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Magnetic moment
Ih = = h I 2
h h= 2
M z (t ) = M (t ) B0 (t ) z R1 (M z (t ) M 0 ) t M x (t ) = M (t ) B0 (t ) x R2 M x (t ) t M y (t ) = M (t ) B0 (t ) y R2 M y (t ) (t )
150
50
= B0 (1 ) 2
S R = 10 6 R
Direct detection
pulse
preparation
acquisition
13C
preparation
acquisition
1H
decoupling
h I S
2r 3
(3 cos 2 1)
13C
acquisition
pulse
Contact Time (CT)
1H
decoupling
Application of solid state NMR spectroscopy to the analysis of the soil organic matter
O 9 OH
12
CH3
11
10
9 8
7 6
5 4
8 1 2
SO4-
6 5
Hexamethylbenzene (HMB)
Ferulic Acid
4 3 O OH CH3 10
OH
* O
6 4 5
HO
O H 2C
2 3
O
O O
Application of solid state NMR spectroscopy to the analysis of the soil organic matter
Methyl C Quaternary Aromatic C
OH
SSB
SSB
HMB
* O
6 4 5
HO
O H2C
2 3
O
O O
COO-
C1
C2-C6
CMC
C10 C11 C12 C1
C2-C9
12
SDS
11
10
9 8
7 6
5 4
SO4-
O 9 OH
C3-C4 C9 SSB
7 1 6 5
8 2
Ferulic Acid
100 0 -100 -200
4 3 O OH CH3 10
400
300
200
Application of solid state NMR spectroscopy to the analysis of the soil organic matter
H A: COOH (CMC), C9 (Ferulic acid) E
Mixture 1 OCT=6ms
C G
A B D
400 300
F
-100 -200
D: C5,6, 8 (Ferulic acid), C1 (CMC) E: C2-C5 (CMC), C1 (SDS) F: C10 (Ferulic acid), -CH2O-, and C6 (CMC) G: C2-C11 (SDS) H: C12 (SDS), Cal(7-12) (HMB)
E G B D C
Mixture 2 OCT=1.2ms
F H
400
300
-100
-200
Application of solid state NMR spectroscopy to the analysis of the soil organic matter
Effect of spin diffusion mediated by water
H3C H3C H3C H3C H3C H3C CH3 CH3 CH3 CH3 SO4 CH3 CH3 H H O H OH CH3 HO HO HO CH3 CH3 OH CH3 H2C CH3 CH3 H OH HO O H CH3 HO HO CH3 CH3 H2C CH3 O H H3C H
H2 C H2 C H2 C H2 C H2 C SO4 H2 C C H2 H2 C H2 C H2 C H2 C H2 C SO4
H3C
C H2
C H2
C H2
C H2
C H2
H2 C
C H2
H2 C
C H2
H2 C
C H2
H2 C
C H2
CH3
C H2
C H2
C H2
C H2
C H2
O H H OH
O H OH
O O H H H2C
CH3 HO
CH3
HO CH3 HO OH
CH3
OH
CH3 CH3
OH CH3
OH CH3
Application of solid state NMR spectroscopy to the analysis of the soil organic matter
Typical 13C-NMR spectra of natural organic matter in the solid state A wood A humic acid
150
100
50
0
ppm (f1)
300
200
100
-100
A protein (prion)
Carboxylic groups Aromatic systems Anomeric carbons C-O groups (i.e. Carbohydrates) C-N groups (i.e. peptides)
200
150
100
50
Aliphatic C
36
131 107 75 60
13C-CPMAS
176
Bulk HA 243 HA4 70 39 28 13 29 HA8 35 28 14 HA9 HA10 HA11 250 200 150 100 50 0
HA1
199
HA5
HA2
HA6
49
69
B 129 56
C 105 30
A = Star Green Tea B = Gu Zhan Mao Jian Green Tea C = Sir Winston Green Tea D = ScelgoBio Green Tea
E = Star Black Tea F = PG-Tips Black Tea G = Gepa Black Tea H = Twinings Lemon Scented Black Tea I = Lipton Yellow Label Black Tea
J = Harrods n. 42 Earl Grey Tea K = Darjeeling Earl Grey Tea L = Twinings Earl Grey Tea M = GS Earl Grey Tea N = Infr Decaffeinated Tea
A = Star Green Tea B = Gu Zhan Mao Jian Green Tea C = Sir Winston Green Tea D = ScelgoBio Green Tea
E = Star Black Tea F = PG-Tips Black Tea G = Gepa Black Tea H = Twinings Lemon Scented Black Tea I = Lipton Yellow Label Black Tea
J = Harrods n. 42 Earl Grey Tea K = Darjeeling Earl Grey Tea L = Twinings Earl Grey Tea M = GS Earl Grey Tea N = Infr Decaffeinated Tea
24h
48h
72h
96h
Cotyledon
Tegument
24h
48h Roots
72h
96h
0h
24h
48h
72h
200 ppm (t1) 150 100 50 0
Cotyledon
Cotyledon
0h
24h 72h
300 ppm (f1) 200 100 0
50 45 40 35 Content (%) 30 25 20 15 10 5 0 189-164 ppm 164-113 ppm 113-46 ppm 46-0 ppm 0h 24h 72h
-100
Tegument 0h
Tegument
24h
72h
300 ppm (f1) 200 100 0
70 60 50 Content (%) 40 30 20 10 0 189-164 ppm 164-113 ppm 113-46 ppm 46-0 ppm 0h 24h 72h
-100
Roots 0h
Root
24h
72h
300 ppm (f1) 200 100 0
70 60 50 Content (%) 40 30 20 10 0 189-164 ppm 164-113 ppm 113-46 ppm 46-0 ppm 0h 24h 72h
-100
Cotyledon
0h
24h
48h
72h
96h
10.0 ppm (t1) 5.0 0.0
Cotyledon
100 90 80 Content (%) 70 60 50 40 30 20 10 0 8-6 ppm 6-5 ppm 4.5-3.0 ppm 3.0-2.5 ppm 2.5-0 ppm 0h 24h 48h 72h 96h
Tegument
0h
24h
48h
96h
10.0 ppm (f1) 5.0 0.0
Tegument
40 35 30 Content (%) 25 20 15 10 5 0 8-6 ppm 6-5 ppm 4.5-3.0 ppm 3.0-2.5 ppm 2.5-0 ppm 0h 24h 48h 96h
Roots
96h
10.0 ppm (f1) 5.0 0.0
Roots
90 80 70 Content (%) 60 50 40 30 20 10 0 8-6 ppm 6-5 ppm 4.5-3.0 ppm 3.0-2.5 ppm 2.5-0 ppm 0h 24h 48h 72h 96h
38 36 34 32 30 28 26 24 22 20 18 16 14 12 10 8 6 4 2
Cotyledons
4.5-3.0 ppm 2.5-0 ppm
24
48
96
20
40
60
80
100
Time (h)
Roots
90 80 4.5-3.0 ppm 2.5-0 ppm
80 70
Time (H)
60 50 40 30 20 10 -10 0 10 20 30 40 50 60
70
80
Time (h)
Conclusions 1. NMR spectroscopy is widely used for structural analyses of natural products. Typical NMR spectra are obtained in liquid state by applying monodimensional sequences for measurements of proton and carbons, or bidimensional sequences useful to obtain HC(=X) correlations 2. Unconventional uses of NMR spectroscopy are those involving solid state samples and materials whose physical state is in between the solid and the liquid one. 3. Solid state NMR spectroscopy allows analyses of soil organic matter and all the systems (i.e. soils, minerals, polymer blends, pharmaceutycal products, and so on) hardly dissolving in the common deuterated solvents. 4. High resolution magic angle spinning (HRMAS) NMR spectroscopy is used for the analyses of complex mixtures such as plant residues or food products.
CERMANU