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Supporting Information Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A. This journal is © The Royal Society of Chemistry 2021 Supporting Information Hierarchically Micro- and Mesoporous Metal-Organic Framework-Based Magnetic Nanospheres for Nontargeted Analysis of Chemical Hazards in Vegetables Yushen Jin,a,b Yan Qi,c Chu Tang,d Bing Shao a,b,c* a Beijing Key Laboratory of Diagnostic and Traceability Technologies for Food Poisoning, Beijing Centre for Disease Preventive Medical Research, Beijing 100013, China b Central Research Laboratory, Beijing Centre for Disease Control and Prevention, Beijing 100013, China. cCollege of Veterinary Medicine, China Agricultural University, Beijing 100193, China. dEngineering Research Centre of Molecular and Neuro Imaging, Ministry of Education, School of Life Science and Technology, Xidian University, Xi’an, 710126, Shaanxi, China. *Corresponding author. Email: [email protected] Figure S1. Size distribution of (a) Fe3O4, (b) H-MOF1@Fe3O4, (c) H-MOF6@Fe3O4, (d) H-MOF15@Fe3O4 and (e) H-MOF30@Fe3O4 tested by DLS Figure S2. FT-IR spectra of Fe3O4, MAA-functionalized Fe3O4 and H-MOF6@Fe3O4 nanospheres. Figure S3. PXRD pattern of H-MOF6@Fe3O4 nanospheres after incubated with various solvents. Figure S4. TG analysis of Fe3O4, MAA-functionalized Fe3O4 and H-MOF6@Fe3O4 nanospheres. Figure S5. Chlorophylls adsorption kinetics characterization of MCOFs by (a) pseudo-first-order, (b) pseudo-second-order kinetic models and (c) intra-particle diffusion model Figure. S6 Separation of spinach extracts by thin layer chromatography Table S1 Conditions of gradient elution(No.1-No.46) Time (min) Mobile phase (%) Flow rate injected Water+0.1% FA Methanol (mL/min) sample volume (µL) 0 90 10 0.3 2 0.3 90 10 0.3 2 4.5 45 55 0.3 2 12 45 55 0.3 2 13 30 70 0.3 2 15 30 70 0.3 2 17 0 100 0.3 2 23 0 100 0.3 2 23.1 90 10 0.3 2 25 90 10 0.3 2 Table S2 Conditions of gradient elution (No.47-No.258) Time (min) Mobile phase (%) Flow rate injected Water+0.1% FA Methanol (mL/min) sample volume (µL) 0 98 2 0.3 5 0.25 98 2 0.3 5 20 1 99 0.3 5 25 1 99 0.3 5 25.1 98 2 0.3 5 30 98 2 0.3 5 Table S3 MRM transitions and other LC-MS/MS parameters Serial Retention Confirmation Quantification Analytes Precursor ion Fragmentor(a) number time (min) ion(a) ion(a) 3- 1 6.11 239.1 163.1(22.5) 181.1(38) 50 Hydroxycarbofuran 4-Bromo-3,5- dimethylphenyl-N- 2 11.9 258 201(15) 122.1(31) 25 methylcarbamate Fenpropidin 3 10.7 274.2 147.2(39) 86.2(35) 50 Fenoxycarb 4 13.34 302.1 88(27) 116.1(15) 40 Dichlofenthion 5 17.42 315 259(24) 268.9(15) 38 Trichlorfon 6 5.64 256.9 109(24) 221(14) 35 Propachlor 7 10.81 212.1 170.1(31) 94.1(31) 40 Dioxathion 8 16.84 479 271.1(20) 293.2(19) 35 Tebuthiuron 9 7.60 229.1 172.1(18) 116.1(34) 40 Lontrel 10 3.43 191.9 174(16) 146(30) 43 Dinotefuran 11 12.93 203.1 105.1(34) 91.1(48) 40 Furanthiocarb 12 16.45 383.2 195(27.5) 252.1(18) 33 Bioallethrin 13 16.66 303.2 121.1(27) 149.1(25) 35 Asulam 14 4.80 231 156(15) 108.1(27) 50 Griseofulvin 15 10.40 353.1 165.1(37) 285.1(34) 40 Sulfosulfuron 16 10.69 471.1 211.1(30) 261.1(27) 50 Benoxacor 17 12.21 260 149.1(26) 134.1(41) 58 Bromuconazol 18 12.50 376 159(40) 70.1(54) 60 Butafenacil 19 13.92 475.1 345(35) 331(38) 25 Thiodicarb 20 9.20 355.1 88(20) 108.1(23) 40 Mesurol 21 11.74 226.1 169.1(17) 121(25) 65 Flazasulfuron 22 11.17 408.1 182.1(30) 301.1(20) 40 Methomyl 23 4.75 163.1 88.1(18) 106.1(18) 33 Aminocarb 24 3.44 209.1 152.1(18) 137.1(32) 31 + Ethofenprox 25 19.38 394.3(NH4 ) 177.2(19) 359.3(17) 35 Promecarb 26 12.07 208.2 109.1(21) 151.1(12) 35 Benodanil 27 11.51 324 230.9(28) 105.2(28) 32 Mecarbam 28 13.95 330 199(21) 142.9(35) 31 Diphenamid 29 11.04 240.1 134.1(24.5) 167.1(31.5) 60 Triflumuron 30 14.32 359.1 156(23) 139(45) 40 Tricyclazole 31 6.99 190.1 163(28) 136(37) 65 Propamocarb 32 3.60 189.2 102.1(24) 144.1(18) 43 Cymoxanil 33 7.34 199.1 128.1(13) 111.1(26) 40 Etoxazole 34 17.46 360.2 141.1(45.2) 304.1(24) 70 Altrenogest 35 12.10 311.1 221.1(23) 269.3(23) 56 Tolfenamic acid 36 14.36 262.1 244.1(22) 209.1(39) 40 Aldicarb-sulfone 37 4.45 223.1 148.1(13) 86.1(19) 41 Aldicarb sulfoxide 38 3.57 207 132(12) 89.1(32) 34 DEF 6 39 18.57 315.1 169(20) 259.1(18) 42 Carboxin 40 10.14 236.1 143.1(22) 87(36) 60 Methoprene 41 12.07 311.1 221.1(23) 261.1(26) 47 EPTC 42 13.80 190.1 128.1(17) 86.1(15) 40 Ethiofencarb 43 10.13 226.1 107.1(20) 164.1(11) 40 Ethion 44 17.21 385 199(14.3) 215.1(15.7) 25 Diethofencarb 45 17.47 268 226.2(15) 180.1(24) 35 Triallate 46 11.81 304 86.1(22) 143(36) 45 Mandestrobin 47 14.61 314 192(18) 132(35) 30 Valifenalate 48 11.68 399.1 155(30) 197(20) 30 Chlormequat 49 0.77 122 63(17) 59(17) 30 Fenpyrazamine 50 10.99 332.1 272(14) 304(14) 30 Fenthion 51 14.44 279.1 169.1(16) 247.1(13) 36 Aclonifen 52 14.1 265 248(18) 182(32) 30 Difenoconazole 53 16.3 406 251.1(25) 111.1(60) 46 Phenothrin 54 17.91 351 156(28) 237(12) 30 Saflufenacil 55 7.98 501 349(25) 459(12) 30 Zoxamide 56 14.72 336 159(38) 187.1(25) 38 Fenamiphos 57 13.98 304.1 217.1(24) 202.1(36) 36 Pyraflufen Ethyl 58 14.85 413 338.8(20) 289(27) 30 pyriproxyfen 59 17.11 322.1 96(14) 227.1(14) 32 Haloxyfop 60 16.57 362 91(30) 288(30) 30 Isopyrazam 61 16.28 360.2 320(20) 258(20) 30 Resmethrin 62 17.77 339.2 171(17) 143(25) 30 Propoxycarbazone- 63 5.8 399 199(12) 367(12) 30 sodium Propiconazole 64 14.95 342 159(34) 69(22) 46 Prothioconazole 65 14.96 344 189(20) 326(12) 22 Oxadiargyl 66 15.28 341 151(25) 258(15) 30 Flumioxazin 67 7.71 355.1 298(28) 326(22) 46 Iprovalicarb 68 17.71 321.2 203.1(10) 119.1(16) 30 Methacrifos 69 7.54 241 125(20) 209.1(8) 20 Isoprothiolane 70 10 291.1 230.9(12) 189(22) 30 Tepraloxydim 71 6.01 342.1 250.1(12) 166.1(20) 30 Diuron 72 7.13 233 71.5(15) 45.5(15) 30 Anilazine 73 9.95 274.9 153(26) 178(24) 46 lodosulfuron-methyl 74 9.45 508.1 167.1(25) 141.1(25) 30 Daminozide 75 1.06 161 143(12) 61(12) 30 Acetamiprid 76 4.24 223 126(20) 56.1(15) 30 Picoxystrobin 77 14.17 368.1 205.1(10) 145.1(22) 20 Carbendazim 78 2.7 192.1 160.1(18) 132.1(28) 30 Sandofan 79 5.04 279.1 219(10) 132(34) 40 Diphenylamine 80 10.82 170.1 93(24) 92(18) 38 Diazinon 81 14.57 305.1 169(22) 97(35) 30 Flutriafol 82 6.72 302.1 122.7(22) 94.7(42) 30 Rimsulfuron 83 6.23 432 182.1(22) 325.1(14) 30 Phosalone 84 15.31 368 181.9(14) 110.9(42) 22 Fluvalinate 85 17.79 503.1 181.1(30) 208.1(12) 24 Fluopyram 86 12.3 397 173(27) 208(20) 30 Fluazinam 87 17.14 464.9 373(26) 338.1(47) 30 Sulfoxaflor 88 4.47 278 174(10) 154(27) 30 Flonicamid 89 3.08 230 203.1(12) 174.1(17) 30 Flusilazole 90 14.09 316.1 247(18) 165(28) 36 Epoxiconazole 91 13.32 330 121(22) 101(50) 34 Tetraconazole 92 13.65 372 70(20) 159(30) 30 Flucythrinate 93 17.32 469 412(10) 198.7(22) 30 Flufenacet 94 12.92 364 194.1(11) 152.1(20) 30 Flutolanil 95 10.37 324.1 262.1(18) 65(40) 30 Procymidone 96 12.08 284 256.1(17) 67.1(28) 30 Thiobencarb 97 15.38 258 125(12) 100(12) 30 Molinate 98 10.13 188.1 126(13) 55(24) 30 Cyproconazole 99 11.81 292.1 69.5(18) 124.6(24) 30 Chromafenozide 100 12.37 395.2 175(22) 339(10) 30 Cyflufenamide 101 15.5 413.1 295.1(15) 203.1(35) 30 Sulcotrione 102 5.37 329 138.8(18) 110.7(27) 30 Metosulam 103 5.89 418 175(28) 140(52) 30 Tolylfluanide 104 14.47 347 137(28) 238(10) 30 Alachlor 105 12.43 270.1 238.1(11) 162.1(20) 30 Metsulfuron methyl 106 5.78 382 167(16) 199(22) 30 Mesosulfuron- 107 6.86 504 182(24) 83(60) 30 methyl Tolclofos-methyl 108 15.35 301 125(17) 175(29) 30 Thiophanate-methyl 109 5.61 343 93(46) 151(22) 30 Carbaryl 110 6.03 202 145(22) 117(28) 30 Metalaxyl 111 7.05 280.1 220.1(13) 192.1(17) 30 Metazachlor 112 6.82 278 134.1(22) 210(10) 30 Tebufenozide 113 14.12 353.1 133(20) 297.1(8) 30 Famoxadone 114 15.3 397 260.9(14) 167.7(16) 30 Emamectin 115 16.42 886.5 158.2(35) 302.2(30) 30 cis and trans- 116 16.21 270.1 86.1(15) 128.1(11) 30 Diallate Chloridazon 117 4.21 222 92(30) 77(30) 30 Pendimethaline 118 17.24 282.1 212.1(10) 194.1(17) 30 Trinexapac-ethyl 119 7.11 253.1 185.1(12) 207.1(12) 30 Spirotetramat 120 12.78 374.2 330.2(15) 302.2(15) 30 Cadusafos 121 15.86 271.1 159(16) 131(22) 30 Quinalphos 122 13.98 299 163(24) 97(30) 30 Orthosulfamuron 123 6.96 425.1 199.1(12) 227.1(15) 30 Cyhalofop-butyl 124 16.57 358.1 256.1(12) 120.1(25) 30 Cyazofamid 125 13.66 325 108(20) 261(10) 30 Lactofen 126 17.09 479 344(15) 223(32) 30 Florasulam 127 4.98 360 129(22) 109(50) 30 Mandipropamid 128 10.18 412.1 328.1(15) 356.1(10) 30 Mesotrione 129 5.74 340 228(18) 104(32) 30 Oxydemeton-methyl 130 2.94 247 168.9(14) 108.9(25) 30 Oxycarboxin 131 4.5 268.1 174.8(16) 146.9(25) 30 Spinetoram L 132 15.79 760.5 142.1(30) 98.1(30) 30 Ethirimol 133 4.32 210.1 140(22) 98(28) 30 Ethoxyquin 134 5.6 218.1 148.1(22) 160.1(32) 30 Propisochlor 135 14.26 284.1 224.1(10) 148.1(17) 30 Isoproturon 136 6.89 207 71.4(17) 45.3(15) 30 Butralin 137 17.42 296.2 239.9(12) 221.8(20) 30 Azocyclotin 138 14.33 437.2 287.1(17) 205.1(22) 30 Amidosulfuron 139 6.46 370 261(15) 218(25) 30 Fentin 140 5.64 351.1 119.9(30) 197(25) 30 Ametoctradin 141 15.3 276.2 149.1(35) 177.1(35) 30 Atrazine 142 6.6 216.1 174.1(18) 96.1(23) 30 Vinclozolin 143 13.11 286 174(35) 218(17) 30 Barban 144 10.95 258 178(10) 143.1(20) 30 Tridemorph 145 13.68 298.3 98(34) 57(28) 30 Bromophos-ethyl 146 17.79 395 339(17) 367(10) 30 Chloroxuron 147 11.8 291.1 72(25) 164.1(15) 30 Bromopropylate 148 17.21 411 209(30) 325(12) 30 Nicosulfuron 149 5.47 411.1 182(32) 106(22) 30 Fenpyroximate 150 17.48 422.2 366.1(15) 138.1(32) 30 Acequinocyl 151 18.17 357.2 329(20) 203(20) 30 Bifenazate 152 12.03 301.1 198(10) 170(20) 30 Trifloxystrobin 153 16.56 409.1 186(16) 145(40) 30 Cyantraniliprole 154 6.09 475 286(12)
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