Sol Gel Derived Materials and Biocompatible Structures: the Solid State NMR Point of View !
C. Bonhomme, C. Gervais, C. Coelho, F. Pourpoint, G. Gasquères , F. Babonneau, T. Azaïs, G. Laurent, B. Alonso and F. Mauri Laboratoire de Chimie de la Matière Condensée de Paris Laboratoire de Minéralogie-Cristallographie Université P. et M. Curie – Paris 6, France
GERM NMR school – march 2008
NMR interactions a tensorial approach of nuclei by local probes: the NMR interactions (CSA, J, quadrupolar, dipolar) ZT
Bo
XT
XPAS (T)
13C
δ(
13C)
1J(29Si-13C)
YPAS (T)
αo
29Si)
29Si
ZPAS (T) Bo βo YT
δ(
X’(α αo)
29Si
O
D(29Si-1H)
anisotropy: anisotropy: highly informative shapes I = 5/2
1H
O
27Al
Q(27Al)
dipolar D
CSA D ∝ 1/r3
...quantum physics
High resolution in solid state NMR O
O
P
29Si
D
O
D(29Si-31P)
31P
OH HO
OH
φ
D and J !
P O
φ
O
OH Si
Si
Si
Si
Cross Polarization B0
recoupling under high resolution conditions !
rotor axis
*
δ
(29Si)
29Si
θm= 54.7°
O
2J(29Si-31P)
δ(
31P)
Bo
*
*
Hop !
31P
solid state J-INEPT,HMQC
Dynamic Angle Spinning (DAS) I > 1/2 or MQMQ-MAS I > 1/2
*
Cross Polarization experiments (under MAS) CP MAS {1H/X}
Bo
1H
Y
transfer
29Si
2D HETCOR CP MAS {X/Y} X
90° 31P
∆
...
90° RD t1
ramp
CW
n
contact
I
rIS
29Si
tCP
t2
S
DIS ~ rIS-3
2D HETCOR CP MAS {1H/X/Y} 90° 1H
t1
31P
1H
CW
ramp
Bo ramp
CW
tCP
Y
29Si
X
tCP
t2
Methods: solid state NMR, first principles calculations, models ■ D and J-derived solid state NMR
■ ab initio calculations Pickard, Mauri, Phys. Rev. B (2001)
90° CW
ramp
1
H
PAW, GIPAW methods
t1
31
P
ramp
CW
tCP 29
CSA
Si tCP
t2
2D triple res. CP MAS
J
EFG
Bo
■ DFT models material 90° 29Si
90°
90°
180°
τ Φ1
C1
Φ12
Φ11
31P
C2
t1/2
Sol Gel chemistry
t1/2 τ Φ2
2D MAS-J-HMQC
t2
Chimie Douce...
Astala et al., Chem. Mater. 2005 Peroos et al., Biomaterials 2006
♦ CHEMICAL SHIFT δ
29Si
O Si
Si
SiO2
17O
O Ti in: Levitt, spin dynamics, 2002
P
TiO2
■ covalent grafting C. Gervais et al., Chem. Mater. 15 (2003) 4098. C. Bonhomme et al., MRS Proceedings (2007) E-paper.
■ oxide nanoparticles
Covalent grafting on silica nanoparticles
SSiO iO
22
cluster integrity
29Si
CP MAS NMR
solution NMR
local dynamics
reactivity
S. de Monredon (PhD) Coll. : A. Pottier (Rhodia)
model compounds
Covalent grafting on TiO2 nanoparticles a particular probe:
17O
I = 5/2
second-order quadrupolar broadening P=O O3
O2
17O
P-OH
P
O1 Ti-O-P
Ti-O-Ti Ti P O
ZrO2 (rotor)
O P OH OH
TiO2
Coll. : H. Mutin (Montpellier)
600
450
300
150 ppm
0
-150
Sol Gel materials: questions ? «playing» with the dipolar D and scalar J interactions... spatial interaction
H
sol gel oxide glasses
H-15N
hybrid materials
OH 29Si
mesoporous materials
chemical bond
Me Si-O-SiMe
SiO2
D
J
■ connectivities in hybrids ■ organic/inorganic interactions biogenic silica (diatoms)
■ ...
♦ DIPOLAR INTERACTION D
(EtO)3Si
rIS D ∝
molecular recognition H-bonding
hydrolysis
1
Si(OEt)3
condensation
rIS3 O 1.5 Si
SiO 1 .5 n
750!
CRMHT, Orléans
Bo
33 kHz !
hybrid material
■ 1H-1H dipolar interaction ■ ureidopyrimidinone models
M. Wong Chi Man et al., Angew. Chem. 43 (2004) 203. M. Wong Chi Man et al., New. J. Chem. 29 (2005) 653.
■ bio-inspired materials
1H
high resolution solid state NMR. A major problem... thymine/solid !
O
3 NH
CH3 N
Bo
1
O
H
a)
NH
thymine - T
CH
300 MHz/14 KHz
O
3 NH
thymine/solution
CH3
b)
N
1
O
H
750 MHz/33 KHz
thymine - T
CH
O
3 NH
NH c)
N
H
500 MHz/67 KHz G. Arrachart et al., J. Mater. Chem. 18 (2008) 392-399.
(ppm)
20
thymine - T
10
0
-10
1
O
Ureidopyrimidinone based systems
biomolecular assembly
XRD of precursors hydrolysis
O Me
N N
ureidopyrimidinone derivatives inorganic pillars
H-bonding
H O
Si(OEt)3
N H
N R H
Ureidopyrimidinones: 1H high resolution solid state NMR
O Me
Bo
400
N N H
15 KHz
N H O N
H
R
(EtO)3Si
C R-Si(OEt)3
D
H
O
H
?
N
H
N
N
B B
N
A H
N
750!
A, B, C, D
O
Me
33 KHz !
H N
H
N
H
O
Me
O
N R
(EtO)3Si
C
H
ppm
20
10
0
-10
Spatial connectivities: DQ 1H fast MAS spectroscopy excitation
reconversion
t1
1H
τR/2 τR/2
DHH ∝ 1/r3 t2
τR/2 τR/2
synchronization with MAS BAck to BAck
ω1 +ω2
2ω1
2ω2
n
ω1
1-2
1
2
1
2
selectivity 1H
dipolar «links» DQ dim. dim.
SQ dim. dim. δiso. iso.: very fast MAS, very high B0!
I=1/2
1H
2-2
1H
DQ
2Q hamiltonian !
1-1 2-1
r
I=1/2 n
ω2
1H
DQ !
1H
Application to ureidopyrimidinone precursors
O Me
N
H
N
O N N R
H
H
C R-Si(OEt)3
D
H
O
H
O
Me
H
N
N
B
N
A H
N
H
H N
N
Me
B
O
H
N R
(EtO)3Si
N
C
O
H
Application to ureidopyrimidinone derived materials: hybrid silica hydrolysis-condensation
1H
HA,HB,HC,HD
H+ 17.6 T MAS 33 kHz
C R-Si
D
A H
N
N
100
0
R
Si
N
B
O
200
H
N N
O O O
N O
Me
C=O
(ppm)
H
O
H 13C
O O O H N
H
N
H
O
Me
B C
H
Towards bio-inspired materials: adenine (A) and thymine (T) derivatives 1H
BABA NMR 750 MHz/33 KHz
O
3 NH
N
T-C11 9
O
T-C11
O
N
3
N
H
N O (CH ) SQ
N
N N DQ A-C11 N H H 6
♦ silicophosphates Si2 Si3
O5
O4
P O2
O3
Si1 Si Si
Si P P
Si2
Silicophosphates and Si-O-P systems Si(OR)4 H3PO4 ∆T Si-O-P
amorphous gels
■ biocompatible materials P-O-SiO5 6
O Si SiO2
P DSi-O-P 2J
Si-O-P
crystalline Si-O-P phases
Si
P P-O-P P-O-SiO3 4
Si O3Si-O-SiO3 4 4
Si P P-O-SiO5 6
■ grafting on nanoparticles
Calcium phosphates and substituted hydroxyapatite (HAp) 100 nm
Brushite, CaHPO4.2H2O
H6
MCPM, Ca(H2PO4)2.H2O β- and γ-Ca(PO3)2 Ca4P2O9 ...
H3 H4
P2 H1
P2
H2
P1
■ calcium phosphates
P2
H5
P2
CHAp
P1 Ca
nano-crystalline CHAp
bone Ca10-x/2[(PO4)6-x(CO3)x] [(OH)2-2y(CO3)y]
Ca10 (PO4)6 (OH)2 ■ hydroxyapatite (HAp)
carbonated hydroxyapatite x ≠ 0 Coll. : S. Hayakawa, A. Osaka, Okayama, Japan.
Crystalline silicophosphates: Si5O(PO4)6 and SiP2O7 polymorphs Si(OR)4 H3PO4
SiP2O7 tetragonal
31P Si2 Si3
O5
O4
∆T
P O2
Si2
O3
Si5O(PO4)6
SiP2O7 monoclinic 1
Si1
SiP2O7 cubic
SiP2O7 monoclinic 2
Si5P6 crystalline phases
-30
-40
-50
-60
-70
Si Si
Si
SiP2O7-monoclinic 1 SiP2O7-monoclinic 2
P
Si(HPO4)2.H2O ?...
Si
P
SiP2O7-tetragonal SiP2O7-cubic Si5O(PO4)6
6× ×
29Si
SiP2O7
4× × Si -100 -120 -140 -160 -180 -200 -220 ppm
ppm
♦ SCALAR INTERACTION J
J
Si(OCH2CH3)4 EtOH H3PO4 NiCl2.6H2O gel 135°C
chemical bonding
Si2 Si3
O5
O4
P O2
Si2
O3
Si
Si1
Si
Si P P
■ 2JP-O-Si couplings Coelho et al., J. Sol Gel Sc. Technol. 40 (2006) 181. Coelho et al., J. Magn. Reson. 179 (2006) 106. Coelho et al., Inorg. Chem. 46 (2007) 1379.
■ silicophosphates ■ biocompatible Si-O-P gels
MAS-J derived experiments MAS-J spectroscopy
homonuclear and heteronuclear correlations
C. Fyfe, H. Eckert 1990s
Si2 Si3
29Si/29Si
O5
O4
P O2
O3 2J P-O-Si
L. Emsley, S. Brown 1998
Si1
15N/15N
Si D. Massiot, J. P. Amoureux 2003
Si
Si P
27Al/31P
...
P
2J P-O-P
Si2
Heteronuclear J correlations:
31P/29Si
MAS-J-HMQC
Heteronuclear J correlations:
31P
→ 29Si MAS-J-INEPT
Insensitive Nuclei Enhanced by Polarization Transfer
90° 180° 90° 180° 31P
Si2 Si3
P O2
Si2
τ
τ
τ’ τ’
CW
180° 90° 180°
INEPT gain ~ |γS/γγI|
O5
O4
-1
29Si
t2
O3
Si1
P Si3
P
O1
P
Si3 P
O4
O4 O4
P
O5
O5 O2
Si2 O2
P
O5 O2
P
P
P
P
O3
O3 O3
P
P
Si2
Si-O-P (× ×3)
Si-O-P (× ×3)
Si3
Si-O’-P (× ×3)
-100 Coelho et al., Inorg. Chem. 46 (2007) 1379.
O3
O3
O3
P Si1
-200
Si1
(ppm)
Si-O-P (× ×6)
P P
Heteronuclear J correlations:
-2
800
Signal intensity
P-O-Si
300
200
400
300
IS3S’3
200
Si1 Si 1 2J P-O-Si ≈ 15Hz J ~ 15 Hz
400
(arb. unit)
600
(arb. unit)
400
Si2 Si2 J2J~≈ 14Hz 14 Hz 1 J 4 Hz 2J ~ 2 ≈ 4Hz
Signal intensity
Si3 Si3 J ~ 12 Hz 2J ≈ 12Hz
500
(arb. unit)
→ 29Si MAS-J-INEPT 500
600
Signal intensity
31P
100
200
IS6
100
0 0
IS3
0
IS3S’3
IS6
-100
-200
-100 0
10
20
30
0
40
10
20
30
-200
40
0
τ’ (ms)
τ’ (ms)
10
20
P Si3 P
O1
P
Si3 P
O4
O4 O4
O2
P P
Si-O-P (× ×3) Coelho et al., Inorg. Chem. 46 (2007) 1379. -100
P
Si2
O5
O2
O2
P
P
O3
O3 O3
P Si2
P Si3
40
P
O5
O5
30
τ’ (ms)
Si-O-P (× ×3)
-200
O3
O3
O3
P Si1
Si-O’-P (× ×3)
Si1
(ppm)
Si-O-P (× ×6)
P P
First principles calculations: the GIPAW approach Pickard, Mauri, Phys. Rev. B (2001)
M. Profeta, C. J. Pickard, F. Mauri et al.
GIPAW
T. Charpentier et al. R. Dupree et al.
DFT periodic systems
R. K. Harris et al.
all-electron hamiltonians
S. Ashbrook et al.
evaluation of
j(1)(r’)
inorganic and organic
I. Farnan et al.
using pseudopotentials
Bin(1)(r) = 1/c ∫ d3r’ j(1)(r’) ×
r-r’ |r-r’|3
derivatives...
J. W. Zwanziger et al. F. Boucher et al. ...
CSA P-O-P
E (r) = ∫ d3r’ n(r’) ×
r-r’ |r-r’|3
Si
29Si, 31P, 17O
P
EFG
! J !
IDRIS
P-O-SiO5 6
δ, Q
Gervais et al., Magn. Reson. Chem. 42 (2004) 445. Gervais et al., J. Phys. Chem. A 109 (2005) 6960. Gervais et al., J. Magn. Reson. 187 (2007) 181.
2J 2 1 P-O-Si, JP-O-P, JP-O
29Si, 31P
and
17O
CSA and Q parameters: Si5O(PO4)6 and SiP2O7 N.A.
31P
→
29Si
static CP
MAS experiment
Si5O(PO4)6
Exp.
P
SiO2
Si
Calc.
*
*
* : ZrO2 -120
-140
-160
-180
-200
-220
Exp.
-240
(ppm)
Si
O
-100
17O
Calc. O5
*H3PO4
O4
δiso
O3
∆CSA ηCSA
Bo
O2 200
150
100
50
0
-50
Exp.
Calc. Collab. L. Montagne, G. Tricot, 31P
-44.0 ppm
P-17O-Si
L. Delevoye, Lille, France 800 MHz spectrometer
O1 ppm
Si-17O-Si
Towards first principles calculations of J coupling constants P
the case study of Si5O(PO4)6 INEPT data: J ~ [4 Hz – 15 Hz] Coelho et al., Inorg. Chem. 46 (2007) 1379.
O2
P 2J
Si5O(PO4)6
(Hz)
Sites
exp
calc
Si(1)-O(3)-P
15 ± 2
-17,08
Si(2)-O(2)-P Si(2)-O(5)-P Si(3)-O(4)-P
12 ± 2
-1,17
61.49
1J P-O5
103.73
O2
O2
P P
800
-14,18
calc. (Hz) 1J P-O3
O5
2 inequivalent Si-O-P bonds
-16,22 14 & 4 ± 2
Si2
P
... by courtesy of S. Joyce, J. Yates, C. J. Pickard and F. Mauri (http://arxiv.org/abs/0708.3589) and J. Chem. Phys. 2007
Signal intensity (arb. unit)
Phase
P-O-Si
O5
O5
P
Si2 Si2 J ~ 14 Hz 2 14Hz J J~1 4≈ Hz
600
400
2J 2
≈ 4Hz
200
0
-200
0
10
20
30
τ’(ms)
40
♦ Calcium phosphates and HAp structures
H6
P2
H5
P2
H3 H4
P2 H1
P2
H2
P1
P1 Ca
Biocompatible calcium phosphates Brushite: the GIPAW approach (31P, 1H) Brushite, CaHPO4.2H2O
H3
MCPM, Ca(H2PO4)2.H2O
H2
β- and γ-Ca(PO3)2
H5
H2
static
H4
31P
H3
Ca4P2O9
H1
P
Ca
Ca
Ca10(PO4)6(OH)2 (HAp)
Exp
...
P
Ca
Calc 200
hydrated, dehydrated, 1H
and hydroxylated
100
0 (ppm)
-100
-200
fast MAS
structures
750 !
H2O P1
Exp
P1 P2
H3
Ca1
P3
Ca2
P4
Ca5
Ca2
H2 H4
H5
P-OH1
H
Calc
Ca3
P2
Ca4
P3
H Ca1
Ca2
15
Ca1
P1 Ca4
P1
12.5
10
7.5
5
(ppm)
2.5
0
-2.5
Collab. B. Alonso, D. Massiot, CRMHT, Orléans, France
Pourpoint et al., Appl. Magn. Reson. (2008), in the press.
More from 1H GIPAW data: H-bonding and CSA tensors 1H
isotropic chemical shifts
Brushite: CaHPO4.2H2O H3
H2
H2 δ22 δ33
H3
Ca
δ33
δ22
H5
δ22
δ33
H4 δ33
δ22
δ22 HH1 1
P
Ca
δ
δ3333 O-H...O direction
Ca
P
H-bonding in calcium phosphates and phosphonic acids
Gervais et al., J. Magn. Reson. 187 (2007) 181.
1H
CSA tensors and orientations
Pourpoint et al., Appl. Magn. Reson. (2008), in the press.
Substituted HAp structures the fundamental role of substitutions...
Ca10 (PO4)6 (OH)2 Mg2+, Zn2+, Na+，K+ …
SO42-, CO32- …
Ca10 (PO4)6 (OH)2
B 2-, CO332-
F-,
Cl-…
A
SiO44- or CO32-
Silicate substituted HAp T1ρ(1H) editing selective CP
-72.8
64 hours
90°
-96.0
OH 1
CP
H
29
H2O
TPPM decoupling
-111.7 29
Si 29 Si
a)
Si τ
t CP
90°90°
46 (2008) 342-346
1
1
H
PO4
c)
29
29
TPPM TPPM decoupling decoupling
CP CP
H
16 hours
-87.2
Si
-97.9
Si
t CP
t CP
Ca(2)
b) 90°90° OH
29Si
1
1
H
SiO4
Ca(1)
H 2O
CP
TPPM TPPM decoupling
decoupling
46 hours
Si
Si
τ
τ
selective CP!
CP
H2O 29
29
O1H
OH
H
t CP
t CP
c) 0
-20
-40
-60
-80
-100
(ppm)
Gasquères et al., Magn. Reson. Chem., 46 (2008), 342-346.
Si: 4.6 wt %
-120
-140
-160
Carbonated HAp Peak4
Peak3
N2 Peak2
■ pH = 10
■ 0.3 M
■ 0.3 M
Ca(NO3)2.4H2O
(NH4)2HPO4 ■ 0.15 M NaH 13C:
13C
31P
O3
99 %
4.8 wt %
Peak1 (A)
1 2 3 4
1H
→ 13C CP MAS dynamics
13C
1H
→ 13C → 31P triple resonance exp. (CP MAS)
distribution of carbonated sites...
DFT models, 2D NMR, ab initio calculations: a combined approach C2
C1 Astala et al., Chem. Mater. 2005 Peroos et al., Biomat. 2006
100 nm
■ DFT models
CHAp 13C 31P
■ 1D, 2D NMR experiments
δ (ppm)
δ (ppm)
δ (ppm)
P1
2.1
P7
1.9
C1
166.7
P2
0.1
P8
2.1
C2
165.7
P3
2.1
P9
1.8
H1
1.1
P4
3.3
P10
4.0
H2
1.1
P5
1.1
P11
3.3
H3
-0.7
P6
1.5
■ first principles calculations
distribution of A-, Band A/B sites...
Further reading Advanced solid state NMR techniques for the characterization of sol-gel-derived materials Bonhomme C., Coelho C., Baccile N., Gervais C., Azaïs T., Babonneau F. Acc. Chem. Res., Vol. 40, 2007, pp. 738-746
http://www.labos.upmc.fr/lcmcp/newsite/ Equipe "Matériaux Sol-Gel et RMN"
