Molecular Classification of Pesticides Including Persistent Organic Pollutants, Phenylurea and Sulphonylurea Herbicides
Abstract
:1. Introduction
2. Results and Discussion
MAPE = 5.39% AEV = 0.0234
MAPE = 5.84% AEV = 0.0214
Compound | Rt (min) | Rt − Rt° (min) | (Rt − Rt°)/Rt° | logP | pKa | D | D’ |
---|---|---|---|---|---|---|---|
1. Methamidophos C2H8NO2PS <001010> | 2.78 | 0.00 | 0.00000 | −0.779 | −0.58 | 1.235 | 1.266 |
2. Carbendazim C9H9N3O2 <100010> | 6.48 | 3.70 | 1.33094 | 1.52 | 5.66 | 1.284 | 1.332 |
3. Thiabendazole C10H7N3S <110010> | 6.91 | 4.13 | 1.48561 | 2.47 | 3.40 | 1.288 | 1.331 |
4. Pyrimethanil C12H13N3 <110010> | 10.43 | 7.65 | 2.75180 | 2.558 | 4.41 | 1.314 | 1.407 |
5. Cyprodinil C14H15N3 <110010> | 11.44 | 8.66 | 3.11511 | 3.012 | 4.22 | 1.344 | 1.470 |
6. TPP (IS) C18H15O4P <111000> | 11.78 | 9.00 | 3.23741 | 4.63 | −5 | 1.394 | 1.504 |
7. Diazinone C12H21N2O3PS <111100> | 11.92 | 9.14 | 3.28777 | 3.766 | 1.21 | 1.398 | 1.509 |
8. Pyrazophos C14H20N3O5PS <111110> | 12.24 | 9.46 | 3.40288 | 2.810 | −1.37 | 1.403 | 1.505 |
9. Chlorpyrifos C9H11NO3PSCl3 <111111> | 13.42 | 10.64 | 3.82734 | 5.004 | −5.28 | 1.394 | 1.494 |
Classification Level b | Number of Classes | Entropy h |
---|---|---|
1.00 | 9 | 32.49 |
0.98 | 7 | 20.01 |
0.96 | 6 | 15.13 |
0.93 | 5 | 10.70 |
0.87 | 4 | 6.77 |
0.76 | 3 | 3.71 |
0.51 | 2 | 1.47 |
0.10 | 1 | 0.08 |
Factor | Eigenvalue | Percentage of Variance | Cumulative Percentage of Variance |
---|---|---|---|
F1 | 2.33109829 | 38.85 | 38.85 |
F2 | 1.62998318 | 27.17 | 66.02 |
F3 | 1.25482746 | 20.91 | 86.93 |
F4 | 0.38517751 | 6.42 | 93.35 |
F5 | 0.33518718 | 5.59 | 98.94 |
F6 | 0.06372637 | 1.06 | 100.00 |
Property | PCA Factor Loadings a | |||||
---|---|---|---|---|---|---|
F1 | F2 | F3 | F4 | F1 | F6 | |
i1 | 0.30822766 | 0.64474701 | 0.02673332 | −0.04594797 | 0.50138891 | −0.48485077 |
i2 | 0.44804795 | 0.45046774 | −0.05731613 | 0.08927231 | −0.76002034 | 0.08629170 |
i3 | 0.40956062 | −0.56947041 | −0.18574529 | 0.04102918 | −0.15327503 | −0.66954134 |
i4 | 0.55772042 | −0.17916516 | 0.17892539 | 0.59525799 | 0.32511366 | 0.40595876 |
i5 | −0.31588577 | 0.04253838 | 0.72852310 | 0.44514023 | −0.20425092 | −0.35748077 |
i6 | 0.35450381 | −0.15222972 | 0.63145758 | −0.66011661 | 0.00822715 | 0.12881324 |
Percentage of i1 a | % of i2 | % of i3 | % of i4 | % of i5 | % of i6 | |
---|---|---|---|---|---|---|
F1 | 9.50 | 20.07 | 16.77 | 31.11 | 9.98 | 12.57 |
F2 | 41.57 | 20.29 | 32.43 | 3.21 | 0.18 | 2.32 |
F3 | 0.07 | 0.33 | 3.45 | 3.20 | 53.07 | 39.87 |
F4 | 0.21 | 0.80 | 0.17 | 35.43 | 19.81 | 43.58 |
F5 | 25.14 | 57.76 | 2.35 | 10.57 | 4.17 | 0.01 |
F6 | 23.51 | 0.74 | 44.83 | 16.48 | 12.78 | 1.66 |
P. | g00100 | g00101 | g01100 | g10000 | g10001 | g10100 | g11000 | g11001 | g11100 | g11110 | g11111 |
---|---|---|---|---|---|---|---|---|---|---|---|
p0 | Chlordecone** | Methamidophos | PFOS** | Metamitron* BDE‑99** Metoxuron Monuron Diuron Linuron Buturon Chlorotoluron Daimuron Fenuron Methyldimuron Fluometuron Siduron Neburon Isoproturon Pencycuron | Carbendazim Metolachlor* Metazachlor | AMS BSM CME CNS EMS MSM NCS OXS PSE TFS TBM TFO 3FS RMS IDS | Carbetamide* Prometryne* Lindane** PCB** | Thiabendazole Pyrimethanil Cyprodinil Carbofuran* | TPP Flazasulphuron Triasulphuron Azimsulphuron Chlorsulphuron | Diazinone | Pyrazophos |
p1 | Chlorfenvinphos** | Chlorpyrifos |
Pmin (P) < P(P+1)
P(P+1) − Pmin (P) >0
3. Experimental
3.1. Classification Algorithm
3.2. Information Entropy
3.3. Equipartition Conjecture of Entropy Production
3.4. Learning Procedure
4. Conclusions
- (1)
- The objective was to develop a structure–property relation for qualitative and quantitative prediction of chromatographic retention times of pesticides. Results of the present work contribute to relation prediction of pesticide residues, in food and environmental samples. Code TOPO allows fractal dimensions, and SCAP, solvation free energies and partition coefficient, which show that for a given atom energies and partitions are sensitive to the presence in the molecule of other atoms and functional groups. Fractal dimensions, partition coefficient, etc. differentiated pesticides. Parameters needed for co-ordination index are molar formation enthalpy, molecular weight and surface area. The morphological and co-ordination indices barely improved equations. Correlation between molecular area and weight points not only to a homogeneous molecular structure of pesticides, but also to the ability to predict and tailor their properties; the latter is nontrivial in environmental toxicology.
- (2)
- Several criteria selected to reduce the analysis to a manageable quantity of pesticides, referred to structural and constituent characteristics related to nonplanarity, and the number of rings, and O, double-bonded S, N and Cl atoms. Classification was in agreement with the principal component analyses. Program MolClas is a simple, reliable, efficient and fast procedure for molecular classification based on equipartition conjecture of entropy production. It was written to analyze equipartition conjecture of entropy production and explore molecular-classification world.
- (3)
- Periodic law does not satisfy physics-law status: (a) pesticides retentions are not repeated; perhaps chemical character; (b) order relations are repeated with exceptions. Analysis forces statement: Relations that any compound p has with its neighbour, p + 1, are approximately repeated for each period. Periodicity is not general; however, if substance natural order is accepted law must be phenomenological. Retention is not used in periodic-table generation and serves to validate it. The analysis of other properties would give an insight into the possible generality of the periodic table. The periodic classification was extended to phenylureas and sulphonylureas.
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Torrens, F.; Castellano, G. Molecular Classification of Pesticides Including Persistent Organic Pollutants, Phenylurea and Sulphonylurea Herbicides. Molecules 2014, 19, 7388-7414. https://doi.org/10.3390/molecules19067388
Torrens F, Castellano G. Molecular Classification of Pesticides Including Persistent Organic Pollutants, Phenylurea and Sulphonylurea Herbicides. Molecules. 2014; 19(6):7388-7414. https://doi.org/10.3390/molecules19067388
Chicago/Turabian StyleTorrens, Francisco, and Gloria Castellano. 2014. "Molecular Classification of Pesticides Including Persistent Organic Pollutants, Phenylurea and Sulphonylurea Herbicides" Molecules 19, no. 6: 7388-7414. https://doi.org/10.3390/molecules19067388