Solid state NMR and diatoms: probing the interfaces

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Solid state NMR and diatoms: probing the interfaces

Sylvie Masse, Guillaume Laurent, T. Coradin

To cite this version:

Sylvie Masse, Guillaume Laurent, T. Coradin. Solid state NMR and diatoms: probing the interfaces.

Biomineralization short course, Dec 2014, Paris, France. �hal-01138970�

Sylvie MASSE, Guillaume LAURENT and Thibaud CORADIN Laboratoire de Chimie de la Matière Condensée de Paris

SDS-TREATED SAMPLE

RIGID SPECIES MOBILE SPECIES

Partnership :

V. MARTIN-JEZEQUEL, B. TESSON Fac. de Sciences et Techniques

ISOMER, NANTES ^{1 H}

1/2 100%

26.75

A X ^{NA I}

γ ⁽¹⁰

⁾

13 C ^1/2 1.1%

6.73 31 P 100% ^1/2

10.84

29 Si 4.7% ^1/2 -5.32

15 N 0.36% ^1/2 -2.71

Gyromagnetic ratio ׀γ׀ Relative sensibility

CHEMICAL TREATMENT INTRODUCTION

Whole-cell, SDS-treated and H ₂ O ₂ -treated samples were isotopically enriched with ²⁹ Si, ¹³ C/ ²⁹ Si/ ¹⁵ N and ¹³ C/ ¹⁵ N, respectively. While SDS is used to clean the frustule, H ₂ O ₂ treatment seems to be much more aggressive, probably leading to partial dissolution-recrystallization.

13 C CP (t _cp =100 µs) ¹⁵ N CP (t _cp =1 ms)

31 P

1 H

Whole-cell

SDS-treated

H ₂ O ₂ -treated

29 Si CP (t _cp =3 ms)

While a lot of work is still needed to fully understand diatoms frustule interface, solid-state NMR appears to be a powerful toolbox. Indeed, this technique is able to selectively probe either mobile or rigid species at a very local scale. Varying methods, species proximity can be checked and connectivity evaluated.

CONCLUSION AND REFERENCES

13 C low power decoupling

13 C short distance INEPT

1 H COSY ¹ H EXSY (t _mix =10 ms)

Liquid-state-inspired NMR experiments mainly highlight the most mobile species: unsaturated lipids. Nevertheless EXSY exp. shows spin diffusion between two broad protons regions.

13 C long distance INEPT

13 C CP (t _cp =500µs) high power decoupling

1 H- ¹³ C FSLG-HETCOR (t _cp =100 µs) ¹⁵ N IRCP t _cp1 =1 ms t _cp2 =5µs-1 ms

1 H- ¹³ C- ¹ H Double CP t _cp1 =1 ms

t _cp2 =100 µs-15 ms

1 H- ¹³ C- ¹ H

1 H- ³¹ P- ¹ H

1 H- ²⁹ Si- ¹ H Double CP

Solid-state NMR experiments allow to probe another part of the sample: the rigid one. Playing with the selected nuclei, spatial proximities can be assessed.

1. Tesson, B., Masse, S., Laurent, G., Maquet, J., Livage, J., Martin-Jézéquel, V. and Coradin, T.

Contribution of multi-nuclear solid state NMR to the characterization of the Thalassiosira pseudonana diatom cell wall. Anal Bioanal Chem 390, 1889–1898 (2008).

2. Hatté, C., Hodgins, G., Jull, A. J. T., Bishop, B. & Tesson, B. Marine chronology based on ¹⁴ C dating on diatoms proteins. Marine Chemistry 109, 143–151 (2008).

3. Baccile, N., Laurent, G., Bonhomme, C., Innocenzi, P. & Babonneau, F. Solid-State NMR Characterization of the Surfactant−Silica Interface in Templated Silicas:  Acidic versus Basic Conditions. Chem. Mater. 19, 1343–1354 (2007).

300 MHz

300 MHz

700 MHz

1 H

13 C

1 H

13 C

1 H

1 H

1 H

1 H

1 H

13 C