Three Cups of Modern nmr spectroscopy espresso

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1 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

University of Cambridge http://www-keeler.ch.

uk/lectures/irvine/ Sir Paul Callaghan (947

2 University of California, Irvine Understanding MR Spectroscopy James Keeler, University of Cambridge Sir Paul Callaghan ( ) Introductory MR & MRI

3 uclear magnetic moment Particle Mass Charge Spin (angular momentum) Magnetic dipole moment Electron Proton eutron eutrino Photon Graviton (?) Carbon-2

4 Angular momentum

5 Kerndipole Magnetic dipole moment DE ~ g E DE > DE F 9 F B 0 Die Stärke der Kernmagneten (gyromagnetisches Verhältnis g ) bestimmt ebenfalls die Größe der Energiedifferenz zwischen den beiden rientierungen.

6 uclear magnetic resonance spectroscopy B E ( ) E ( ) DE 2 B DE h Dv B 50 5 T Dv 2 h B 2000 z

Boltzmann distribution The potential energy of a molecule : E( h) m g h, The pressure of the idealize gass: P nk T, dp dn Let's assume for simplicity that T does not depend on h, then: k T.

7 Boltzmann distribution The potential energy of a molecule : E( h) m g h, The pressure of the idealize gass: P nk T, dp dn Let's assume for simplicity that T does not depend on h, then: k T. dh dh The pressure of a gas column of the height h on unit area is: P P m g nh we have dp m g ndh. 0 dp dn mg h E k T m g n n exp( ) exp( ) dh dh k T k T E E2 n( h) Aexp( ) and n( h2) Aexp( ) k T k T n( h ) E E2 exp( ) nh ( ) kt 2 n DE T n0 exp( k )

8 Boltzmann distribution B E ( ) E ( ) 5 B 50 T und T 300 K B 50 5 T

9 MR spectrometer B B 5 50 T 7 T 4 T 24 T Dv Mz 300 Mz 600 Mz 000 Mz

10 Superconducting magnet flüssiger Stickstoff T = C flüssiges elium T = C B 0

11 uclear magnetic resonance spectroscopy B E ( ) E ( )

12 MR spectrometer B 0 M M MR coil B voltage in the coil ref 0 FID = free induction decay time transmitting receiving transmitter receiver

13 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

14 B 0 E β ~ μ B 0 B RF E α ~ μ B 0

15 Longitudinal and transverse relaxation z z z z u u u u

16 Longitudinal and transverse relaxation

17 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

18 Chemical shift B z B z z DE B e z B e

19 Chemical shift C= C=C C 3 - C 3 - C 3 -C= C C 2 C 3 TMS 3 C ppm v C= Probe v Ref v Ref CDCl 3 C 3 - C C 2 C 3 TMS ppm

20 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

21 Scalar spin-spin coupling no coupling A M X J AM > J AX > J MX J AM J AM J AM J AM and J AX J AX J AX J AX J AM, J AX and J MX J MX J MX J MX J MX

22 A AX AX 2 AX 3 AX 4 Scalar spin-spin coupling Coupling with spins /2 Coupling with spins A AX AX 2 AX 3 AX o. o

23 2 J a,b,c,d a, Scalar spin-spin coupling C 4 ( ) 2.3 ppm 2 J -2 z ClC 3 ( ) 3.0 ppm 2 J -2 z

24 2 C= C 2 ( ) 5.3 ppm 3 J 2 z Scalar spin-spin coupling 2 J -2 z 3 J 9 z 0.20 ( 3) 6.3 ppm 3 J 8 z 3 ( 2) 5.5 ppm ( ) 5.4 ppm 2 J -2 z 2 3 J 5 z Cl

25 Scalar spin-spin coupling Me a b Br C a b C Cl Br c C 3 Cl c ppm

26 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

27 Pople nomenclature Cl δ( ) = 3.7 ppm δ( ) = 3.63 ppm 2 J = -9.4 z ABX

28 Second rder Effects in Coupled Systems ( ) 7.3 ppm 3 J 8 z 4 J 2 z 5 J z ( ) 7.2 ppm ( ) 8.6 ppm 3 J 5 z 4 J 2 z 5 J z J 8 z AA BB X ( ) 7.6 ppm

29 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

30 Proton exchange intermolecular case intramolecular case + ** k * + * k singlet () or () W o k/s ()() ()() ()() ()() triplet W o z 5 J 00 5 () () () () doublet /z doublet 0 J

31 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

32 Spin echoes ffset (chemical shift) J coupling refocused evolves for 2 ffset (chemical shift) J coupling refocused refocused ffset (chemical shift) J coupling evolves for 2 refocused

33 2D-MR t = 0,, 2, 3,, 00 preparation mixing 2 Full magnetization transfer preparation mixing o magnetization transfer preparation mixing 2 Partial magnetization transfer

34 2D-MR. EXSY (Exchange Spectroscopy) Chemical exchange between I and I 2 C 3 I T 360K C 3 I 2 C 3 I 2 C 3 I t = = 2sw 2ms 32 τ s

35 2D-MR. EXSY (Exchange Spectroscopy) τ opt T + k AB + k BA

36 L-istidin, MR in D 2

37 L-istidin, MR in D 2 3 J = 7.97 z 3 J = 4.72 z 2 J = 5.45 z 3 J = 4.72 z 2 J = 5.45 z 3 J = 7.97 z

38 L-istidin, MR in D 2 3 J = 7.97 z 3 J = 4.72 z 2 J = 5.45 z 3 J = 4.72 z 2 J = 5.45 z 3 J = 7.97 z

39 L-istidin, CSY MR in D 2 The intensity is proportional to sin Jt.

40 L-istidin, CSY MR in D 2 The intensity is proportional to sin Jt.

41 L-istidin, MR in D 2

42 L-istidin, MR in D 2

43 L-istidin, CSY MR in D 2

44 L-istidin, MR in D 2 J( 3 C) = z J( 3 C) = z J( 3 C) = z

45 L-istidin, DEPT-35 MR in D 2

46 L-istidin, SQC-DEPT MR in D 2 55 ppm 28 ppm, ppm 3 C, ppm 2.93 & ppm 37 ppm

47 L-istidin, MBC MR in D 2 28 ppm 55 ppm, ppm 3 C, ppm 2.93 & ppm 37 ppm 32 ppm 74 ppm

48 L-istidin, ESY MR in D 2

49 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

50 MR Chemical Shifts of Common Laboratory Solvents as Trace Impurities rganometallics 200, 29, (DI: 0.02/om0006e)

51 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

52 (-)-Borneol (+)-Borneol C 0 8 Spectrometer (6:44 min) MR (:25 min) DEPT-35 (3:37 min) CSY (0:33 min) SQC-DEPT (20: min) MBC (20:44 min) ESY (28:58 min) 3 C MR (55:05 min) (+)-Isoborneol (-)-Isoborneol

53 Karplus equation: Borneol J φ 2 cos 2 φ cos φ a 4a (-2a) 5 0 J(-2a) z (-2b) 25 0 J(-2b) 5 z (3-2a) 40 0 J(3-2a) 7 z (3-2b) 80 0 J(3-2b) z (3-4a) 40 0 J(3-4a) 7 z (3-4b) 80 0 J(3-4b) z 2b 4b

54 Karplus equation: Iso-Borneol J φ 2 cos 2 φ cos φ + 2 2a 3 4a (-2b) 6 0 J(-2b) z (-2a) 26 0 J(-2a) 5 z 2b 4b (3-2a) 45 0 J(3-2a) 7 z (3-2b) 75 0 J(3-2b) z (3-4a) 45 0 J(3-4a) 7 z (3-4b) 75 0 J(3-4b) z

55 MR in DMS

56 MR in DMS

57 MR in DMS

58 2 + (.56 ppm)? MR in CDCl 3

59 MR in CDCl 3 J = 0.00 z J = 3.48 z J =.80 z

60 J = 3.43 z J = 9.97 z MR in CDCl 3 J = 4.73 z J = 3.28 z

61 J = 3.43 z J = 9.97 z J = 4.73 z J = 3.28 z

62 MR in CDCl 3

63 ID, ppm Int C x Multiplet Commectivity 3 C x = Type J,z MBC CSY 3.97 ddd dddd

64 MR in CDCl (.56 ppm)? J = z

65 ID, ppm Int C x Multiplet Commectivity 3 C x = Type J,z MBC CSY 3.97 ddd dddd M 4.70 M 5.59 dd

66 MR in CDCl 3 J = 3.3 z J = 3.5 z

67 ID, ppm Int C x Multiplet Commectivity 3 C x = Type J,z MBC CSY 3.97 ddd dddd M 4.70 M 5.59 dd M dd s s s

68 CSY MR in CDCl ,9,

69 ID, ppm Int C x Multiplet Commectivity 3 C x = Type J,z MBC CSY 3.97 ddd , dddd M 4,6, M 3,5,6, dd ,4, M 3,4, dd s s s 3

70 DEPT-35 MR in CDCl3

71 SQC MR in CDCl

72 ID, ppm Int C x Multiplet Commectivity 3 C x = Type J,z MBC CSY 2,7 5 3,6 4, ddd dddd M 4,6, M 3,5,6, dd ,4, M 3,4, dd s s s 3

73 Borneol Iso-Borneol 3,6 2a 2b (-2a) 5 0 J(-2a) z (-2b) 25 0 J(-2b) 5 z (3-2a) 40 0 J(3-2a) 7 z (3-2b) 80 0 J(3-2b) z (3-4a) 40 0 J(3-4a) 7 z (3-4b) 80 0 J(3-4b) z 3 4b 4a 2,7 4,6 5 J(,2) = 0 z J(,7) = 3.5 z J(2,5) = 4.7 z J(7,5) = 0 z J(5,4) = 4.5 z J(5,6) = 0 z 2a 2b 4b 3 (3-2a) 45 0 J(3-2a) 7 z (3-2b) 75 0 J(3-2b) z 4a (-2b) 6 0 J(-2b) z (-2a) 26 0 J(-2a) 5 z (3-4a) 45 0 J(3-4a) 7 z (3-4b) 75 0 J(3-4b) z

74 MBC MR in CDCl 3 9 0,

75 2, ,6 4,6 ID, ppm Int C x Multiplet Commectivity 3 C x = Type J,z MBC CSY ddd dddd С,3C, 5C, 6C, 9C C, 3C, 4C, 6C M C, 3C, 4C, 6C, 7C M C, 2C, 3C, 5C, 6C ,6,0 3,5,6, dd C, 5C, 6C, 0C, C 2,4, M C, 2C, 3C, 4C, 5C, 6C, 7C, 9C 3,4, dd C, 3C, 4C, 7C s 3C, 7C s 3C, 7C s C, 5C, 6C, 7C, C 3

76 ESY MR in CDCl 3 0 3,6,Me 2,Me 2,7 5 4,6,2 2,Me,Me

77 Borneol 3,6 2,7 5 4,6 5 Iso-Borneol 2 7 E: -2, -Me, 2-Me

78 Solvent Effect D 2 CDCl 3 DMS

79 Solvent Effect MR in CDCl 3 J = 0.00 z J = 3.48 z J =.8 z MR in D 2 J = 0.6 z J = 3.48 z J = 2.2 z

80 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

81 artificial sweetener Leichte Suesse kaufland : atriumcyclamat, Saccharin, natriumhydrogencarbonat, lactose, natriumcitrate MR LeiChTe Suesse kaufland in D 2 MR Saccharose in D 2

84 artificial sweetener Leichte Suesse kaufland : Part Saccharin (4 mg/tablet): i times sweeter than Sucrose. ii. 5 mg/kg body-weight (ca. 60 Tabletten, 275 g Sucrose). iii. Do not provoke tooth decay. iv. as a bitter taste. 2 Parts atriumcyclamate (40 mg/tablet): i. 30 times sweeter than Sucrose. ii. 7 mg/kg body-weight (ca. 9 Tablet, 39 g Sucrose). iii. Provoke cancer? 0.05 Parts Lactose (a table top sweetene?): i. Milk sugar, 6 times less sweet than Sucrose..4 Parts atriumcitrate (shelf-life extension?): i. Acidity regulator. ii. Contributing a tart flavor. 4 Parts Sodium bicarbonate (shelf-life extension?): i. Baking soda. (dissolution assistance?)

85 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

86 Chemical shift anisotropy B 0 B induced B 0 B induced contribution of electrons in contribution of electrons in F contribution of electrons in contribution of electrons in F B 0 F F

87 Chemical shift anisotropy [(C) 5 CrCCCr(C) 5 ] AsPh 4 + B o II iso 2II 3 iso ppm reference: solid 5 4 Cl -.Benedict,..Limbach, M. Wehlan, W. P. Fehlhammer,. S. Golubev, R. Janoschek, J. Am. Chem. Soc. 998, 20, 2939

88 Magic-angle-spinning 2 3cos 0, 5444'

89 Magic-angle-spinning [(C) 5 CrCCCr(C) 5 ] B o r AsPh cos ' B o II iso 2II 3 iso ppm reference: solid 5 4 Cl -.Benedict,..Limbach, M. Wehlan, W. P. Fehlhammer,. S. Golubev, R. Janoschek, J. Am. Chem. Soc. 998, 20, 2939

90 MAS sidebands

91 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

92 Internal Spin Interactions: Dipolar Coupling B 0 2 E d 2 2 3cos 3 r B 0 2 r E d 2 2 3cos 3 r r B 0 r 2 E d 2 2 3cos 3 r B 0 r 2 E d 2 2 3cos 3 r

93 Internal Spin Interactions: Dipolar Coupling B 0 2 B 0 2 r r nucleus 2 in 90 D gg r 2 3 nucleus 2 in ' 0 0 Pake doublet

94 Internal Spin Interactions: Dipolar Coupling B 0 2 E d 2 2 3cos 3 r B 0 2 r Ed 0 E d 2 2 3cos 3 r r B 0 r 2 Ed 0 E d 2 2 3cos 3 r B 0 r 2 E d 2 2 3cos 3 r

95 Internal Spin Interactions: Dipolar Coupling E d 2 3 3cos r 2 B r E d 2 3 r E d 2 3 r B Ed 0 2 r E d r E d r

96 Internal Spin Interactions: Dipolar Coupling D gg r cos 0 m m 5444' / kz

97 - 5 and 2-5 dipolar interaction without CSA D 3 C r =.096 Å 3 C r D =.083 Å D 3 C 5 C l 3 C 5 D C l D 3 C 3 C slow spinning B 0 r 5444' static B { 2 } 0 kz 0 Ch. oelger,..limbach, J. Phys.Chem., 994, 98, kz 4

98 MAS 0 kz Ph. Lorente, I.G.Shenderovich, G.Buntkowsky,.S.Golubev, G.S.Denisov,.. Limbach, Magn. Reson. Chem. 200, 39, S8

99 5 CSA of solid : complexes of collidine- 5 with acids t r r t t r r t ( 5 )/ppm iso ( 5 )/ppm Ph. Lorente, I.G.Shenderovich, G.Buntkowsky,.S.Golubev, G.S.Denisov,.. Limbach, Magn. Reson. Chem. 200, 39, S8

100 5-2 Dipolar Coupling Ph. Lorente, I.G.Shenderovich, G.Buntkowsky,.S.Golubev, G.S.Denisov,.. Limbach, Magn. Reson. Chem. 200, 39, S8 MAS /D isotop effect on chemical shift static chemical shift tensor 5-2 dipolar coupling D D R -3 D

101 5 MR Chemical Shift as a Measure of Acidity" R /Å pk a 5 ( 5 ) /ppm ( 5 ) /ppm Ph. Lorente, I.G.Shenderovich, G.Buntkowsky,.S.Golubev, G.S.Denisov,.. Limbach, Magn. Reson. Chem. 200, 39, S8

102 Cross polarisation (CP) before contact pulse rotating frame 0 initial states z M B z during 90 pulse z M after 90 pulse z M u u u z z z 5 rotating frame 0 M M M u u u

103 Cross polarisation (CP) contact pulse in the beginning of and 5 contact pulses z at the end of and 5 contact pulses z u B M * * u B M * * z z 5 u M B * * 5 u M B * * g B g B artmann-ahn condition

104 3 3 cellulose LysCel a b 3 3 cellulose LysCel a b Wet paper tears easily 30% wet-tensile-strength improvement Cellulose Grafted with Aminocarboxyl Groups R. Manriquez, F.A. Lopez-Dellamary, J. Frydel, T. Emmler,. Breitzke, G. Buntkowsky,.-. Limbach, I.G. Shenderovich J. Phys. Chem. B 2009, 3, 934.

105 a p c L-Leucine Lyophilized at Different p 5 b 3 C L-leucine + 3 R R ppm a 2 d neutral dimer cation + 3 R cation cation/ neutral zwitterionic 5 dimer 2 anion zwitterionic netwo cation d neutral anion R = (C + 3 ) 2 C-C 2 3 Covalent bonds R (cross linking) LysCell 3 R R C R b R neutral R ne R = (C 3 ) 2 C-C R neutral R R R + R 3 C cation R R = (C 3 ) 2 c cation neutral ani 3 C + R

106 Isotopically Labeled Aminocarboxyl Groups Cellulose % 50% 2 C 3 C R C nm

107 umber of 5 in Close Proximity to 3 C Cellulose a) dimer b) dimer ribbon c) tetramer % 50% 2 C 3 C C C C C C C C C C C DS/S o r 2 3 C 5 r n = x = 0.5 d) tetramer stack C C C C n = 2 x = 0.75 e) dimer stack C C C C n = 2 x = 0.75 f) sheet C C C C dephasing time / ms n = 3 x=0.875 n = 3 x = n = 4 x =

108 R. Manriquez, F.A. Lopez-Dellamary, J. Frydel, T. Emmler,. Breitzke, G. Buntkowsky,.-. Limbach, I.G. Shenderovich J. Phys. Chem. B 2009, 3, 934. Cellulose Grafted with Aminocarboxyl Groups 30% wet-tensile-strength improvement is provided by zwitterionic dimers organized in ribbons or tetramers

109 ISTITUT FÜR RGAISCE CEMIE UIVERSITÄT REGESBURG Three Cups of Modern nmr spectroscopy espresso Ilya G. Shenderovich Classical and quantummechanical descriptions 2. T and T2 Relaxations 3. Chemical shift 4. Spin-spin scalar coupling 5. Spin systems of the first and the second orders 6. Chemical exchange 7. Two-dimensional MR. MR in solution. From spectrum to structure.2. Typical protocol for structure elucidation 2. MR in the solid state 2. rientation-dependent interactions 2. Measurements of internuclear distances 2.3 MR of surfaces and amorphous solids MR Study of ydrogen Bonding in Solution Down to 00 K

110 Pure siliceous materials 3 Idealized Surface Surface Si- Lattice Si Q 3 species Q 4 species Si Si Si Si Si Si Rough Surface Geminal Si-() 2 Q 2 species

111 MR of Surfaces Mesoporous Silica Materials MCM-4, SBA-5 silica MCM-4, 2 4 nm SBA-5, 7 20 nm Surface ~ 000 m 2 /g

112 MR at 300 K from a flask dried in high vacuum at 400 K Si Si Si Si Si Si D. Mauder, D. Akcakayiran, S. B. Lesnichin, G.. Findenegg, I. G. Shenderovich J. Phys. Chem. C 2009, 3: 985.

113 5 -pyridine as a sensor of acidity R /Å ( 5 ) /ppm P. Lorente, I.G. Shenderovich,.S. Golubev, G.S. Denisov, G. Buntkowsky G.,.-. Limbach Magn. Reson. Chem. 200, 39: S8

114 5 30K Dry surface Crystal.67 Å C 2 C C 3 Propionic acid ( 5 ) /ppm I.G. Shenderovich, G. Buntkowsky, A. Schreiber, E. Gedat, S. Sharif, J. Albrecht,.S. Golubev, G.. Findenegg,.-. Limbach J. Phys. Chem. B 2003, 07: Density of -groups: MCM nm -2 SBA nm -2

5 MR @ 300K I.G. Shenderovich, G. Buntkowsky, A. Schreiber, E. Gedat, S. Sharif, J.

115 5 300K I.G. Shenderovich, G. Buntkowsky, A. Schreiber, E. Gedat, S. Sharif, J. Albrecht,.S. Golubev, G.. Findenegg,.-. Limbach J. Phys. Chem. B 2003, 07:

116 Pyridine dynamics inside MCM-4 and 300K Q 3 Q 2 Q 4 SBA-5 Q 2 Q 3 Q 4 MCM-4 5 MR 29 Si MR I.G. Shenderovich, G. Buntkowsky, A. Schreiber, E. Gedat, S. Sharif, J. Albrecht,.S. Golubev, G.. Findenegg,.-. Limbach J. Phys. Chem. B 2003, 07:

117 Morphology of Mesoporous Silica 5 MAS 300K Static MAS SBA-5, 8.9 nm Static MAS Static SBA-5, 7.5 nm 300K MAS Static MAS MCM-4, 3.7 nm MCM-4, 3.3 nm Surface diffusion Pyridine Rotation is Restricted =35 0 Static MAS MCM-4, 2.9 nm 30K δ/ppm 7

118 Inner surface of mesoporous silica Rough surface SBA-5 Idealized surface MCM-4

95 nm a 0 Transmission electron microscopy MCM-4 Q 4 Q 3 Circular Pores Model MCM-4 Q

119 Structure of Amorphous Materials Mesoporous Silica Materials Input exp.: Silanol density (3 nm -2 ); Pore diameter D; Lattice parameter a 0 D 20 nm a 0 w 0.95 nm a 0 Transmission electron microscopy MCM-4 Q 4 Q 3 Circular Pores Model MCM-4 Q 3 : Q 4 exagonal Pores Model Exp. circular hexagonal sample sample

120 Distribution of the surface hydroxyl groups

121 Distribution of the surface hydroxyl groups Si Si 29 Si CPMAS MR, 300K Si Si Si Si + (Si(C 3 ) 3 ) (C 3 ) 2 -Si-Cl 2 Si -Si-(C 3 ) 3 Si + 3 -Si-(C 3 ) 3 Si Si -Si- (C 3 ) Cl 5 CPMAS MR, 30K

122 Distribution of the surface hydroxyl groups 5 Å Me Me Me Me Si Me Me Si Me Me Si Me Si Si Si Si Si Uniform distribution assumption 5.8 Å Density of Si- groups: 2.9 nm -2 (MCM-4)

123 Surface functionalization I.G. Shenderovich, D. Mauder, D. Akcakayiran, G. Buntkowsky,.-. Limbach, G.. Findenegg J. Phys. Chem. B 2007, : Me Me D D 2 SBA-5 Si Si Si D 2 MCM-4 Me Si Me D * 0. M aq. Cl Si Si MR /ppm

124 Surface functionalization I.G. Shenderovich, D. Mauder, D. Akcakayiran, G. Buntkowsky,.-. Limbach, G.. Findenegg J. Phys. Chem. B 2007, : SBA-5 T T2 T 3 Si Me Si Si Si T 3 Me Si T 2 Si Si MCM-4 0. M aq. Cl Me Si Si T

125 Surface functionalization I.G. Shenderovich, D. Mauder, D. Akcakayiran, G. Buntkowsky,.-. Limbach, G.. Findenegg J. Phys. Chem. B 2007, :

126 Surface functionalization I.G. Shenderovich, D. Mauder, D. Akcakayiran, G. Buntkowsky,.-. Limbach, G.. Findenegg J. Phys. Chem. B 2007, :

127 Propionic Acid Functionalized SBA K r.67 Å W/Py = 0 r.67 Å C W/Py = Si Si W/Py = 0 A.A. Gurinov, D. Mauder, D. Akcakayiran, G.. Findenegg, I.G. Shenderovich ChemPhysChem 202, 202, 3: ( 5 ) /ppm

128 Propionic Acid Functionalized SBA-5 A.A. Gurinov, D. Mauder, D. Akcakayiran, G.. Findenegg, I.G. Shenderovich ChemPhysChem 202, 3:

129 Strong Acids Functionalized SBA-5 pk a 5.2 5? 5 5?.67 Å S 2 P C 3 6 pk a 4.9 pk a -0.6 C 2 4 pk a 2.4 pk a 7.8 Si Si Si Si Si D. Mauder, D. Akcakayiran, S. B. Lesnichin, G.. Findenegg, I. G. Shenderovich J. Phys. Chem. C 2009, 3: 985.

130 Strong Acids Functionalized SBA-5 Bulk Pyr Si Pyr A - [ Pyr] + 5 MR 30 K δ/ppm P() 2 S D. Mauder, D. Akcakayiran, S. B. Lesnichin, G.. Findenegg, I. G. Shenderovich J. Phys. Chem. C 2009, 3: 985.

131 Conclusion ur ability to manipulate the chemical reactivity of a surface by a fluid filling is limited by: steric hindrance caused by the structure of the surface presence of chemisorbed species

Coupling of Functional Hydrogen Bonds in Pyridoxal-5 -phosphate- Enzyme Model Systems Observed by Solid State NMR

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