Post on 23-May-2020
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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Spectrom. Ion Processes, 78 (1987), 53
6) W. C. Wiley and I. H. McLaren, Rev. Sci. Instr, 226 (1955), 1150
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179
11) ,