1
A new multiwalled carbon nanotubes functionalized sulfonate composites with cryogel
solid phase extraction sorbent for the determination of beta-agonists in animal feeds
Supattri Noosang1,2,3, Opas Bunkoed1,2,3, Panote Thavarungkul1,2,4,
Proespichaya Kanatharana1,2,3*
1
Higher Education Research Promotion and National Research University Project of
Thailand, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand.
2
Trace Analysis and Biosensor Research Center and Center of Excellence for Innovation in
Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla 90112,
Thailand.
3
Department of Chemistry, Faculty of Science, Prince of Songkla University, Hat Yai,
Songkhla 90112, Thailand.
4
Department of Physics, Faculty of Science, Prince of Songkla University, Hat Yai, Songkhla
90112, Thailand.
Supporting Information
2
Table S1 The analytical performance of the HPLC system under optimal conditions
-agonist
Linear range
(µg L-1)
Regression equation
R2
LOD
LOQ
(µg L-1) (µg L-1)
Salbutamol
0.50-500
y = (1740±6)x -(2.310±0.570)
0.9999
0.50
2.0
Ractopamine
0.50-500
y = (2278±6)x - (1.052±0.530)
0.9999
0.50
2.0
Clenbuterol
2.0-500
y = (632±5)x - (0.535±0.410)
0.9997
2.0
5.0
Table S2 The reproducibility of the MWCNTs-SO3-/PVA cryogel sorbent
Salbutamol
Sorbent
Ractopamine
Clenbuterol
Recovery
(%)
RSD (%)
Recovery
(%)
RSD (%)
Recovery
(%)
RSD (%)
1
95.5
4.5
94.4
2.8
82.8
2.9
2
98.8
2.5
97.1
3.3
83.2
5.4
3
88.9
2.6
96.0
5.1
84.0
3.3
4
88.7
4.1
96.1
4.9
88.8
7.1
5
96.1
4.6
99.4
3.2
89.9
4.5
6
94.9
3.7
98.0
3.6
88.3
2.4
3
Table S3 Comparison of the proposed method with other methods for determination of -agonists in animal feeds
Detection
Clean-up
Extraction
Extraction
Recovery
RSDs
LODs
LOQs
methods
(sorbents)
volume (mL)
time (min)
(%)
(%)
(µg kg-1)
(µg kg-1)
-
4
20
90.3-104.3
<5
-
10
120
94.84-95.29
4.10-4.72
-
10
120
92.2-103.7
4.1-6.2
SPE (SCX)
10
30
66.1-84.2
<15
950-1,070
(µg L-1)
90-170
(µg L-1)
500-700
(µg L-1)
2-4
3,170-3,570
(µg L-1)
310-590
(µg L-1)
800-900
(µg L-1)
-
70
30
83-110
-
10
50
[7]
25
30
54-85
-
-
< 10
[6]
LC-MS-MS
SPE (Oasis MCX)
SPE (Bond elute
certify mixed mode)
SPE (Plexa TM PCX)
20
10
66-110
7-12
0.46-0.87
0.50-0.92
[5]
LC-MS-MS
QuEChERS
35
2
95.4-108.9
2.2-5.6
0.10-0.26
0.20-0.37
[38]
LC-MS-MS
SPE (Oasis MCX)
20
15
70.1-110
<15
0.2-0.5
0.5-2.0
[40]
UPLC-Q-TOF-MS
SPE (Oasis MCX)
20
5
87.3-111.7
<4.12
-
5-50
[39]
UPLC-FLD
SPE (Oasis MCX)
20
3
90.1-101.4
<8
6.0-6.5
20.1-21.7
[19]
HPLC-FLD
-
100
30
81.9-98.2
-
480
-
[41]
HPLC-FLD,
HPLC-UV
SPE (Oasis MCX and
MWCNTs-SO3-/PVA
cryogel)
10
90.1-92.0
and
92.7-104.4
<6
40 (FLD)
400 (UV)
200 (FLD)
800 (UV)
This
work
Capillary
electrophoresis
Capillary
electrophoresis
Capillary
electrophoresis
GC-MS
LC-MS
LC-MS-MS
5
Ref.
[42]
[32]
[33]
[12]
4
Salbutamol
Ractopamine
Clenbuterol
100
% Recovery
80
60
40
20
0
2.0
3.0
4.0
5.0
6.0
Extraction solvent (mL)
Fig. S1 Effect of the volume of extraction solvent on the recovery of -agonists
5
Salbutamol
Ractopamine
Clenbuterol
100
% Recovery
80
60
40
20
0
5
10
20
30
Extraction time (min)
Fig. S2 Effect of the extraction time on the recovery of -agonists
6
Fig. S3 The HPLC-FLD (A) and HPLC-DAD (B) chromatograms of -agonists
standard solution (a), non-spiked porcine feed (b) and spiked porcine feed at 1.0 mg kg1
(C); 1=Salbutamol, 2=Bamethan (internal standard), 3=Ractopamine, 4=Clenproperol
(internal standard), 5=Clenbuterol