département de chimie des fundp 2 pôles...
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2 pôles d’excellence
Chimie du vivant
BIO
Chimie des surfaces et
nanomatériaux
MATERIAUX
Département de Chimie des FUNDP
Chimie du vivant
BIO§
Chimie des surfaces et
nanomatériaux
MATERIAUX*
Groupe de Chimie Physique Théorique et Structurale(GCPTS)D.Vercauteren§, J.Wouters§, JM.André*
Groupe de Chimie Organique et Bio-organiquesupramoléculaire (GCOBS)
S.Vincent§, D.Bonifazi*, A.Krief§ (successeur)
Groupe de Chimie des nanomatériaux (GCNM)BL.Su*, L.BNagy* (successeur)
Groupe de Chimie et d’Electrochimie des Surfaces (GCES)Z.Mekhalif*, J.Delhalle*
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BIO MATERIAUX
Structural Biological ChemistryLaboratory
J.WOUTERS et al.
BIO MAT
Competences- Organic Synthesis- Carbohydrate Chemistry- Rational Design of Inhibitors- Enzyme kinetics- Binding constants measurements- Use of enzymes for preparative chemistry
Scientific area- mechanistic enzymology- glycosciences- medicinal chemistry
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Bio-Organic ChemistryLaboratory
S.VINCENT et al.
BIO MAT
Carbohydrate processing enzymes
Unknown mechanisms – Novel biosynthetic pathways
Targetsmicroorganisms : essential enzymes
therapeutic applications : infectious diseasesmammalians : essential oligosaccharides
therapeutic applications : cancer, anti-inflammation
Two levels of creativity
- Organic Chemistry : synthetic methodologies and preparation ofbiologically relevant molecules
- Strategies for enzyme inhibition (mechanistic studies)
Bio-Organic ChemistryLaboratory
S.VINCENT et al.
BIO MAT
NH2
OH
OH
HOOH
OHOH
OHOR
O
NH2
OH
OH
OH
ribitol side-chain
HopaneC5C30
OHOH
OHO
OHOH
OHO
D-glucosamine
Cyclopentitol
O
OH
RO
HOOH
R O
Acetal
Ether
Glycosyltransferase
?
Zymomonas mobilis
Novel Biosynthetic Pathways
Chem. Eur. J., 2007, 1471-1480 ; Chem. Commun. 2005, 3445-7Chem. Commun. 2003, 782-3
- Total synthesis of the « D-glucosamine » hopanoid- Biological evaluations on bacterial cultures
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Bio-Organic ChemistryLaboratory
S.VINCENT et al.
BIO MAT
Design and Synthesis of InhibitorsTarget : an essential enzyme of Mycobacterium tuberculosis
OHO OH
HO
OHOUDP
O
HO
HO
OH OHO
UDP
UDP-GalfUDP-Galp
Bacterial glycoconjugatesUGM
HO
OH
O
OOH
3
PO
HO
OH
O
OOH O UMP
OH
O
HOOH
HO
OH
PO
UMPO
OH
Conformational Probes
1 21,4B
OHO OH
HOHO
PO
O UMPOH
4C1 E4
O
HOOH
HO
OH
PO
UMPO
OH
Mechanistic Probes
5
O
HOOH
HO
OH
PO
UMPO
OH(Z)-6(E)-6
FO
HO OH
HOHO
PO
UMPOHO7
Chem. Eur. J. 2006, 11, 3114-23 ; Chem. Commun. 2004, 1216-7 Chem Eur. J. 2003, 23, 5888-98 ; Bioorg. Med. Chem. Lett.. 2006, 16, 1123-5
Structural Biological ChemistryLaboratory
J.WOUTERS et al.
BIO MAT
Competences- crystallography- protein purification- physico-chemistry of proteins- structure-based drug design
Scientific area- structural chemistry and biochemistry- structure-function relationships- medicinal chemistry
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Structural Biological ChemistryLaboratory
J.WOUTERS et al.
BIO MAT
0,1 mm
Structural Biological ChemistryLaboratory
J.WOUTERS et al.
BIO MAT
R6R97
W219 FMN
IPP
7
Structure-Based Drud Design
Physico-chemical phenomena in life sciences using quantum
chemistry approaches
Example of research project in progress :
Analyzing the nonlinear optical (NLO) responses of Green Fluorescent Protein as a function of the protonation state in comparison with their absorption and emission spectra.
Chromophore in protonated form
Proposal : unraveling the behavior and properties of “active molecules” in living environments (in particular, chromophores, radicals, and chiral species).
B.Champagne et al.
BIO MAT
COMS Research Areas
Creation of functional molecular architectures characterized by innovating targeted synthesis, physical-organic studies, and material-based
design
Research Areas
COMS
Exploring Weak Interactions
Organic Nanochemistry
Carbon-based Materials
•Molecular organic emitting diodes (OLEDs)
•Organic nanopatteringof surfaces
•Molecular electronics
•Organic modifications of silicon surfaces
•New supramolecular resins for art conservation
•Molecular organic emitting diodes (OLEDs)
•Organic nanopatteringof surfaces
•Molecular electronics
•Organic modifications of silicon surfaces
•New supramolecular resins for art conservation
•Fullerene-based materials
•Carbon nanotubes(molecular imaging and photovoltaic devices)
•Synthetic porphyrinchemistry
•Highly-luminescent polycyclic modules
•Fullerene-based materials
•Carbon nanotubes(molecular imaging and photovoltaic devices)
•Synthetic porphyrinchemistry
•Highly-luminescent polycyclic modules
•Host-guest chemistry (fluorescent capsules)
•Hydrogen-bonding interactions
•Hydrophobic interactions
•Host-guest chemistry (fluorescent capsules)
•Hydrogen-bonding interactions
•Hydrophobic interactions
CES Research Areas
Electrochemistry and Surface Chemistry for Functional Materials
Synthesis and Analysis
CES
Surface ChemistryLarge and Nano surfaces
Electrochemistry for Synthesis and
Analysis
CNTs-based Materials
•Electrochemistry in Ionic liquids
•Materials Synthesis : Composites, Nanowires, Conducting and Insulating Polymers
•ElectrochromicMaterials
Local techniques (SVET, SKP, SECM)
•Functinalization, new methods
•Composites Polymers/CNTs
•Composites Metals/CNTs
•Exploring covalent bonds
•Self-Assembly on active metals
•Biomaterial Surfaces
Research Areas
Synergy and Complementarities between COMS and CES
D. BONIFAZI, J. DELHALLE, Z. MEKHALIF
PÔLE MATERIAUX
Chemistry and Material Synthesis :
Organic Chemistry and Electrochemistry
Surface Chemistry and Self-Assembly :
Monolayer and Multilayers Assembly : Covalent Interactions
Supramolecular Assembly : Non Covalent Interactions
Nanomaterials :
Carbon Nanotubes and Fullerenes Functionalisation
Carbon Nanotubes Functionalisation, Nanowires andNanocomposites
Single-walled Carbon Nanotubes coated with Eu(III) complexes
G. Accorsi, N. Armaroli,* A. Parisini,* M. Meneghetti,* R. Marega, M. Prato, and D. Bonifazi,* Adv. Funct. Mater., 2007, in press.
Z-contrast ADF-STEM micrographs
Cover page, in press.
COMS
Oxidation Single Walled Carbon Nanotubes
R. C. Haddon and co., Chem. Phys. Lett. 2001, 347, 8; R. E. Smalley and co., Chem. Phys. Lett. 2000, 324, 213; A. Hirsch, Angew. Chem. Int. Ed., 2002, 41, 1857; D. Tasis, N. Tagmatarchis, V. Georgakilas, M. Prato, Chem. Eur. J. 2003, 9, 4000.
35nm
STM Investigation of sh-SWNT Functionalized with n-C18H37NH2 (Endcaps)
32nm
123nm
16nm
Substrate: Au(111) deposited on micaT = 298 K (in air); Tip = TiPercentage of functionalization: 78 ± 9 %Linear density of bumps [μm-1]: 16 ± 3
D. Bonifazi, C. Nacci, R. Marega, G. Ceballos, S. Modesti, M. Meneghetti, and M. Prato, Nano Lett., 2006, 6,1408.
COMS
CES
L.VAST et Al‘Chemical functionalization by a fluorinated trichlorosilane of multi-walled carbon nanotubes’Nanotechnology, 15 (2004) 781-785.
L.VAST et Al‘Dispersion of organic functionalized multi-walled carbon nanotubes in silicone base’Composites Science and Technology, 67 (2006) 880-889.
L.VAST et Al‘Note on the dispersion in perfluoropolyether lubricants of multi-walled carbon nanotubes functionalized with (tridecafluoro-1,1,2,2-tetrahydrooctyl)trichlorosilane’Journal of Nanoscience and Nanotechnology (2007) in press
L. VAST et Al ‘Formation of an adherent polyacrylonitrile/carbon nanotubes composite film onto a polyacrylonitrile brush electrografted on copper’Nanoscience and Nanotechnology (2007), in press
SiO
O
OY x
SiO
O
OSi
O
O
Y
Y
x
x
CES Covalent Covalent FunctionalizedFunctionalized MWNTs (f MWNTs)MWNTs (f MWNTs)
Silicone
PANFomblin®
10 nm 5 nm10 nm
SiO
O
OY x
SiO
O
OSi
O
O
Y
Y
x
x
continuous organic coating on carbon nanotubes walls and ends (~2nm)
MechanicalMechanical PropertiesProperties
O
COOH
OH C=O
HOOC H
C=
OOH O
SiO
O
SiOO Si
O
O SiO O
MWCNTsMWCNTs+n+n--OTCSOTCS
O
COOH
O
H C=O
HOOC H
C=
O
OH OSi
OO
SiOO Si
O
O SiO O
MWCNTsMWCNTs+7+7--OTCSOTCS
Mesures par microindentation
0.0 0.1 0.2 0.3 0.4 0.5
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
Mod
ule
de Y
oung
(MPa
)
Taux de charge (% en poids)
Sylgard 184 Sylgard 184/MWNTs purifiés Sylgard 184/MWNTs + n-OTCS Sylgard 184/MWNTs + 7-OTCS
réactivité du 7-OTCS avec le silicone → augmentation de 50% du Y pour taux de charge de 0.2% en poids en nanotubes
Composite silicone/MWNTs
Futurs in Futurs in CNTsCNTs ResearchResearch Area in CESArea in CES
New Insight in New Insight in FunctionalizationFunctionalization
New New waysways for for ChemicalChemical FunctionalizationFunctionalization
ElectrochemicalElectrochemical FunctionalizationFunctionalization of of CNTsCNTs
New Applications in the Frame of new New Applications in the Frame of new ProjectsProjects
CES
‘NanoMembranes against Global Warming’. NANOGLOWA, European Project PC6, IP-026735-2.
Project leader : KEMA (NL) and 25 partners including LCES-FUNDP, [2007-2011].
‘Non-conventional Matrix/Carbon Nanotubes ReinforcedComposite for Applications in Space’. ESA
CSL, CRIF, NANOCYL et LCES-FUNDP, [2007-2009].
2 PhD Students (FRIA, Assistant) In the CNTs Research Area
Some Exemples of
Achievements in Surface Chemisty and in particular Self-Assembly Chemistry
and
Ongoing Research
COMS
Linker:
Surfaces Modifications with Fullerene Monolayers
400
nm
Tuning electronic properties of Semiconductor Surfaces (GaAs, ZnO)
Modifications of Au surfaces (AFM picture)
Chem. Soc. Rev. 2007, in press.Adv. Mat. 2002, .
Paper to be submitted.
COMSAnother Soft Method: Conductive Probe (CP) AFM
Vtip
Au (111)
TIP
Conductive Tip: Au coated with TiTip Diameter: 40 nmApplied Forces: 15-20 nNSensitivity: 50-100 pA
Coated with Ti
AFM = Atomic Force Microscopy
COMS STM Image of a Partially Covered Monolayer of a Porphyrin Monomer on Ag(111): A Porous Phase
Scan range: 96 × 83 nm2, It = 15 pA, Vbias = 3 V, T = 298 K
3.3 ± 0.1 nm
Adv. Mater. 2006, 18, 275.
COMS Chain-like Assembly of C60 on Pre-organized Diporphyrin-containing Monolayers
Porphyrin layer
Preferential C60 order
Scan range: 77 × 65 nm2, It = 22 pA, Vbias = 2.59 V, T = 298 K
Minor growth direction
Major growth direction
•The carbon spheres are not located on the diporphyrin cores!!
•No Strong C60…C60 cohesive interactions (~ 31 kcal mol–1)
The longest chains (~15.5 nm) are composed of eight C60
molecules with an intermolecular C60…C60 distance of ~2.2 nm.
CES Fundamental Study
Self-Assembly on active MetalsNi, Cu, Zn, Alloys, NiTi….
S
(CF2)nn = 4,6,8
Au
SH
S
SH
S
SH
S
SH
S
SH
Agelectrodeposition
SAu
S
S
S
S
S
S
S
S
S
BMC
ReferenceCES
F. Laffineur, Z. Mekhalif, L. Tristani and J. Delhalle Chemistry of Materials
Applications to Connectors
Bio-corrosion COST-D33
Nanoscale Electrochemical and Bio-processes (Corrosion) at Solid-aqueousInterfaces of Industrial Materials
Hydroxyapatite Growth
Visibility to MRI
Radio-Opacity
Anti-Fouling
Biosensors
Application to Biomaterials
RW- VISMAT, CARDIATIS, CHU de Genève
CES
Application in Bioelectrochemical Sensors
R = chaîne hydrocarbonnée greffée sur l’or via la fonction thiolateR’-NH2 = microperoxydase 8
2R O
O
N
O
O
R' NH+S R
O
N R'
H
HO N
O
O
+S
CES
Sophie BERNAD, Tewfik SOULIMANE, Zineb MEKHALIF, Sophie LECOMTE, Bioplymers, 81, 407-4018
Collaboration with CNRS
Approaching to an insulating surface
Insulating surface
Ox OxOx Ox
Ox OxOx Ox
Ox Ox
Ox Ox
- negative feed-back
Ox Ox
Ox OxOx Ox
RedOx
Approaching to a conductive surface
Conducting surface
Ox Ox
Ox OxOx Ox
Ox Ox
Ox Ox
RedOxOx OxRedOx
-positive feedback
Gold
Gold
Gold GoldStep 1 : modification of nickel clusters with silanes Step 2 : modification of gold with thiols
Step 3 : modification of nickel clusters and gold
GoldGold
Gold
GoldGold GoldGoldStep 1 : modification of nickel clusters with silanes Step 2 : modification of gold with thiols
Step 3 : modification of nickel clusters and gold
Theoretical design of (supra)molecular systems with outstanding optical, electronic, and
magnetic properties
CTA
B. Champagne
CTA
Examples of research projects in progress:
Elaboration of acidochromic and photochromic molecular switches
Understanding structure-folding relationships to master circular dichroism and nonlinear optical responses in helical systems
Need: synthesis and characterization of supramolecular systems with a potential to exhibit outstanding properties
x
y
z
or H+
z
xy
CTA