Structural and dynamic characterization by Solid State NMR and Modeling




Solid-state NMR of organic polymers



13C NMR under MAS is an important tool for the study of organic polymers including biopolymers. By means of cross-polarization, often also constituents in smaller concentrations can be detected. We study for example natural rubbers in order to reveal its composition (industrial collaboration, projet CANAOPT). Another line is the study of modern materials used in fine arts (collaboration with Pratt Institute, New York). A common problem is the degradation of these materials with time. These processes are studied in vitro by solid state NMR as well as non-invasively by unilateral low field NMR.



- composition of natural rubber, industrial collaboration (project CANAOPT, coordinator JF Pilard,


- degradation of polymeric materials used in fine arts – collaboration with
   C. Kehlet, Pratt Institute, New York

- the chemical structure of the green-blue pigment marennine, a 10 kDa
   polymer found in diatoms (and in green oysters) at the French atlantic
   coast – collaboration with JL Mouget, MMS, and MMS Nantes






NMR-crystallography for inorganic fluorides and oxyfluorides

Our laboratory is specialized on the structural study of fluorides and oxyfluorides in close collaboration with groups from the French Fluorine Network. NMR can help to fine tune the structure by (i) comparing the experimental parameters with those issued from DFT calculations on the base of structural models; (ii) applying high resolution solid state NMR sequences, including 2D correlation experiments, to characterize the environment of probed nuclei. As an example, the assignment of fluorine sites to NMR lines from 2D 19F DQ-SQ experiment is shown for α-LaZr2F11.



- structure refinement of oxyfluorides by means of measurements and DFT calculations of NMR

  parameters (19F and cation)  (thesis Jamal Dabachi)

- characterization of fluorine environments in anodes and electrolytes for fluoride ionic conductor

  batteries (ANR project FLUOBAT, coordinator V. Maisonneuve, FLUO)







Solid-state NMR in the presence of paramagnetic centers

NMR is the art of dealing with various interactions that locally change the resonance frequencey and that are usually treated as perturbations of the Zeeman interaction. Chemical shift, J -, dipolar - , and quadrupolar coupling are well studied, and there have been techniques developed to deal with them. The hyperfine interaction of the nucleus with unpaired electron(s) in the presence of paramagnetic centers is however less investigated in solid state NMR. Line broadening and very fast relaxation make common techniques not applicable. We develop new methods that allow NMR experiments despite the hyperfine interactions and that exploit this interaction. It has for example allowed to measure copper-carbon distances in a Cu-cyclam complex.



- Cu-cyclam as model system for testing new methods in NMR of
   paramagnetics (thesis S. Kumara Swamy, collaboration with A. Kassiba
   (NF) and M Makowska (Czestochowa, Poland)







NMR of ion conductors



In addition to the structure, the ion mobility is the central interest in the study of ion conductors. In particular the lithium ions can well be investigated by NMR of the isotopes 6Li and 7Li. The quadrupolar relaxation of the latter reflects the Li motion. Its interpretation yields a measure for the average time for hopping from site to site, t c, and the activation energy needed for this hopping. 



- Li+ and H+ mobility in the Li garnet Li7-xHxLa3Sn2O12 (with F Le Berre and
   MP Crosnier-Lopez, OETPS)

- the distibution of phosphorus dopants in LAMOX (with G. Corbel and
   P. Lacorre, OETPS)





Publications (since 2009)


Incorporation of antimicrobial peptides into membranes: a combined liquid-state NMR and Molecular Dynamics study of alamethicin in DMPC/DHPC bicelles

J. Dittmer, L. Thogersen, J. Underhaug, K. Bertelsen, T. Vosegaard, J. M. Pedersen, B. Schiott, E. Tajkhorshid, T. Skrydstrup, N. C. Nielsen

J. Phys. Chem. B 113 (2009), 6928-6937, doi: 10.1021/jp811494p                  



Sensitivity enhancement of 29Si double-quantum dipolar recoupling spectroscopy by Carr-Purcell-Meiboom-Gill acquisition method
M. Goswami, P.K. Madhu, J. Dittmer, N.C. Nielsen, and S. Ganapathy

Chem. Phys. Lett. 478 (2009), 287-291, doi: 10.1016/j.cplett.2009.07.066



Efficient Ion Exchange of H+ for Li+ in (Li0.30La0.57¨(0.13))TiO3 Perovskite in Water: Protons As a Probe for Li Location

A. Boulant, P. Maury, J. Emery, J.-Y. Buzaré, O. Bohnke

Chem. Mat. 21 (2009), 2209-2217                           



Effect of fluoride ion incorporation on the structural aspects of barium–sodium borosilicate glasses

R. K. Mishra, V. Sudarsan, C. P. Kaushik, K. Raj, R. K. Vatsa, M. Body, A. K. Tyagi

J. Non-Cryst. Solids 335 (2009), 414-419, doi:10.1016/j.jnoncrysol.2009.01.002



On the assignment of F-19 MAS NMR spectra of fluoroaluminates using through-space spectral edition of F-19-(27) Al and 19F-19F connectivities

C. Martineau, C. Legein, J.-Y. Buzaré, F. Fayon

Phys. Chem. Chem. Phys. 11 (2009), 950-957         



NMR investigations of Li+ ion dynamics in the NASICON ionic conductors Li1-xLax/3¨Zr(PO4)3

M. Barre, J. Emery, P. Florian, F. Le Berre, M.-P. Crosnier-Lopez, J.-L. Fourquet

J. Physics: Cond. Matter 21 (2009), 175404



Peculiarities of ionic transport in Li1.3Al0.15Y0.15Ti1.7(PO4)3 ceramics

T. Salkus, E. Kazakevicius, A. Kezionis, A. Dindune, Z. Kanepe, J. Ronis, J. Emery, A. Boulant, O. Bohnke, A. F. Orliukas

J. Phys.: Condensed Matter 21 (2009), 185502                   



Properties of amorphous silica generated by the fluoride method

L. P. Demyanova, A. Tressaud, J.Y. Buzaré, C. Martineau, C. Legein, Y. N. Malovitski, V. S. Rimkevich

Inorg. Mat. 45 (2009), 151-156                                                                                                       


Highly Fluorinated Silica Obtained by Direct F2-Gas Fluorination: Stability and Unprecedented Fluorosilicate Species Revealed by Solid State NMR Investigations

E. Lataste, C. Legein, M. Body, J.-Y. Buzaré, A. Tressaud, A. Demourgues

J. Phys. Chem. C 113 (2009), 18652-18660, doi: 10.1021/jp9087628                   



Double-quantum F-19-F-19 dipolar recoupling at ultra-fast magic angle spinning NMR: application to the assignment of F-19 NMR spectra of inorganic fluorides

Q. Wang, B. Hu, F. Fayon, J. Trebosc, C. Legein, O. Lafon, F. Deng, J.-P. Amoureux

Phys. Chem. Chem. Phys. 11 (2009), 10391-10395, doi:10.1039/b914468d                       



Solid-state F-19 MAS NMR investigation of fluoride ion mobility in lead fluorides: correlation with anionic conductivity

C. Martineau, F. Fayon, C. Legein, J.Y. Buzaré, G. Corbel

Chem. Mat. 22 (2010), 1585-1594                  



Reaction mechanisms of Li0.30La0.57TiO3 powder with ambient air: H+/Li+ exchange with water and Li2CO3 formation

A. Boulant, J.F. Bardeau, A. Jouanneaux, J. Emery, J.Y. Buzaré, O. Bohnke

Dalton Trans. 39 (2010), 3968-3975



Evolution of guanazolium fluoroaluminates within the composition-space diagram and with the temperature

A. Cadiau, A. Le Bail, A. Hémon-Ribaud, M. Leblanc, M. Body, F. Fayon, E. Durand, J.-C. Boulou, V. Maisonneuve

Cryst. Growth Des. 10 (2010), 5159-5168, doi: 10.1021/cg100909x                                 



New oxyfluoride pyrochlores Li2-xLa(1+x)/3(2x-1)/3B2O6F (B = Nb, Ta): average and local structure characterization by XRD, TEM and 19F solid-state NMR spectroscopy

C. Galven, C. Legein, M. Body, J.-L. Fourquet, J.-Y. Buzaré, F. Le Berre, M.-P. Crosnier-Lopez

Eur. J. Inorg. Chem. 33 (2010), 5272-5283, doi: 10.1002/ejic.201000599                



Probing short and medium range order in Al-based fluorides using high resolution solid state nuclear magnetic resonance and parameter modelling" in "Functionalized Inorganic Fluorides

C. Legein, M. Body, J.-Y. Buzaré, C. Martineau, G. Silly, edited by A. Tressaud, John Wiley & Sons, 2010, p 141-174, doi: 10.1002/9780470660768



2D zirconium fluorides: synthesis, structure and NMR spectroscopy

A. Ben Ali, M. Body, M. Leblanc, V. Maisonneuve

Solid State Sci. 13 (2011), 394-398, doi: 10.1016/j.solidstatesciences.2010.11.044



NMR parameters in alkali, alkaline earth and rare earth fluorides from first principle calculations

A. Sadoc, M. Body, C. Legein, M. Biswal, F. Fayon, X. Rocquefelte, F. Boucher

Phys. Chem. Chem. Phys. 111 (2011), 11873-11884, doi:10.1039/c1cp21253b



In-115 and F-19 MAS NMR study of (NH4)3InF6 phases

G. Scholz, T. Krahl, M. Ahrens, C. Martineau, J.-Y. Buzaré, C. Jaeger, E. Kemnitz

J. Fluor. Chem. 132 (2011), 244-249, doi: 10.1016/j.jfluchem.2011.01.010



From micro- to nanostructured fast ionic conductor Li0.30La0.56¨0.13TiO3: size effects on NMR properties

A. Boulant, J. Emery, A. Jouanneaux, J.-Y. Buzaré, J.-F. Bardeau

J. Phys. Chem. C 115 (2011), 15575-15585, doi: 10.1021/jp2048794



Characterizing gum natural rubber samples through advanced techniques

J. L. Leblanc, J.-F. Pilard, E. Pianhanuruk, I. Campistron, J.-Y. Buzaré

J. Appl. Polym. Sci. 119 (2011), 3058-3071, doi: 10.1002/app.33052



H+/Li+ exchange property of Li3xLa2/3-xTiO3 in water and in humid atmosphere

O. Bohnke, Q. N. Pham, A. Boulant, J. Emery, T. Salkus, M. Barré

Solid State Ionics 188 (2011), 144-147, doi: 10.1016/j.ssi.2010.09.058 



Structural investigation of α- and β-sodium hexafluoroarsenate, NaAsF6, by variable temperature X-ray powder diffraction and multinuclear solid-state NMR and DFT calculations

M. Biswal, M. Body, C. Legein, G. Corbel, A. Sadoc, F. Boucher

J. Phys. Chem. C 116 (2012), 11682-11693, doi: 10.1021/jp3040727



Instability of lithium garnets against moisture. Structural characterization and dynamics of Li7-xHxLa3Sn2O12 and Li5-xHxLa3Nb2O12

C. Galven, J. Dittmer, E. Suard, F. Le Berre, M.-P. Crosnier-Lopez

Chem. Mat. 24 (2012), 3335-3345, doi: 10.1021/cm300964k



Analysis of the local structure of phosphorus-substituted LAMOX oxide ion conductors

B. Pahari, N. Mhadhbi, G. Corbel, P. Lacorre, J. Dittmer

Dalton Trans. 41 (2012), 5696-5703, doi: 10.1039/c2dt12389d



Structural investigation of α-LaZr2F11 by coupling X-ray powder diffraction, 19F solid state NMR and DFT calculations

C. Martineau, C. Legein, M. Body, O. Peron, B. Boulard, F. Fayon

J. Solid State Chem. 199 (2013), 326-333, doi: 10.1016/j.jssc.2012.12.016     



NbF5 and TaF5: assignment of 19F NMR resonances and chemical bond analysis from GIPAW Calculations

M. Biswal, M. Body, C. Legein, A. Sadoc, F. Boucher

J. Solid State Chem. 207 (2013), 208-217, doi:10.1016/j.jssc.2013.09.001



Solid-state NMR correlation experiments and distance measurements in paramagnetic metalorganics exemplified by Cu-cyclam

S. K. Kumara Swamy, A. Karczmarska, M. Makowska-Janusik, A. Kassiba, J. Dittmer

ChemPhysChem. 4 (2013), 1864-1870,  doi: 10.1002/cphc.201300119



Non-invasive characterization of polymeric materials in relation to art conservation using unilateral NMR combined with multivariate data analysis

C. Kehlet, E. Del Federico, H. Schahbaz, A. Catalano, J. Dittmer, N. C. Nielsen

Anal. Methods 5 (2013), 4480-4486, doi: 10.1039/c3ay40650d



Noncovalent chalcogen bonds and disulfide conformational change in the cystamine-based hybrid perovskite [H3N(CH2)2SS(CH2)2NH3]PbIII4

N. Louvain, G. Frison, J. Dittmer, C. Legein, N. Mercier

Eur. J. Inorg. Chem. (2014), 364-376, doi: 10.1002/ejic.201301017



NMR parameters in column 13 metal fluoride compounds (AlF3, GaF3, InF3 and TlF) from first principle calculations

A. Sadoc, M. Biswal, M. Body, C. Legein, F. Boucher, D. Massiot, F. Fayon

Solid Sate Nucl. Magn. Reson. 59-60 (2014) 1-7. doi: 10.1016/j.ssnmr.2014.01.001



Marennine, promising blue pigments from a widespread Haslea diatom species complex
R. Gastineau, F. Turcotte, J.-B. Pouvreau, M. Morançais, J. Fleurence, E. Windarto, F. S. Prasetiya, S. Arsad, P. Jaouen, M. Babin, L. Coiffard, C. Couteau, J.-F. Bardeau, B. Jacquette, V. Leignel, Y. Hardivillier, I. Marcotte, N. Bourgougnon, R. Tremblay, J.-S. Deschênes, H. Badawy, P. Pasetto, N. Davidovich, G. Hansen, J. Dittmer, J.-L. Mouget
Mar. Drugs 12 (2014) 3161-3189. doi: 10.3390/md12063161



F-/OH- substitution in [H4tren]4+ and [H3tren]3+ hydroxyfluorotitanates(IV) and classification of tren cation configurations
J. Lhoste, M. Body, C. Legein, A. Ribaud, M. Leblanc, V. Maisonneuve
J. Solid State Chem., in press. doi: 10.1016/j.jssc.2014.05.008



Degradation of natural rubber in works of art studied by unilateral NMR and high field NMR spectroscopy

C. Kehlet, A. Catalano, J. Dittmer

Polym. Degrad. Stabil., in presss. doi:10.1016/j.polymdegradstab.2013.12.039