Toxins, Vol. 15, Pages 19: Kinetics, Thermodynamics and Mechanism of Enzymatic Degradation of Zearalenone in Degummed Corn Oil

Conceptualization, C.Z.; Methodology, P.X.; Software, J.J.; Validation, C.Z., Q.J. and X.W.; Formal Analysis, X.W.; Investigation, J.J.; Resources, Q.J.; Data Curation, P.X.; Writing—Original Draft Preparation, C.Z.; Writing—Review and Editing, C.Z. and P.X; Visualization, J.J.; Supervision, J.J. and Q.J.; Project Administration, C.Z.; Funding Acquisition, Q.J. and X.W.; All authors have read and agreed to the published version of the manuscript.

Figure 1. The mechanism of ZHD.

Figure 1. The mechanism of ZHD.

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Figure 2. Effects of pH on initial rates of ZEN degradation.

Figure 2. Effects of pH on initial rates of ZEN degradation.

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Figure 3. Effects of ZHD dosage on initial rate of ZEN degradation.

Figure 3. Effects of ZHD dosage on initial rate of ZEN degradation.

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Figure 4. Effect of ZEN concentration on initial rate of ZEN degradation.

Figure 4. Effect of ZEN concentration on initial rate of ZEN degradation.

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Figure 5. Reciprocal initial reaction rate versus reciprocal ZEN concentration.

Figure 5. Reciprocal initial reaction rate versus reciprocal ZEN concentration.

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Figure 6. Effect of temperature on initial rate of ZEN degradation.

Figure 6. Effect of temperature on initial rate of ZEN degradation.

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Figure 7. Arrhenius plot to calculate activation energy Ea of ZHD.

Figure 7. Arrhenius plot to calculate activation energy Ea of ZHD.

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Figure 8. HPLC-MS TIC of ZEN in DCO before reaction. ((A), the chromatogram of ZEN, and (B), the mass spectrum of ZEN).

Figure 8. HPLC-MS TIC of ZEN in DCO before reaction. ((A), the chromatogram of ZEN, and (B), the mass spectrum of ZEN).

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Figure 9. HPLC-MS chromatogram of zearalenone (A) and zearalenone hydrolysate (B,C) (ES-scan mode).

Figure 9. HPLC-MS chromatogram of zearalenone (A) and zearalenone hydrolysate (B,C) (ES-scan mode).

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Figure 10. HPLC-MS mass spectrum of zearalenone hydrolysates (ESI-scanning mode). ((A), HPLC-MS mass spectrum of water-added product and (B), HPLC-MS mass spectrum of decarboxylation product).

Figure 10. HPLC-MS mass spectrum of zearalenone hydrolysates (ESI-scanning mode). ((A), HPLC-MS mass spectrum of water-added product and (B), HPLC-MS mass spectrum of decarboxylation product).

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Figure 11. HPLC-MS chromatogram of zearalenone hydrolysate (ESI + scan mode).

Figure 11. HPLC-MS chromatogram of zearalenone hydrolysate (ESI + scan mode).

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Figure 12. Identification of hydrolysates with retention time of 6.30 min (ESI + scan mode).

Figure 12. Identification of hydrolysates with retention time of 6.30 min (ESI + scan mode).

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Figure 13. Identification of hydrolysates with retention time of 8.13 min (ESI + scan mode).

Figure 13. Identification of hydrolysates with retention time of 8.13 min (ESI + scan mode).

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Figure 14. Degradation pathway of ZEN by ZHD.

Figure 14. Degradation pathway of ZEN by ZHD.

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Table 1. Estimation solution by Wilkinson statistical method.

Table 1. Estimation solution by Wilkinson statistical method.

[S]VX = V2Y = V2/[S]VXX2VYXYY25000.040.0016633.33 × 10−66.78 × 10−52.76 × 10−61.356 × 10−75.529 × 10−91.106 × 10−1110000.080.0071567.16 × 10−60.61 × 10−45.12 × 10−56.053 × 10−75.120 × 10−85.120 × 10−1130000.210.0447011.49 × 10−50.00950.001993.150 × 10−66.660 × 10−72.220 × 10−1050000.270.0727981.46 × 10−50.01960.00533.928 × 10−61.059 × 10−62.119 × 10−1070000.380.1439072.06 × 10−50.05460.02077.798 × 10−62.958 × 10−64.226 × 10−10Σ 0.08440.02811.561 × 10−54.741 × 10−69.189 × 10−10code αβγδε

Table 2. Exact solution by Wilkinson statistical method.

Table 2. Exact solution by Wilkinson statistical method.

[S][S] + Km0Vm[S]ff`f2f`fvfvf`50011,551.78476.90.0413−3.574 × 10−60.00171.277 × 10−11−1.475 × 10−70.00168100012,051.78953.80.0791−6.567 × 10−60.00634.312 × 10−11−5.197 × 10−70.00669300014,051.782861.40.2036−1.449 × 10−50.04152.100 × 10−10−2.951 × 10−60.04305500016,051.7847690.2971−1.851 × 10−50.08833.420 × 10−10−5.499 × 10−60.08016700018,051.786676.60.3699−2.049 × 10−50.13684.198 × 10−10−7.578 × 10−60.14030Σ 0.27451.028 × 10−9−1.669 × 10−50.27189code α`β`γ`δ`ε`

Table 3. Thermodynamic parameters for ZEN degradation by ZHD.

Table 3. Thermodynamic parameters for ZEN degradation by ZHD.

Temp. (°C)Kcat
(sec−1)Ea
(kJ × mol−1)ΔH
(kJ × mol−1)ΔG
(kJ × mol−1)ΔS
(kJ × mol−1 × K−1)250.267970.3767.4670.58 −0.0104 300.256970.3767.4271.91 −0.0148 350.246370.3767.3873.24 −0.0190 400.236270.3767.3474.58 −0.0231

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