??? ??????? (NMR)

1
??? ??????? (NMR)
2
1 ??

• ??????(Nuclear Magnetic Resonance
  spectroscopy, NMR)????????????,????????????
• ?????????????????(4600MHz)???,?????????
  ????????????????????????,????????????????????????,
  ?????????????????????????????????????????,????????
  ????????????????????????????

3
1930??,?????????????????????????????????????,????
?????,????????????????????????????????????????????
????,???1944????????????
4
Related Nobel Prize
1952???????????(Felix Bloch ) ??? (Edward
Purcell)???????????????????????????
???(Felix Bloch )
??? (Edward Purcell)
5
1991??????????R.R.Ernst(1933-) ???????
????????????????????????????????????
?.???????????? ?.???????
?.??????
6
2002?????? ????????. ????for his
development of nuclear magnetic resonance
spectroscopy for determining the
three-dimensional structure of biological
macromolecules in solution". ????2002?????????????
?
If one knows all the measurements of a house
one can draw a three-dimensional picture of that
house. In the same way, by measuring a vast
number of short distances in a protein, it is
possible to create a three-dimensional picture of
that protein.
7
2003??????? ??????????? (Paul
Lauterbur)?????????????(Peter Mansfield )
Peter
???????????????
8
MRI is used for imaging of all organs in the
body.
9
NMR???

• 1????????,????????????
• 2?????????,???????,??????????????????
• 3??????,?????????,????????????????,???????????
• 4????,????????????
• 5 ??????(MRI)

10
????????

• ??????
• ???????????,??????????,????????????????????

p????,???????,?????????
??h??????(6.6310-34Js)-I??
????,???????????????
11
???????????????????,???????????????????????,??????
???,??????????,? µ ? p
???????,???????????????,???????????,??????????µ
???,??????,1???????5.0510-27JT-1
12
????????????????????

• ???A ????Z ????? NMR?? ???
• ?? ?? 0 ? 12C6 16O832S16
  
• ?? ? ½ ? 1H1,13C6
  19F9,15N7,31P15
• ?? ?? 3/2,5/2 ? 17O8,33S16
• ?? ?? 1,2,3 ? 2H1,14N7

13
?????????

• I0,?16O?12C?32S?28Si ?
• ???,???????????????
• ? I1????,
• I3/2 11B?35Cl?79Br?81Br?
• I5/2 7O?127I?
• I1 2H?14N?
• ?????????????????,??
  ?????,???????????????,??????

14
? I1/2???? 1H? 19F? 31P? 13C?
?????????????????,?????????,?????????????????????
1H? 19F? 31P ???????? ?????100,????????,??
?1H,??????????????????,??1H?NMR???,???????????
15

• ?I0?,p0,???????,???????Igt0?,p?
  0,????????,??????
• I1/2???????????????????????,??(b)????????,?????
  ????,?NMR????????Igt1/2????,????????????????

????????
16

• ??????????13C?1H?15N?19F?31P?????????,????????
  1/2,??????????,???????????????
• ??,????????????????????????????????,?1H??????9
  9.985,19F?31P?????100,??,?????????,????,?13C????
  ???1.1,????15N?17O??????1??,??????????,?????????
  ???????????????????????

17
????????????????

• ????????,????????????????????,??????
• ????? 2I1
• ?H???,?I 1/2,???????,?????2(1/2)12,?????????
  ?????,?????????????B0??????,???????B0???

18
H????????
19
??????????????
20

• ??,I1/2??????,?????,????????????,?????????????
  ??????????(µF)lt(µH),?????????????????,????????????
  

21
????

• ??????????????B0 ?,????????,????????????????,??
  ???????,???????????????????,??????Larmor???

22

• ??????????, ???????????????????????????
• ???????????,??????????,??????????????????????
  ?,????????????,???????????????????????????????????
  ??Larmor????
• ??v ????(????)? ???(?????)

23

• ?Larmor????,??????????????????????????B0
  ???,?????????,??????????1H???,?????B0?1.4092T(1T1
  04)???,????????v?60??(? 26. 753107
  radT-1s-1)B0?2.3487T???,????????v?100???

24
????????(????)

• ?????????????????,??????,??,??????????????????
  ?????????????????????1H??,???????
• E? h v?
  

25

• ????????????????????,???????????,????????????
  ??????,??????????E??E,????????????
• 
  
• ?
  
• ???????????B0?????,??????????,????????,??????
  ??????????

26
???????

• ???????
• ????,??NMR??????????
• ?E(????) ?E,(???)
• ? 2µB0 h v

27
2µB0 h v

• ?????????,??????
• (1)B0??,??v
• ??????????????????,???????????????,????????,??
  ?????(frequency sweep)?
• (2)v??,??B0
• ?????????????????,????????????,???????????????
  ?(field sweep)?
• ??,????????NMR??????

28
??????????????????????(?????)???
29
(1)??

• ???????,???????,????????????????????
  ??????????1.409T?,?????????????????????,??????????
  ???????????????,?????????????????????,????????????
  ???????????????????,??????,?????
• ????????????????????2.4T,????????????10
  0MHz???200MHz???????????????????????????????????,?
  ???????????,??????????????(???????????),?????????,
  ??????????,??????????????????????????????,???1017
  .5T???,???????????400750 MHz?

30
(2)?????

• ?????????????,NMR?????????????????????????????
  ,?????????????????????,????????,?????60MHz(??1.409
  T??)?100MHz(??2.350T??)????????????????????????,?1
  9F,13C,11B,????????????

31
(3)?????

• ??????????????,???????????????,???????????
  v0?????B0?????????,??????????????????????????,????
  ??????????????,????????????????????????????

32
(4)??

• ????????????????????????????,??????????,??
  ???????????,???????????????????????????,??????????
  ??????????

33

• ?????????,?????????,????????????
• NMR??????,????(?????????)????????????,?
  ??????(?5060?/s)??,????????????????????????????,?
  ????????(?100MHz?200MHz)??????????????????????????
  ?????????????????????,????????,??????,????????????
  ??,????????,??????,?????????????????????????????

34
????

• ?????,?????????????????,???????????,????
  ????????????????,???????????????(?????4mm????,??0.
  4mL??????10?????)?????
• ????????,????????,????????????????????
  ???????????????????????,??????????????????????????
  ???????????,???????????????????????????,???????

35
NMR???

• ??????
• ????,????????????????,????v ? B0 /
  2p????????????,??,?1H???60MHz??????,?????????1.409
  T?????????????(1H)???????,????????????,???????????
  ???????1950?Protor?Dickinson????????,???????????,?
  ???????????????????????,??????????????????????????
  ?????????????????????????,?????????????????,??????
  ???????????

36
????B0??????
37

• ?????????????,??????,????????????????,????????
  ??????,??,???????????????????,??????????,??,??????
  ?????BB0(1?s)(s?????)???????????????????

38

• ?????,?????????????,??????????????,???????(???
  ??????s???)????????????????????????????,??????????
  ?????????????????????????,???????????????????????

39
????????

• ??????????,???????????????????,???????????????
  ??????,????????????,??????????????B0(sample)?????(
  ?TMS,?????)?????????B0(ref) ????,?????????????,??d
  ??

40

• ??,????(d)???????????,??v?Hz
  ?????????,???Hz,???MHz???,??,d???????(ppm)??????(?
  v?v (ref) ?????????)

41
????

• ??????????????????????,??????????????????
  ??????????,????????????????????????????(tetramethy
  lsilane ??TMS)?????????,???????????????????????,?
  ????????,????????????????????????,????????????????
  ????????,??????,?????,????????????????????????????

42

• ??IUPAC???,???TMS??????,????????????????,?
  ??d?-d???
• ??,?60MH??????1H-NMR??,?????CH3?????TMS??
  ?134Hz,?CH2?????TMS??240Hz,????????????
• d(CH3)(134-0/60106106 2.23
• d(CH2)(240-0/60106106 4.00

43

• ???????100MHz?????1H-NMR??,???????(d)????,
  ????TMS?????????????(?v)???????CH3??223Hz,CH2???40
  0Hz?????,??????????????,??????NMR?????????????,???
  ???????

44
?????????

• 1H????????????????,??????,?????????????
  ???,??????????????????????1H??????????,??????????,
  ???????????????

45
(1)????

• ???????1H?,?????????,???????????????,???
  ???????????????????????????????????????????,??????
  ??????????????????????,???????????????????????????
  ?????(?????),??????????????(?????),???????????????
  ,??????????????(?????),??????????????(????),?????
  ??????????,???????

46
(2)???????

• ????????,?????????????????????,??????p?,
  ?????????????????,????????????????????????????????
  ?,????????????,?????????????,???????,?????????????
  ?(?????),?????????????????????,???????,??????????
  ????(????),???????????????????????(magnetic
  anisotropic effect)
• ???p?????,???????????????,??????????????
  ??????? ?

47

• i ??
• ?????,?????B0???,??p?????????????????????

????p??????????
48

• ??,?????????,???????????????,????????????
  ????,???????,???????????,?????,??????????,????????
  ??????,?????????,???????
• ???????????,??????????,????1H??d
  7.27ppm

49

• ii ?????
• ?????,??????B0???,?CO?p????????????,??

????????
50

• ??,???????CO??,????????,???????,?????????
  ????????????1H?? d 910ppm?
• ?????????,????(??)??p???????????????????
  ,???????,?????????????????,d 4.55.7ppm

51

• iii ??
• ?????????
• ?????,??????p?????????,??p???????,?????
  ?????????????,??????????,?????????d2.03.0ppm?

52
(3)????

• ????????????,??????????,??????,????1H???
  ????????,1H?????????,?d????
• ????????????????,????????,??????,?d?????
  ???????????,????????????,?d????

53
(4)????

• ????????????????,1H???????,???????????????
  ??,?????????????????????????????????????????

54
??????

• ????60MHz?????????????,????d?????????????(
  ????),??????(????)?d0??????????TMS???????????????
  ??????(CH3)???????????????????,?????????????????,
  ????????????

55
?????????
56
?????????,????????

• (1)??????????????????????????5.10?????,??????????
  ????????
• (2)????????d?????????????
• (3)????????????(????????),???????????
• (4)??????????????????????

57
?????????

• ?????????????????,?????????????????,??????
  ???????????????????,????????????????,????????,????
  ??????????????????????????????????????????????????
  ???????

58
?????????????
59
????(????)

• ?1HNMR???,???????????????CH3?CH2??,?CICH2
  C- (CI)2CH3?,??????????,??CH3CH2CI????????????????
  ????(CH3)??????????????(CH2),????????????

60
????????

• ???????????????(?)????????????(spin-sp
  in coupling)???-????(spin-spin interaction)???????
  ??,??HF????????
• ??(19F) ?????I??1/2,???(1H)??,??????????
  ?????????????,?????????????(?? ? ),m
  1/2??????????????(?? ? ),m -1/2
  ??HF???,?19F?1H?????,?19F???????????????????????,?
  ??1H????????????????????????????(?)????????????(s
  pin-spin coupling)???-????(spin-spin
  interaction)?????????,??HF????????

61
HF???????
62

• ?19F??????? ? ?m 1/2?,??????????,???1
  H???????????,?19F??????? ? ?m
  -1/2?,???????????,???1H??????????
• ??,??????????????????????
• ??????m 1/2?,???????????????,?????????
  ????????????,?????m -1/2?,???????????????,?????
  ????????????????

63

• ??19F?????????????,?FH?1H?????????,?????????

1H?F?????
64

• ???????????????????(11),??????19F??????
  ??????,???????????????????????????????????????,?19
  F?????? ? ?m 1/2 ?????????????????,?19F???????
  ? ?m -1/2??????HF??19F??????1H??????,??????????
  ???,????,??19F?????1H?????,??????????????,?FH?1H-N
  MR??????19F??1H??????,?????19F??????

65

• ???????????,???????????????????,????????????
  ?????????????,?????????????????????????,??????????
  ?????????,?????????????????????????,??????????????
  

66
????

• ???????????????,?????????,?????????n1??,
  ???????????????????????,d?J???????????????????????

67
????

• ????????????????????,???????????n1??,????
  ????,??????????,d?J??????????,????????????????????
  ????????

68
1H NMR????

• ??????????????????????????????????????
  ???????????,??????????????????????????,??????????
  ??????????,???????????????????????????????????????
  ??????????????????????????????????????,??????????

69

• 1HNMR??????????(1)??????TMS??????(2)??
  ?????????????H?(3)??????(d1016)???COOH?????????
  ??OH???(4)????????????????,????????(5)?????????
  ??????(6)???????,????????UV?IR?MS???????????

70
????

• ?1 ?????????C6H10O3,??????????,??????????

C6H10O3??????
71

• ????????C6H10O3???????????2,????????CO?CC??????
  ??????5???????,????????????4??,????????????d4.1pp
  m(???),d3.5ppm(??),d2.2ppm(??),d1.2ppm(???),??????
  ????2233,??????????????????????????d4.1ppm?d1.2
  ppm?????,?????????,??????????
  (COOCH2CH3)?d3.5ppm?CH2 ,d2.2ppm?CH3,?????????,??
  ????d2.2ppm??????????,?CH3CO?

72

• ????,???????????
• CH3CO,COOCH2CH3, CH2
• ???????????????????,??????????

73
?2 ???????C11H12ON2,???????,??????????
74
?????????????????????????122232,???????d????
,?????????????????,???????-CH2-CH2-??-CH3?
C11H12ON2,??????5?????,????????7?????,3???????????
?,??????,???,????????,????????????????????????7???
??????????
75
???
P 143 ?3???4? P 144 ?5???6?
76
Thank You