ICR Mass Spectrometer
Transcript of ICR Mass Spectrometer
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
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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