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Transcript of Chimie douce Sol-Gel Chemistry. diatoms are making silica glasses at room temperature from solute...
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Chimie douce
Sol-Gel Chemistry
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diatoms are making silica glasses
at room temperature
from solute silica in water
Chemists at the school of diatoms
Chimie douce
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Si(OH)4
Fe2O3
Silica from the soils is dissolved by water and goes to the sea
silicic acid Si(OH)4
Si
OH
HO OHOH
SiO2 + 2H2O Si(OH)4
≈ mg/l
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Si
OH
HO OHOH
0
Proton exchange between Si(OH)4 and the aqueous solvant
protonation or deprotonation depending on pH
Silicic acid is a weak acid
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Si
OH
HO OHOH
Si
OH
O OHOH
Si
OH
O OHO
OH-
0- 2-
pH ≈ 3
deprotonation
Proton exchange between Si(OH)4 and the aqueous solvant
protonation or deprotonation depending on pH
Silicic acid is a weak acid
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Si
OH
HO OHOH
Si
OH
O OHOH
Si
OH
O OHO
Si
OH
H2O OHOH
OH-H+
+ 0- 2-
pH ≈ 3
Point of Zero Charge
SiO2
precipitation of silica
Proton exchange between Si(OH)4 and the aqueous solvant
protonation or deprotonation depending on pH
Silica is soluble
at high pH
silicates
Silicic acid is a weak acid
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Si(OH)4SiO(OH)3-
SiO2(OH)22-
6 8 10 12 pH
20
40
60
80
100%
[Si(OH)3(OH2)]+ [Si(OH)4]0 [SiO(OH)3]- [SiO2(OH)2]2-
2 9,9 13pH
Precipitation of silica
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Precipitation of silica via the acidification of an aqueous solution of silicate
Silica gardens
Na2O.SiO2
water glass
H+
Precipitated silica Industrial product : charge, chromatography, ….
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Silicate gardens
Aqueous solution of Na2SiO3
pH ≈ 12
Metal salt CuSO4
FeCl3 Ni(NO3)2
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Magic Rocks10
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Si(OH)4 SiO2 + 2H2O
Condensation
Si - OH + HO - Si Si - O - Si + H2O
Solute silica = Si(OH)4
silicic acidOH
OHHOHO
Si≈ mg/l
Biogenic synthesis of silica by diatoms
Si(OH)4SiO2 + 2H2O Si(OH)4
7
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R = CH3, C2H5, ...
Synthesis of silica by chemists
Silicon alkoxide = Si(OR)4
OR
ORRORO
SiMolecular precursor
Si - OR + HO-H Si-OH + ROH
Hydrolysisalkoxide
water
OH
OHHOHO
Si
Condensation
Si(OR)4 + 2H2O Si(OH)4 + 4ROH
Si - OH + HO - Si Si - O - Si + H2O
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M+ + X-
MX
Polycondensation ≠ precipitation
Si-OH + HO-Si
Si-O-Si +
H2O
monomer dimer
trimer
tetramer
particle
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silicate silica
[SiO4] SiO2
inorganic polymerization
nm 10 nmmolecules oligomers colloïds powderm
Colloidal silica particles
drying
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Two basic reactions
Hydrolysis Si - OR + HOH Si - OH + ROH
CondensationSi - OH + HO - Si Si - O - Si + H2O
Si - OR + HO - Si Si - O - Si + ROH
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Nucleophilic substitution SN2
Hydrolysis of silicon alkoxides Si(OR)4
Si - OR + HO - H Si - OH + ROH
coordination 5
O
Si
OR
RO OROR
H H
Si
OH
RO OROR
+ ROHSi
OR
RO OROR
OH
-
H
Si
OR
RO OROR
OH
H
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Nucleophilic substitution SN2
Polycondensation of silicon alkoxides Si(OR)4
Si - OR + HO - Si Si - O - Si + ROH
Si
O
O OHO
Si
OR
O OO
Si
O
OO
Si
O
O OO
coordination 5
+ ROH
Si
OR
O OO
Si
O
O OO
H
-
Si
OR
O OO
Si
O
O OO
H
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base catalysisacid catalysis
PZC
acid and base catalysis
V depends on the pH of water
The chemical reactivity of silicon alkoxides is very low
Si(OR)4 + 2H2O Si(OH)4 + 4ROH SiO2 + 2H2Ohydrolysis condensation
small positive charge + of the cation
electronegativity
coordination expansion difficult
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Silica gel formation
Si(OEt)4 + 2H2O SiO2 + 4EtOH
Catalyst pH Tg (h)
nothing 7 1000
HF 2 12
HCl 0 92
AcOH 3,7 72
NH3 10 107
no catalyst ≈ 103 hours
acid or base ≈ 102 hours
bio-silicification ≈ 1 hour
c ≈ 1 mole/l
c ≈ 10-3 mole/l
20
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Acid catalysis (pH < 3)
H+
RO - Si - OR
OR
OR
ROH-
protonation of Si-OH or Si-OR that become better leaving groups
Base catalysis (pH > 3)
RO - Si - OR
OR
OR
OH-
Si-O-OH- and Si-O- better nucleophile than H2O or Si-OH
catalysis does not only speed up the reactions
it also controls the shape of the silica particles
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Acid catalysis pH < 3
Si OH
A +0.50 -0.06
B +0.58 +0.06
C +0.54 0.00
Partial charges
chain polymers
H+ toward the most negative Si-OH
HO
HO
HOOH
HO
HO
HO
HO
OH
OH
HO
HO
A
C
B
A
A
B
HO
OH
H+ H+
OHHO
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Base catalysis pH > 3
Si OH
A +0.50 -0.06
B +0.58 +0.06
C +0.54 0.00
branched polymers
OH- toward the most positive Si+ - OH
Partial chargesHO
HO
HOOH
HO
HO
HO
HO
OH
OH
HO
HO
A
C
B
A
A
B
HO
OH
OH-
OH-
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Catalysis
RO - Si - O - Si - O - Si - OR
O
Si
OR
RO
Si
O
OR
H+SiO-
Acid catalysis Base catalysis
end groups midle Si
chain polymers branched polymers
catalysis speeds up the reactions
And controls the shape of the silica particles
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nanoparticles
fibres
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Acid catalysis (pH < 3)
fast hydrolysis
chain polymers
microporous gels (pores < 20Å)
Base catalysis (pH >3)
fast condensation
spherical particles (Stöber silica)
mesoporous gels (pores > 20Å)
Si(OR)4 + 4H2O Si(OH)4 + 4ROH SiO2 + 2H2Ohydrolysis condensation
Catalysis controls the shape of silica particles
Sol (1-2 nm)
Gel
pH > 3
Sol(10-100 nm)
pH < 3
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Colloidal silica in diatoms
Girdle bands
Raphe
20 m
500 nm 150 nm
Silica walls are build up from ca. 5nm particles to give ca. 40nm diameter particles that are organised within the frustule.
pH ≈ 5
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Stöber silica
monodispersed silica colloids
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hydrated silica - SiO2,nH2O
Si-OH
Si(OH)4 SiO2 + 2H2O
30
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- Si - O - Si - O - Si -
H HO
- Si - O - Si - O - Si -
HOH
- Si - O - Si - O - Si -
H HO
water- silica interface1. Adsorption - dissociation
2. Acid ionisation
Si - OH + H2O
Si - O- + H3O+
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Some definitions
Colloid = small solid particle (diameter < 0,1 m)
Sol or colloidal solution = suspension of colloidal particles in a solvent
gravity
Brownian motion
Brownian motion > gravity
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interactions between particles increase with concentration
Percolation
sol-gel transition
Sol = solid colloidal particles dispersed in a solvent
Gel = solvent trapped within a particleframework
Sols and gels
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colloidal solutions are not stable
collision aggregation flocculation
Small particles tend to aggregate
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water- silica interface
3. Electrostatic stabilisation the surface is negatively charged
-
-
- -
-
- -
-
- -
-
-
≠
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Stabilisation by surface charges = peptisation
H+ +
+ +
++
Electrostatic repulsion
+
+ +
++
+
+ +
++
+
+ +
++
Stabilisation of sols
Stabilisation by steric hindrance
Grafted polymers
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Si
Ti
Transition metal alkoxides are highly reactive toward hydrolysis and condensation
electronegativity
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Si(OPri)4
Si4+ = 0,40 Å
= 1,74
Ti(OPri)4
Ti4+ = 0,64Å
= 1,32
Speed up gelation via catalysis Slow down the reaction via complexation
[SiO4] [TiO6]
SiO2 gelation takes several days Fast precipitation of TiO2
SiO2 TiO2
TiSi
Coordination expansion is easy
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iOPrOPriH C3OPri OOCH CCH C3TiOPriPriOOPriOPriTiOOC3OOCOPriOPriPriOPriOPriOTiTiPriO3CHCHacetic acidacetylacetone
coordination saturationslowly hydrolyzable complexing ligands
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Questions and Answers
which genes are involved in the formation of bio-silica ?
which proteins control the formation of silica and how ?
can we mimic nature and make silica in similar conditions ?
Genetics
Biology
Chemistry
Biogenic Silica40
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GlycineLysineProlineSerine….
2. Check their activity toward the condensation of silica
The biologist approach
1. Extraction and characterisation of proteins associated with biosilica
Sponge spicules Silicatein
D. Morse - Santa Barbara - USA
Diatom frustules Silaffins
N. Kröger et M. Sumper : Regensburg -Germany
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Diatom frustules
Silaffins
N. Kröger et M. Sumper : Regensburg -Germany
Manfred Sumper
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cationic polypeptides
interactions with negatively charged silica
silaffin
silaffin
Proteins involved in the formation of the silica shell
Silaffins
dissolution of silica frustules in HF
N. Kröger, M. Sumper, J. Bio. Chem. 276 (2001) 26066
Bio-synthesis of silica by diatoms
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Silaffin = cationic polypeptide
two ‘lysine’ groups linked to long chain polyamines
Catalytic activity due to these lysines
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Precipitation of silica with silaffins
Spherical nanoparticles
Coprecipitation of silaffins with silica
SiO2/ silaffin ≈ 12
N. Kröger, M. Sumper, J. Bio. Chem. 276 (2001) 26066
silaffins catalysts for the condensation of silicic acid
1A1
1A2
pH = 6,4
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Sponge spicules
Silicatein
D. Morse - G. Stucky - Santa Barbara - USA
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Spicules are formed
around organic filaments that behave as
templates and catalysts
Spicules of Tehya aurantia
HF
1. Sponges spicules
D. Morse et al. PNAS 95 (1998) 6234
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Silicatein
disulfur bridges
serine histidine
active site
Strong relation of amino-acid sequence between
Silicatein and Cathepsin (hydrolase)
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Silicatein and Cathepsine L
2 of the 3 amino-acids of the active site are the same
Serine-26 and Histidin-165
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Silicatein filament
precipitation of silica
Cellulose filamentNo reaction with TEOS
Formation of silica from TEOS
before
after
G. Stucky, D. Morse, PNAS 96 (1999) 361
50
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Catalytic mechanism
Role of the serine-histidine couple
Serine-26
nucleophilic substitution
Histidine-165
nucleophilic activationpentavalent Si
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The chemist approach catalytic role of amino-acids
silica [Si(OH)4]0 + [SiO(OH)3]- (HO)3Si-O-Si(OH)3 + OH-
Species in aqueous solutions at pH ≈ 7
amino acids -OOC NH3+
Interactions between silica species and amino-acids
Electrostatic interactions
Hydrogen bonds
-NH3+ -O-Si-
-COO- HO-Si-
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+H3N COO-
NH3+
LysineArginine NH3
+
COO-
NH
H2N
NH2+
HONH3
+
COO-
Serine
Precipitation of silica in the presence of amino-acids and peptides
dilute aqueous solution
of silica
pH ≈ 7
peptides
Chemical titration number of Si(OH)4 monomers
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pH5.4 6.3 7.2 8.3
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Nanoparticles of silica precipitated
from silicic acid in the presence of polyamines
M. Sumper et al. Nano Letters 2 (2002) 91
penta propylene hexamine
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Precipitation speed increases with ‘n’
Amino-acids and peptides
Chain length
Side groups Small effect
+H3N COO-
NH3+
LysineArginine NH3
+
COO-
NH
H2N
NH2+
HONH3
+
COO-
Serine
Poly-Lysine
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-COO-
-NH3+
-O-Si-(OH)3
HO-Si(OH)3
[Si(OH)4]0 and [SiO(OH)3]-
Silica precursors are attracted by the peptide chain
They come close together and can react
Silica condensation in the presence of peptides
+H3N COO-
NH3+
Lysine