In October 1994 he was appointed to a Professorship (Professeur associé) at the Ecole normale supérieure in Lyon, and became Full Professor in 1995. In Lyon he was the head of the Experimental Chemistry Laboratory from 1999 to 2002, and director of the Chemistry Department from 2006 to 2014. In 2002 he became a member of the Institut Universitaire de France.[10]
The newly completed ISA area in August 2012; the CRMN building is on the left
In 2012 he was promoted to Senior Member of the Institut Universitaire de France.[10]
In June 2014 he moved to the EPFL as a professor of Physical Chemistry,[12] where he is currently director of the Laboratoire de résonance magnétique of the ISIC (Institute of chemical sciences and engineering).[5]
In 2015 he received the Bourke award "for the development of experimental methods that have transformed the field of solid-state NMR and enabled new applications across chemistry".[5]
Research
Emsley's main research field is solid-state NMR spectroscopy, specifically the development of new spectroscopic methods for the determination the atomic-level structure, the dynamics and the reactivity of a wide range of materials and molecular systems, that have been inaccessible with other analytical methods.[12][13][14]
His work has involved several collaborations with the Bruker Corporation. In 2010, under his supervision as Scientific Director, the CRMN acquired and began using the world's most powerful currently operating NMR spectrometer, which breaks the billion-hertz barrier.[7][20] CRMN was also one of the first laboratories in the world to install a high field (800 MHz proton resonant frequency) solid state DNP accessory[21] and to test the new very fast 0.7 mm MAS rotors.[22]
Solid-state NMR sequences
Emsley worked with colleague Anne Lesage to introduce new through-bond carbon-proton correlation techniques in CP-MAS NMR, namely the MAS-J-HSQC and MAS-J-HMQC experiments, both used to improve resolution of two-dimensional heteronuclear correlation spectra through bond homonuclear correlations with the refocused INADEQUATE experiment in solids. They showed also the feasibility of ssNMR spectral editing techniques making use of heteronuclear scalar couplings.[23]
These implementations paved the way to the spectral characterization of solid samples at natural isotopic abundance, in a manner similar to liquid-state NMR.[23]
It was therefore possible use scalar couplings to probe weak bonding interactions in solids and provide the
first ever direct detection of a hydrogen bond in the solid-state,[24] as well as the first experimental demonstration of the presence of agostic interactions in surface species, indicated by carbenic.
His team also introduced a theoretical framework for the application of continuously phase modulated radio-frequency pulses for homonuclear decoupling in solid-state NMR, allowing new families of decoupling sequences.[25] This allowed them to obtain high-resolution proton spectra in solids.[26] a key step for three-dimensional structure determination of organic and inorganic materials at natural isotopic abundance.
The improvements in the area of proton ssNMR, specifically homonuclear decoupling, set the field for the development of NMR Crystallography.[27]
Contrary to X-ray, single crystals are not necessary with ssNMR and structural information can be obtained from high-resolution spectra of disordered solids.[28]
In 2009 Emsley's group showed the possibility of total structure determination of drug-sized organic molecules through the combination of density functional theory and solid-state NMR.[15][29]
Surface catalysis
Emsley and co-workers have shown that multi-dimensional solid state NMR can be exploited to chemically and structurally characterize catalytic surface species at a molecular level, such as reaction intermediates and catalytic centres of heterogeneous catalysts.[30]
DNP-enhanced surface NMR spectroscopy
In the field of surface chemistry, Emsley and co-workers introduced a new approach in the characterization of surfaces through ssNMR, called Surface Enhanced NMR Spectroscopy (SENS). Some systems on various support materials of great chemical interest are below the sensitivity limit of detection for the technique, but such low detection limit can be boosted using DNP, coupled with isotopic labeling and high magnetic fields. This approach enhances surface NMR signals allowing the analysis of near-surface species or materials with surface areas three orders of magnitude lower than before (around 1 m2/g, instead of 1000 m2/g).[31]
Through DNP, transfer of polarization and relevant signal enhancement can occur from the protons of the solvent batch to the rarer nuclei at natural isotopic abundance on the surface framework, including species covalently bonded to the latter one.[32]
Thanks to the description of physicochemically distinct adsorption interactions, new insights can also be offered in hydratation phenomena.[33]
Paramagnetic systems
Another subject concerns the study of paramagnetic systems, such as 4Fe-4S,[34] high spin Fe(II) catalyst, lanthanide-containing complexes or paramagnetic centers in proteins, with specific attention to the development of NMR methods specifically aimed at paramagnetic solids.
Solid-state NMR of proteins and bioaggregates
The CRMN was one of the groups developing tools and protocols for the structural and dynamic characterization of proteins in solid phase, including preparations of micro-crystalline samples, role of solvent,[35] paramagnetic systems and sequential assignment,[36] with a progressive introduction thanks to ultra-fast MAS of direct proton acquisition mimicking the sequences used for liquid NMR spectra.[37]
In collaboration with Martin Blackledge his team published some of the first ssNMR methods for the characterization of atom-specific dynamics in biosolids and its relation with solvent behaviour and function, providing detailed insight about the hierarchy of motions in proteins with the increase of temperature.[38][39]
Whole organism NMR
With Laurent Ségalat Emsley showed on the model organismCaenorhabditis elegans the possibility to use ssNMR on a whole organism for the understanding of its metabolic pattern and the influence of drug assumption or genetic modifications.[40]
Honours and awards
1991: Fellow of the Miller Institute for Basic Research in Science, Berkeley, CA
2015: Fellow of the Royal Society of Chemistry.[1]
Patents
DE Patent 3839820, Lyndon Emsley & Geoffrey Bodenhausen, "Verfahren zum selektiven Anregen von nmr-Signalen", issued 31 May 1990
DE Patent 3940633, Lyndon Emsley & Geoffrey Bodenhausen, "Gauss-Impuls-Kaskade", issued 13 June 1991
US Patent 6184683, Lyndon Emsley; Dimitri Sakellariou & Anne Lesage et al., "Method to improve resolution of two-dimensional heteronuclear correlation spectra in solid-state NMR", issued 6 February 2001
WO Patent 2004088332, Sabine Hediger; Lyndon Emsley & Jay Baltisberger, "METHOD AND INSTALLATION FOR MULTI-DIMENSIONAL INHOMOGENEOUS-FIELD MAGNETIC RESONANCE IMAGING", issued 14 October 2004
US Patent 20150219734, "POROUS AND STRUCTURED MATERIALS FOR DYNAMIC NUCLEAR POLARIZATION, PROCESS FOR THEIR PREPARATION AND NMR ANALYSIS METHOD", issued 6 August 2015
References
^ ab"Fellows (FRSC)". The Times. 27 October 2015. p. 57.
^Blanc, Frédéric; Copéret, Christophe; Lesage, Anne; Lyndon, Emsley (2008). "High resolution solid state NMR spectroscopy in surface organometallic chemistry: access to molecular understanding of active sites of well-defined heterogeneous catalysts". Chem. Soc. Rev. 37 (3): 518–526. doi:10.1039/b612793m. PMID18224261. Lyndon and Anne have been developing new NMR methods for the study of the structure and dynamics of a wide range of solidstate compounds at the Chemistry Department of the Ecole Normale Supérieure de Lyon (ENS Lyon)
^ abLesage, Anne; Steuernagel, Stefan; Emsley, Lyndon (1998). "Carbon-13 Spectral Editing in Solid-State NMR Using Heteronuclear Scalar Couplings". J. Am. Chem. Soc. 120 (28): 7095–7100. Bibcode:1998JAChS.120.7095L. doi:10.1021/ja981019t.
^Brown, S. P.; Torralba, M. P.; Sanz, D.; Claramunt, R. M.; Emsley, Lyndon (January 2002). "The Direct Detection of a Hydrogen Bond in the Solid State by NMR through the Observation of a Hydrogen-Bond Mediated 15N−15N J Coupling". J. Am. Chem. Soc. 124 (7): 1152–1153. Bibcode:2002JAChS.124.1152B. doi:10.1021/ja0172262. PMID11841267.
^Sakellariou, Dimitris; Lesage, Anne; Hodgkinson, Paul; Emsley, Lyndon (March 2000). "Homonuclear dipolar decoupling in solid-state NMR using continuous phase modulation". Chem. Phys. Lett. 319 (3–4): 253–260. Bibcode:2000CPL...319..253S. doi:10.1016/S0009-2614(00)00127-5.
^Lesage, Anne; Luminita, Duma; Sakellariou, Dimitris; Emsley, Lyndon (2001). "Improved Resolution in Proton NMR Spectroscopy of Powdered Solids". J. Am. Chem. Soc. 123 (24): 5747–5752. Bibcode:2001JAChS.123.5747L. doi:10.1021/ja0039740. PMID11403608.
^Bradley, David (15 August 2005). "Crystallography by NMR". SpectroscopyNOW. Retrieved 8 January 2016.
^Sakellariou, Dimitris; Brown, Steven P.; Lesage, Anne; Hediger, Sabine; Bardet, Michel; Meriles, Carlos A.; Pines, Alexander; Emsley, Lyndon (2003). "High Resolution NMR Correlation Spectra of Disordered Solids". J. Am. Chem. Soc. 125 (14): 4376–4380. Bibcode:2003JAChS.125.4376S. doi:10.1021/ja0292389. PMID12670262. S2CID8079811.
^Salager, Elodie; Stein, Robin S.; Pickard, Chris J.; Elena, Bénédicte; Emsley, Lyndon (April 2009). "Powder NMR crystallography of thymol". Phys. Chem. Chem. Phys. 11 (15): 2610–21. Bibcode:2009PCCP...11.2610S. doi:10.1039/b821018g. PMID19421517.
^Blanc, Frédéric; Christophe, Copéret; Lesage, Anne; Emsley, Lyndon (2008). "High resolution solid state NMR spectroscopy in surface organometallic chemistry: access to molecular understanding of active sites of well-defined heterogeneous catalysts". Chem. Soc. Rev. 37 (3): 518–526. doi:10.1039/B612793M. PMID18224261.
^Crozet, M.; Chaussade, M.; Bardet, M.; Emsley, L.; Lamotte, B.; Mouesca, J. M. (2000). "13 C Solid State NMR Studies on Synthetic Model Compounds of [4Fe 4S] Clusters in the 2+ State". J. Phys. Chem. A. 104 (44): 9990–10000. Bibcode:2000JPCA..104.9990C. doi:10.1021/jp002005o.
