Towards A New Approach for the Description of Cyclo–2,4-Dihydroxybenzoate, A Substance Which Effectively Mimics Zearalenone in Imprinted Polymers Designed for Analyzing Selected Mycotoxins in Urine
Abstract
:1. Introduction
2. Results and Discussion
2.1. Characterization of CDHB
2.1.1. FT-IR Analysis
2.1.2. NMR
2.1.3. UV–VIS
2.1.4. Mass Spectrum
2.2. Characterization of Polymers
2.3. Quantum-Chemical Calculations
2.4. Crystal Structure of CDHB
2.5. Validation Method
Calibration Curves, Limits of Detection, and Quantification
2.6. Optimization of MISPE Parameters Influencing ZEA Adsorption
2.6.1. Sample pH
2.6.2. MIP Amount
2.6.3. Desorption
2.6.4. Kinetic Study
2.6.5. Adsorption Isotherm
2.6.6. Selectivity
2.7. Effectiveness of Isolating ZEA from Urine
3. Materials and Methods
3.1. Reagents and Materials
3.2. Chromatographic Conditions
3.3. Synthesis
3.4. Polymer Synthesis: MIP and NIP
3.5. Characterization of CDHB crystals
3.6. Characterization of Polymers
3.6.1. Physicochemical Characterization of Polymers
3.6.2. Adsorption Studies
3.6.3. Binding Analysis of Molecularly-Imprinted Polymers
3.7. Urine Sample Preparation
3.8. Validation Procedure
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Adsorbent | Recovery (SD) (%) | Methods | LOD/LOQ | Concentration Range | Subjects | Ref. |
---|---|---|---|---|---|---|
ELISA | not specified | LC-MS/MS | 1)0.02/0.007 mg·kg−1 | 0.3–100 ng·mL−1 | Pigs | [11] |
RP C18 Phenomenex | 96.6 (3.8) | LC-MS/MS | 0.1/0.5 pg | 0.5–100 pg | Cow, pigs | [19] |
ISOLUTE® C18/immunoaffinity column Easi-Extract® Zearalenone | 108.2 (7.5) | HPLC–APCI–MS | 0.1/0.5 μg·L−1 | 0.5–100 μg·L−1 | Horse | [20] |
2)LLE/BakerBond C18 and NH2 | 94.3–114.0 (9–19.8) | LC-MS/MS | Detection limit: 0.11 μg·L−1 | 0.18–5 μg·L−1 | Animal | [21] |
SAX SPE cartridge | not specified | LC-MS/MS | LOD: 61 pg·mL−1 α-ZEL; 117 pg·mL−1 β-ZEL14GlcA | - | Human | [22] |
Supelco Titan C18 | not specified | UHPLC-MS/MS | LOD: 0.31 μg·L–1 ZEA; 0.11 μg·L−1 α-ZEL | - | Pregnant women | [23] |
C18 | 94.3 | LC-ESI/MS/MS | 0.02/0.05 ng·ml−1 | 1.81 pg·mg−1 Creatinine | Mares | [24] |
MIP-CDHB | 95.2–98.2 | HPLC-FLD | 3)LOQ: 5.4 ng·mL−1 | 10–1000 ng·mL−1 | Lyophilized human urine | [this work] |
(1.5–2.0) | ||||||
MIP-ZEA | 94.1–97.1 | 6.3 ng·mL−1 | ||||
(1.6–1.9) 4) | ||||||
NIP | 72.1–80.0 | 36.9 ng·mL−1 | 50–1000 ng·mL−1 | |||
(8.2–11.2) 4) | ||||||
ImmunoClean C ZON | 86.5–92.5 | 10.8 ng·mL−1 | 15–500 ng·mL−1 | |||
(2.3–5.2) 4) | ||||||
ImmunoClean C+ ZON | 88.2–92.1 | 8.3 ng·mL−1 | ||||
(1.9–3.8) 4) |
Wavenumber (cm−1) | Frequency Assignment |
---|---|
3402 | O-H stretching, and possibly intra molecular hydrogen bonded –OH groups |
3200 | O-H stretching, and possibly intra molecular hydrogen bonded –OH groups |
2953 | C-H stretching |
1686 | C=O stretching |
1469 | C-C stretching in aromatic ring |
1255 | C-O stretching |
850 | C-H out of plane |
Conformer | Energy (kcal/mol, [au]) | Dipole Moment (Debye) | φ1 (°) | EXP φ1 (°) | φ3 (°) | EXP φ3 (°) |
---|---|---|---|---|---|---|
K1 | 0.00 [−1041.672265] | 2.00 | 179.97 | −172.1 | −149.53 | −138.96 |
K2 | 3.28 | 1.10 | 0.18 | 6.03 | −149.44 | −139.96 |
K3 | 4.98 | 4.05 | 179.92 | −172.1 | −83.79 | −78.63 |
K4 | 7.85 | 1.50 | 0.56 | 6.03 | −83.79 | −78.63 |
D-H | A | d(D-H) | d(H...A) | d(D...A) | <(DHA) | |
---|---|---|---|---|---|---|
Mol 1 | O1-H101 | O3 | 0.82 | 1.9 | 2.6218(17) | 145.3 |
O1W-H1W1 | O3[x−1/2, −y+3/2, z−1/2] | 0.95 | 1.90 | 2.8449(18) | 174.2 | |
O2-H1O2 | O23[−x, −y+1, −z] | 0.82 | 1.96 | 2.7820(18) | 175.5 | |
Mol 2 | O21-H21A_a | O23 | 0.82 | 1.93 | 2.635(2) | 143.4 |
O21B-H21B_b | O24 | 0.82 | 1.83 | 2.528(5) | 141.9 | |
O22-H22O | O1W | 0.82 | 1.84 | 2.6596(19) | 174.8 | |
O1W-H2W1 | O22[−x−3/2, y+1/2, −z−1/2] | 0.94 | 1.91 | 2.8393(17) | 168.7 |
Type of SPE Sorbent | Range of Concentration (ng mL−1) | Calibration Equation y = mx ± b | r2 | LOD (ng mL−1) | LOQ (ng mL−1) | % ME |
---|---|---|---|---|---|---|
MIP-CDHB | 10–1000 | y = 0.0254x + 0.6721 | 0.9990 | 1.8 | 5.4 | 15.1% |
MIP-ZEA | y = 0.0240x + 0.4383 | 0.9985 | 2.1 | 6.3 | 19.7% | |
NIP | 50–1000 | y = 0.0185x + 1.7157 | 0.9815 | 11.2 | 36.9 | 38.1% |
ImmunoClean C ZON | 15–500 *) | y = 0.0226x – 0.0549 | 0.9918 | 3.2 | 10.8 | 24.4% |
ImmunoClean C+ ZON | y = 0.0241x + 0.8189 | 0.9990 | 2.5 | 8.3 | 19.4% |
Type of SPE Sorbent | t/qe = const∙t | r2 | qe |
---|---|---|---|
MIP-CDHB | t/qe = 2.2454·t | 0.999 | 1.8 |
MIP-ZEA | t/qe = 2.1311·t | 0.999 | 2.1 |
Sorbent | ZEA Concentration | |||||||
---|---|---|---|---|---|---|---|---|
20 ng·mL−1 | 100 ng·mL−1 | 400 ng·mL−1 | 500 ng·mL−1 | |||||
R (%) | RSD (%) | R (%) | RSD (%) | R (%) | RSD (%) | R (%) | RSD (%) | |
MIP-CDHB | 98.2 | 1.5 | 97.3 | 1.9 | 95.2 | 2.0 | 96.5 | 1,8 |
MIP-ZEA | 97.1 | 1.6 | 96.5 | 1.7 | 94.1 | 1.9 | 95.1 | 1.9 |
NIP | 72.1 | 9.6 | 80.0 | 8.2 | 78.1 | 10.3 | 75.2 | 11.2 |
ImmunoClean C ZON | 90.0 | 4.5 | 92.5 | 2.3 | 90.1 | 4.3 | 86.5 | 5.2 |
ImmunoClean C+ ZON | 91.8 | 3.2 | 92.1 | 1.9 | 91.4 | 2.2 | 88.2 | 3.8 |
Empirical Formula | C38H56O9 |
---|---|
Formula weight | 656.83 |
Temperature; K | 293(2) |
Wavelength; Å | 0.71073 |
Crystal system, space group | Monoclinic, P21/n |
Unit cell dimensions; Å and ° | a = 17.1943(7) |
b = 8.1870(4) | |
c = 25.8661(11) | |
beta = 92.282(4) | |
Volume; Å3 | 3638.3(3) |
Z, Calculated density; Mg/m3 | 4, 1.199 |
Absorption coefficient; mm−1 | 0.084 |
F(000) | 1424 |
Crystal size; mm | 0.45 × 0.26 × 0.13 |
Theta range for data collection | 2.37 to 28.15º |
Limiting indices | −22 ≤ h ≤ 22, −9 ≤ k ≤ 10, −34 ≤ l ≤ 31 |
Reflections collected/unique | 23663/7895 [R(int) = 0.0524] |
Completeness to theta | 26.00 99.9% |
Max. and min. transmission | 0.9902 and 0.9667 |
Refinement method | Full-matrix least-squares on F2 |
Data/restraints/parameters | 7895/0/434 |
Goodness-of-fit on F2 | 0.779 |
Final R indices [I > 2sigma(I)] | R1 = 0.0420, wR2 = 0.0805 |
R indices (all data) | R1 = 0.1415, wR2 = 0.0978 |
Largest diff. peak and hole; e.A−3 | 0.214 and −0.147 |
Polymer Code | SBET (m2·g−1) | Vp (cm3·g−1) | dp (nm) |
---|---|---|---|
NIP | 182.24 ± 3.24 | 0.396 | 7.62 |
MIP-CDHB | 247.52 ± 2.12 | 0.495 | 10.15 |
MIP-ZEA | 251.25 ± 1.96 | 0.504 | 11.24 |
Polymer Code | QMIP | QNIP | α |
---|---|---|---|
NIP | - | 38.18 | |
MIP-CBHB | 48.40 | - | 1.27 |
MIP-ZEA | 47.85 | - | 1.25 |
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Gadzała-Kopciuch, R.; Kwaśniewska, K.; Ludwiczak, A.; Skrzyniarz, P.; Jakubowski, R.; Nowak, W.; Wojtczak, A.; Buszewski, B. Towards A New Approach for the Description of Cyclo–2,4-Dihydroxybenzoate, A Substance Which Effectively Mimics Zearalenone in Imprinted Polymers Designed for Analyzing Selected Mycotoxins in Urine. Int. J. Mol. Sci. 2019, 20, 1588. https://doi.org/10.3390/ijms20071588
Gadzała-Kopciuch R, Kwaśniewska K, Ludwiczak A, Skrzyniarz P, Jakubowski R, Nowak W, Wojtczak A, Buszewski B. Towards A New Approach for the Description of Cyclo–2,4-Dihydroxybenzoate, A Substance Which Effectively Mimics Zearalenone in Imprinted Polymers Designed for Analyzing Selected Mycotoxins in Urine. International Journal of Molecular Sciences. 2019; 20(7):1588. https://doi.org/10.3390/ijms20071588
Chicago/Turabian StyleGadzała-Kopciuch, Renata, Katarzyna Kwaśniewska, Agnieszka Ludwiczak, Piotr Skrzyniarz, Rafał Jakubowski, Wiesław Nowak, Andrzej Wojtczak, and Bogusław Buszewski. 2019. "Towards A New Approach for the Description of Cyclo–2,4-Dihydroxybenzoate, A Substance Which Effectively Mimics Zearalenone in Imprinted Polymers Designed for Analyzing Selected Mycotoxins in Urine" International Journal of Molecular Sciences 20, no. 7: 1588. https://doi.org/10.3390/ijms20071588