New chelatingglucose-based surfactants

Nadège FERLIN

Laboratoire des Glucides – UMR 6219

Université de Picardie Jules VERNE

AMIENS

A Greener Chemistry for Industry – 2 au 5 octobre 2007 – Villeneuve d’Ascq

I. GENERAL : Heavy metals pollution

In France, more than 3800 sites are polluted by heavy metalsPollution due to human activitiesCause environmental and health problems

To treat :

Biological treatements : phytoremediationPermeabilisationPhysical and chemical treatments : oxido-reduction, precipitation, extractions, flotation

I. GENERAL : FlotationEvacuate metallic pollutants of an aqueous phase with surfactants and an air bubbling

Surfactant :Amphiphilic molecule

Hydrophilic moiety:Polar head ionic or non-ionic

Hydrophobic moietyCarbon chain

Adsorption at the interfaces then formation of micelles :decrease superficial and interfacial tensions, detergency, emulsion, foaming,…

What about flotation ?

Pollutedwater

Adding ofsurfactants

Adsorption

Air bubbling Evacuation of pollutantswith the foam

S

S-

RO

S

S-

N

R

R

I. GENERAL : Chelating Surfactant

Koide et al.

NO2

R

H2N

R N N

SO3 -

-O3S

X

X

X = COOH, SO3-

R N N X

Uranium’s flotation Bull. Chem. Soc. Jpn., 56, 3364-69, (1983) Bull. Chem. Soc. Jpn., 59, 715-720, (1986)

Woller et al. : Quinoline and oxime derivatesfor liquid-liquid extraction

N

OH

R

N

OH

R

Colloid surface A, 117, 189-200, (1996)

Sawada et al. : hydrophobicallymodified EDTA for cosmetic use

N

N

COOR

COO-

-OOC

-OOC

US Patent Application 0030032573, (2003)

II. SYNTHESIS : Our molecules

Chelating functionY = OH, aminoacids skeleton

Hydrophilichead

(glucose)

Hydrophobic tailGlycosidation of fatty alcohol

O

OH

OH

OH

OR

HN

O

Y

In 3 steps :Oxidation of theprimary alcohol

Target :Best efficiency as possible for metalextraction combined with easy, fastand non-expensive reactions

Sugar :Good solubility in water, non-toxicNatural and cheap ressources

Sugar-based surfactants are known as biogradable and good foaming agents

II. SYNTHESIS : Glycosidation

O

OAc

OAc

OAc

OAc

OR

O

OAc

OAc

OAc

OAc

OAc

a) ROH (2eq), ZnCl2, µ-waves

b) Ac2O, Py

ρ = 70-80 %

O

OH

OH

OH

OR

OH

MeONa, MeOH

ρ > 90 %

Use of microwaves irradiation : often use in green chemistryNo solvent, economy of energiesVery fast reactions with good yieldUseful with different fatty alcohols R = CnH(2n+1) avec n=6, 8, 10, 12, 16Control of the anomers ratio

II. SYNTHESIS : Glycosidation

% alpha

0

0.2

0.4

0.6

0.8

1

0.5 1 2 3 4 5 7 9 10 11

reaction time (min)

Hexanol

Octanol

Decanol

Dodecanol

Hexadecanol

Control of the anomers ratio

Difficulties to separate the anomers

II. SYNTHESIS : Oxidation

Oxidation on protected glucosides

Direct oxidation

O

OH

OH

OH

OC8H17

COOH

O

OH

OH

OH

OH

OC8H17

TEMPO : ρ = 89 %Very long reaction, purification problems

O2/Pt in basic medium : ρ = 36 %Long reaction and expensive

O

OH

OH

OH

OH

OC8H17

O

OAc

OAc

OAc

OTr

OC8H17

O

OH

OH

OH

OC 8H17

COOH

O

OAc

OAc

OAc

OC 8H17

COOH

a) TrCl, Pyb) Ac2O

ρ = 84 %

CrO3 cat., H5IO6CH3CN/H2O

ρ = 85 %

MeONa, MeOH

ρ > 90 %

II. SYNTHESIS : Coupling – Hydroxamic acid

Unprotected coumpond

Protected compound

O

OH

OH

OH

OC8H17

COOH

O

OH

OH

OH

OC8H17

COOMe

O

OH

OH

OH

OC8H17

CONHOH

Anh MeOH, H2SO4

ρ = 90%

NH2OH 50% aqueous, MeOH

ρ = 73%

O

OAc

OAc

OAc

OC8H17

COOH

O

OAc

OAc

OAc

OC8H17

COOMe

O

OH

OH

OH

OC8H17

CONHOH

MeI, Bu4NIKHCO3,anh. DMF

ρ = 75%

NH2OH 50% aqueous, MeOH

ρ = 67%

III. INTERFACIAL PROPERTIES

γ

Log (C)

CMC critical micellar concentration

Measure the superficial tension depending on the log of the concentration

water

air

micelle

HLB calculated by modelisation

Other properties are also determined

III. INTERFACIAL PROPERTIES

20,6 ± 2,6 C8 β CONHOH

20,7 ± 1,3C8 α CONHOH

15,6 ± 1,5C8β COOH

13,1 ± 1,8C8α COOH

CMC (mM)Compounds

The « capillar » method (Castro et al, J. Chem. Educ., 78, 347, (2001))

Method reposing on Laplace law

Capillar in a solution of surfactants Difference of pression is proportional to the tension

γ = (r/2)*d*g*∆h

Octyl-α-D-glucopyranoside : 10.0

IV. METAL EXTRACTIONFlotation test

Tested metals : Fe(III), Cu(II), Cd(II), Cr(III), Ni(II), Zn(II)

3 times reapeted

Mixing of surfactant and metal introduced in a column reliated to a pump air

Quantification by ICPUse the « adding method » because of the matrix effect of the surfactants

III. METAL EXTRACTION

Visual good resultswith iron and C8bCONHOH

Initial Residual liquid Foam

0

0.5

1

1.5

2

2.5

3

3.5

Ef

C8aCOOH C8bCOOH C8aCONHOH C8bCONHOH

Fe

Cd

Cu

Extraction factor

Ef =liquidmetal

foammetal

C

C

ACKNOWLEGMENTS

Laboratoire des GlucidesUPJV-AMIENS (France)

Pr. José KOVENSKY and Dr. Eric GRANDGaétane SERVANT, Thomas MEYER, Sébastien DAUPHIN and Danavathani KANTHASANY

Centro de Estudios Transdiciplinarios

del Agua (CETA)Facultad veterinarias

de BUENOS AIRES (Argentina)

Pr. Alicia FERNÀNDEZ-CIRELLIDr. Mariano CASTRO, Carlos OJEDA and Diego GRASSI

Financial supports: Délegation Générale pour l’Armement CNRS - CONICET

Thanks for your attention

Any questions ?