combination of direct analysis in real tiem with ft-icr ms
TRANSCRIPT
CC28
C30
CnH
2n+
1CO
ON
a+
O2 C
lass
15
C26
CnH
2n+
1CO
ON
a
DBE10 5C
32C
24
1040
20
5 030
Rel
ativ
e A
bu
nd
ance
(%
to
tal)
Car
bo
n N
um
ber
1040
2030
C34
C22
m/z
200
300
400
500
600
700
Freq
uenc
y (k
Hz)
m/z
Diff
eren
tial
ampl
ifier
Freq
uenc
y sp
ectr
umM
ass
Spec
trum
Tran
sien
tA
B
CD
B
F LF Cv
r•
Excitation plates
Det
ecti
on p
late
sB
F LF Cv
r•
Excitation plates
Det
ecti
on p
late
s
(-)
DA
RT
FT-
ICR
MS
of
Bio
tar
30O
5O
4O
3
BE20
O5
1525O
4O
3
DB 10 515 0
O6
O7
O8
30 25 DBE20 15 10 5 0 Rel
ativ
e A
bu
nd
ance
(% t
ota
l)C
arb
on
Nu
mb
er10
4060
200
3050
1040
6020
3050
1040
6020
3050
(-)
DA
RT
FT
-IC
R M
S o
f B
iota
rs
am
ple
Hete
roato
m C
lass D
istr
ibu
tio
n P
lot
m/z
C60H
+
C60O
H+
Fu
lle
ren
eC
60
INT
OD
UC
TIO
N
Ultra
-hig
hre
solu
tion
and
mass
accura
cy
pro
vid
ed
by
Fourier
Tra
nsfo
rmIo
nC
yclo
tron
Resonance
Mass
Spectr
om
etr
y(F
T-I
CR
MS
)enable
sunam
big
uous
assig
nm
ent
of
thousands
of
ele
menta
lcom
positio
ns
for
com
ponents
constitu
ting
com
ple
xorg
anic
mix
ture
.“S
oft”,
non-d
istr
uctive
atm
ospheric
ioniz
ation
meth
ods
such
as
ele
ctr
ospra
yio
niz
ation
(ES
I),
atm
ospheric
pre
ssure
chem
ical
ioniz
ation
(AP
CI)
and
atm
ospheric
pre
ssure
photo
ioniz
ation
(AP
PI)
are
wid
ely
used
incom
bin
ation
with
FT-I
CR
MS
for
analy
sis
ofpetr
ole
um
and
petr
ole
um
derived
pro
ducts
,bio
-fuels
,environm
enta
lsam
ple
setc
.H
ow
ever
their
applic
ation
som
etim
es
require
tedio
us
sam
ple
pre
para
tion
and
there
fore
can
be
affecte
dby
the
com
pounds
solu
bili
ty,
inte
rfere
nce
with
conta
min
ants
,and
matr
ixsig
nals
.U
ltim
ate
lyth
islim
its
the
range
of
sam
ple
sand
com
pounds
that
can
be
successfu
llyanaly
zed
with
these
ioniz
ation
techniq
ues.
This
isw
here
directa
naly
sis
inre
alt
ime
(DA
RT
)becom
es
rele
vant.
DA
RT
isa
new
ioniz
ation
techniq
ue
thatenable
sra
pid
analy
sis
ofvarious
sam
ple
satam
bie
ntconditio
ns,re
quirin
gno
sam
ple
pre
para
tion.Its
been
show
nth
atD
AR
Tin
com
bin
ation
with
tim
e-o
f-flig
ht
mass
spectr
om
ete
rsw
as
successfu
llyused
for
targ
ete
danaly
sis
of
low
mole
cula
rw
eig
ht
com
pounds
(up
to800
Da)
indiffe
rent
matr
ices.
Inth
efr
am
es
oft
his
work
we
couple
the
DA
RT
®io
nsourc
eto
FT-I
CR
mass
spectr
om
ete
rto
investigate
applic
abili
tyof
such
configura
tion
for
analy
sis
of
com
ple
xorg
anic
mix
ture
sand
indiv
idualc
om
pounds.
Acusto
m-b
uilt
9.4
TF
T-I
CR
mass
spectr
om
ete
rw
as
used
toacquire
mass
spectr
a.
Calib
ration
of
the
instr
um
ent
was
carr
ied
out
with
Agile
nt
HP
mix
by
ES
I.A
modula
rIC
Rdata
acquis
itio
nsyste
m(M
IDA
S)colle
cte
dand
pro
cessed
the
ICR
data
.
EX
PE
RIM
EN
TA
L
FT-I
CR
MS
.
Th
eC
om
bin
ati
on
of
Dir
ec
tA
na
lys
isin
Re
al
Tim
ew
ith
Fo
uri
er
Tra
ns
form
Ion
Cy
clo
tro
nR
es
on
an
ce
Ma
ss
Sp
ec
tro
me
try
AC
KN
OW
LE
DG
EM
EN
TS
The
auth
ors
acknow
ledge
IonS
ense,
Inc.
for
pro
vid
ing
DA
RT
sourc
eand
NS
Ffo
rfinancia
lsupport
(gra
nt#
DM
R-0
0-8
4173).
One
ofus
(Terr
ieK
weifio
)th
anks
NS
Fand
the
National
Hig
hM
agnetic
Fie
ldLabora
tory
(Talla
hassee,
FL)
for
researc
hexperience
pro
vid
ed
thro
ugh
the
RE
Upro
gra
m.
CO
NC
LU
SIO
NS
● ● ●
DA
RT
sourc
ecouple
dw
ith
FT-I
CR
MS
dem
onstr
ate
dsuccessfu
lanaly
sis
of
com
pounds
within
acom
ple
xm
atr
ix.W
edete
cte
dtr
aces
ofcocain
eon
all
analy
zed
dolla
rbill
s.
The
dete
ction
of
DA
RT
dem
onstr
ate
spote
ntialofth
isio
niz
ation
meth
od
for
analy
sis
of
com
pounds
with
hig
hboili
ng
(sublim
ation)
tem
pera
ture
exceedin
gopera
tionalt
em
pera
ture
oft
he
DA
RT
sourc
e.
Com
bin
ation
ofD
AR
Tw
ith
FT-I
CR
MS
was
successfu
llyused
for
directanaly
sis
of
com
ple
xm
ixtu
res
such
as
naphth
enate
deposits
and
bio
tar.
This
appro
ach
required
no
sam
ple
pre
para
tion
and
pro
vid
es
rapid
identification
ofc
om
ponents
oft
he
mix
ture
s.
targ
ete
d
and
nic
otine
into
bacco
ofc
igare
tte
Cfu
llere
ne
with
60
RE
SU
LT
SA
ND
DIS
CU
SS
ION
Fig
ure
1.
Tra
nsfo
rmation
of
ion
cyclo
tron
motion
into
am
ass
spectr
um
.(A
)sche-
matic
repre
senta
tion
ofio
ncyclo
tron
rota
tion
inan
ICR
cell
,(B
)tim
e-d
om
ain
image-
curr
ent
sig
nalfr
om
opposed
dete
ction
ele
ctr
odes,
(C)
frequency-d
om
ain
spectr
um
obta
ined
by
fastF
ourier
transfo
rmofth
edig
itiz
ed
tim
e-d
om
ain
sig
nal,
and
(D)
mass
spectr
um
obta
ined
by
frequency-t
o-m
/zconvers
ion.
Fig
ure
2.S
chem
eoft
he
DA
RT
sourc
e.
Fig
ure
6.(-
)D
AR
TF
T-I
CR
mass
spectr
um
ofsodiu
mnaphth
enate
deposit.S
odiu
mnaphth
enate
sare
natu
rals
ufa
cta
nts
and
sta
bili
ze
wate
r-oil
em
uls
ion.A
naly
sis
ofth
enaphth
enate
sw
ith
(-)
ES
Ire
quires
tedio
us
sam
ple
pre
para
tion,
where
as
DA
RT
enable
sstr
aig
htf
orw
ard
analy
sis
thro
ugh
directs
am
ple
intr
oduction.
Fig
ure
7.
(-)
DA
RT
FT-I
CR
MS
of
Bio
tar
sam
ple
.In
set
isa
hete
roato
mcla
ss
dis
trib
ution
plo
twhic
hshow
sth
ere
lative
abundance
ofO
cla
sses
dete
cte
d.
x
Fig
ure
3.
Analy
sis
of
over
ten
U.S
.curr
ency
bill
sw
ith
DA
RT
show
ed
traces
ofcocain
edete
cte
don
every
bill
.
(+)
DA
RT
FT-I
CR
spectr
um
from
the
surf
ace
of
U.S
.dolla
rbill
.T
he
most
abundant
peak
inm
ass
spectr
um
corr
esponds
topro
tonate
dcocain
e.
Fig
ure
4.
cig
are
tte
(Marlboro
gold
pack).
The
most
abundant
peak
corr
esponds
topro
tonate
dnic
otine
mole
cule
.Nic
otine
isa
natu
rala
lkalo
idconstitu
ting
up
to3%
oft
obacco
dry
weig
ht.
(+)
DA
RT
FT-I
CR
spectr
um
of
tobacco
leaf
obta
ined
from
a
Fig
ure
5.(+
)D
AR
TF
T-I
CR
spectr
um
ofC
fulle
rene.
The
dete
ction
of
fulle
rene
at
these
conditio
ns
issurp
risin
gbecause
sublim
ation
tem
pera
ture
(of
60
The
mass
spectr
um
dis
pla
ys
[M+
H]
ion
as
the
main
peak,
where
as
[M+
O+
H]
ion
corr
esponds
toanaly
teoxid
ation.
T)
Cis
~
Cfr
om
the
pro
be
surf
ace.
++
sub
60
60
500
Cand
sig
nific
antly
hig
her
than
tem
pe
ratu
reo
fth
eD
AR
Ts
ou
rce
(37
0C
).W
eh
yp
oth
es
ize
dir
ec
tdesorp
tion/ioniz
ation
of
o o
Te
rrie
Kw
eif
io,
Vla
dis
lav
V.
Lo
bo
din
,A
lan
G.
Ma
rsh
all
12
2
1
2
Depart
ment
of
Chem
istr
y,V
irgin
iaP
oly
technic
Institu
teand
Sta
teU
niv
ers
ity,
Bla
cksb
urg
,V
A2
40
61
-00
02
NationalH
igh
Magnetic
Fie
ldLabora
tory
,F
lorida
Sta
teU
niv
ers
ity,
1800
East
PaulD
ira
cD
rive
,Ta
llah
asse
e,F
L3
23
10
-40
05
m/z
304.
230
4.18
930
4.17
930
4.16
930
4.15
930
4.14
830
4.13
830
4.12
830
4.11
830
4.10
8
m/z
163.
149
163.
144
163.
139
163.
133
163.
128
163.
123
163.
118
163.
113
163.
108
163.
103
Dir
ectA
naly
sis
InR
ealT
ime
(DA
RT
).
Fig
ure
2
Within
the
DA
RT
sourc
e,
ioniz
ation
occurs
from
exposure
ofsam
ple
with
meta
-sta
ble
heate
dgas
mole
cule
sem
erg
ing
from
the
sourc
etip.
Various
com
ponents
of
DA
RT
can
be
regula
ted
and
modifie
dto
accom
plis
hdesired
ioniz
ation
fordiffe
rentcom
pounds.F
acto
rssuch
as
tem
pera
ture
,gas
flow
,voltage
pote
ntial,
and
gas
sourc
ecan
be
contr
olle
dto
uniq
uely
accom
plis
hio
niz
ation
().
Four
ier
Tran
sfor
m
He(
23 S)
+nH
O 2�
[(H
2O) n
-1+
H]+
+O
H-+
He(
11 S)
Me
ta-s
tab
leh
eliu
mg
as
iscre
ate
dth
rou
gh
me
ch
an
ism
of
ele
ctr
icg
low
dis
charg
ew
here
an
ele
ctr
iccurr
ent
ispassed
thro
ugh
gas
mole
cule
sth
us
excitin
gth
eato
mto
ahig
her
energ
etic
sta
tecre
ating
pla
sm
a.
Heliu
m,
with
a19.8
eV
energ
etic
excited
sta
te,
isan
ideal
gas
sin
ce
ioniz
ation
energ
ies
of
most
atm
ospheric
gases
and
org
anic
mole
cule
sare
low
erth
an
19.8
eV
.
Excited
He
ato
ms
inte
ract
with
atm
ospheric
gases
(N,
HO
,O
)and
analy
tem
ole
cule
sw
hic
hle
ads
toio
nfo
rmation
by
directP
ennin
gio
niz
ation
ofr
eagenti
ons
(Eq.2
)and
subsequenti
oniz
ation
of
analy
te(
.
22
2(E
q.1)as
well
as
form
ation
Eq.3
)
[(H
2O) n
-1+
H]+
+M�
[M+
H]+
+nH
2O
Fig
ure
7.
Isoabundance
colo
rconto
ure
dplo
tsof
double
bond
equiv
ale
nt
(DB
E=
num
ber
of
rings
plu
sdouble
bonds)
vs.
carb
on
num
ber
for
six
most
abundant
hete
roato
mcla
sses
dete
cte
din
bio
tar
sam
ple
.T
he
incre
ase
inD
BE
indic
ate
sin
cre
ase
inaro
maticity
.
Co
ca
ine
MW
=3
03
.35
g/m
ol
[M+
H]+
[M+
H]+ N
ico
tin
e
MW
=1
62
.26
g/m
ol
m/z
=304.1
543
m/z
=163.1
297
=~
Tsub
500
Co
He*
+M�
M+
.
+H
e+
ē
(3)
(2)
(1)
U.S
.D
oll
ar
Bil
l
Cig
are
tte
(Marl
bo
roG
old
)
m/z
m/z
m/z