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Molecularly imprinted polymers for the removal of Iprodione from wine : experimental design and synthesis
optimization
Manal Bitar, Elias Bou-Maroun, Philippe Cayot
To cite this version:
Manal Bitar, Elias Bou-Maroun, Philippe Cayot. Molecularly imprinted polymers for the removal of Iprodione from wine : experimental design and synthesis optimization. MIP (Molecularly Imprinted Polymers) 2012, 2012, Paris, France. �10.13140/RG.2.2.19190.45124�. �hal-02529027�
-5 -4 -3 -2 -1 0 1 2 3 4 5
PM MF C
K
1- Synthesis
Substantial evidence demonstrates the potential for transfer of fungicides during the winemaking process. In order to remove these fungicides from wine samples, molecularly imprinted polymers (MIP) have been prepared and tested in a hydro‐alcoholic solution containing Iprodione. Iprodione was chosen as fungicide because it was detected in more than 90 % of the French wine according to a survey done by the French ministry of agriculture [1].
Materials and methods
4- Binding experiments
Introduction
Molecularly imprinted polymers for the removal of Iprodione from wine:
experimental design and synthesis optimization
M. Bitar
,E. Bou-Maroun
,P. Cayot
e.bou-maroun@agrosupdijon.fr
Unité Procédés Alimentaires et Microbiologiques UMR A02.102, Agrosup Dijon/Université de Bourgogne, 1 Esplanade Erasme F-21000, Dijon, France
2- Template removal
Factor 1 Functional Monomer (FM)
Factor 2
Crosslinker (C)
Factor 3
Polymerization method (PM)
• -1 Methacrylamide
• +1 Methacrylamide + styrene
• -1 Trimethylolpropane trimethacrylate (TRIM)
• +1 Ethylene glycol trimethacrylate (EGDMA)
• -1 Monolith
• +1 Precipitation
• 20 mL ethanol/water
• 10-5 M < C(iprodione) < 10-3 M
• 10 mg polymer
• 25 0C
Iprodione solutions
• Batch extraction
• Magnetic stirring
Extraction
Freundlich isotherms -10000
0 10000 20000 30000 40000 50000 60000 70000
Intensity
Time (min) ---MIP ---NIP
---Iprodione solution before extraction (C = 50 µM)
Template
iprodione
Porogen solvent
2,2-dimethoxy-2-phenyl acetophenone (DMPAP)
Under UV radiation
Initiator
toluene
23 factorial experimental design
8 iprodione- MIPs
Iprodione-MIPs’ non-covalent synthesis
8 NIPs were synthesized in a similar manner without template
HPLC
C18 stationary phase
Acetonitrile/water (60/40) Mobile phase
UV detection
2h Fig. 1 : iprodione chromatograms supperpostition before and after extraction by MIP5 and NIP5
(methacrylamide, TRIM, precipitation).
Fig. 2 : Freundlich isotherm exemple MIP5 and NIP5.
B = a F m
B : binded iprodione F : free iprodione
a, m : Freundlich parameters
5- Response variables 3- NIPs synthesis
acetic acid/ethanol + ultrasonication
Results
Fig. 3 : Factors significant influence on the apparent affinity.
*6 repetitions for MIP5 =>Degree of freedom = 5; 95% confidence interval Table 1 : full experimental design
MIP PM FM C K N K(MIP)/K(NIP)
1 - - - 8.78 702 1.76
2 - - + 5.32 538 1.39
3 - + - 8.81 667 1.60
4 - + + 10.27 726 4.50
5 + - - 3.38 1093 6.46
6 + - + 19.36 1172 1.17
7 + + - 7.36 623 1.01
8 + + + 7.49 685 1.01
The precipitation polymerization
increases the apparent affinity and the sites
number.
Fig. 5 : Factors significant influence on the sites number.
K : apparent weighted average affinity
N : apparent number of sites
K(MIP)/K(NIP)
Fig. 4 : Factors significant influence on the ratio K(MIP)/K(NIP).
The addition of styrene decreases the apparent affinity and the sites
number.
The use of TRIM
increases the apparent affinity and
K(MIP)/K(NIP).
N N
Cl
Cl
O
O
O NH
CH3
CH3
CH3 O
O O
CH3
CH3
C H3
CH2 O
NH2
C H3
CH2 O
NH2
CH2
O
O O O
O O
CH3
C H2
O O
O O
CH2
CH3
-0.4 -0.2 0 0.2 0.4
PM FM C
K(MIP)/K(NIP)
0.4
0.2
- 0.4 - 0.2
-150 -100 -50 0 50 100 150
PM MF C
N
0 2 4 6 8 10 12 14 16
0 5 10 15 20 25
TRIM EGDMA
K
K(MIP)/K(NIP)
Effect of crosslinker on the apparent affinity and the ratio K(MIP)/K(NIP)
K K(MIP)/K(NIP)
0 5 10 15 20 25
0 400 800 1200 1600 2000
metacrylamide metacrylamide + Styrene
KN
Effect of functional monomer on the sites number and the apparent affinity
N K
0 5 10 15 20 25
0 200 400 600 800 1000 1200 1400
monolith precipitation
K
N
Effect of the polymerization on the apparent affinity and the sites number
N K
Conclusion
1.96 σ *
References
[1]Cugier, J.‐P., & Bruchet, S.. Plan de surveillance résidus en Viticulture. Campagnes viticoles 1990‐2003. Direction Générale de l’Alimentation. Sous Direction de la Qualité et de la Protection des Végétaux, 2005.
P A M
UMR PAM (AgroSup, uB) 1 Esplanade Erasme
21000 Dijon, France
http://www.umr-pam.fr/
y = 2549.5x0,428.
y = 1588x0.4068
0 500 1000 1500 2000 2500
0 0.2 0.4 0.6 0.8
B (µmol/g)
F (mM)
Freundlich isotherm : MIP5 and NIP5
MIP5 NIP5
0.2 0.4 0.6 0.8
The optimal MIP : MIP5
F1 : precipitation
F2 : TRIM
F3 : methacrylamide
+
C H3
CH2 O
NH2
C H3
CH2 O
NH2
CH2
+
O
O O O
O O
CH3
C H2
O O
O O
CH2
CH3
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