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

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NMR 1 Nuclear Magnetic Resonance spectroscopy, NMR ... – PowerPoint PPT presentation

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Title: ??? ??????? (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
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