

r pr

essu

re, c

ollis

ion-

indu

ced

frag

men

tatio

n in

the

ion

funn

el r

egio

n an

d in

the

hexa

pole

acc

umul

atio

n io

n tr

ap c

ause

loss

es b

y di

ssoc

iatio

n(c

f. [4

, p. 1

321]

). Te

chni

ques

and

pa

ram

eter

s fo

r im

prov

emen

t are

bei

ng e

xplo

red.

Refe

renc

es[1

] Lin

den,

H.B

. Liq

uid

Inje

ctio

n Fi

eld

Des

orpt

ion

Ioni

zatio

n: a

New

Too

l for

Sof

t Ion

izat

ion

of S

ampl

es

Incl

udin

g Ai

r-Se

nsiti

ve C

atal

ysts

and

Non

-Pol

ar H

ydro

carb

ons.

Eur

. J. M

ass

Spec

trom

.200

4, 1

0, 4

59-4

68.

[2] G

ross

, J.H

.; N

ieth

, N.;

Lind

en, H

.B.;

Blum

bach

, U.;

Rich

ter,

F.J.;

Tau

cher

t, M

.E.;

Tom

pers

, R.;

Hof

man

n, P

. Li

quid

Inje

ctio

n Fi

eld

Des

orpt

ion/

Ioni

zatio

n of

Rea

ctiv

e Tr

ansi

tion

Met

al C

ompl

exes

. Ana

l. Bi

oana

l. Ch

em.

2006

, 386

, 52-

58.

[3] S

chau

b, T

.M.;

Rodg

ers,

R.P

.; M

arsh

all,

A.G

.; Q

ian,

K.;

Gre

en, L

.A.;

Olm

stea

d, W

.N. S

peci

atio

n of

Ar

omat

ics

in P

etro

leum

Ref

iner

y St

ream

s by

Con

tinuo

us F

low

FD

-FT-

ICR

Mas

s Sp

ectr

omet

ry. E

nerg

y &

Fuel

s20

05, 1

9, 1

566-

1573

.[4

] Sch

aub,

T.M

.; H

endr

icks

on, C

.L.;

Qui

nn, J

.P.;

Rodg

ers,

R.P

.;M

arsh

all,

A.G

. Ins

trum

enta

tion

and

Met

hod

for

Ultr

ahig

h Re

solu

tion

FD-F

T-IC

R-M

S of

Non

pola

r Spe

cies

. Ana

l. Ch

em.2

005,

77,

131

7-13

24.

[5] G

ross

, J.H

. Liq

uid

Inje

ctio

n Fi

eld

Des

orpt

ion/

Ioni

zatio

n M

ass

Spec

trom

etry

of I

onic

Liq

uids

. J. A

m. C

hem

. So

c. M

ass

Spec

trom

.200

7, 1

8, 2

254-

2262

.

Fina

l Sta

tem

ents

LIFD

I spe

ctra

of p

olar

and

ioni

c co

mpo

unds

ar

e re

adily

obt

aine

d.

LIFD

I spe

ctra

of n

onpo

lar

arom

atic

hy

droc

arbo

ns e

xhib

it in

tens

e m

olec

ular

ions

.

Mas

s ac

cura

cy is

equ

al to

ESI

mod

e.

Sour

ce c

an e

asily

be

switc

hed

back

and

fo

rth

betw

een

ESI a

nd L

IFD

I ope

ratio

n.

The

first

ESI

-to-

LIFD

I sw

itcha

ble

com

bina

tion

ion

sour

ce is

pre

sent

ed a

s a

wor

king

pro

toty

pe.

Colli

sion

s du

ring

ther

mal

izat

ion

and

trap

ping

pro

babl

y pr

even

t lab

ile m

olec

ular

io

ns fr

om s

urvi

ving

.

The

tran

smis

sion

of t

he io

n fu

nnel

can

be

redu

ced

upon

eva

cuat

ion

from

1.8

mba

r st

anda

rd p

ress

ure

to le

ss th

an 1

0-4

mba

r.

Mol

ecul

ar io

ns o

f alip

hatic

hyd

roca

rbon

s ha

ve n

ot y

et b

een

obse

rved

.

LIFD

I spe

ctru

m o

f po

lyst

yren

e 10

50