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2006
1
1.
2.
3. TOF-MS
4.
5. MULTUM Linear plus
6.
7.
8.
9.
2
3
7
14
23
24
48
49
50
2
1.
TOF-MS
TOF-MS
TOF-MS 1)2)
TOF-MS
MULTUM Linear Plus
350,000 3)
TOF-MS
TOF-MS 1
1
3
2.
2-1 (Mass Spectrometer)
EI CI FAB
ESI
MALDI PD FD
ICP APCI
MCP
4
2-2 (Time of Flight-MS)
(TOF-MS) 1946 Stephens 4)
1970
(MALDI) 5)
TOF
2-2-1 TOF-MS
TOF-MS
ms
6)7) 8)
2-2-2 TOF-MS
TOF-MS
e
m z V v
2
2
1mvzeV =
L t t
(2-2-1)
5
==z
m
eVL
v
Lt
2
1
Fig. 2-2-1 TOF-MS
2-2-3 TOF-MS
R t t
t
t
m
mR ==
2
(2-2-2)
(2-2-3)
6
Fig. 2-2-2
7
3. TOF-MS
3-1 TOF-MS
TOF-MS (2-2-3) t
t
t
MULTUM MULTUM
TOF-MS t
t
MULTUM 2000
MULTUM Linear plus MULTUM
Linear plus 4 28
Q MULTUN Linear plus
2000 2.5km
350000
MULTUM Linear plus
4 MULTUM 9)
MULTUM S MULTUN
8
3-2
TOF-MS
Transfer matrix
3-2-1 Transfer matrix
Fig.3-2-2 m0 U0
v0=(2U0/ m0)1/2
m=m0(1+ ) U=U (1+ )
(x, ,y, , , ,l)
x y
(x, ,y, , , ,l)
(x0, 0,y0, 0, 0, 0,l0) Transfer matrix
Transfer matrix
=
0
0
0
0
0
1)|()|(00)|()|(
0100000
0010000
000)|()|(00
000)|()|(00
0)|()|(00)|()|(
0)|()|(00)|()|(
l
y
x
lllxl
y
yyy
x
xxxxx
l
y
x
1 1
Transfer matrix
Transfer matrix Transfer matrix
(3-2-1)
9
Fig. 3-2-2
3-2-2 MULTUM
Transfer matrix
±
±
±
±
=
0
0
0
0
0
10)|(0000
0100000
0010000
0001000
0000100
0000010
0000001
l
y
x
lRl
y
x
0 1± 0 1±
Transfer matrix10)
MULTUM MULTUM 4
Q 8
(3-2-3)
(3-2-2)
10
0 1 0 1
=
0
0
0
0
0
100005.065388.00000321.000000.0
0100000
0010000
00000000.100445.000
00000076.000000.100
000033.000099996.000805.0
000160.000000001.099996.0
l
y
x
l
y
x
TOF-MS
Q
MULTUM
Fig.
3-2-3 MULTUM
(3-2-3)
11
Fig. 3-2-3 MULTUM
12
3-3-2 TOF-MS
TOF-MS MULTUM
TOF-MS MULTUM Linear Plus
MULTUM Linear Plus Fig.
3-3-1 1
4
4 1 2
3 4
4
8
3
2
Q
Q Q
Fig. 3-3-3
Fig. 3-3-1 MULTUM Linear Plus
13
Fig. 3-3-2
TOF-MS
14
4.
4-1 TOF-MS
TOF-MS
TOF-MS
TOF-MS
Fig. 4-1-1
Fig. 4-1-1
90 95 100 105 110
Inte
nsity (
arb
.unit)
Time of flight ( µs)
Fig. 4-1-1
15
4-2
TOF
TOF-MS
4-2-1 TOF-MS
TOF-MS 1 L
L
n L
10LnLL +=
n
t
( )m
z
eVLnL
v
LnL
v
Lt
2
1
10
10 +=+
==
Ti
t 0
i0T+= ntt
(4-2-3)
1 t
2 t
(4-2-1)
(4-2-2)
(4-2-3)
16
t t
( ) TT1212
=== nnnttt
n1 n2 n (4-2-4)
T
1
T
T
4-2-2 (Correlation function)
TOF-MS
n T
T f (t)
x t
+=+=2/T
2/TT)()(
T
1lim)()()( dttxtxtxtxC
TOF f (t)
TOF f1 (t) f2 (t) fn (t)
TOF
(4-2-4)
(4-2-5)
17
Fig. 4-2-1 TOF
Fig. 4-2-1
TOF-MS
T Fig.4-2-1 ni
i t 0
T
TOF
T
TOF f1 f2 fn
T
( ) ( ) dtnttfnttfnttfC nnn ++++++= )T(TT)T( 0202101 L
ni fi
fi fi T
T T
1 TOF
A f1 f2 fn
T A f1 f2 fn
T 0
T Ti i
T
t0 1
T =2T
(4-2-5)
18
TOF
T T
Fig. 4-2-2 T
T T
T T
m/z
Fig. 4-2-2
19
4-3
TOF-MS
TOF-MS
4-3-1 MULTUM linear plus
TOF-MS
’ MULTUM linear plus Fig. 4-3-1
0
TOF-MS
MULTUM linear plus
20
Fig. 4-3-1 MULTUM Linear Plus
4-3-2
MULTUM linear plus
946.4mm 1085.9mm
MULTUM linear plus
n
( ) ( )11
0859.129464.0 Lnz
meVLn ++
m/z
(4-3-1)
(4-3-1)
21
4-3-3
(4-3-1)
TOF-MS
(4-3-1) T n
( ) ( )T84572.0T73707.0 nn ++
(4-3-2)
(4-3-2)
( ) ( ) +++ T84572.0T73707.0 nn
(4-3-2)
(4-3-3)
22
4-4 New calibration method
TOF-MS
(f1 f2 fn)
T
(4-3-3)
T T
6
( ) ( ) dtnttfnttfnttfCt
t
nnn ++++++= )T(TT)T( 0202101 L
T
t FORTRAN
(4-4-1)
23
5. MULTUM linear plus
TOF-MS MULTUM
linear plus
Fig.2-3-1 Wiley-McLaren
EI EI
d1=6mm D=8mm
Fig. 5-1 EI
MULTUM 5cm
156.87 7.5mm 8
10mm 10mm Q
4
8 Q
1.284m 0.429m
6mm
24
40cm 40cm
60cm 70cm 20cm
Fig. 5-2 Fig. 5-3
Fig. 5-2 MULTUM Linear Plus
25
Fig. 5-3 MULTUM Linear Plus
TOF-MS
(F4655-10 )
10 m
106
LC564A
26
6.
TOF-MS MULTUM linear plus
MCP
MCP
6-1
26 40 51 66 s TOF
MCP 2.3 V 2GS/s
1000 Fig.
6-1-1-(a) (d)
30 35 40 45
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(a) 26 s
27
40 45 50 55 60
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(b) 40 s
55 60 65 70
0.0
0.1
0.2
0.3
0.4
0.5
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(c) 51 s
28
70 75 80 85
0.0
0.1
0.2
0.3
0.4
0.5
0.6
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(d) 66 s
Fig. 6-1-1 TOF
4 T
( ) ( ) ( ) ( )++++++++=t
tdtTnttfTnttfTnttfTnttfTC 4
40303202101)(
nstnsdTsTs 5005.0155.7 ==µµ
Fig. 6-1-2
Table. 6-1
TOF-MS
Bz
mAtof +=
A B systematic constant
A B
A B
29
TOF-MS
z
mAT =
N11)
8 10 12 14
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
T (µs/cycle)
Fig. 6-1-2
Table. 6-1
30
TOF Fig. 6-1-2
T TOF-MS
Table. 6-1 ppm
6-2 Xe
Xe Xe
15 34 55 73 s TOF
MCP 2.3 V
2GS/s 1000
Fig. 6-2-1 (a) (d)
31
15 20 25 30 35
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
urb
.unit)
Time of flight ( µs)
(a) 15 s
35 40 45 50
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(b) 34 s
32
55 60 65 70 75
0.0
0.2
0.4
0.6
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(c) 55 s
75 80 85 90
0.0
0.2
0.4
0.6
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(d) 73 s
Fig. 6-2-1 Xe TOF
4 T
33
( ) ( ) ( ) ( )++++++++=t
tdtTnttfTnttfTnttfTnttfTC 4
40303202101)(
nstnsdTsTs 505.0255 ==µµ
Fig. 6-2-2
Table. 6-2-1
z
mAT =
130Xe+
5 10 15 20 25-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
Inte
nsity (
arb
.unit)
T (µs/cycle)
34
21.0 21.5
0.0
0.2In
tensity (
arb
.unit)
T (µs/cycle)
Fig. 6-2-2 Xe
Table.6-2-1
Xe
Table. 6-2-1
0.01
Xe
35
TOF
Xe
Xe130Xe+ 136Xe+
129Xe+ Table. 6-2-2
Table. 6-2-2 Xe+
36
6-3
31 47 72 93 s TOF MCP
2.3 V 2GS/s 1000
Fig. 6-3-1 (a)
(d)
35 40 45 50
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(a) 31 s
37
50 55 60 65
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(b) 47 s
75 80 85 90
0.0
0.1
0.2
0.3
0.4
0.5
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(c) 72 s
38
95 100 105 110
0.00
0.05
0.10
0.15
0.20
0.25
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(d) 93 s
Fig. 6-3-1 TOF
4 T
( ) ( ) ( ) ( )++++++++=t
tdtTnttfTnttfTnttfTnttfTC 4
40303202101)(
nstnsdTsTs 5005.0155.7 ==µµ
Fig. 6-3-2 (a)
4 Fig. 6-3-2 (a)
N N Fig.
6-3-1 (b)
(4-3-3)
T
( ) ( ) ++++ T84572.0T73707.0 nn
( ) ( ) dtnttfnttfnttfCt
t
nnn ++++++= )T(TT)T( 0202101 L
nsnstnsdTsTs 3005005.0155.7 ===µµ
39
Fig.4-3-2 (b)
N
Table. 6-3
Bz
mAT +=
A B
m/z
6 8 10 12 14
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
T (µs/cycle)
(a)
40
6 8 10 12 14
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
T (µs/cycle)
(b)
Fig. 6-3-2
Table. 6-3
TOF-MS
TOF-MS
41
6-3
MULTUM linear plus
TOF-MS
22ns
2500V MULTUM linear plus
70 175 300 420 s
Fig. 6-4-1 (a) (d)
70 75 80 85 90
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(a) 70 s
42
175 180 185 190 195
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(b) 175 s
300 305 310 315 320
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(c) 300 s
43
420 425 430 435 440
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.unit)
Time of flight ( µs)
(d) 420 s
Fig. 6-4-1 TOF
4 T
( ) ( ) ( ) ( )++++++++=t
tdtTnttfTnttfTnttfTnttfTC 4
40303202101)(
nstnsdTsTs 505.0355 ==µµ
Fig.4-4-5
Table.4-4
44
5 10 15 20 25 30 35
0.0
0.2
0.4
0.6
0.8
1.0
Inte
nsity (
arb
.un
it)
T (µs/cycle)
Fig. 6-4-2
Table. 6-4
Fig. 6-4-1 (a) (d)
TOF-MS T
TOF
45
6-5
T=10 s FWHM=20ns
( ) ( )++=t
tdtTntfTntfTC 2211)(
n1=1 n2
Fig. 6-5-1 n=n2 n1
Fig. 6-5-1
Fig. 6-5-1 n
T t
n
tA
nn
tAT ==
12
(6-5-1)
46
A
t
N2+
2GS/s 1000
N2+ n1=1 n2=2 4 7 9 12
( ) ( )++=t
tdtTntfTntfTC 2211)(
Fig. 6-5-2
50ns
Fig. 6-5-2 N2+
47
Fig. 6-5-1 Fig. 6-5-2
22ns N2+ 50ns
48
7.
6 TOF-MS
1 TOF
TOF-MS
TOF-MS
TOF-MS
1 TOF
TOF-MS
MULTUM Linear plus
MULTUM
TOF-MS
49
8.
50
9.
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Rosenbauer, J. Mass Spectrom., 35 (2000), 163
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Mass Spectrom. 115 (2001), 437
4) W. E. Stephens, Phys. Rev., 669 (1946), 691
5) M. Karas, D. Backmann, U. Bahr, and F. Hillenkamp, Int. J. Mass
Spectrom. Ion Processes, 78 (1987), 53
6) W. C. Wiley and I. H. McLaren, Rev. Sci. Instr, 226 (1955), 1150
7) C. Weichharedt et al, Mass Spectrometry Rev, 115 (1996), 139
8) V. I. Karataev, B. A. Mamyrim, and D. V. Shmikk, Sov. Phys. Tech. Phys.
16 (1972), 1177
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Soc. Jpn. 551 (2003), 349
10) M. Ishikhara, M. Toyoda, T. Matsuo, Int. J. Mass Spectrom. 1197 (2000),
179
11) ,
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