Applicazioni della spettroscopia di risonanza magnetica nucleare (NMR) nel settore ambientale,...

7/30/2019 Applicazioni della spettroscopia di risonanza magnetica nucleare (NMR) nel settore ambientale, vegetale e agro-alimentare

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Applicazioni della spettroscopia dirisonanza magnetica nucleare (NMR) nelsettore ambientale, vegetale e agro-

alimentare

Dr. Pellegrino Conte

Dipartimento di Scienze del Suolo, dellaPianta e dellAmbiente


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Short introduction to the theory of nuclear

magnetic resonance spectroscopy (NMR)

IhI

h

==

2Magnetic moment

gyromagnetic ratio

2

h=h Planck constant


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magnetic resonance spectroscopy (NMR)CSA, strong dipolar couplings


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magnetic resonance spectroscopy (NMR)Elimination of the Chemical Shift Anisotropy (CSA)

)1cos3(2

23

r

SIS

h

Magic angle spinning (MAS)

=


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Static, no decoupling

Static, decoupling

MAS, no decoupling

MAS, decoupling and/or CP


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Application of solid state NMR spectroscopy to the


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Application of solid state NMR spectroscopy to theanalysis of the soil organic matter

-200-1000100200300400

Mixture 1

OCT=6ms

A: COOH (CMC), C9 (Ferulic acid)

A

B: C3,4,7 (Ferulic acid)

B

C: C1,2 (Ferulic acid), Car(1-6) (HMB)

C

D: C5,6, 8 (Ferulic acid), C1 (CMC)D

E: C2-C5 (CMC), C1 (SDS)

E

F: C10 (Ferulic acid), -CH2O-, and C6 (CMC)

F

Chemical Shift (ppm)

G: C2-C11 (SDS)

G

H: C12 (SDS), Cal(7-12) (HMB)

H

-200-1000100200300400


A

B

C

D

E

F

Mixture 2

OCT=1.2ms

G

H


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Application of solid state NMR spectroscopy to the


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Application of solid state NMR spectroscopy to theanalysis of the soil organic matter

Typical 13C-NMR spectra of natural organic matter in the solid state

ppm(t1)050100150200

A wood

ppm(t1)050100150200250

A protein (prion)

ppm(f1)-1000100200300

A humic acid

Carboxylic groups

Aromatic systems

Anomeric carbons

C-O groups (i.e. Carbohydrates)

C-N groups (i.e. peptides)

Aliphatic C


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5

36

13C-CPMAS


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28

13

199

176

131

107

75

60

35 28

14

69

49

70

39

29

Bulk HA

HA1

243

HA4

HA5

HA8

HA9

HA2 HA6 HA10

HA11HA3 HA7

01001502002500100150200250 50 010015020025050 50


Analyses of Tea leaves by CPMAS 13C-NMR and 1H-HRMAS


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Analyses of Tea leaves byCPMAS 13C NMRand 1H HRMAS

Chemical Shift (ppm)-1000100200300

J

K

L

M

N

174

156

145

129

105

97

73

63

56

30

E

F

G

H

I

A

B

C

D



A = Star Green Tea

B = Gu Zhan Mao Jian Green Tea

C = Sir Winston

Green TeaD = ScelgoBio Green Tea

E = Star Black Tea

F = PG-Tips Black Tea

G = Gepa

Black TeaH = 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 TeaM = GS Earl Grey Tea

N = Infr Decaffeinated Tea

Analyses of Tea leaves by CPMAS 13C-NMR and 1H-HRMAS


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Analyses of Tea leaves by CPMAS 13C NMR and1H HRMAS

E = Star Black Tea

F = PG-Tips Black Tea

G = Gepa

Black TeaH = Twinings Lemon Scented Black Tea

I = Lipton Yellow Label Black Tea

A = Star Green Tea

B = Gu Zhan Mao Jian Green Tea

C = Sir Winston

Green TeaD = ScelgoBio Green Tea

J = Harrods n. 42 Earl Grey Tea

K = Darjeeling Earl Grey Tea

L = Twinings

Earl Grey TeaM = GS Earl Grey Tea

N = Infr Decaffeinated Tea

Analyses of Radish seeds during germination


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y g g

24h 48h 72h 96h

Analyses of Radish seeds during germination


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y g g

24h 48h 72h 96h

Tegument

Cotyledon

Roots

Analyses of Radish seeds during germination: CPMAS 13C-NMR


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y g g

ppm (t1)050100150200

0h

24h

48h

72h



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ppm (f1)-1000100200300

Cotyledon

0h

24h

72h

0

5

10

15

20

25

30

35

40

45

50

189-164 ppm 164-113 ppm 113-46 ppm 46-0 ppm

Content

(%)

0h

24h

72h

Cotyledon



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Tegument

ppm (f1)-1000100200300

0h

24h

72h

0

10

20

30

40

50

60

70

189-164 ppm 164-113 ppm 113-46 ppm 46-0 ppm

Content

(%)

0h

24h

72h

Tegument



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Roots

0h

24h

72h

ppm (f1)-1000100200300

0

10

20

30

40

50

60

70

189-164 ppm 164-113 ppm 113-46 ppm 46-0 ppm

Content

(%)

0h

24h

72h

Root

Analyses of Radish seeds during germination: HRMAS 1H-NMR


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ppm (t1)0.05.010.0

24h

48h

72h

96h

Cotyledon

0h



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Cotyledon

010

20

30

40

50

60

7080

90

100

8-6 ppm 6-5 ppm 4.5-3.0

ppm

3.0-2.5

ppm

2.5-0 ppm

Content(%) 0h

24h

48h

72h

96h



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ppm (f1)0.05.010.0

24h

48h

96h

Tegument

0h



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Tegument

0

5

10

15

20

25

30

35

40

8-6 ppm 6-5 ppm 4.5-3.0

ppm

3.0-2.5

ppm

2.5-0 ppm

Conten

t(%)

0h

24h

48h

96h



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ppm(f1)0.05.010.0

0h

24h

48h

72h

96h

Roots



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Roots

0

10

20

30

40

50

60

70

80

90

8-6 ppm 6-5 ppm 4.5-3.0

ppm

3.0-2.5

ppm

2.5-0 ppm

Conte

nt(%) 0h

24h

48h72h

96h



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0 24 48 72 960

10

20

30

40

50

60

70

80

90 4.5-3.0 ppm2.5-0 ppm

1H-HRMASContent

(%)

Time (h)

Roots

0 24 48 96

2468

10121416

1820222426283032343638 4.5-3.0 ppm

2.5-0 ppm

1H-HRMA

SContent(%)

Time (h)

Teguments

0 20 40 60 80 1000

10

20

30

40

50

60

70

80

904.5-3.0 ppm2.5-0 ppm

1H-HRMA

SContent(%)

Time (H)

Cotyledons

-10 0 10 20 30 40 50 60 70 80

10

20

30

40

50

60

70

80

4.5-3.0 ppm

2.5-0 ppm

1H-HRMASConten

t(%)

Time (h)

Total Seeds

Conclusions


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1. NMR spectroscopy is widely used for structural analyses of natural

products. Typical NMR spectra are obtained in liquid state by applyingmonodimensional 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 solidstate 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 andall 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


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CERMANU

Applicazioni della spettroscopia di risonanza magnetica nucleare (NMR) nel settore ambientale,...

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