Jürg

en H

. Gro

ss

Jürg

en H

. Gro

ss 11

, H. B

ernh

ard

Lind

en

, H. B

ernh

ard

Lind

en 22

1In

stitu

te o

f Org

anic

Che

mis

try,

Hei

delb

erg

Univ

ersi

ty, I

m N

euen

heim

er F

eld

270,

691

20 H

eide

lber

g, G

erm

any.

2

Lind

en C

MS,

Auf

dem

Ber

ge 2

5, 2

8844

Lee

ste,

Ger

man

y.

Com

bine

d ES

I/LI

FDI

Com

bine

d ES

I/LI

FDI --

Ion

Sour

ce fo

r a

FTIo

n So

urce

for

a FT

-- ICR

Mas

s Sp

ectr

omet

erIC

R M

ass

Spec

trom

eter

Conc

ept o

f the

Bru

ker

Dua

l Sou

rce

MTP

The

Dua

l Sou

rce

MTP

™ a

vaila

ble

with

Bru

ker

Apex

Qe

FT-I

CR

mas

s sp

ectr

omet

ers

sim

ulta

neou

sly

hand

les

ions

ent

erin

g vi

a th

e el

ectr

ospr

ay in

terf

ace

and

ions

em

ergi

ng fr

om th

e (M

A)LD

I tar

get.

ESI i

ons

are

defle

cted

into

an

ion

funn

el w

hile

th

ose

from

MAL

DI a

re tr

avel

ing

on-a

xis.

Oth

er io

niza

tion

sour

ces

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

ry, D

enve

r, C

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

er

Gla

ss In

sula

tor w

ithD

rille

d H

ole

Uppe

r ph

otog

raph

: Sta

ndar

d co

nfig

urat

ion

of th

e D

ual S

ourc

e M

TP.

The

rear

pan

el w

ith th

e en

tire

MAL

DI u

nit i

s re

plac

ed b

y th

e LI

FDI

unit.

Bot

h ca

ble

conn

ectio

ns a

re e

xten

ded

to a

void

err

ors

of th

eda

ta

syst

em.

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

losi

ng th

e re

ar p

anel

the

LIFD

I pro

be c

an fu

rthe

r be

in

sert

ed u

ntil

the

tip is

loca

ted

betw

een

the

first

ele

ctro

des

of th

e io

n fu

nnel

. The

em

itter

is il

lum

inat

ed b

y a

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

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 <

4×

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.;

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n M

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. J. A

m. C

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. So

c. M

ass

Spec

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.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