1. Supplementary data
1.1 Detailed polymerization conditions for MIP-coated fiber preparation
The prometryn, tetracycline, and propranolol molecularly imprinted polymer (MIP)-coated fibers
used for final characterization and extraction performance investigation were prepared under the
following conditions.
Prometryn MIP-coated fiber: 482.7 mg prometryn; 0.68 mL methacrylic acid (MAA); 2.48 mL
trimethylolpropane trimethacrylate (TRIM); 25.6 mg azo(bis)-isobutyronitrile (AIBN); and 18.96
mL toluene; polymerization time was 6 h.
Tetracycline MIP-coated fiber: 55.6 mg tetracycline; 71.1 mg acrylamide (AA); 1.24 mL TRIM;
12.4 mg AIBN; and 11.2 mL acetone; polymerization time was 6 h.
Propranolol MIP-coated fiber: 74.0 mg propranolol; 0.17 mL MAA; 2.56 mL TRIM; 25.6 mg
AIBN; 16.4 mL acetonitrile; polymerization time was 3 h.
1.2 Detailed polymerization conditions for solvent investigation
Prometryn MIP-coated fiber: 48.3 mg prometryn; 0.068 mL MAA; 0.76 mL EGDMA; 7.6 mg
AIBN; solvent was toluene, benzene, ethyl acetate, chloroform, acetone, or acetonitrile of 4 mL;
polymerization time was 6 h.
Tetracycline MIP-coated fiber: 111.1 mg tetracycline; 0.17 mL MAA; solvent was acetone of
4.90 mL, ethyl acetate of 4.90 mL, tetrahydrofuran of 7.30 mL, or dimethyl sulfoxide of 14.60 mL;
cross linker was TRIM of 0.64, 0.64, 1.05, or 2.26 mL, respectively; initiator was AIBN of 6.4, 6.4,
10.5 or 22.6 mg, respectively; polymerization time was 6 h.
Propranolol MIP-coated fiber: 74.0 mg propranolol; 0.17 mL MAA; solvent was dimethyl
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sulfoxide of 4.86 mL, chloroform of 8.66 mL, acetonitrile of 16.40 mL, or acetone of 39.20 mL;
cross linker was TRIM of 0.64, 1.28, 2.56, or 6.40 mL, respectively; initiator was AIBN of 6.4, 12.8,
25.6 or 64.0 mg, respectively; polymerization time was 3 h.
1.3 Detailed polymerization conditions for investigation of volume ratio of monomer plus cross
linker to polymerization solvent
Prometryn MIP-coated fiber: polymerization time was 6 h, other conditions as following.
Prometryn
(mg)
MAA
(mL)
EGDMA
(mL)
AIBN
(mg)
Toluene
(mL)
Volume ratio of monomer plus cross
linker to polymerization solvent
60.4
0.085
0.95
9.5
1.04
1:1
60.4
0.085
0.95
9.5
2.08
1:2
60.4
0.085
0.95
9.5
4.16
1:4
60.4
0.085
0.95
9.5
6.24
1:6
60.4
0.085
0.95
9.5
9.32
1:9
Tetracycline MIP-coated fiber: polymerization time was 6 h, other conditions as following.
Tetracycline
(mg)
MAA
(mL)
TRIM
(mL)
AIBN
(mg)
Acetone
(mL)
Volume ratio of monomer plus cross
linker to polymerization solvent
55.6
0.085
0.32
3.2
2.43
1:6
55.6
0.085
0.32
3.2
3.65
1:9
55.6
0.085
0.32
3.2
6.08
1:15
55.6
0.085
0.32
3.2
12.15
1:30
Propranolol MIP-coated fiber: polymerization time was 3 h, other conditions as following.
Propranolol
(mg)
MAA
(mL)
TRIM
(mL)
AIBN
(mg)
Acetonitrile
(mL)
Volume ratio of monomer plus cross
linker to polymerization solvent
74.0
0.170
2.56
25.6
16.40
1:6
37.0
0.085
1.28
12.8
12.30
1:9
37.0
0.085
1.28
12.8
20.50
1:15
37.0
0.085
1.28
12.8
41.00
1:30
1.4 Detailed polymerization conditions for monomer investigation
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Prometryn MIP-coated fiber: polymerization time was 6 h, other conditions as following.
Prometryn (mg)
Monomer
EGDMA (mL)
AIBN (mg)
Toluene (mL)
60.4
0.085 mL MAA
0.95
9.5
6.24
60.4
71.1 mg AA
0.95
9.5
5.70
60.4
0.106 mL
4-vinylpyridine (4-VP)
0.95
9.5
6.24
Tetracycline MIP-coated fiber: polymerization time was 6 h, other conditions as following.
Tetracycline (mg)
Monomer
TRIM (mL)
AIBN (mg)
Acetone (mL)
55.6
0.085 mL MAA
0.32
3.2
3.65
55.6
71.1 mg AA
0.32
3.2
2.88
55.6
0.106 mL 4-VP
0.32
3.2
3.83
Propranolol MIP-coated fiber: polymerization time was 3 h, other conditions as following.
Propranolol (mg)
Monomer
TRIM (mL)
AIBN (mg)
Acetonitrile (mL)
74.0
0.170 mL MAA
2.56
25.6
16.40
74.0
142.2 mg AA
2.56
25.6
15.40
74.0
0.212 mL 4-VP
2.56
25.6
16.60
1.5 Detailed polymerization conditions for cross linker investigation
Prometryn MIP-coated fiber: polymerization time was 6 h, other conditions as following.
Prometryn (mg)
MAA (mL)
Cross linker
AIBN (mg)
Toluene (mL)
60.4
0.085
0.95 mL EGDMA
9.5
6.24
60.4
0.085
0.32 mL TRIM
3.2
2.43
Tetracycline MIP-coated fiber: polymerization time was 6 h, other conditions as following.
Tetracycline (mg)
AA (mg)
Cross linker
AIBN (mg)
Acetone (mL)
55.6
71.1
0.19 mL EGDMA
1.9
4.19
55.6
71.1
0.32 mL TRIM
3.2
2.88
Propranolol MIP-coated fiber: polymerization time was 3 h, other conditions as following.
Propranolol (mg)
MAA (mL)
Cross linker
AIBN (mg)
Acetonitrile (mL)
74.0
0.170
1.52 mL EGDMA
15.2
10.10
74.0
0.170
2.56 mL TRIM
25.6
16.60
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1.6 Detailed polymerization conditions for investigation of molar ratio of monomer to cross linker
Prometryn MIP-coated fiber: polymerization time was 6 h, other conditions as following.
Prometryn
(mg)
MAA (mL)
30.2
60.4
120.8
241.6
483.2
724.8
0.043
0.085
0.170
0.340
0.680
1.020
TRIM (mL) AIBN (mg) Toluene (mL)
0.65
0.65
0.65
0.65
0.65
0.65
6.5
6.5
6.5
6.5
6.5
6.5
Molar ratio of monomer
to cross linker
4.10
4.40
4.90
5.90
7.90
10.00
1:4
1:2
1:1
2:1
4:1
6:1
Tetracycline MIP-coated fiber: polymerization time was 6 h, other conditions as following.
Tetracycline
(mg)
AA (mg)
TRIM (mL)
55.6
71.1
1.28
12.8
11.5
1:4
55.6
71.1
0.640
6.4
5.76
1:2
55.6
71.1
0.320
3.2
2.88
1:1
55.6
71.1
0.160
1.6
2.88
2:1
55.6
71.1
0.080
1.6
2.88
4:1
55.6
71.1
0.060
1.1
2.88
6:1
AIBN (mg) Toluene (mL)
Molar ratio of monomer
to cross linker
Propranolol MIP-coated fiber: polymerization time was 3 h, other conditions as following.
Propranolol
(mg)
MAA (mL)
TRIM (mL)
AIBN
(mg)
Acetonitrile Molar ratio of monomer
(mL)
to cross linker
74.0
0.170
2.56
25.6
16.60
1:4
37.0
0.170
1.28
12.8
8.70
1:2
18.5
0.170
0.640
6.4
4.86
1:1
18.5
0.340
0.640
3.2
5.88
2:1
37.0
0.680
0.640
1.6
7.92
4:1
37.0
1.02
0.640
1.2
9.96
6:1
1.7 Detailed polymerization conditions for polymerization time investigation
Except the polymerization time as the investigation object, other polymerization conditions for
the preparation of prometryn, tetracycline, and propranolol MIP coatings were according to
optimized conditions applied in the section of 1.1 in this supplementary material.
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1.8 Investigations of extraction capacity and selectivity for three MIP-coated fibers
For the investigations of extraction capacity and selectivity of three MIP-coated fibers, an
LC-10ATvp high-performance liquid chromatography (HPLC) (Shimadzu, Japan) was used with an
ultraviolet or a fluorimetric detector and a solid-phase microextraction (SPME)-HPLC coupling
device (Supelco, Bellefonte, PA, USA) in which a desorption chamber was linked with a
hand-controlled six-way valve. The standard solution or sample solution was added into a 5-mL
glass vial and dried with a stream of nitrogen, and then 3 mL of extraction solvent and a magneton
were added. An MIP- or non-imprinted polymer (NIP)-coated fiber was immersed into the solution
to extract analytes for 30 min under stirring. Pulled out the fiber, and then the six-way valve was
switched to the LOAD position. The desorption solvent was injected into the desorption chamber by
a syringe, and then the fiber was immersed into the chamber to desorb the analytes for 10 min.
Subsequently, the six-way valve was switched to the INJECT position, all desorption solution was
injected into a Luna C18 column (250 mm×4.60 mm I.D., 5 m packing, Phenomenex, USA) for
analysis. The extraction amounts of triazines, tetracyclines, or propranolol -blockers were
calculated by the respective area of chromatographic peak and relative standard curves.
Prometryn MIP-coated fiber: The extraction capacities of the MIP- and NIP-coated fibers were
investigated with a series of prometryn solutions of 0.500–15.0 g/L in benzene. Stirring speed was
1000 rpm. Desorption solvent was methanol. The mobile phase was acetonitrile/water (50:50, v/v)
at the flow rate of 1.0 mL/min. Determination wavelength was 225 nm.
Prometryn, atrazine, simetryn, terbutylazin, ametryn, propazine, terbutryn, and benzene were
selected to investigate the selectivity of the MIP-coated fibers. Atrazine, simetryn, terbutylazin,
ametryn, propazine, and terbutryn were selected as the structural analogues of prometryn and
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benzene as comparison compound. Prometryn, analogues, and comparison compound solutions
were prepared individually with the concentration of 5.00 g/L. Extraction solvent was chloroform
when benzene was investigated.
Tetracycline MIP-coated fiber: The extraction capacities of the MIP- and NIP-coated fibers
were investigated with a series of tetracyclines mixed standard solutions of 2.00–800 g/L in
benzene. Stirring speed was 750 rpm. Desorption solvent was mobile phase. The mobile phase was
methanol/buffer (0.1 mol/L malonate, 0.05 mol/L magnesium chloride, pH 6.5 with NH3·H2O)
(30:70, v/v) at the flow rate of 0.6 mL/min. A fluorimetric detector was used, and the excitation and
fluorimetric wavelength were 375 and 535 nm, respectively.
The selectivity was investigated with oxytetracycline, doxycycline, and chlortetracycline as the
structural analogues of tetracycline template and phenol and propranolol as comparison compounds.
The NIP-coated fiber was used for comparison. To avoid the competitive adsorption, tetracycline,
structural analogues and comparison compound solutions were prepared individually with the
concentration of 50.0 g/L.
Propranolol MIP-coated fiber: A series of propranolol and pindolol mixed standard solutions of
20–6000 g/L in toluene were used to investigate the extraction capacities of the MIP- and
NIP-coated fibers. Stirring speed was 750 rpm. Desorption solvent was 10% (v/v) acetic acid in
acetonitrile. The chromatographic elution was performed with a gradient of acetonitrile and
phosphate buffer (pH 3.8). The acetonitrile content was increased linearly from 10 to 50% (v/v)
during 25 min, and then adjusted back to 10% (v/v) and held for 10min. The mobile phase was used
at a constant flow rate of 1.0 mL/min. An ultraviolet detector was set 220 nm for -blockers
detection.
The selectivity of the MIP- and NIP-coated fibers was investigated with atenolol, pindolol, and
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alprenolol -blockers as the structural analogues of propranolol template, prometryn and phenol as
the comparison compounds. To avoid the competitive adsorption, propranolol, structural analogue
and comparison compound solutions were prepared individually with the concentration of 500.0
g/L. To ensure the effective desorption, acetonitrile–phosphate buffer (1:9, v/v) was used as the
desorption solvent for atenolol and pindolol, and acetic acid–acetonitrile (1:9, v/v) was used for
propranolol, alprenolol, and comparison compounds.
1.9 Extraction conditions for commercial SPME coatings
For the commercial polydimethylsiloxane/divinylbenzene (PDMS/DVB), polydimethylsiloxane
(PDMS) and polyacrylate (PA) coatings, the extraction of prometryn, four tetracyclines or two
-blockers was all performed in water solution for 60 min at the stirring speed of 750 rpm.
Desorption was performed for 10 min with corresponding mobile phase as the solvent in the
commercial SPME-HPLC interface.
2. Supplementary figures
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Figure 1S. Infrared (KBr pellet) spectra for prometryn (a), tetracycline (b) and propranolol (c) MIP
coatings.
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9
Figure 2S. Thermogravimetric analysis (TGA) curves (continuous lines) and derivative of TGA
curves (dotted lines) for prometryn (a), tetracycline (b) and propranolol (c) MIP coatings.
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