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Limites et Potentiel de la RMNpour la caractérisation structurale
de l’environnement des éléments « traces »
25 Novembre 2013
USTV - REACH | Thibault Charpentier
23 septembre 2013 | PAGE 1CEA | 10 AVRIL 2012
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NMR of Glasses
Solid State Nuclear Magnetic Resonance (ssNMR)is a powerful spectroscopy to probethe glass structure at the atomic scale.
Composition ⇔ Structure ⇔ Properties
S. SchullerCEA/DEN
F. Angeli P. JollivetCEA/DEN
N. OllierCEA/DSMS. PeugetCEA/DEN
| PAGE 2Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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23 septembre 2013 | PAGE 3
Basic Principles of NMR
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NMR : the polarization
NMR : low frequency (10-1000 MHz)
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NMR and the periodic table
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RMN pulsée
Sample
ExcitationDetection Coil
B0
BRF
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NMR interactions and the local atomic environment
Only for I>1/2Quadrupolar Interaction
δiso
CQ
η
Main NMR parameters :
Isotropic chemical shift (position of the line)
Quadrupolar coupling constant(width of the line)
Asymmetry parameter (lineshape )
speciation / structural units
ConnectivitiesProximities
(2D)
(1)
(2)
(2)
(1)
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NMR : Liquid versus Solid
| PAGE 8Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
Rigid lattice(powder)
Tissues -Food
Brownian MotionNarrow lines
Peak Aera = Quantification
NH2-CH2-COOH
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RMN : Une spectroscopie non-destructive
Using NMR to study full intact Wine bottles, A.J. Weekley et al., JMR 161 (2003) 91-98
13C NMR, 2.01 T100-1000 scans
Detection of cocaine (1min, 5mM 1.5g/L) ! (Gambarota et al. 2011) Drug testing and Analysis 3 (2011) 544
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Magic Angle Sample Spinning (MAS) NMR
Static
Low MAS
MAS
* : Spinning sidebands
Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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| PAGE 11
MAS NMR of 29Si in binary Na 2O-SiO2 glasses
(1)
(2)
(1)Chemical disorder
(2)Geometrical
disorder
Geochimica et Cosmochimica Acta 75 (2011) 2453
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23 septembre 2013 | PAGE 12
Advanced NMR techniques : two spin interactions
Double-Quantum (DQ) MAS NMR
Probing spin pairsThrough chemical bonds
Coll. S. Schuller, F. Angeli, CEA/DEN
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RMN MAS : résolution de la structure des verres à l’échelle moléculaire
| PAGE 13Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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| PAGE 14
MAS NMR of Quadrupolar Nuclei (I>1/2)
MAS removes only partially Second Order
Quadrupolar (SOQ) Broadening
∆Q(2) ∝1/νO
Multiple-Quantum MAS (2D) removes
SOQ anisotropy
Central Transition(-1/2) ↔ (+1/2)
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23 septembre 2013 | PAGE 15
11B MAS NMR in borosilicate glasses
See F. Angeli et al., JACerS 93 (2010) Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
1-10%mol Texp~min
Detection level ~ 10-100 ppm
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RMN : Importance de la spéciation des traces
| PAGE 16Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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RMN : Importance de la spéciation des traces
| PAGE 17Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
11B MAS NMR, 16.4 T100-1000 scans
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RMN : spéciation de traces
| PAGE 18Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
Spéciation du bore = mesuredu pH de l’océan ( µµµµmol/kg)
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RMN : spéciation de traces
| PAGE 19Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
11B MAS NMR, 20 kHz40-50h (1s*15-18 104)
18.8 T
9.4 T
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17O MAS & MQMAS NMR
See F. Angeli et al., JNCS 354 (2008) Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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23 septembre 2013 | PAGE 21Angeli et al. GCA 2011
Application to MoO 3 ( in low concentation) incorporation in silicates
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23 septembre 2013 | PAGE 22
Help of DFT to identify NMR fingerprint
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23 septembre 2013 | PAGE 23
95Mo MAS NMR
5%mol MoO3
2%mol MoO3
2%mol MoO3
11.72 T (500WB)Texp ~ 1-2 days
Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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17O NMR : indirect detection of heavy element ?
60SiO2 – 35Na2O – 5La2O3
La contribution
La contribution
B0=11.7 T B0=7.1 T
Separation between Si-O-Na/Si-O-Si is enhanced at lower magnetic field
(-> enables to refine the quantifications)| PAGE 24Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
~1-0.1%mol La2O3 can be resolved if resolution is achieved (and fingerprint known)
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17O MAS / MQMAS NMR
� Agreement with experiment considering La-Na mixing: 3.3 Na+ for 1 La3+
∑
−−=−−O
OLaxOBBONaNaOSi Na )*(2 3232
]4[2
∑
+=−−O
OLaxOLaLaNaOSi Na )3(2
),( 3232
La-Na mixing: 6.3 positive charge
- requires the same NBOs
- La coordination ~ 6
B0=11.7 T B0=7.1 T
F. Angeli et al., JNCS (2013)| PAGE 25Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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RMN de métaux lourd dans des verres
| PAGE 26Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
Texte
207Pb NMR 29Si NMR
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RMN des métaux lourds en solution ( RMN liquide )
| PAGE 27Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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NMR Sensitivity is (still) an issue !
Filling factor
SampleCoil Detection
NMR peak aera is proportional to the number of spins (Quantitativity)
+ Higher Resolution : higher sensitivity
NMR sensitivity = Polarisation x Detection x Resolu tion
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Low temperature MAS-NMR
| PAGE 29Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
25K
40K
79K
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RMN MAS : CryoMAS
| PAGE 30Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013 http://www.dotynmr.com/solids/sol_cryocoilpg.htm
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HR-MACS-NMR : RMN miniaturisée (A. Wong, D. Sakellariou, LSDRM)
| PAGE 31Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013 Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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DNP MAS NMR : use high frequency polarization
| PAGE 32Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
Hig
h fr
eque
ncy
Coupling
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RMN MAS : DNP et surface
| PAGE 33Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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RMN MAS : DNP et surface
| PAGE 34Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
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RMN MAS : Dynamic Nuclear Polarization - DNP (Hyperpolarisation)
| PAGE 35Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
!!! Nat. Abund. 17O excited near or on the surface !!!
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129Xe NMR : Hyperpolarization (LSDRM)
| PAGE 36Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
Optical Pumping
Angularmomenta of
photons
Electronspins of
an alkali-metal
Nuclear spins of a noble gas
1 2
1
2
Lifetime of Xenon polarization ~hours !!
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129Xe NMR: detecting trace elements in solution (LSDRM)
| PAGE 37Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013
NTACryptophane
Spacer
�Specific chemical shift effect to Zn2+ (Pb2+, Cd2+, …)
(d)
(c)
(b)
(a)(one-scan)�Towards nM detection !
P. Berthault et al. , LSDRM
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Conclusion
NMR provides valuable information on chemical environment in crystalline
and amorphous materials (High-Resolution) (and in s olution)
Standard Sensitivity 1-100 mg . 0.1 (-0.01%mol) ( 0 .1%weight 27Al )
27Al, 11B, 7Li, 31P, 23Na … min @1% mol (but background signal)
113Cd (I=1/2), 207Pb (I=1/2), 205Tl (I=1/2), 199Hg (I=1/2) ? (~1 days)
NMR sensitivity is « still » an issue by Hyper-NMR is coming (x100)
Hyper-Polarisation (DNP, Xenon, Parahydrogen , …)
Hyper-Dectection (Optical detection, …)
Effective Methodologies for surface studies now exi sts !
Sensitive (indirect) probe of trace elements exist with Hyper Resolution (129Xe)
NMR is also a tool for Food profiling ( 1H, 13C, 23Na)Thibault Charpentier - USTV – REACH 2013 | 25 Novembre 2013