Jens Dittmer

Professeur des Universités

Solid-state NMR


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, with JF Pilard (IMMM-MSP), Hutchinson)

- degradation of oil paint and other 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





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
   (OLoRM) and M Makowska (Czestochowa, Poland)

-  The structure and electronic spin density of a bipyridinium radical studied by solid-state NMR
   in comparison with DFT calculations (with S. Kumara Swamy, A. Kassiba (OLoRM) and N.
   Mercier, MOLTECH Angers)







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, τc, 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 B. Pahari, G. Corbel and
   P. Lacorre, OETPS)




 NMR of hybrid perovskites




Hybrid perovskites recently have drawn interest as material for new generation photovoltaics. Variations of the prototype MAPI (CH3NH3)PbI3 are developped in order to tune properties as stability and PCE. NMR is an excellent tool to study the structure and dynamics of the organic part.


Project ANR MORELESS, 2019-2021, with N. Mercier, MOLTECH Angers






Co‐doping effects of (Al, Ti, Mg) on the microstructure and electrical behavior of ZnO based ceramics
Q. Sun, G. Li, T. Tian, J. Zeng, K. Zhao, L. Zheng, M. Barré, J. Dittmer, F. Goutenoire, A. Rousseau, A.H. Kassiba
J. Am. Ceram. Soc., accepted for publication. doi: 10.1111/jace.16999


Controllable microstructure tailoring for regulating conductivity in Al-doped ZnO ceramics
Q. Sun, G. Li, T. Tian, Z. Man, L. Zheng, M. Barré, J. Dittmer, F. Goutenoire, A.H. Kassiba
J. Eur. Ceram. Soc. 40 (2020), 349-354. doi: 10.1016/j.jeurceramsoc.2019.10.011


CO2 capture by Na2TeO4: structure of Na2-xHxTeO4 and kinetic aspects 
C. Galven, T. Pagnier, J. Dittmer, F. Le Berre, M.-P. Crosnier-Lopez
Inorg. Chem. 58 (2019), 8866-8876. doi: 10.1021/acs.inorgchem.9b01282


Enhanced stability and band gap tuning of α-[HC(NH2)2]PbI3 hybrid perovskite by large cation integration
A. Leblanc, N. Mercier, M. Allain, J. Dittmer, T. Pauporte, V. Fernandez, F. Boucher, M. Kepenekian, C. Katan
ACS Appl. Mater. Interfaces
11 (2019), 20743-20751. doi: 10.1021/acsami.9b00210


Electronic active defects and local order in doped ZnO ceramics inferred from EPR and  27Al NMR investigations
Q. Sun, T. Tian, L. Zheng, Z. Man, G. Li, M. Barré, J. Dittmer, A. Bulou, A.H. Kassiba
J. Eur. Ceram. Soc. 39 (2019), 3070-3076. doi: 10.1016/j.jeurceramsoc.2019.04.024


Insight into the factors influencing NMR parameters in crystalline materials from the KF–YF3 binary system
J. Dabachi, M. Body, J. Dittmer, A. Rakhmatullin, F. Fayon, C. Legein
Dalton Trans. 48 (2019), 587-601. doi: 10.1039/C8DT03241F


Microstructural properties and dielectric relaxations of partially fluorinated copolymers
J.A.S. Puente, L. Delbreilh, J. Dittmer, V. Briand, S. Vernay, E. Dargent
Polymer 157 (2018), 50-58. doi: 10.1016/j.polymer.2018.10.020


Nuclear magnetic resonance analysis for treatment decisions: the case of a white sculptural environment by Louise Nevelson
C. Kehlet, S. Nunberg, S. Alcala, J. Dittmer
Microchem. J. 137 (2018), 480-484. doi: 10.1016/j.microc.2017.12.004


Marennine-like pigments: blue diatom or green oyster cult?
R. Gastineau, F.S. Prasetiya, C. Falaise, B. Cognie, P. Decottignies, M. Morançais, V. Méléder, N. Davidovich, F. Turcotte, R. Tremblay, P. Pasetto, J. Dittmer, J.-F. Bardeau, J.-B. Pouvreau, J.-L. Mouget
In: Blue biotechnology: Production and use of marine molecules, 1st edition, 2018, pp. 529-553, ed. S. La Barre and S. Bates. Viley-VCH, Weinheim


Lead- and iodide-deficient (CH3NH3)PbI3 (d-MAPI): the bridge between 2D and 3D hybrid perovskites
N. Mercier, A. Leblanc, M. Allain, J. Dittmer, V. Fernandez, T. Pauporté
Angew. Chem. Int. Ed. 57 (2017), 16067-16072. doi: 10.1002/anie.201710021


Conservation of a white Louise Nevelson installation: treatment choices based on ethical discussions and analytical studies
S. Nunberg, C. Kehlet, S. Alcala, C. Tomkiewicz, C. McGlinchy, M.C. Henry, J. Dittmer
In: ICOM-CC 18th triennial conference preprints, 2017, ed. J. Bridgland, art. 1706. Paris: International Council of Museums.


Conservation of a white Louise Nevelson installation: gel systems explored
S. Nunberg, C. Tomkiewicz, S. Alcala, C. Kehlet, C. McGlinchey, J. Dittmer
in: Gels in conservation, Archetype Publications, London, 2017


Effects of orthophosphate and calcium on the self assembly of dense sodium caseinate solutions
P. Thomar, A. Gonzalez-Jordan, J. Dittmer, T. Nicolai
Int. Dairy J. 64 (2017), 1-8. doi: 10.1016/j.idairyj.2016.08.010


A porous coordination polymer based on bipyridinium carboxylate linkers with high and reversible ammonia uptake
M. Leroux, N. Mercier, M. Allain, M.-C. Dul, J. Dittmer, A. Kassiba, J.P. Bellat, G. Weber, I. Bezverkhyy
Inorg. Chem. 55 (2016), 8587-8594. doi: 10.1021/acs.inorgchem.6b01119


Bipyridinium-bis-carboxylate radical based materials: X-ray, EPR and paramagnetic solid state NMR investigations
O. Toma, M. Leroux, N. Mercier, M. Allain, A. Kassiba, S. K. Kumara Swamy, J. Dittmer
Eur. J. Inorg. Chem. (2016), 1036-1043. doi: 10.1002/ejic.201501206


Spectroscopy analyses of hybrid unsaturated polyester composite reinforced by alfa, wool and thermo-binder fibres
A. Triki, J. Dittmer, M. Ben Hassen, M. Arous, A. Bulou, M. Gargouri
Polym. Sci. Ser. A 58 (2016), 255-264. doi: 10.1134/S0965545X16020188


Solid-state NMR for the study of Asger Jorn’s paintings
C. Kehlet, F. Kuvvetli, A. Catalano, J. Dittmer
Microchem. J. 125 (2016), 308-314. doi: 10.1016/j.microc.2015.11.010


Formation of stable phases of the Li–Mn–Co oxide system at 800 °C under ambient oxygen pressure
A. Ye. Shpak, S. K. Kumara Swamy, J. Dittmer, N. Ye. Vlasenko, N. I. Globa, A. A. Andriiko
J. Solid State Electrochem. 20 (2016), 87-94. doi: 10.1007/s10008-015-3001-x


Structural refinement of the RT LaOF phases by coupling powder X-ray diffraction, 19F and 139La solid state NMR and DFT calculations of the NMR parameters
J. Dabachi, M. Body, J. Dittmer, F. Fayon, C. Legein
Dalton Trans. 44 (2015), 20675-20684. doi: 10.1039/C5DT04028K


The effect of pH on the structure and phosphate mobility of casein micelles in aqueous solution
A. Gonzalez-Jordan, P. Thomar, T. Nicolai, J. Dittmer
Food Hydrocolloid 51 (2015) 88-94. doi: 10.1016/j.foodhyd.2015.04.024


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. 107 (2014), 270-276. doi:10.1016/j.polymdegradstab.2013.12.039


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


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


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


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


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


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


An unusual intrinsically disordered protein from the model legume Lotus japonicus stabilizes proteins in vitro
S. Haaning, S. Radutoiu, S.V. Hoffmann, J. Dittmer, L. Giehm, D.E. Otzen, and J. Stougaard
J. Biol. Chem. 283 (2008), 31142 – 31152.


Quantitative Analysis of Constituents in Heavy Fuel Oil by 1H Nuclear Magnetic Resonance (NMR) Spectroscopy and Multivariate Data Analysis
K. E. Nielsen, J. Dittmer, A. Malmendal, and N.C. Nielsen
Energy & Fuels 22 (2008), 4070–4076.


The three-dimensional structure of CsmA: A small antenna protein from the green sulfur bacterium Chlorobium tepidum.
M.Ø. Pedersen, J. Underhaug, J. Dittmer, M. Miller and N.C. Nielsen
FEBS Lett. 582 (2008), 2869-2874.


Early Stages of amyloid fibril formation studied by liquid-state NMR: The peptide hormone glucagon.
A.S.P. Svane, K. Jahn, T. Deva, A. Malmendal, D.E. Otzen, J. Dittmer and N.C. Nielsen
Biophys. J. 95 (2008), 366-377.


Kinetics of RNA refolding in dynamic equilibrium by 1H-detected 15N exchange NMR spectroscopy.
P. Wenter, G. Bodenhausen, J. Dittmer and S. Pitsch
J. Am. Chem. Soc. 128 (2006), 7579-7587.


Quenching echo modulations in NMR spectroscopy.
J. Dittmer and G. Bodenhausen
ChemPhysChem 7 (2006), 831-836.


Slow diffusion by singlet-state NMR spectroscopy.
S. Cavadini, J. Dittmer, S. Antonijevic and G. Bodenhausen
J. Am. Chem. Soc. 127 (2005), 15744-15748.


Structural and oxidation state changes of the photosystem II manganese complex in four transitions of the water oxidation cycle (S0-S1, S1-S2, S2-S3, S3,4-S0) characterized by X-ray absorption spectroscopy at 20 K and at room temperature.
M. Haumann, C. Müller, P. Liebisch, L. Iuzzolino, J. Dittmer, M. Grabolle, T. Neisius, W. Meyer-Klaucke and H. Dau
Biochemistry 44 (2005), 1894-1908.


Multiple refocusing in NMR: compensation of pulse imperfections by scalar couplings.
J. Dittmer and G. Bodenhausen
ChemPhysChem 5 (2004), 1750-1754.


Evidence for slow motion in proteins by multiple refocusing of heteronuclear nitrogen/proton multiple quantum coherences in NMR.
J. Dittmer and G. Bodenhausen
J. Am. Chem. Soc. 126 (2004), 1314-1315.


Similarities between intra- and intermolecular hydrogen bonds in RNA kissing complexes found by means of cross-correlated relaxation.
J. Dittmer, C.-H. Kim and G. Bodenhausen
J. Biomol. NMR 26 (2003), 259-275.


Stepwise transition of the tetra-manganese complex of photosystem II to a binuclear Mn2(µ-O)2 complex in response to a temperature jump: a time-resolved structural investigation employing X-ray absorption spectroscopy.
P. Pospíšil, M. Haumann, J. Dittmer, V.A. Solé and H. Dau
Biophys. J. 84 (2003), 1370-1386.


First steps towards time-resolved BioXAS at room temperature: State transitions of the manganese complex of oxygenic photosynthesis.
M. Haumann, P. Pospíšil, M. Grabolle, C. Müller, P. Liebisch, V.A. Solé, T. Neisius, J. Dittmer, L. Iuzzolino and H. Dau
J. Synchrotron Rad. 9 (2002), 304-308.


NMR solution structure, backbone mobility and homology modeling of c-type cytochromes from gram-positive bacteria.
L. Banci, I. Bertini, S. Ciurli, A. Dikiy, J. Dittmer, A. Rosato, G. Sciara and A. Thompsett
ChemBioChem 3 (2002), 299-310.


The tetra-manganese complex of photosystem II during its redox cycle- X-ray absorption results and mechanistic implications.
H. Dau, L. Iuzzolino and J. Dittmer
Biochim. Biophys. Acta 1503 (2001), 24-39.


The manganese complex of Photosystem II: A structural model for the S1, S2, and S3 oxidation state derived from dichroism EXAFS spectroscopy at 20 K and at room temperature
M. Haumann, M. Grabolle, M. Werthammer, L. Iuzzolino, J. Dittmer, W. Meyer-Klaucke, T. Neisius and H. Dau
In: PS2001 Proceedings, S10-013, 2001, pp. 1-5, CSIRO Publishing, Collingwood, Australia.


Stepwise transition of the tetra-manganese complex of Photosystem II to a binuclear Mn2(µ-O)2 complex in response to a temperature jump: an X-ray absorption study.
P. Pospisil, M. Haumann, J. Dittmer, A. Sole and H. Dau
In: PS2001 Proceedings, S13-007, 2001, pp. 1-4, CSIRO Publishing, Collingwood, Australia.


Bromine K-edge EXAFS studies of bromide binding to bromoperoxidase from Ascophyllum nodosum.
H. Dau, J. Dittmer, M. Epple, J. Hanss, E. Kiss, D. Rehder, C. Schulzke and H. Vilter
FEBS Letters 457 (1999), 237-240.


X-ray absorption spectroscopy on layered photosystem II membrane particles suggests manganese-centered oxidation of the oxygen-evolving complex for the S0-S1, S1-S2 and S2-S3 transitions of the water-oxidation cycle.
L. Iuzzolino, J. Dittmer, W. Dörner, W. Meyer-Klaucke and H. Dau
Biochemistry 37 (1998), 17112-17119.


Theory of the linear dichroism in the extended X-ray absorption fine structure (EXAFS) of partially vectorially-ordered systems.
J. Dittmer and H. Dau
J. Phys. Chem. B 102 (1998), 8196-8200.


A correlation method for quantification of the magnitude of the S-2-state multiline EPR signal
L. Iuzzolino, J. Dittmer, W. Dörner, H. Dau
In: Photosynthesis: Mechanisms and Effects; ed. G. Garab. Vols I-V, 1998, 1315-1318.


A new method for determination of the edge position of x-ray absorption spectra
J. Dittmer, L. Iuzzolino, W. Dörner, H.F. Nolting, W. Meyer-Klaucke and H. Dau
In: Photosynthesis: Mechanisms and Effects; ed. G. Garab. Vols I-V, 1998, 1339-1342.


Structure and orientation of the oxygen-evolving manganese complex of green algae and higher plants investigated by X-ray absorption linear dichroism spectroscopy on oriented photosystem II membrane particles.
H. Schiller, J. Dittmer, L. Iuzzolino, W. Dörner, W. Meyer-Klaucke, V.A. Solé, H.-F. Nolting and H. Dau
Biochemistry 37 (1998), 7340-7350.


X-ray absorption linear dichroism spectroscopy (XALDS) on the photosystem II manganese complex: Radiation damage and S1-state K-edge spectra.
H. Dau, J. Dittmer, L. Iuzzolino, H. Schiller, W. Dörner, I. Heinze, V.A. Solé and H.-F. Nolting
J. Phys. IV France 7 (1997), 607-610.


Comparison of electron paramagnetic resonance lineshape, orientation and power saturation of the TyrD radical from spinach and the green alga Scenedesmus obliquus.
H. Schiller, L. Iuzzolino, J. Dittmer and H. Dau
Ber. Bunsenges. Phys. Chem. 100 (1996), 1999-2002.


On the influence of multiple scattering contributions to the extended X-ray absorption fine structure (EXAFS) spectra of the photosystem II manganese complex.
J. Dittmer and H. Dau
Ber. Bunsenges. Phys. Chem. 100 (1996), 1993-1998.