Building Blocks for Water Ananlysis and. Purification. Lei Ye, Changgang Xu,
Xiantao Shen. Division of Pure and Applied Biochemistry, Lund University, ...
Molecularly Imprinted Polymers as Modular Building Blocks for Water Ananlysis and Purification Lei Ye, Changgang Xu, Xiantao Shen Division of Pure and Applied Biochemistry, Lund University, Sweden
Contents § MIP nanoparticles as modular building blocks § Water-compatible MIPs by Pickering emulsion polymerization
Molecularly Imprinted Polymer (MIP) Non-Imprinted Polymer (NIP)
Precipitation polymerization
Porous monolith
monomer
Macrogel particles
Microgels
solvent
Propranolol-imprinted particles
Poly(MAA-co-TRIM)
Poly(MAA-co-TRIM-co-DVB)
Poly(MAA-co-DVB)
Yoshimatsu, et al, Anal Chim Acta 2007, 584, 112
MIP particles as modular building blocks
Ligand binding assay
UPLC
Microarray
Microfluidic device MEM sensor
Click chemistry: “a set of powerful, highly reliable, and selective reactions...” - K. Barry Sharpless
N3
+
Cu(I)
N N N
Copper-catalyzed azide-alkyne cycloaddition (CuAAC)
Clickable tags on MIP nanoparticles
Xu and Ye, Chem Commun 2011, 47, 6096
O
HO
O
O
HO
COOH
COOH S O O N3
O
N H
S N H
O
N H
N H
Conjugation of MIP nanoparticles
Construction of magnetic composites N3 O
N H OH
Cu(I)
Molecular recognition in water Accessibility of binding sties Water compatibility Group selectivity
Pickering emulsion polymerization
Shen and Ye, Macromolecules 2011, 44, 5631
Template
Target
O OH
NH2
O OH
O OH O
O O
O
N H
MIP-I
After removing silica
FITC
Before removing silica
MIP-I -Si
Selectivity of MIP-I and MIP-II O OH
N H
NH2
O OH
O OH
N H
O OH
N H
O OH N H
O NH2
O
N H
O OH
N H
Kinetics of propranolol binding
Increasing the capacity of MIP beads
Shen and Ye, Chem Commun 2011, 47, 10359
Shen and Ye, Chem Commun 2011, 47, 10359
Synthetic method
Solvent
Pickering emulsion
Bulk
a
Uptake of propranolol (%)
Specific uptake (%) b
MIP
NIP
Water
45.5
11.3
34.2
Toluene
15.8
7.74
8.1
Mixture a
14.6
3.33
11.3
water
87.2
88.9
-1.7
Toluene
59.2
44.5
13.7
Mixture a
24.1
8.67
15.4
Toluene with 0.5% acetic acid, b Differential uptake between MIP and NIP.
O
N H OH
55
Displacement / %
Propranolol 45
N H
O OH
35
25
Timolol
H 2N
O
Pindolol Metoprolol Naphthol
OH
15
Competitor Radioligand propranolol: 246 pM Concentration of competing compounds: 3.38 µM Solvent: water
Characterization by liquid chromatography Column size: 100 × 4.6 mm Analyte conc. 0.5 mM
Detection of atenolol (1.5 ppb) in tap water SPE condition: MIP 50 mg, sample volume 50 mL
No SPE
SPE
Acknowledgement
EU (WATERMIM)
