1

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*

2

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

3

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

4

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

5

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

6

Structural Biology : mechanisms ofenzymes

Ligand-Based and Target-Based Drud Design

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

Ongoing Projects and Synergy within the

'PÔLE MATERIAUX'

Key Words

Chemistry

Surfaces , Materials

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

Some Exemples of

Achievements in Materials

and

Ongoing Research

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

Fomblin®/pMWNTs(0.5 wt.%)

CES

PAN/pMWNTs(4 wt.%)

CES

Silicone/pMWNTs(0.5 wt.%)

CES

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

Surface Chemistry

From Large to Nano surfaces

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

Scanning Electrochemical Microscopy

Local Analysis, Local Fabrication and Patterning

CES

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