Supporting Information Compositional analysis of commercial ...
Supporting Information
Compositional analysis of commercial oligomeric organophosphorus flame retardants used as alternatives for PBDEs: Concentrations and potential environmental emissions of oligomers and impurities
Hidenori Matsukami,*,†,‡ Go Suzuki,† Hidetaka Takigami†,‡
†
Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506, Japan
‡
Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8563, Japan
Number of pages: 24 Number of tables: 6 Number of figures: 9
1
Detailed information for the identification of oligomers and impurities based on the study of their fragmentation behaviors 1. CR-733S CR-733S consisted mainly of 1,3-phenylene bis(diphenyl phosphate) (PBDPP) oligomers including dimer, trimer, tetramer, and pentamer, and three impurities including triphenyl phosphate (TPHP). MS/MS fragment ions of the constituents in CR-733S are presented in Table S3. Based on fragment ions, the fragmentation behaviors are proposed as shown in Fig. S6. The constituents PBDPP-O4, PBDPP-O3, PBDPP-O2, and PBDPP-O1 in the MS investigation respectively gave protonated molecule ions at m/z 1319, m/z 1071, m/z 823, and m/z 575. The presence of the product ions at m/z 1225 (losses of C6H4 and H2O from protonated molecule of PBDPP-O4), m/z 1069 (losses of C6H4 and HPO3 from m/z 1225), m/z 977 (losses of C6H4O from m/z 1069 or C6H4 and H2O from protonated molecule of PBDPP-O3), m/z 821 (losses of C6H4 and HPO3 from m/z 977), m/z 729 (losses of C4H6O from m/z 821 or C6H4 and H2O from protonated molecule of PBDPP-O2), m/z 573 (losses of C6H4 and HPO3 from m/z 653), m/z 481 (losses of C4H6O from m/z 573 or C6H4 and H2O from protonated molecule of PBDPP-O1), m/z 325 (losses of C6H4 and HPO3 from m/z 809), m/z 233 (loss of C4H6O from m/z 325), m/z 153 (loss of HPO3 from m/z 233), and m/z 77 (loss C6H4 from m/z 153) showed the structural compositions of the oligomers of PBDPP. Four oligomers, dimer to pentamer, were identified from the elemental compositions of protonated molecule and fragment ions using accurate mass measurements. The constituent PBDPP-IM1 gave a protonated molecule at m/z 591. The product ions of protonated molecules of R4 at m/z 499, m/z 481, m/z 419, m/z 405, m/z 387, m/z 343, m/z 325, m/z 311, m/z 307, m/z 251, m/z 233, m/z 215, m/z 153, and m/z 77 were identical to the product ions of the skeletons of the oligomers PBDPP. The product ion at m/z 343 further fragmented to give the product ions at m/z 169 (loss of C6H7PO4 from m/z 343), m/z 141 (loss of CO from m/z 169), m/z 93 (loss of C6H4 from m/z 169), and m/z 65 (loss C6H4 from m/z 141) supported the structural components of PBDPP-IM1. The constituent PBDPP-IM2 gave a protonated molecule at m/z 343. The MS/MS investigations gave the product ion at m/z 251 (loss of C6H4O), m/z 249 (losses of C6H6O), and m/z 169 (loss of C6H7PO4) from a protonated molecule of PBDPP-IM2. The product ion at m/z 249 further fragmented to give product ions at m/z 231 (loss of H2O from m/z 249) and m/z 151 (loss of HPO3 from m/z 231). The product ion at m/z 169 further fragmented to give product ions at m/z 141 (loss of CO from m/z 169), m/z 93 (loss of C6H4 from m/z 169), and m/z 65 (loss C6H4 from m/z 141), supporting the structural components of PBDPP-IM2. Structures of the two impurities PBDPP-IM1 and PBDPP-IM2 were characterized as a part of the skeleton and a loss of diphenyl phosphate moiety of trimer and dimer PBDPP. Therefore, the constituents PBDPP-IM1 and PBDPP-IM2 were estimated, respectively, to be phosphoric acid, [3-[(diphenoxyphosphinyl)oxy]phenyl] 3-hydroxyphenyl phenyl ester (HPPHP-HP-DPHP) for PBDPP-IM1 and 3-hydroxyphenyl diphenyl phosphate (HP-DPHP) for PBDPP-IM2. The constituent PBDPP-IM3 in MS investigation gave a protonated molecule ion at m/z 327. The product ions of the protonated molecule at m/z 251 (loss of C6H4 from m/z 327), m/z 233 (loss of H2O from m/z 251), m/z 153 (loss of HPO3 from m/z 233), and m/z 77 (loss of C6H4 from m/z 153) were characteristic for the structure of TPHP. In addition, the ionic products from the reaction of C6H4 with C6H5+ were observed at m/z 229 (C6H4 + C6H4 + C6H5+ → C18H13+), m/z 228 (C6H4 + C6H4 + C6H5+ → C18H12+ + H), m/z 153 (C6H4 + C6H5+ → C12H9+), and m/z 152 (C6H4 + C6H5+ → C12H8+ + H). 2
2. CR-741 CR-741 consisted mainly of bisphenol A bis(diphenyl phosphate) (BPA-BDPP) oligomers including dimer, trimer, and tetramer, and three impurities including TPHP. MS/MS fragment ions of the constituents in CR-741 are shown Table S4. Based on the fragment ions, the fragmentation behaviors were proposed as shown in Fig. S7. Results of MS and MS/MS investigations indicated that CR-741 was composed of three oligomers including BPA-BDPP dimer to tetramer. The constituents BPABDPP-O3, BPABDPPO2, and BPABDPP-O1 in MS investigation respectively gave protonated molecules at m/z 1425, m/z 1059, and m/z 693. When fragmented in the MS/MS investigation, these protonated molecules yielded a series of prominent ions deriving from the successive losses of C18H15PO4 or C3H4. The product ions at m/z 1099 (loss of C18H15PO4 from protonated molecule of BPABDPPO3), m/z 1059 (loss of C3H4 from m/z 1099), m/z 733 (losses of C18H15PO4 from m/z 1059 or protonated molecule of BPABDPP-O2), m/z 693 (loss of C3H4 from m/z 733), m/z 367 (losses of C18H15PO4 from m/z 693 or protonated molecule of BPABDPP-O1), m/z 327 (loss of C3H4 from m/z 367), m/z 135 (loss of C18H15PO4 from m/z 367), and m/z 107 (loss C3H4 from m/z 135) were characteristic for the proposed structural components of oligomers. Results in this study of the fragmentation behaviors indicated that BPABDPP-O3, BPABDPP-O2, and BPABDPP-O1 were, respectively, tetramer, trimer, and dimer BPA-BDPP. The constituents BPABDPP-IM1 and BPABDPP-IM2 gave protonated molecules at m/z 827 and m/z 461. The MS/MS investigations gave the product ions at m/z 733 and m/z 367, which were losses of C6H4 and H2O from protonated molecules of BPABDPP-IM1 and BPABDPP-IM2. The product ion at m/z 367 further fragmented to give the product ions at m/z 327 (loss of C3H4 from m/z 367), m/z 135 (loss of C18H15PO4 from m/z 367), and m/z 107 (loss of C3H4 from m/z 135). The product ions of protonated molecules of BPABDPP-IM1 and BPABDPP-IM2 at m/z 733, m/z 693, m/z 367, m/z 327, m/z 135, and m/z 107 were identical to the product ions of the skeletons of the trimer and dimer BPA-BDPP. The studies of fragmentation behaviors revealed the constituents BPABDPP-IM1 and BPABDPP-IM2, which were estimated respectively as phosphoric acid, [4-[1-[4-[(diphenoxyphosphinyl)oxy]phenyl]-1-methylethyl]phenyl] [4-[2-(4hydroxyphenyl)propan-2-yl]phenyl] phenyl ester (BPA-PHP-BPA-DPHP) and 4-[2-(4hydroxyphenyl)propan-2-yl]phenyl diphenyl phosphate (BPA-DPHP). The fragmentation pathway of the constituent BPABDPP-IM3 was the same result as those of the constituent PBDPP-IM3 in CR-733S. The constituent BPABDPP-IM3 was identified as TPHP.
3. PX-200 PX-200 consisted mainly of 1,3-phenylene bis[di(2,6-dimethylphenyl ) phosphate] (PBDMPP) oligomers including dimer and trimer, and two impurities including tris(dimethylphenyl) phosphate (TDMPP). MS/MS fragment ions of the constituents in PX-200 are shown Table S5. Based on fragment ions, the fragmentation behaviors were proposed in Fig. S8. Constituents PBDMPP-O2 and PBDMPP-O1 respectively gave protonated molecules at m/z 963 and m/z 687. The presence of the product ions at m/z 779 (losses of C8H8 and HPO3 from protonated molecule of PBDMPP-O2), m/z 675 (loss of C8H8 from m/z 779), m/z 503 (losses of C6H4 and HPO3 from m/z 675 or C8H8 and HPO3 from protonated molecule of PBDMPP-O1), m/z 399 (loss of C8H8 from m/z 503), m/z 209 (losses of C6H6O and HPO3 from m/z 399), and 3
m/z 105 (loss of C8H8 from m/z 209) were characteristic for the structural compositions of trimer and dimer PBDMPP. Constituents PBDMPP-O2 and PBDMPP-O1 were identified respectively as trimer and dimer PBDMPP. The constituent PBDMPP-IM1 gave a protonated molecule at m/z 399. MS/MS investigations gave the product ion at m/z 209 (losses of C6H6O2 and HPO3 from protonated molecule of PBDMPP-IM1) and m/z 105 (loss of C8H8 from 209). The product ions from protonated molecule of PBDMPP-IM1 were also formed as those from protonated molecules of dimer PBDMPP in their MS/MS spectrum. The structure of PBDMPP-IM1 corresponded to a part of the skeleton of dimer PBDMPP. The constituent PBDMPP-IM1 was estimated as 3hydroxyphenyl di(2,6-dimethylphenyl) phosphate (HP-DDMPP). MS/MS investigations of the constituent PBDMPP-IM2 gave the product ions at m/z 289 (loss of C8H10O from m/z 411), m/z 209 (loss of HPO3 from m/z 289), and m/z 105 (loss of C8H8 from 209), which characterized the structural composition of TDMPP. The ionic products at m/z 209 (C8H8 + C8H9+ → C16H17+), m/z 207 (C8H8 + C8H9+ → C16H15+ + H2), m/z 194 (C8H8 + C7H6+ → C15H14+), m/z 192 (C8H8 + C7H6+ → C15H12+ + H2) and m/z 179 (C8H8 + C6H3+ → C14H11+) were derived from the reaction of C8H8 with C8H9+, C7H6+, and C6H3+. The constituent PBDMPP-IM2 was identified as TDMPP. 4. CR-504L CR-504L consisted mainly of diethylene glycol bis[di(2-chloroisopropyl) phosphate] (DEGBDCIPP) oligomers including dimer, trimer, tetramer, and pentamer, and seven impurities including tris(2-chloroisopropyl) phosphate (TCIPP). MS/MS fragment ions of the constituents in CR-504L are shown Table S6. Based on the fragment ions, the fragmentation behaviors were proposed as shown in Fig. S9. The constituents DEGBDCIPP-O4, DEGBDCIPP-O3, DEGBDCIPP-O2, and DEGBDCIPP-O1 respectively gave protonated molecules at m/z 1303, m/z 1059, m/z 815, and m/z 571. The presence of the product ions at m/z 1227 (loss of C3H5Cl from protonated molecule of DEGBDCIPP-O4), m/z 1151 (loss of C3H5Cl from m/z 1227), m/z 1053 (loss of H3PO4 from m/z 1151), m/z 983 (losses of C4H6O from m/z 1053 or C3H5Cl from protonated molecule of DEGBDCIPP-O3), m/z 907 (loss of C3H5Cl from m/z 983), m/z 809 (loss of H3PO4 from m/z 907), m/z 739 (losses of C4H6O from m/z 809 or C3H5Cl from protonated molecule of DEGBDCIPP-O2), m/z 663 (loss of C3H5Cl from m/z 739), m/z 565 (loss of H3PO4 from m/z 663), m/z 495 (losses of C4H6O from m/z 565 or C3H5Cl from protonated molecule of DEGBDCIPP-O1), m/z 419 (loss of C3H5Cl from m/z 495), m/z 321 (loss of H3PO4 from m/z 419), m/z 245 (loss of C3H5Cl from m/z 321), m/z 169 (loss of C3H5Cl from m/z 245), and m/z 125 (loss of C2H4O from m/z 169) were characteristic of the structural components of the oligomers DEG-BDCIPP. Results of this study of the fragmentation behaviors respectively identified DEGBDCIPP-O4, DEGBDCIPP-O3, DEGBDCIPP-O2, and DEGBDCIPP-O1 as a pentamer, tetramer, trimer, and dimer. Constituents DEGBDCIPP-IM1, DEGBDCIPP-IM2, and DEGBDCIPP-IM3 respectively showed protonated molecules at m/z 785, m/z 629, and m/z 601. MS/MS investigations gave losses of C9H17Cl2PO4, C6H11ClO, and C4H7ClO moieties, respectively, for protonated molecules of DEGBDCIPP-IM1, DEGBDCIPP-IM2, and DEGBDCIPP-IM3, respectively. The product ions were observed at m/z 495 (respective losses of C9H17Cl2PO4 and C6H11ClO moieties from protonated molecules of DEGBDCIPP-IM2 and DEGBDCIPP-IM3), m/z 419 (loss of C3H5Cl from m/z 495), m/z 321 (losses of H3PO4 from m/z 419 or C3H5Cl, H3PO4, and C4H7ClO moieties from protonated molecule of DEGBDCIPP-IM3), m/z 245 (loss of C3H5Cl from m/z 4
321), m/z 169 (loss of C3H5Cl from m/z 245), and m/z 125 (loss of C2H4O from m/z 169). The presence of the same ions as dimer indicated that the structures of DEGBDCIPP-IM1, DEGBDCIPP-IM2, and DEGBDCIPP-IM3 have a part of the skeleton of DEG-BDCIPP. The product ions at m/z 709 (loss of C3H5Cl from m/z 785), m/z 535 (loss of C3H8ClPO4 from m/z 709), and m/z 495 (loss of C3H4 from m/z 535) showed the structural composition of C9H17Cl2PO4 moiety in DEGBDCIPP-IM1. The presence of a part of the skeleton of DEGBDCIPP and the moieties of C9H17Cl2PO4, C6H11ClO, and C4H7ClO suggest that DEGBDCIPPIM1, DEGBDCIPP-IM2, and DEGBDCIPP-IM3 might be byproducts of DEG-BDCIPP. The constituent DEGBDCIPP-IM5 gave a protonated molecule at m/z 357. The MS/MS investigations gave the product ions at m/z 281 (loss of C3H5Cl from m/z 357) and m/z 205 (loss of C3H5Cl from m/z 281) followed by a loss of C4H7ClO moiety, which were characteristic for the proposed structural composition of DEGBDCIPP-IM5. The constituent DEGBDCIPP-IM5 might also be a byproduct of DEG-BDCIPP. MS/MS investigation of the constituent DEGBDCIPP-IM6 showed intense fragments at m/z 251, m/z 175, and m/z 99, corresponding to the loss of C3H5Cl, which were characteristic of the structure of TCIPP. The constituent DEGBDCIPP-IM6 was identified as TCIPP. Constituents DEGBDCIPP-IM4 and DEGBDCIPPIM7 gave protonated molecules at m/z 489 and m/z 245. The MS/MS investigations showed the product ions at m/z 413 (loss of C3H5Cl from protonated molecule of DEGBDCIPP-IM4), m/z 245 (loss of C4H9PO5 from m/z 413), m/z 169 (losses of C3H5Cl from m/z 245 or C3H5Cl from a protonated molecule of DEGBDCIPP-IM7), and m/z 125 (loss of C2H4O from m/z 169). It is noteworthy that the protonated molecules of DEGBDCIPP-IM4 and DEGBDCIPP-IM7 were also formed as the product ions of protonated molecules of trimer and dimer DEG-BDCIPP in their MS/MS spectra. Structures of DEGBDCIPP-IM4 and DEGBDCIPP-IM7 were estimated similarly to a part of the skeleton and losses of C3H5Cl and H3PO4 moieties of trimer and dimer DEG-BDCIPP. Additional NMR analysis must be done to elucidate those structures of DEGBDCIPP-IM4 and DEGBDCIPP-IM7. Results of fragmentation pathway MS/MS investigations suggest that the constituents DEGBDCIPP-IM1, DEGBDCIPP-IM2, DEGBDCIPP-IM3, DEGBDCIPP-IM4, DEGBDCIPP-IM5, DEGBDCIPP-IM6, and DEGBDCIPP-IM7 are impurities in CR-504L.
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Table S1. Precursor ion and collision voltage in MS/MS investigation. Constituent names are shown in Table 1. Flame retardant CR-733S 1,3-Phenylene bis(diphenyl phosphate) (PBDPP)
CR-741 Bisphenol A bis(diphenyl phosphate) (BPA-BDPP)
PX-200 1,3-Phenylene bis[di(2,6dimethylphenyl ) phosphate] (PBDMPP) CR-504L Diethylene glycol bis[di(2chloroisopropyl) phosphate] (DEG-BDCIPP)
Constituent name PBDPP-O4 PBDPP-O3 PBDPP-O2 PBDPP-IM1 PBDPP-O1 PBDPP-IM2 PBDPP-IM3 BPABDPP-O3 BPABDPP-O2 BPABDPP-IM1 BPABDPP-O1 BPABDPP-IM2 BPABDPP-IM3 PBDMPP-O2 PBDMPP-O1 PBDMPP-IM1 PBDMPP-IM2 DEGBDCIPP-O4 DEGBDCIPP-O3 DEGBDCIPP-O2 DEGBDCIPP-IM1 DEGBDCIPP-IM2 DEGBDCIPP-IM3 DEGBDCIPP-O1 DEGBDCIPP-IM4 DEGBDCIPP-IM5 DEGBDCIPP-IM6 DEGBDCIPP-IM7
Precursor ion m/z 1319.2 1071.1 823.1 591.1 575.1 343.1 327.1 1425.4 1059.3 827.3 693.2 461.2 327.1 963.3 687.2 399.1 411.2 1303.1 1059.1 815.1 785.0 629.1 601.0 571.0 489.1 357.0 327.0 245.0
6
Collision voltage (eV) 65 55 40 30 30 15 15 40 30 10 15 10 15 40 25 20 15 20 15 10 10 5 5 5 5 5 5 5
Table S2. CAS numbers and full names of major constituents in commercial PBDPP and BPA-BDPP reported in the previous study (Rossi and Heine, 2007). Chemical Commercial PBDPP 1,3-Phenylene bis(diphenyl phosphate) Phosphoric acid, bis[3-[(diphenoxyphosphinyl)oxy]phenyl] phenyl ester Triphenyl phosphate
Type Dimer Trimer Impurity
CAS no. 125997-21-9 57583-54-7 98165-92-5 115-86-6
Commercial BPA-BDPP Bisphenol A bis(diphenyl phosphate) Phosphoric acid, bis[4-[1-[4-[(diphenoxyphos-phinyl)oxy]phenyl]1-methylethyl]phenyl] phenyl ester Triphenyl phosphate
Dimer
181028-79-5 5945-33-5
Trimer
83029-72-5
Impurity
115-86-6
7
Table S3. MS/MS fragment ions of constituents in CR-733S. Constituent names are shown in Table 1. Constituent name PBDPP-O4
PBDPP-O3
PBDPP-O2
Observed m/z 1319.1697 1225.1275 1163.1695 1069.1306 977.1035 975.0870 915.1479 883.0607 821.1086 729.0820 727.0675 667.1246 653.0493 635.0414 591.0904 573.0849 481.0556 479.0429 231.0181 215.0252 1071.1477 977.1054 915.1494 883.0667 821.1077 729.0824 727.0678 667.1248 653.0498 635.0392 591.0944 573.0857 481.0589 479.0424 419.1021 343.0707 231.0203 215.0255 823.1248 729.0831 667.1272 653.0509 635.0403 591.0951 573.0850 481.0592 479.0433 419.1033 343.0724 231.0202 215.0255
Theoretical m/z 1319.1740 1225.1321 1163.1764 1069.1345 977.1083 975.0926 915.1525 883.0664 821.1107 729.0845 727.0688 667.1287 653.0532 635.0426 591.0974 573.0868 481.0606 479.0450 231.0211 215.0262 1071.1502 977.1083 915.1525 883.0664 821.1107 729.0845 727.0688 667.1287 653.0532 635.0426 591.0974 573.0868 481.0606 479.0450 419.1048 343.0735 231.0211 215.0262 823.1263 729.0845 667.1287 653.0532 635.0426 591.0974 573.0868 481.0606 479.0450 419.1048 343.0735 231.0211 215.0262
Error (ppm) -3.26 -3.75 -5.93 -3.65 -4.91 -5.74 -5.03 -6.45 -2.56 -3.43 -1.79 -6.15 -5.97 -1.89 -11.84 -3.32 -10.39 -4.38 -12.99 -4.65 -2.33 -2.97 -3.39 0.34 -3.65 -2.88 -1.38 -5.85 -5.21 -5.35 -5.08 -1.92 -3.53 -5.43 -6.44 -8.16 -3.46 -3.26 -1.82 -1.92 -2.25 -3.52 -3.62 -3.89 -3.14 -2.91 -3.55 -3.58 -3.21 -3.90 -3.26
8
Proposed formula C66H52O20P5 C60H46O19P5 C60H47O17P4 C54H41O16P4 C48H37O15P4 C48H35O15P4 C48H38O13P3 C42H31O14P4 C42H32O12P3 C36H28O11P3 C36H26O11P3 C36H29O9P2 C30H24O11P3 C30H22O10P3 C30H25O9P2 C30H23O8P2 C24H19O7P2 C24H17O7P2 C12H8O3P C12H8O2P C54H43O16P4 C48H37O15P4 C48H38O13P3 C42H31O14P4 C42H32O12P3 C36H28O11P3 C36H26O11P3 C36H29O9P2 C30H24O11P3 C30H22O10P3 C30H25O9P2 C30H23O8P2 C24H19O7P2 C24H17O7P2 C24H20O5P C18H16O5P C12H8O3P C12H8O2P C42H34O12P3 C36H28O11P3 C36H29O9P2 C30H24O11P3 C30H22O10P3 C30H25O9P2 C30H23O8P2 C24H19O7P2 C24H17O7P2 C24H20O5P C18H16O5P C12H8O3P C12H8O2P
Proposed neutral loss C6H6O C6H5O3P C12H11O4P C18H15O5P C18H17O5P C18H14O7P2 C24H21O6P C24H20O8P2 C30H24O9P2 C30H26O9P2 C30H23O11P3 C36H28O9P2 C36H30O10P2 C36H27O11P3 C36H29O12P3 C42H33O13P3 C42H35O13P3 C54H44O17P4 C54H44O18P4 C6H6O C6H5O3P C12H12O2 C12H11O4P C18H15O5P C18H17O5P C18H14O7P2 C24H19O5P C24H21O6P C24H18O7P2 C24H20O8P2 C30H24O9P2 C30H26O9P2 C30H23O11P3 C36H27O11P3 C42H35O13P3 C42H35O14P3 C6H6O C6H5O3P C12H10O C12H12O2 C12H9O3P C12H11O4P C18H15O5P C18H17O5P C18H14O7P2 C24H18O7P2 C30H26O9P2 C30H26O10P2
Table S3. (Continued) Constituent name PBDPP-IM1
PBDPP-O1
PBDPP-IM2
Observed m/z 591.0976 499.0705 481.0597 435.0991 419.1047 405.0286 387.0185 343.0726 325.0617 310.9867 307.0506 251.0467 231.0208 215.0255 169.0648 153.0694 141.0699 93.0339 77.0393 65.0397 575.1011 499.0690 481.0592 419.1037 405.0279 387.0173 343.0724 325.0618 310.9860 307.0516 251.0464 231.0204 226.0774 215.0255 169.0646 153.0696 141.0698 77.0393 343.0722 251.0458 249.0311 231.0202 169.0647 141.0699 93.0323 65.0389
Theoretical m/z 591.0974 499.0712 481.0606 435.0998 419.1048 405.0293 387.0187 343.0735 325.0630 310.9874 307.0524 251.0473 231.0211 215.0262 169.0653 153.0704 141.0704 93.034 77.0391 65.0391 575.1025 499.0712 481.0606 419.1048 405.0293 387.0187 343.0735 325.0630 310.9874 307.0524 251.0473 231.0211 226.0783 215.0262 169.0653 153.0704 141.0704 77.0391 343.0735 251.0473 249.0317 231.0211 169.0653 141.0704 93.034 65.0391
Error (ppm) 0.34 -1.40 -1.87 -1.61 -0.24 -1.73 -0.52 -2.62 -4.00 -2.25 -5.86 -2.39 -1.30 -3.26 -2.96 -6.53 -3.54 -1.07 2.60 9.23 -2.43 -4.41 -2.91 -2.62 -3.46 -3.62 -3.21 -3.69 -4.50 -2.61 -3.58 -3.03 -3.98 -3.26 -4.14 -5.23 -4.25 2.60 -3.79 -5.98 -2.41 -3.90 -3.55 -3.54 -18.27 -3.08
9
Proposed formula C30H25O9P2 C24H21O8P2 C24H19O7P2 C24H20O6P C24H20O5P C18H15O7P2 C18H13O6P2 C18H16O5P C18H14O4P C12H9O6P2 C18H12O3P C12H12O4P C12H8O3P C12H8O2P C12H9O C12H9 C11H9 C11H9 C6H5O C5H5 C30H25O8P2 C24H21O8P2 C24H19O7P2 C24H20O5P C18H15O7P2 C18H13O6P2 C18H16O5P C18H14O4P C12H9O6P2 C18H12O3P C12H12O4P C12H8O3P C18H10 C12H8O2P C12H9O C12H9 C11H9 C6H5 C18H16O5P C12H12O4P C12H10O4P C12H8O3P C12H9O C11H9 C6H5O C5H5
Proposed neutral loss C6H4O C6H6O2 C6H5O3P C6H5O4P C12H10O2 C12H12O3 C12H9O4P C12H11O5P C18H16O3 C12H13O6P C18H13O5P C18H17O6P C18H17O7P C18H16O8P2 C18H16O9P2 C19H16O9P2 C24H20O8P2 C24H20O9P2 C25H20O9P2 C6H4 C6H6O C6H5O3P C12H10O C12H12O2 C12H9O3P C12H11O4P C18H16O2 C12H13O5P C18H13O4P C18H17O5P C12H15O8P2 C18H17O6P C18H16O7P2 C18H16O8P2 C19H16O8P2 C24H20O8P2 C6H4O C6H6O C6H8O2 C6H7O4P C7H7O5P C12H11O4P C13H11O5P
Table S3. (Continued) Constituent name PBDPP-IM3
Observed m/z 327.0777 251.0462 233.0359 229.1006 228.0930 215.0255 153.0698 152.0617 77.0394
Theoretical m/z 327.0786 251.0473 233.0368 229.1017 228.0939 215.0262 153.0704 152.0626 77.0391
Error (ppm) -2.75 -4.38 -3.86 -4.80 -3.95 -3.26 -3.92 -5.92 3.89
10
Proposed formula C18H16O4P C12H12O4P C12H10O3P C18H13 C18H12 C12H8O2P C12H9 C12H8 C6H5
Proposed neutral loss C6H4 C6H6O H3O4P H4O4P C6H8O2 C6H7O4P C6H8O4P C12H11O4P
Table S4. MS/MS fragment ions of constituents in CR-741. Constituent names are shown in Table 1. Constituent name BPABDPP-O3
BPABDPP-O2
BPABDPP-IM1
BPABDPP-O1
BPABDPP-IM2
BPABDPP-IM3
Observed m/z 1425.3794 1099.3100 1059.2812 733.2087 693.1777 407.1379 367.1091 1059.2819 733.2105 693.1782 407.1396 367.1089 827.2498 733.2100 693.1783 693.1795 367.1087 327.0777 461.1497 367.1075 327.0766 135.0802 107.0489 327.0776 251.0460 233.0363 229.0993 228.0929 215.0255 153.0696 152.0612 77.0392
Theoretical m/z 1425.3849 1099.3141 1059.2828 733.2120 693.1807 407.1412 367.1099 1059.2828 733.2120 693.1807 407.1412 367.1099 827.2539 733.2120 693.1807 693.1807 367.1099 327.0786 461.1518 367.1099 327.0786 135.0810 107.0497 327.0786 251.0473 233.0368 229.1017 228.0939 215.0262 153.0704 152.0626 77.0391
Error (ppm) -3.86 -3.73 -1.51 -4.50 -4.33 -8.11 -2.18 -0.85 -2.05 -3.61 -3.93 -2.72 -4.96 -2.73 -3.46 -1.73 -3.27 -2.75 -4.55 -6.54 -6.11 -5.92 -7.47 -3.06 -5.18 -2.15 -10.48 -4.38 -3.26 -5.23 -9.21 1.30
11
Proposed formula C81H73O16P4 C63H58O12P3 C60H54O12P3 C42H39O8P2 C39H35O8P2 C24H24O4P C21H20O4P C60H54O12P3 C42H39O8P2 C39H35O8P2 C24H24O4P C21H20O4P C48H45O9P2 C42H39O8P2 C39H35O8P2 C39H35O8P2 C21H20O4P C18H16O4P C27H26O5P C21H20O4P C18H16O4P C9H11O C7H7O C18H16O4P C12H12O4P C12H10O3P C18H13 C18H12 C12H8O2P C12H9 C12H8 C6H5
Proposed neutral loss C18H15O4P C21H19O4P C39H34O8P2 C42H38O8P2 C57H49O12P3 C60H53O12P3 C18H15O4P C21H19O4P C36H30O8P2 C39H34O8P2 C6H6O C9H10O C18H15O4P C21H19O4P C6H6O C9H10O C18H15O4P C20H19O4P C6H4 C6H6O H 3O 4P H 4O 4P C6H8O2 C6H7O4P C6H8O4P C12H11O4P
Table S5. MS/MS fragment ions of constituents in PX-200. Component names are shown in Table 1. Constituent name PBDMPP-O2
PBDMPP-O1
PBDMPP-IM1
PBDMPP-IM2
Observed m/z 963.2816 857.2014 841.2069 779.2517 737.1455 675.1890 503.1962 399.1357 209.1311 194.1090 179.0851 105.0701 79.0546 687.2266 581.1479 565.1529 503.1976 194.1090 179.0855 105.0699 79.0549 399.1348 293.0570 277.0627 195.0802 194.1081 182.0719 179.0852 105.0700 103.0547 79.0549 77.0388 411.1713 305.0924 289.0984 209.1319 207.1163 194.1090 192.0926 179.0855 105.0701 103.0544 79.0547 77.0392
Theoretical m/z 963.2828 857.2046 841.2097 779.2539 737.1471 675.1913 503.1987 399.1361 209.1330 194.1096 179.0861 105.0704 79.0548 687.2277 581.1494 565.1545 503.1987 194.1096 179.0861 105.0704 79.0548 399.1361 293.0579 277.0630 195.0810 194.1096 182.0732 179.0861 105.0704 103.0548 79.0548 77.0391 411.1725 305.0943 289.0994 209.1330 207.1174 194.1096 192.0939 179.0861 105.0704 103.0548 79.0548 77.0391
Error (ppm) -1.25 -3.73 -3.33 -2.82 -2.17 -3.41 -4.97 -1.00 -9.09 -3.09 -5.58 -2.86 -2.53 -1.60 -2.58 -2.83 -2.19 -3.09 -3.35 -4.76 1.26 -3.26 -3.07 -1.08 -4.10 -7.73 -7.14 -5.03 -3.81 -0.97 1.26 -3.89 -2.92 -6.23 -3.46 -5.26 -5.31 -3.09 -6.77 -3.35 -2.86 -3.88 -1.26 1.30
12
Proposed formula C52H54O12P3 C44H44O12P3 C44H44O11P3 C44H45O9P2 C36H36O11P3 C36H37O9P2 C30H32O5P C22H24O5P C16H17 C15H14 C14H11 C8H9 C6H7 C38H41O8P2 C30H31O8P2 C30H31O7P2 C30H32O5P C15H14 C14H11 C8H9 C6H7 C22H24O5P C14H14O5P C14H14O4P C14H11O C15H14 C13H10O C14H11 C8H9 C8H7 C6H7 C6H5 C24H28O4P C16H18O4P C16H18O3P C16H17 C16H15 C15H14 C15H12 C14H11 C8H9 C8H7 C6H7 C6H5
Proposed neutral loss C8H10 C8H10O C8H9O3P C16H18O C16H17O3P C22H22O7P2 C30H30O7P2 C36H37O12P3 C37H40O12P3 C38H43O12P3 C44H45O12P3 C46H47O12P3 C8H10 C8H10O C8H9O3P C23H27O8P2 C24H30O8P2 C30H32O8P2 C32H34O8P2 C8H10 C8H10O C8H13O4P C7H10O5P C9H14O4P C8H13O5P C14H15O5P C14H17O5P C16H17O5P C16H19O5P C8H10 C8H10O C8H11O4P C8H13O4P C9H14O4P C9H16O4P C10H17O4P C16H19O4P C16H21O4P C18H21O4P C18H23O4P
Table S6. MS/MS fragment ions of constituents in CR-504L. Component names are shown in Table 1. Constituent name DEGBDCIPP-O4
DEGBDCIPP-O3
DEGBDCIPP-O2
Observed m/z 1303.1139 1227.1061 1151.0961 1053.1224 983.0889 977.1068 809.0906 739.0477 733.0859 657.0735 565.0625 489.0613 321.0417 245.0313 239.0662 169.0243 124.9994 1059.0873 983.0781 907.0650 809.0942 739.0496 733.0843 565.0671 489.0593 413.0504 321.0415 245.0330 239.0672 169.0257 124.9996 815.0607 739.0524 663.0437 565.0665 489.0585 321.0410 245.0330 169.0258 124.9996
Theoretical m/z 1303.1156 1227.1076 1151.0997 1053.1228 983.0809 977.1148 809.0960 739.0542 733.0880 657.0801 565.0693 489.0613 321.0425 245.0346 239.0685 169.0266 125.0004 1059.0889 983.0809 907.0729 809.0960 739.0542 733.0880 565.0693 489.0613 413.0533 321.0425 245.0346 239.0685 169.0266 125.0004 815.0621 739.0542 663.0462 565.0693 489.0613 321.0425 245.0346 169.0266 125.0004
Error (ppm) -1.30 -1.22 -3.13 -0.38 8.14 -8.19 -6.67 -8.80 -2.86 -10.04 -12.03 0.00 -2.49 -13.47 -9.62 -13.61 -8.00 -1.51 -2.85 -8.71 -2.22 -6.22 -5.05 -3.89 -4.09 -7.02 -3.11 -6.53 -5.44 -5.32 -6.40 -1.72 -2.44 -3.77 -4.96 -5.73 -4.67 -6.53 -4.73 -6.40
13
Proposed formula C37H75Cl7O24P5 C34H70Cl6O24P5 C31H65Cl5O24P5 C31H62Cl5O20P4 C27H56Cl5O19P4 C28H57Cl4O20P4 C24H48Cl4O15P3 C20H42Cl4O14P3 C21H43Cl3O15P3 C18H38Cl2O15P3 C17H34Cl3O10P2 C14H29Cl2O10P2 C10H20Cl2O5P C7H15ClO5P C8H16O6P C4H10O5P C2H6O4P C30H61Cl6O19P4 C27H56Cl5O19P4 C24H51Cl4O19P4 C24H48Cl4O15P3 C20H42Cl4O14P3 C21H43Cl3O15P3 C17H34Cl3O10P2 C14H29Cl2O10P2 C11H24ClO10P2 C10H20Cl2O5P C7H15ClO5P C8H16O6P C4H10O5P C2H6O4P C23H47Cl5O14P3 C20H42Cl4O14P3 C17H37Cl3O14P3 C17H34Cl3O10P2 C14H29Cl2O10P2 C10H20Cl2O5P C7H15ClO5P C4H10O5P C2H6O4P
Proposed neutral loss C3H5Cl C6H10Cl2 C6H13Cl2O4P C10H19Cl2O5P C9H18Cl3O4P C13H27Cl3O9P2 C17H33Cl3O10P2 C16H32Cl4O9P2 C19H37Cl5O9P2 C20H41Cl4O14P3 C23H46Cl5O14P3 C27H55Cl5O19P4 C30H60Cl6O19P4 C29H59Cl7O18P4 C33H65Cl7O19P4 C35H69Cl7O20P4 C3H5Cl C6H10Cl2 C6H13Cl2O4P C10H19Cl2O5P C9H18Cl3O4P C13H27Cl3O9P2 C16H32Cl4O9P2 C19H37Cl5O9P2 C20H41Cl4O14P3 C23H46Cl5O14P3 C22H45Cl6O13P3 C26H51Cl6O14P3 C28H55Cl6O15P3 C3H5Cl C6H10Cl2 C6H13Cl2O4P C9H18Cl3O4P C13H27Cl3O9P2 C16H32Cl4O9P2 C19H37Cl5O9P2 C21H41Cl5O10P2
Table S6. (Continued) Constituent name DEGBDCIPP-IM1
DEGBDCIPP-IM2
DEGBDCIPP-IM3
DEGBDCIPP-O1
DEGBDCIPP-IM4
Observed m/z 785.0502 709.0436 535.0573 495.0246 459.0477 383.0405 321.0413 291.0310 245.0328 215.0228 209.0549 169.0253 139.0156 125.0004 629.0756 495.0251 419.0192 343.0069 267.0030 245.0359 169.0254 125.0006 601.0448 525.0363 449.0264 321.0407 275.0417 245.0337 169.0264 124.9992 571.0343 495.0259 419.0177 321.0415 245.0339 169.0259 124.9997 489.0595 413.0522 245.0339 169.0260 124.9994
Theoretical m/z 785.0516 709.0436 535.0587 495.0274 459.0507 383.0428 321.0425 291.0320 245.0346 215.0240 209.0579 169.0266 139.0160 125.0004 629.0773 495.0274 419.0194 343.0115 267.0035 245.0346 169.0266 125.0004 601.0460 525.0380 449.0300 321.0425 275.0451 245.0346 169.0266 125.0004 571.0354 495.0274 419.0194 321.0425 245.0346 169.0266 125.0004 489.0613 413.0533 245.0346 169.0266 125.0004
Error (ppm) -1.78 0.00 -2.62 -5.66 -6.54 -6.00 -3.74 -3.44 -7.35 -5.58 -14.35 -7.69 -2.88 0.00 -2.70 -4.65 -0.48 -13.41 -1.87 5.31 -7.10 1.60 -2.00 -3.24 -8.02 -5.61 -12.36 -3.67 -1.18 -9.60 -1.93 -3.03 -4.06 -3.11 -2.86 -4.14 -5.60 -3.68 -2.66 -2.86 -3.55 -8.00
14
Proposed formula C22H45Cl5O13P3 C19H40Cl4O13P3 C16H32Cl3O9P2 C13H28Cl3O9P2 C13H27Cl2O9P2 C10H22ClO9P2 C10H20Cl2O5P C9H18Cl2O4P C7H15ClO5P C6H13ClO4P C7H14O5P C4H10O5P C3H8O4P C2H6O4P C19H39Cl4O10P2 C13H28Cl3O9P2 C10H23Cl2O9P2 C7H18ClO9P2 C4H13O9P2 C7H15ClO5P C4H10O5P C2H6O4P C17H35Cl4O10P2 C14H30Cl3O10P2 C11H25Cl2O10P2 C10H20Cl2O5P C8H17ClO6P C7H15ClO5P C4H10O5P C2H6O4P C16H33Cl4O9P2 C13H28Cl3O9P2 C10H23Cl2O9P2 C10H20Cl2O5P C7H15ClO5P C4H10O5P C2H6O4P C14H29Cl2O10P2 C11H24ClO10P2 C7H15ClO5P C4H10O5P C2H6O4P
Proposed neutral loss C3H5Cl C6H13Cl2O4P C9H17Cl2O4P C9H18Cl3O4P C12H23Cl4O4P C12H25Cl3O8P2 C13H27Cl3O9P2 C15H30Cl4O8P2 C16H32Cl4O9P2 C15H31Cl5O8P2 C18H35Cl5O8P2 C19H37Cl5O9P2 C20H39Cl5O9P2 C6H11ClO C9H16Cl2O C12H21Cl3O C15H26Cl4O C12H24Cl3O5P C15H29Cl4O5P C17H33Cl4O6P C3H5Cl C6H10Cl2 C7H15Cl2O5P C9H18Cl3O4P C10H20Cl3O5P C13H25Cl4O5P C15H29Cl4O6P C3H5Cl C6H10Cl2 C6H13Cl2O4P C9H18Cl3O4P C12H23Cl4O4P C14H27Cl4O5P C3H5Cl C7H14ClO5P C10H19Cl2O5P C12H23Cl2O6P
Table S6. (Continued) Constituent name DEGBDCIPP-IM5
DEGBDCIPP-IM6
DEGBDCIPP-IM7
Observed m/z 357.0179 281.0098 205.0021 174.9915 107.0260 98.9844 63.0001 327.0070 250.9995 174.9920 98.9844 245.0329 169.0257 124.9993
Theoretical m/z 357.0192 281.0112 205.0033 174.9927 107.0264 98.9847 63.0002 327.0087 251.0007 174.9927 98.9847 245.0346 169.0266 125.0004
Error (ppm) -3.64 -4.98 -5.85 -6.86 -3.74 -3.03 -1.59 -5.20 -4.78 -4.00 -3.03 -6.94 -5.32 -8.80
15
Proposed formula C10H21Cl3O5P C7H16Cl2O5P C4H11ClO5P C3H9ClO4P C4H8ClO H 4O 4P C2H4Cl C9H19Cl3O4P C6H14Cl2O4P C3H9ClO4P H 4O 4P C7H15ClO5P C4H10O5P C2H6O4P
Proposed neutral loss C3H5Cl C6H10Cl2 C7H12Cl2O C6H13Cl2O4P C10H17Cl3O C8H17Cl2O5P C3H5Cl C6H10Cl2 C9H15Cl3 C3H5Cl C5H9ClO
Figure S1. Total and extracted ion chromatograms of constituents in CR-733S using atmospheric pressure photoionization-quadrupole time-of-flight mass spectrometry compatible with gel permeation chromatography. Constituent names are shown in Table 1. Intensity 3236908
TIC
0 14912
m/z 1319.1740
0 109688
m/z 1071.1502
0 527635
m/z 823.1263
0 4937
m/z 591.0974
PBDPP-IM1
0 1693059
m/z 575.1025
PBDPP-O1
PBDPP-O4
PBDPP-O3
PBDPP-O2
0 m/z 343.0735
PBDPP-IM2
4485 0 17077
m/z 327.0786
PBDPP-IM3
0 0
2
4
6
8
10
Retention time (min)
16
Figure S2. Total and extracted ion chromatogram of constituents in CR-741 by an atmospheric pressure photoionization-quadrupole time-of-flight mass spectrometry compatible with gel permeation chromatography. Constituent names are shown in Table 1. Intensity TIC
4727066
0 7652
m/z 1425.3849
0 226768
m/z 1059.2828
BPABDPP-O3
BPABDPP-O2
0 2327
m/z 827.2539
BPABDPP-IM1
0 2252911
m/z 693.1807
BPABDPP-O1
0 10962
m/z 461.1518
0 10506
m/z 327.0786
BPABDPP-IM2
BPABDPP-IM3
0 0
2
4
6
8
10
Retention time (min)
17
Figure S3. Total and extracted ion chromatogram of constituents in PX-200 by an atmospheric pressure photoionization-quadrupole time-of-flight mass spectrometry compatible with gel permeation chromatography. Constituent names are shown in Table 1. Intensity 4993753
TIC
0 10121
m/z 963.2828
0 2422997
m/z 687.2277
PBDMPP-O2
PBDMPP-O1
0 m/z 399.1361
PBDMPP-IM1
m/z 411.1725
PBDMPP-IM2
18424 0 17933 0 0
2
4
6
8
10
Retention time (min)
18
Figure S4. Total and extracted ion chromatogram of constituents in CR-504L by an atmospheric pressure photoionization-quadrupole time-of-flight mass spectrometry compatible with gel permeation chromatography. Constituent names are shown in Table 1. Intensity TIC
2820360
0 7212
m/z 1303.1156
DEGBDCIPP-O4
0 49810
m/z 1059.0889
DEGBDCIPP-O3
0 197425
m/z 815.0621
DEGBDCIPP-O2
0 6507
m/z 785.0516
DEGBDCIPP-IM1
0 2168
m/z 629.0773
0 3360
m/z 601.0460
DEGBDCIPP-IM3
0 696472
m/z 571.0354
DEGBDCIPP-O1
0 2346
m/z 489.0613
DEGBDCIPP-IM4
0 5255
m/z 357.0192
DEGBDCIPP-IM5
0 7374
m/z 327.0087
DEGBDCIPP-IM2
DEGBDCIPP-IM6
0 m/z 245.0346
DEGBDCIPP-IM7
3947 0 0
2
4
6
8
10
Retention time (min)
19
Figure S5. Chromatograms of (a) CR-733S, (b) CR-741, (c) PX-200, and (d) CR-504L by a refractive index detector compatible with gel permeation chromatography. Constituent names are shown in Table 1. 100000
a) CR-733S
150000
CR-733S_RI - CH2
PBDPP-O12
PX-200_RI - CH2
c) PX-200
PBDMPP-O1
Intensity [µV]
Intensity [µV]
100000
50000
PBDPP-O2 PBDPP-IM2
PBDPP-O3
PBDPP-IM1 PBDMPP-O2
PBDMPP-IM2
0
0
6.0
150000
50000
PBDPP-IM3
PBDPP-O4
6.2
6.4
6.6
6.8 7.0 7.2 Retention Time [min]
7.4
7.6
7.8
6.0
CR-741_RI - CH2
b) CR-741 BPABDPP-O1
6.2
6.4
6.6
6.8 7.0 7.2 Retention Time [min]
7.4
7.6
7.8
CR-504L_RI - CH2
d) CR-504L DEGBDCIPP-O1 30000
50000
Intensity [µV]
Intensity [µV]
100000
BPABDPP-O2
20000
DEGBDCIPP-O2 DEGBDCIPP-O3
10000
BPABDPP-O3
BPABDPP-IM3
DEGBDCIPP-IM6
DEGBDCIPP-O4 0
0
6.0
6.2
6.4
6.6
6.8 7.0 7.2 Retention Time [min]
7.4
7.6
7.8
6.0
6.2
20
6.4
6.6
6.8 7.0 7.2 Retention Time [min]
7.4
7.6
7.8
Figure S6. Proposed fragmentation pathways of constituents in CR-733S. Constituent names are shown in Table 1. -H2 O
m/z 1225
-HPO3
m/z 1163
PBDPP-O4 -C6 H4 m/z 1243 [M+H]+ = 1319
-C6 H4
-C6 H4
PBDPP-O3 -C6 H4 [M+H]+ = 1071
m/z 1149
-HPO3
m/z 1087
-H2 O
m/z 1069 -C6 H4 O -H2 O
-H2 O
m/z 977
-HPO3
m/z 915
-C6 H4 PBDPP-IM3 (TPHP) [M+H]+ = 327 -H3 PO4
m/z 251
m/z 229
-C6 H4
m/z 233
m/z 228
-H2 O
-HPO3 -C6 H4 m/z 153
H
m/z 901
-C6 H4
-C6 H4
-H2 O
m/z 839
-C6 H4 O
-H2 O
m/z 729
-HPO3
m/z 667
m/z 635
-H2 O
-C6 H4
m/z 653
m/z 747 -C6 H4
m/z 591
m/z 215
-H2 O PBDPP-O1 (PBDPP) -C6 H4 [M+H]+ = 575
-HPO3 m/z 573 -H2 O
m/z 481
-HPO3
m/z 419
H -C6 H4
-C6 H4 O PBDPP-IM1 (HP-PHP-HP-DPHP) [M+H]+ = 591
m/z 499
-C6H5 PO3
m/z 435
-HPO3
-C6 H4 O
m/z 481
m/z 419
-C6 H4
m/z 387
-C6 H4
m/z 405
m/z 343
-HPO3 m/z 325
-C6H4 O
m/z 251
-H2 O
-CO
m/z 311
m/z 307 -H2 O
m/z 215
-HPO3
m/z 153
m/z 233
m/z 141
-C6 H4
m/z 65
m/z 231 m/z 141
-HPO3 -C6 H4
m/z 93
m/z 151 m/z 65
m/z 169 -C6 H4
m/z 405
-C6 H4
m/z 343
m/z 251
m/z 169
m/z 251
-C6H7 PO4
-H2O
-H2O
-CO
-C6 H7 PO4
m/z 249
-C6 H4
-H2 O
-C6 H4 -C6 H6 O
-H2 O
-C6 H4
m/z 387
-HPO3 m/z 325 -H2 O
m/z 93
21
-C6 H4
m/z 77
-H2 O
-C6 H4
-H2 O
m/z 311
m/z 307
-H2 PO3
m/z 226
-C6 H4 O
-C6 H4 O
m/z 152
-H2 O
-C6 H4 O
m/z 499
m/z 77
-H2 O
PBDPP-IM2 (HP-DPHP) [M+H]+ = 343
m/z 883 -HPO3 m/z 821
m/z 995
PBDPP-O2 [M+H]+ = 823
-H2 O
-C6 H4
-H2 O
m/z 215
-HPO3
m/z 153
m/z 233 -C6 H4
m/z 77
Figure S7. Proposed fragmentation pathways of constituents in CR-741. Constituent names are shown in Table 1. BPABDPP-O3 - C18 H15 PO4 m/z 1099 -C3 H4 m/z 1059 [M+H]+ = 1425 - C18 H15 PO4
- C6 H4
BPABDPP-O2 - C18 H15 PO4 m/z 733 [M+H]+ = 1059
-C3 H4
-H2 O
m/z 809
m/z 693
- C18 H15 PO4
- C6 H4
BPABDPP-O1 (BPA-BDPP) - C18H15 PO4 m/z 367 [M+H]+ = 693 - C18 H15 PO4 m/z 135
-C6 H4
m/z 251
BPABDPP-IM3 (TPHP) [M+H]+ = 327 -H3 PO4
m/z 229
-H2 O
-C6 H4
H m/z 228
m/z 233
-H2 O
-HPO3 -C6 H4 m/z 153
BPABDPP-IM1 (BPA-PHP-BPA-DPHP) [M+H]+ = 827
-C3 H4
-C3 H4
m/z 443
-H2 O
BPABDPP-IM2 (BPA-DPHP) [M+H]+ = 461
m/z 327
m/z 107
m/z 215
m/z 77
H -C6 H4
m/z 152
22
Figure S8. Proposed fragmentation pathways of constituents in PX-200. Constituent names are shown in Table 1. -C8 H10
m/z 857
-C8 H10 O
PBDMPP-O2 [M+H]+ = 963
-C8 H9 PO3
-C8 H10 O
-C8 H10 O -C6 H6 O2 -HPO3
m/z 305
PBDMPP-IM2 (TDMPP) [M+H]+ = 411 m/z 289
-C6 H4 O -HPO3
m/z 565
-C8 H10
-C8 H10
m/z 675
m/z 581
-C8 H9 PO3
PBDMPP-IM1 (HP-DDMPP) [M+H]+ = 399
m/z 737
-C8 H8
m/z 779
-C8 H10
PBDMPP-O1 (PBDMPP) [M+H]+ = 687
-C8 H8
m/z 841
m/z 503
m/z 293
m/z 277
- H3 PO4
- HPO3
-C8 H8
m/z 399
m/z 195
m/z 197
-C6 H6 O2 -HPO3
-C6 H4 O
-CH3
m/z 209
m/z 103
-C2 H2
-CH3
m/z 194
-CH3
m/z 179
m/z 77
m/z 182 -C6 H4 O
m/z 209
- H3 PO4
- HPO3
-CH3
m/z 207
m/z 209
-CH3
-CH3
m/z 194
-CH3
m/z 192
m/z 194
-CH3
-CH3
m/z 179
-C6 H2
m/z 177
m/z 179
-C6 H2
-C6 H2
m/z 105
-C2 H2
m/z 103
m/z 105
-C2 H2
-C2 H2
m/z 79
m/z 77
m/z 79
-C8 H10 O
23
-C6 H2
m/z 105
-C2 H2
m/z 79
Figure S9. Proposed fragmentation pathways of constituents in CR-504L. Constituent names are shown in Table 1. DEGBDCIPP-O4 -C3 H5 Cl -C3 H5 Cl m/z 1227 m/z 1151 [M+H]+ = 1303 -H3 PO4 -C3 H5 Cl m/z 1053 m/z 977 -C4 H6 O DEGBDCIPP-O3 -C3 H5 Cl -C3 H5 Cl m/z 907 m/z 983 [M+H]+ = 1059 DEGBDCIPP-IM4 -H3 PO4 [M+H]+ = 489 -C3 H5 Cl -C3 H5 Cl m/z 809 m/z 733 m/z 657 -C3 H5 Cl -C4 H6 O -C4 H6 O -C3 H5 Cl DEGBDCIPP-O2 -C3 H5 Cl DEGBDCIPP-IM7 m/z 739 m/z 663 [M+H]+ = 815 [M+H]+ = 245 -H3 PO4 -C H Cl -C H Cl -C3 H5 Cl m/z 565 3 5 m/z 489 3 5 m/z 413 -C4 H6 O -C4 H6 O -C4 H6 O DEGBDCIPP-O1 (DEG-BDCIPP) -C3 H5 Cl -C H Cl -C H Cl m/z 495 3 5 m/z 419 3 5 m/z 343 [M+H]+ = 571 -H3 PO4 -H3 PO4 -C2 H4 O -C H Cl -C H Cl m/z 321 3 5 m/z 245 3 5 m/z 169 m/z 125 -C4 H10 ClPO5 -C4 H10 ClPO5 -C4 H7 ClO -C3H 8ClPO4 DEGBDCIPP-IM3 -C3 H5 Cl -C H Cl m/z 525 3 5 m/z 449 m/z 275 [M+H]+ = 601
DEGBDCIPP-IM2 -C6 H11 ClO [M+H]+ = 629 -C3 H4 -C3H 8ClPO4 -C3H 8ClPO4 DEGBDCIPP-IM1 -C3 H5 Cl -C H Cl -C H Cl m/z 709 m/z 535 3 5 m/z 459 3 5 m/z 383 m/z 209 [M+H]+ = 785 -C4 H9 PO5 -C4 H9 PO5 -C4 H6 O -C H Cl -C H Cl m/z 291 3 5 m/z 215 3 5 m/z 139
DEGBDCIPP-IM6 (TCIPP) -C3 H5 Cl -C H Cl -C H Cl m/z 99 m/z 251 3 5 m/z 175 3 5 [M+H]+ = 327 -C4 H7 ClO
-C4 H7 ClO
DEGBDCIPP-IM5 -C3 H5 Cl -H3 PO4 -C H Cl -C2 H4 O m/z 107 m/z 281 3 5 m/z 205 m/z 63 [M+H]+ = 357
24
Compositional analysis of commercial oligomeric organophosphorus flame retardants used as alternatives for PBDEs: Concentrations and potential environmental emissions of oligomers and impurities
Hidenori Matsukami,*,†,‡ Go Suzuki,† Hidetaka Takigami†,‡
†
Center for Material Cycles and Waste Management Research, National Institute for Environmental Studies (NIES), 16-2 Onogawa, Tsukuba 305-8506, Japan
‡
Graduate School of Frontier Sciences, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa 277-8563, Japan
Number of pages: 24 Number of tables: 6 Number of figures: 9
1
Detailed information for the identification of oligomers and impurities based on the study of their fragmentation behaviors 1. CR-733S CR-733S consisted mainly of 1,3-phenylene bis(diphenyl phosphate) (PBDPP) oligomers including dimer, trimer, tetramer, and pentamer, and three impurities including triphenyl phosphate (TPHP). MS/MS fragment ions of the constituents in CR-733S are presented in Table S3. Based on fragment ions, the fragmentation behaviors are proposed as shown in Fig. S6. The constituents PBDPP-O4, PBDPP-O3, PBDPP-O2, and PBDPP-O1 in the MS investigation respectively gave protonated molecule ions at m/z 1319, m/z 1071, m/z 823, and m/z 575. The presence of the product ions at m/z 1225 (losses of C6H4 and H2O from protonated molecule of PBDPP-O4), m/z 1069 (losses of C6H4 and HPO3 from m/z 1225), m/z 977 (losses of C6H4O from m/z 1069 or C6H4 and H2O from protonated molecule of PBDPP-O3), m/z 821 (losses of C6H4 and HPO3 from m/z 977), m/z 729 (losses of C4H6O from m/z 821 or C6H4 and H2O from protonated molecule of PBDPP-O2), m/z 573 (losses of C6H4 and HPO3 from m/z 653), m/z 481 (losses of C4H6O from m/z 573 or C6H4 and H2O from protonated molecule of PBDPP-O1), m/z 325 (losses of C6H4 and HPO3 from m/z 809), m/z 233 (loss of C4H6O from m/z 325), m/z 153 (loss of HPO3 from m/z 233), and m/z 77 (loss C6H4 from m/z 153) showed the structural compositions of the oligomers of PBDPP. Four oligomers, dimer to pentamer, were identified from the elemental compositions of protonated molecule and fragment ions using accurate mass measurements. The constituent PBDPP-IM1 gave a protonated molecule at m/z 591. The product ions of protonated molecules of R4 at m/z 499, m/z 481, m/z 419, m/z 405, m/z 387, m/z 343, m/z 325, m/z 311, m/z 307, m/z 251, m/z 233, m/z 215, m/z 153, and m/z 77 were identical to the product ions of the skeletons of the oligomers PBDPP. The product ion at m/z 343 further fragmented to give the product ions at m/z 169 (loss of C6H7PO4 from m/z 343), m/z 141 (loss of CO from m/z 169), m/z 93 (loss of C6H4 from m/z 169), and m/z 65 (loss C6H4 from m/z 141) supported the structural components of PBDPP-IM1. The constituent PBDPP-IM2 gave a protonated molecule at m/z 343. The MS/MS investigations gave the product ion at m/z 251 (loss of C6H4O), m/z 249 (losses of C6H6O), and m/z 169 (loss of C6H7PO4) from a protonated molecule of PBDPP-IM2. The product ion at m/z 249 further fragmented to give product ions at m/z 231 (loss of H2O from m/z 249) and m/z 151 (loss of HPO3 from m/z 231). The product ion at m/z 169 further fragmented to give product ions at m/z 141 (loss of CO from m/z 169), m/z 93 (loss of C6H4 from m/z 169), and m/z 65 (loss C6H4 from m/z 141), supporting the structural components of PBDPP-IM2. Structures of the two impurities PBDPP-IM1 and PBDPP-IM2 were characterized as a part of the skeleton and a loss of diphenyl phosphate moiety of trimer and dimer PBDPP. Therefore, the constituents PBDPP-IM1 and PBDPP-IM2 were estimated, respectively, to be phosphoric acid, [3-[(diphenoxyphosphinyl)oxy]phenyl] 3-hydroxyphenyl phenyl ester (HPPHP-HP-DPHP) for PBDPP-IM1 and 3-hydroxyphenyl diphenyl phosphate (HP-DPHP) for PBDPP-IM2. The constituent PBDPP-IM3 in MS investigation gave a protonated molecule ion at m/z 327. The product ions of the protonated molecule at m/z 251 (loss of C6H4 from m/z 327), m/z 233 (loss of H2O from m/z 251), m/z 153 (loss of HPO3 from m/z 233), and m/z 77 (loss of C6H4 from m/z 153) were characteristic for the structure of TPHP. In addition, the ionic products from the reaction of C6H4 with C6H5+ were observed at m/z 229 (C6H4 + C6H4 + C6H5+ → C18H13+), m/z 228 (C6H4 + C6H4 + C6H5+ → C18H12+ + H), m/z 153 (C6H4 + C6H5+ → C12H9+), and m/z 152 (C6H4 + C6H5+ → C12H8+ + H). 2
2. CR-741 CR-741 consisted mainly of bisphenol A bis(diphenyl phosphate) (BPA-BDPP) oligomers including dimer, trimer, and tetramer, and three impurities including TPHP. MS/MS fragment ions of the constituents in CR-741 are shown Table S4. Based on the fragment ions, the fragmentation behaviors were proposed as shown in Fig. S7. Results of MS and MS/MS investigations indicated that CR-741 was composed of three oligomers including BPA-BDPP dimer to tetramer. The constituents BPABDPP-O3, BPABDPPO2, and BPABDPP-O1 in MS investigation respectively gave protonated molecules at m/z 1425, m/z 1059, and m/z 693. When fragmented in the MS/MS investigation, these protonated molecules yielded a series of prominent ions deriving from the successive losses of C18H15PO4 or C3H4. The product ions at m/z 1099 (loss of C18H15PO4 from protonated molecule of BPABDPPO3), m/z 1059 (loss of C3H4 from m/z 1099), m/z 733 (losses of C18H15PO4 from m/z 1059 or protonated molecule of BPABDPP-O2), m/z 693 (loss of C3H4 from m/z 733), m/z 367 (losses of C18H15PO4 from m/z 693 or protonated molecule of BPABDPP-O1), m/z 327 (loss of C3H4 from m/z 367), m/z 135 (loss of C18H15PO4 from m/z 367), and m/z 107 (loss C3H4 from m/z 135) were characteristic for the proposed structural components of oligomers. Results in this study of the fragmentation behaviors indicated that BPABDPP-O3, BPABDPP-O2, and BPABDPP-O1 were, respectively, tetramer, trimer, and dimer BPA-BDPP. The constituents BPABDPP-IM1 and BPABDPP-IM2 gave protonated molecules at m/z 827 and m/z 461. The MS/MS investigations gave the product ions at m/z 733 and m/z 367, which were losses of C6H4 and H2O from protonated molecules of BPABDPP-IM1 and BPABDPP-IM2. The product ion at m/z 367 further fragmented to give the product ions at m/z 327 (loss of C3H4 from m/z 367), m/z 135 (loss of C18H15PO4 from m/z 367), and m/z 107 (loss of C3H4 from m/z 135). The product ions of protonated molecules of BPABDPP-IM1 and BPABDPP-IM2 at m/z 733, m/z 693, m/z 367, m/z 327, m/z 135, and m/z 107 were identical to the product ions of the skeletons of the trimer and dimer BPA-BDPP. The studies of fragmentation behaviors revealed the constituents BPABDPP-IM1 and BPABDPP-IM2, which were estimated respectively as phosphoric acid, [4-[1-[4-[(diphenoxyphosphinyl)oxy]phenyl]-1-methylethyl]phenyl] [4-[2-(4hydroxyphenyl)propan-2-yl]phenyl] phenyl ester (BPA-PHP-BPA-DPHP) and 4-[2-(4hydroxyphenyl)propan-2-yl]phenyl diphenyl phosphate (BPA-DPHP). The fragmentation pathway of the constituent BPABDPP-IM3 was the same result as those of the constituent PBDPP-IM3 in CR-733S. The constituent BPABDPP-IM3 was identified as TPHP.
3. PX-200 PX-200 consisted mainly of 1,3-phenylene bis[di(2,6-dimethylphenyl ) phosphate] (PBDMPP) oligomers including dimer and trimer, and two impurities including tris(dimethylphenyl) phosphate (TDMPP). MS/MS fragment ions of the constituents in PX-200 are shown Table S5. Based on fragment ions, the fragmentation behaviors were proposed in Fig. S8. Constituents PBDMPP-O2 and PBDMPP-O1 respectively gave protonated molecules at m/z 963 and m/z 687. The presence of the product ions at m/z 779 (losses of C8H8 and HPO3 from protonated molecule of PBDMPP-O2), m/z 675 (loss of C8H8 from m/z 779), m/z 503 (losses of C6H4 and HPO3 from m/z 675 or C8H8 and HPO3 from protonated molecule of PBDMPP-O1), m/z 399 (loss of C8H8 from m/z 503), m/z 209 (losses of C6H6O and HPO3 from m/z 399), and 3
m/z 105 (loss of C8H8 from m/z 209) were characteristic for the structural compositions of trimer and dimer PBDMPP. Constituents PBDMPP-O2 and PBDMPP-O1 were identified respectively as trimer and dimer PBDMPP. The constituent PBDMPP-IM1 gave a protonated molecule at m/z 399. MS/MS investigations gave the product ion at m/z 209 (losses of C6H6O2 and HPO3 from protonated molecule of PBDMPP-IM1) and m/z 105 (loss of C8H8 from 209). The product ions from protonated molecule of PBDMPP-IM1 were also formed as those from protonated molecules of dimer PBDMPP in their MS/MS spectrum. The structure of PBDMPP-IM1 corresponded to a part of the skeleton of dimer PBDMPP. The constituent PBDMPP-IM1 was estimated as 3hydroxyphenyl di(2,6-dimethylphenyl) phosphate (HP-DDMPP). MS/MS investigations of the constituent PBDMPP-IM2 gave the product ions at m/z 289 (loss of C8H10O from m/z 411), m/z 209 (loss of HPO3 from m/z 289), and m/z 105 (loss of C8H8 from 209), which characterized the structural composition of TDMPP. The ionic products at m/z 209 (C8H8 + C8H9+ → C16H17+), m/z 207 (C8H8 + C8H9+ → C16H15+ + H2), m/z 194 (C8H8 + C7H6+ → C15H14+), m/z 192 (C8H8 + C7H6+ → C15H12+ + H2) and m/z 179 (C8H8 + C6H3+ → C14H11+) were derived from the reaction of C8H8 with C8H9+, C7H6+, and C6H3+. The constituent PBDMPP-IM2 was identified as TDMPP. 4. CR-504L CR-504L consisted mainly of diethylene glycol bis[di(2-chloroisopropyl) phosphate] (DEGBDCIPP) oligomers including dimer, trimer, tetramer, and pentamer, and seven impurities including tris(2-chloroisopropyl) phosphate (TCIPP). MS/MS fragment ions of the constituents in CR-504L are shown Table S6. Based on the fragment ions, the fragmentation behaviors were proposed as shown in Fig. S9. The constituents DEGBDCIPP-O4, DEGBDCIPP-O3, DEGBDCIPP-O2, and DEGBDCIPP-O1 respectively gave protonated molecules at m/z 1303, m/z 1059, m/z 815, and m/z 571. The presence of the product ions at m/z 1227 (loss of C3H5Cl from protonated molecule of DEGBDCIPP-O4), m/z 1151 (loss of C3H5Cl from m/z 1227), m/z 1053 (loss of H3PO4 from m/z 1151), m/z 983 (losses of C4H6O from m/z 1053 or C3H5Cl from protonated molecule of DEGBDCIPP-O3), m/z 907 (loss of C3H5Cl from m/z 983), m/z 809 (loss of H3PO4 from m/z 907), m/z 739 (losses of C4H6O from m/z 809 or C3H5Cl from protonated molecule of DEGBDCIPP-O2), m/z 663 (loss of C3H5Cl from m/z 739), m/z 565 (loss of H3PO4 from m/z 663), m/z 495 (losses of C4H6O from m/z 565 or C3H5Cl from protonated molecule of DEGBDCIPP-O1), m/z 419 (loss of C3H5Cl from m/z 495), m/z 321 (loss of H3PO4 from m/z 419), m/z 245 (loss of C3H5Cl from m/z 321), m/z 169 (loss of C3H5Cl from m/z 245), and m/z 125 (loss of C2H4O from m/z 169) were characteristic of the structural components of the oligomers DEG-BDCIPP. Results of this study of the fragmentation behaviors respectively identified DEGBDCIPP-O4, DEGBDCIPP-O3, DEGBDCIPP-O2, and DEGBDCIPP-O1 as a pentamer, tetramer, trimer, and dimer. Constituents DEGBDCIPP-IM1, DEGBDCIPP-IM2, and DEGBDCIPP-IM3 respectively showed protonated molecules at m/z 785, m/z 629, and m/z 601. MS/MS investigations gave losses of C9H17Cl2PO4, C6H11ClO, and C4H7ClO moieties, respectively, for protonated molecules of DEGBDCIPP-IM1, DEGBDCIPP-IM2, and DEGBDCIPP-IM3, respectively. The product ions were observed at m/z 495 (respective losses of C9H17Cl2PO4 and C6H11ClO moieties from protonated molecules of DEGBDCIPP-IM2 and DEGBDCIPP-IM3), m/z 419 (loss of C3H5Cl from m/z 495), m/z 321 (losses of H3PO4 from m/z 419 or C3H5Cl, H3PO4, and C4H7ClO moieties from protonated molecule of DEGBDCIPP-IM3), m/z 245 (loss of C3H5Cl from m/z 4
321), m/z 169 (loss of C3H5Cl from m/z 245), and m/z 125 (loss of C2H4O from m/z 169). The presence of the same ions as dimer indicated that the structures of DEGBDCIPP-IM1, DEGBDCIPP-IM2, and DEGBDCIPP-IM3 have a part of the skeleton of DEG-BDCIPP. The product ions at m/z 709 (loss of C3H5Cl from m/z 785), m/z 535 (loss of C3H8ClPO4 from m/z 709), and m/z 495 (loss of C3H4 from m/z 535) showed the structural composition of C9H17Cl2PO4 moiety in DEGBDCIPP-IM1. The presence of a part of the skeleton of DEGBDCIPP and the moieties of C9H17Cl2PO4, C6H11ClO, and C4H7ClO suggest that DEGBDCIPPIM1, DEGBDCIPP-IM2, and DEGBDCIPP-IM3 might be byproducts of DEG-BDCIPP. The constituent DEGBDCIPP-IM5 gave a protonated molecule at m/z 357. The MS/MS investigations gave the product ions at m/z 281 (loss of C3H5Cl from m/z 357) and m/z 205 (loss of C3H5Cl from m/z 281) followed by a loss of C4H7ClO moiety, which were characteristic for the proposed structural composition of DEGBDCIPP-IM5. The constituent DEGBDCIPP-IM5 might also be a byproduct of DEG-BDCIPP. MS/MS investigation of the constituent DEGBDCIPP-IM6 showed intense fragments at m/z 251, m/z 175, and m/z 99, corresponding to the loss of C3H5Cl, which were characteristic of the structure of TCIPP. The constituent DEGBDCIPP-IM6 was identified as TCIPP. Constituents DEGBDCIPP-IM4 and DEGBDCIPPIM7 gave protonated molecules at m/z 489 and m/z 245. The MS/MS investigations showed the product ions at m/z 413 (loss of C3H5Cl from protonated molecule of DEGBDCIPP-IM4), m/z 245 (loss of C4H9PO5 from m/z 413), m/z 169 (losses of C3H5Cl from m/z 245 or C3H5Cl from a protonated molecule of DEGBDCIPP-IM7), and m/z 125 (loss of C2H4O from m/z 169). It is noteworthy that the protonated molecules of DEGBDCIPP-IM4 and DEGBDCIPP-IM7 were also formed as the product ions of protonated molecules of trimer and dimer DEG-BDCIPP in their MS/MS spectra. Structures of DEGBDCIPP-IM4 and DEGBDCIPP-IM7 were estimated similarly to a part of the skeleton and losses of C3H5Cl and H3PO4 moieties of trimer and dimer DEG-BDCIPP. Additional NMR analysis must be done to elucidate those structures of DEGBDCIPP-IM4 and DEGBDCIPP-IM7. Results of fragmentation pathway MS/MS investigations suggest that the constituents DEGBDCIPP-IM1, DEGBDCIPP-IM2, DEGBDCIPP-IM3, DEGBDCIPP-IM4, DEGBDCIPP-IM5, DEGBDCIPP-IM6, and DEGBDCIPP-IM7 are impurities in CR-504L.
5
Table S1. Precursor ion and collision voltage in MS/MS investigation. Constituent names are shown in Table 1. Flame retardant CR-733S 1,3-Phenylene bis(diphenyl phosphate) (PBDPP)
CR-741 Bisphenol A bis(diphenyl phosphate) (BPA-BDPP)
PX-200 1,3-Phenylene bis[di(2,6dimethylphenyl ) phosphate] (PBDMPP) CR-504L Diethylene glycol bis[di(2chloroisopropyl) phosphate] (DEG-BDCIPP)
Constituent name PBDPP-O4 PBDPP-O3 PBDPP-O2 PBDPP-IM1 PBDPP-O1 PBDPP-IM2 PBDPP-IM3 BPABDPP-O3 BPABDPP-O2 BPABDPP-IM1 BPABDPP-O1 BPABDPP-IM2 BPABDPP-IM3 PBDMPP-O2 PBDMPP-O1 PBDMPP-IM1 PBDMPP-IM2 DEGBDCIPP-O4 DEGBDCIPP-O3 DEGBDCIPP-O2 DEGBDCIPP-IM1 DEGBDCIPP-IM2 DEGBDCIPP-IM3 DEGBDCIPP-O1 DEGBDCIPP-IM4 DEGBDCIPP-IM5 DEGBDCIPP-IM6 DEGBDCIPP-IM7
Precursor ion m/z 1319.2 1071.1 823.1 591.1 575.1 343.1 327.1 1425.4 1059.3 827.3 693.2 461.2 327.1 963.3 687.2 399.1 411.2 1303.1 1059.1 815.1 785.0 629.1 601.0 571.0 489.1 357.0 327.0 245.0
6
Collision voltage (eV) 65 55 40 30 30 15 15 40 30 10 15 10 15 40 25 20 15 20 15 10 10 5 5 5 5 5 5 5
Table S2. CAS numbers and full names of major constituents in commercial PBDPP and BPA-BDPP reported in the previous study (Rossi and Heine, 2007). Chemical Commercial PBDPP 1,3-Phenylene bis(diphenyl phosphate) Phosphoric acid, bis[3-[(diphenoxyphosphinyl)oxy]phenyl] phenyl ester Triphenyl phosphate
Type Dimer Trimer Impurity
CAS no. 125997-21-9 57583-54-7 98165-92-5 115-86-6
Commercial BPA-BDPP Bisphenol A bis(diphenyl phosphate) Phosphoric acid, bis[4-[1-[4-[(diphenoxyphos-phinyl)oxy]phenyl]1-methylethyl]phenyl] phenyl ester Triphenyl phosphate
Dimer
181028-79-5 5945-33-5
Trimer
83029-72-5
Impurity
115-86-6
7
Table S3. MS/MS fragment ions of constituents in CR-733S. Constituent names are shown in Table 1. Constituent name PBDPP-O4
PBDPP-O3
PBDPP-O2
Observed m/z 1319.1697 1225.1275 1163.1695 1069.1306 977.1035 975.0870 915.1479 883.0607 821.1086 729.0820 727.0675 667.1246 653.0493 635.0414 591.0904 573.0849 481.0556 479.0429 231.0181 215.0252 1071.1477 977.1054 915.1494 883.0667 821.1077 729.0824 727.0678 667.1248 653.0498 635.0392 591.0944 573.0857 481.0589 479.0424 419.1021 343.0707 231.0203 215.0255 823.1248 729.0831 667.1272 653.0509 635.0403 591.0951 573.0850 481.0592 479.0433 419.1033 343.0724 231.0202 215.0255
Theoretical m/z 1319.1740 1225.1321 1163.1764 1069.1345 977.1083 975.0926 915.1525 883.0664 821.1107 729.0845 727.0688 667.1287 653.0532 635.0426 591.0974 573.0868 481.0606 479.0450 231.0211 215.0262 1071.1502 977.1083 915.1525 883.0664 821.1107 729.0845 727.0688 667.1287 653.0532 635.0426 591.0974 573.0868 481.0606 479.0450 419.1048 343.0735 231.0211 215.0262 823.1263 729.0845 667.1287 653.0532 635.0426 591.0974 573.0868 481.0606 479.0450 419.1048 343.0735 231.0211 215.0262
Error (ppm) -3.26 -3.75 -5.93 -3.65 -4.91 -5.74 -5.03 -6.45 -2.56 -3.43 -1.79 -6.15 -5.97 -1.89 -11.84 -3.32 -10.39 -4.38 -12.99 -4.65 -2.33 -2.97 -3.39 0.34 -3.65 -2.88 -1.38 -5.85 -5.21 -5.35 -5.08 -1.92 -3.53 -5.43 -6.44 -8.16 -3.46 -3.26 -1.82 -1.92 -2.25 -3.52 -3.62 -3.89 -3.14 -2.91 -3.55 -3.58 -3.21 -3.90 -3.26
8
Proposed formula C66H52O20P5 C60H46O19P5 C60H47O17P4 C54H41O16P4 C48H37O15P4 C48H35O15P4 C48H38O13P3 C42H31O14P4 C42H32O12P3 C36H28O11P3 C36H26O11P3 C36H29O9P2 C30H24O11P3 C30H22O10P3 C30H25O9P2 C30H23O8P2 C24H19O7P2 C24H17O7P2 C12H8O3P C12H8O2P C54H43O16P4 C48H37O15P4 C48H38O13P3 C42H31O14P4 C42H32O12P3 C36H28O11P3 C36H26O11P3 C36H29O9P2 C30H24O11P3 C30H22O10P3 C30H25O9P2 C30H23O8P2 C24H19O7P2 C24H17O7P2 C24H20O5P C18H16O5P C12H8O3P C12H8O2P C42H34O12P3 C36H28O11P3 C36H29O9P2 C30H24O11P3 C30H22O10P3 C30H25O9P2 C30H23O8P2 C24H19O7P2 C24H17O7P2 C24H20O5P C18H16O5P C12H8O3P C12H8O2P
Proposed neutral loss C6H6O C6H5O3P C12H11O4P C18H15O5P C18H17O5P C18H14O7P2 C24H21O6P C24H20O8P2 C30H24O9P2 C30H26O9P2 C30H23O11P3 C36H28O9P2 C36H30O10P2 C36H27O11P3 C36H29O12P3 C42H33O13P3 C42H35O13P3 C54H44O17P4 C54H44O18P4 C6H6O C6H5O3P C12H12O2 C12H11O4P C18H15O5P C18H17O5P C18H14O7P2 C24H19O5P C24H21O6P C24H18O7P2 C24H20O8P2 C30H24O9P2 C30H26O9P2 C30H23O11P3 C36H27O11P3 C42H35O13P3 C42H35O14P3 C6H6O C6H5O3P C12H10O C12H12O2 C12H9O3P C12H11O4P C18H15O5P C18H17O5P C18H14O7P2 C24H18O7P2 C30H26O9P2 C30H26O10P2
Table S3. (Continued) Constituent name PBDPP-IM1
PBDPP-O1
PBDPP-IM2
Observed m/z 591.0976 499.0705 481.0597 435.0991 419.1047 405.0286 387.0185 343.0726 325.0617 310.9867 307.0506 251.0467 231.0208 215.0255 169.0648 153.0694 141.0699 93.0339 77.0393 65.0397 575.1011 499.0690 481.0592 419.1037 405.0279 387.0173 343.0724 325.0618 310.9860 307.0516 251.0464 231.0204 226.0774 215.0255 169.0646 153.0696 141.0698 77.0393 343.0722 251.0458 249.0311 231.0202 169.0647 141.0699 93.0323 65.0389
Theoretical m/z 591.0974 499.0712 481.0606 435.0998 419.1048 405.0293 387.0187 343.0735 325.0630 310.9874 307.0524 251.0473 231.0211 215.0262 169.0653 153.0704 141.0704 93.034 77.0391 65.0391 575.1025 499.0712 481.0606 419.1048 405.0293 387.0187 343.0735 325.0630 310.9874 307.0524 251.0473 231.0211 226.0783 215.0262 169.0653 153.0704 141.0704 77.0391 343.0735 251.0473 249.0317 231.0211 169.0653 141.0704 93.034 65.0391
Error (ppm) 0.34 -1.40 -1.87 -1.61 -0.24 -1.73 -0.52 -2.62 -4.00 -2.25 -5.86 -2.39 -1.30 -3.26 -2.96 -6.53 -3.54 -1.07 2.60 9.23 -2.43 -4.41 -2.91 -2.62 -3.46 -3.62 -3.21 -3.69 -4.50 -2.61 -3.58 -3.03 -3.98 -3.26 -4.14 -5.23 -4.25 2.60 -3.79 -5.98 -2.41 -3.90 -3.55 -3.54 -18.27 -3.08
9
Proposed formula C30H25O9P2 C24H21O8P2 C24H19O7P2 C24H20O6P C24H20O5P C18H15O7P2 C18H13O6P2 C18H16O5P C18H14O4P C12H9O6P2 C18H12O3P C12H12O4P C12H8O3P C12H8O2P C12H9O C12H9 C11H9 C11H9 C6H5O C5H5 C30H25O8P2 C24H21O8P2 C24H19O7P2 C24H20O5P C18H15O7P2 C18H13O6P2 C18H16O5P C18H14O4P C12H9O6P2 C18H12O3P C12H12O4P C12H8O3P C18H10 C12H8O2P C12H9O C12H9 C11H9 C6H5 C18H16O5P C12H12O4P C12H10O4P C12H8O3P C12H9O C11H9 C6H5O C5H5
Proposed neutral loss C6H4O C6H6O2 C6H5O3P C6H5O4P C12H10O2 C12H12O3 C12H9O4P C12H11O5P C18H16O3 C12H13O6P C18H13O5P C18H17O6P C18H17O7P C18H16O8P2 C18H16O9P2 C19H16O9P2 C24H20O8P2 C24H20O9P2 C25H20O9P2 C6H4 C6H6O C6H5O3P C12H10O C12H12O2 C12H9O3P C12H11O4P C18H16O2 C12H13O5P C18H13O4P C18H17O5P C12H15O8P2 C18H17O6P C18H16O7P2 C18H16O8P2 C19H16O8P2 C24H20O8P2 C6H4O C6H6O C6H8O2 C6H7O4P C7H7O5P C12H11O4P C13H11O5P
Table S3. (Continued) Constituent name PBDPP-IM3
Observed m/z 327.0777 251.0462 233.0359 229.1006 228.0930 215.0255 153.0698 152.0617 77.0394
Theoretical m/z 327.0786 251.0473 233.0368 229.1017 228.0939 215.0262 153.0704 152.0626 77.0391
Error (ppm) -2.75 -4.38 -3.86 -4.80 -3.95 -3.26 -3.92 -5.92 3.89
10
Proposed formula C18H16O4P C12H12O4P C12H10O3P C18H13 C18H12 C12H8O2P C12H9 C12H8 C6H5
Proposed neutral loss C6H4 C6H6O H3O4P H4O4P C6H8O2 C6H7O4P C6H8O4P C12H11O4P
Table S4. MS/MS fragment ions of constituents in CR-741. Constituent names are shown in Table 1. Constituent name BPABDPP-O3
BPABDPP-O2
BPABDPP-IM1
BPABDPP-O1
BPABDPP-IM2
BPABDPP-IM3
Observed m/z 1425.3794 1099.3100 1059.2812 733.2087 693.1777 407.1379 367.1091 1059.2819 733.2105 693.1782 407.1396 367.1089 827.2498 733.2100 693.1783 693.1795 367.1087 327.0777 461.1497 367.1075 327.0766 135.0802 107.0489 327.0776 251.0460 233.0363 229.0993 228.0929 215.0255 153.0696 152.0612 77.0392
Theoretical m/z 1425.3849 1099.3141 1059.2828 733.2120 693.1807 407.1412 367.1099 1059.2828 733.2120 693.1807 407.1412 367.1099 827.2539 733.2120 693.1807 693.1807 367.1099 327.0786 461.1518 367.1099 327.0786 135.0810 107.0497 327.0786 251.0473 233.0368 229.1017 228.0939 215.0262 153.0704 152.0626 77.0391
Error (ppm) -3.86 -3.73 -1.51 -4.50 -4.33 -8.11 -2.18 -0.85 -2.05 -3.61 -3.93 -2.72 -4.96 -2.73 -3.46 -1.73 -3.27 -2.75 -4.55 -6.54 -6.11 -5.92 -7.47 -3.06 -5.18 -2.15 -10.48 -4.38 -3.26 -5.23 -9.21 1.30
11
Proposed formula C81H73O16P4 C63H58O12P3 C60H54O12P3 C42H39O8P2 C39H35O8P2 C24H24O4P C21H20O4P C60H54O12P3 C42H39O8P2 C39H35O8P2 C24H24O4P C21H20O4P C48H45O9P2 C42H39O8P2 C39H35O8P2 C39H35O8P2 C21H20O4P C18H16O4P C27H26O5P C21H20O4P C18H16O4P C9H11O C7H7O C18H16O4P C12H12O4P C12H10O3P C18H13 C18H12 C12H8O2P C12H9 C12H8 C6H5
Proposed neutral loss C18H15O4P C21H19O4P C39H34O8P2 C42H38O8P2 C57H49O12P3 C60H53O12P3 C18H15O4P C21H19O4P C36H30O8P2 C39H34O8P2 C6H6O C9H10O C18H15O4P C21H19O4P C6H6O C9H10O C18H15O4P C20H19O4P C6H4 C6H6O H 3O 4P H 4O 4P C6H8O2 C6H7O4P C6H8O4P C12H11O4P
Table S5. MS/MS fragment ions of constituents in PX-200. Component names are shown in Table 1. Constituent name PBDMPP-O2
PBDMPP-O1
PBDMPP-IM1
PBDMPP-IM2
Observed m/z 963.2816 857.2014 841.2069 779.2517 737.1455 675.1890 503.1962 399.1357 209.1311 194.1090 179.0851 105.0701 79.0546 687.2266 581.1479 565.1529 503.1976 194.1090 179.0855 105.0699 79.0549 399.1348 293.0570 277.0627 195.0802 194.1081 182.0719 179.0852 105.0700 103.0547 79.0549 77.0388 411.1713 305.0924 289.0984 209.1319 207.1163 194.1090 192.0926 179.0855 105.0701 103.0544 79.0547 77.0392
Theoretical m/z 963.2828 857.2046 841.2097 779.2539 737.1471 675.1913 503.1987 399.1361 209.1330 194.1096 179.0861 105.0704 79.0548 687.2277 581.1494 565.1545 503.1987 194.1096 179.0861 105.0704 79.0548 399.1361 293.0579 277.0630 195.0810 194.1096 182.0732 179.0861 105.0704 103.0548 79.0548 77.0391 411.1725 305.0943 289.0994 209.1330 207.1174 194.1096 192.0939 179.0861 105.0704 103.0548 79.0548 77.0391
Error (ppm) -1.25 -3.73 -3.33 -2.82 -2.17 -3.41 -4.97 -1.00 -9.09 -3.09 -5.58 -2.86 -2.53 -1.60 -2.58 -2.83 -2.19 -3.09 -3.35 -4.76 1.26 -3.26 -3.07 -1.08 -4.10 -7.73 -7.14 -5.03 -3.81 -0.97 1.26 -3.89 -2.92 -6.23 -3.46 -5.26 -5.31 -3.09 -6.77 -3.35 -2.86 -3.88 -1.26 1.30
12
Proposed formula C52H54O12P3 C44H44O12P3 C44H44O11P3 C44H45O9P2 C36H36O11P3 C36H37O9P2 C30H32O5P C22H24O5P C16H17 C15H14 C14H11 C8H9 C6H7 C38H41O8P2 C30H31O8P2 C30H31O7P2 C30H32O5P C15H14 C14H11 C8H9 C6H7 C22H24O5P C14H14O5P C14H14O4P C14H11O C15H14 C13H10O C14H11 C8H9 C8H7 C6H7 C6H5 C24H28O4P C16H18O4P C16H18O3P C16H17 C16H15 C15H14 C15H12 C14H11 C8H9 C8H7 C6H7 C6H5
Proposed neutral loss C8H10 C8H10O C8H9O3P C16H18O C16H17O3P C22H22O7P2 C30H30O7P2 C36H37O12P3 C37H40O12P3 C38H43O12P3 C44H45O12P3 C46H47O12P3 C8H10 C8H10O C8H9O3P C23H27O8P2 C24H30O8P2 C30H32O8P2 C32H34O8P2 C8H10 C8H10O C8H13O4P C7H10O5P C9H14O4P C8H13O5P C14H15O5P C14H17O5P C16H17O5P C16H19O5P C8H10 C8H10O C8H11O4P C8H13O4P C9H14O4P C9H16O4P C10H17O4P C16H19O4P C16H21O4P C18H21O4P C18H23O4P
Table S6. MS/MS fragment ions of constituents in CR-504L. Component names are shown in Table 1. Constituent name DEGBDCIPP-O4
DEGBDCIPP-O3
DEGBDCIPP-O2
Observed m/z 1303.1139 1227.1061 1151.0961 1053.1224 983.0889 977.1068 809.0906 739.0477 733.0859 657.0735 565.0625 489.0613 321.0417 245.0313 239.0662 169.0243 124.9994 1059.0873 983.0781 907.0650 809.0942 739.0496 733.0843 565.0671 489.0593 413.0504 321.0415 245.0330 239.0672 169.0257 124.9996 815.0607 739.0524 663.0437 565.0665 489.0585 321.0410 245.0330 169.0258 124.9996
Theoretical m/z 1303.1156 1227.1076 1151.0997 1053.1228 983.0809 977.1148 809.0960 739.0542 733.0880 657.0801 565.0693 489.0613 321.0425 245.0346 239.0685 169.0266 125.0004 1059.0889 983.0809 907.0729 809.0960 739.0542 733.0880 565.0693 489.0613 413.0533 321.0425 245.0346 239.0685 169.0266 125.0004 815.0621 739.0542 663.0462 565.0693 489.0613 321.0425 245.0346 169.0266 125.0004
Error (ppm) -1.30 -1.22 -3.13 -0.38 8.14 -8.19 -6.67 -8.80 -2.86 -10.04 -12.03 0.00 -2.49 -13.47 -9.62 -13.61 -8.00 -1.51 -2.85 -8.71 -2.22 -6.22 -5.05 -3.89 -4.09 -7.02 -3.11 -6.53 -5.44 -5.32 -6.40 -1.72 -2.44 -3.77 -4.96 -5.73 -4.67 -6.53 -4.73 -6.40
13
Proposed formula C37H75Cl7O24P5 C34H70Cl6O24P5 C31H65Cl5O24P5 C31H62Cl5O20P4 C27H56Cl5O19P4 C28H57Cl4O20P4 C24H48Cl4O15P3 C20H42Cl4O14P3 C21H43Cl3O15P3 C18H38Cl2O15P3 C17H34Cl3O10P2 C14H29Cl2O10P2 C10H20Cl2O5P C7H15ClO5P C8H16O6P C4H10O5P C2H6O4P C30H61Cl6O19P4 C27H56Cl5O19P4 C24H51Cl4O19P4 C24H48Cl4O15P3 C20H42Cl4O14P3 C21H43Cl3O15P3 C17H34Cl3O10P2 C14H29Cl2O10P2 C11H24ClO10P2 C10H20Cl2O5P C7H15ClO5P C8H16O6P C4H10O5P C2H6O4P C23H47Cl5O14P3 C20H42Cl4O14P3 C17H37Cl3O14P3 C17H34Cl3O10P2 C14H29Cl2O10P2 C10H20Cl2O5P C7H15ClO5P C4H10O5P C2H6O4P
Proposed neutral loss C3H5Cl C6H10Cl2 C6H13Cl2O4P C10H19Cl2O5P C9H18Cl3O4P C13H27Cl3O9P2 C17H33Cl3O10P2 C16H32Cl4O9P2 C19H37Cl5O9P2 C20H41Cl4O14P3 C23H46Cl5O14P3 C27H55Cl5O19P4 C30H60Cl6O19P4 C29H59Cl7O18P4 C33H65Cl7O19P4 C35H69Cl7O20P4 C3H5Cl C6H10Cl2 C6H13Cl2O4P C10H19Cl2O5P C9H18Cl3O4P C13H27Cl3O9P2 C16H32Cl4O9P2 C19H37Cl5O9P2 C20H41Cl4O14P3 C23H46Cl5O14P3 C22H45Cl6O13P3 C26H51Cl6O14P3 C28H55Cl6O15P3 C3H5Cl C6H10Cl2 C6H13Cl2O4P C9H18Cl3O4P C13H27Cl3O9P2 C16H32Cl4O9P2 C19H37Cl5O9P2 C21H41Cl5O10P2
Table S6. (Continued) Constituent name DEGBDCIPP-IM1
DEGBDCIPP-IM2
DEGBDCIPP-IM3
DEGBDCIPP-O1
DEGBDCIPP-IM4
Observed m/z 785.0502 709.0436 535.0573 495.0246 459.0477 383.0405 321.0413 291.0310 245.0328 215.0228 209.0549 169.0253 139.0156 125.0004 629.0756 495.0251 419.0192 343.0069 267.0030 245.0359 169.0254 125.0006 601.0448 525.0363 449.0264 321.0407 275.0417 245.0337 169.0264 124.9992 571.0343 495.0259 419.0177 321.0415 245.0339 169.0259 124.9997 489.0595 413.0522 245.0339 169.0260 124.9994
Theoretical m/z 785.0516 709.0436 535.0587 495.0274 459.0507 383.0428 321.0425 291.0320 245.0346 215.0240 209.0579 169.0266 139.0160 125.0004 629.0773 495.0274 419.0194 343.0115 267.0035 245.0346 169.0266 125.0004 601.0460 525.0380 449.0300 321.0425 275.0451 245.0346 169.0266 125.0004 571.0354 495.0274 419.0194 321.0425 245.0346 169.0266 125.0004 489.0613 413.0533 245.0346 169.0266 125.0004
Error (ppm) -1.78 0.00 -2.62 -5.66 -6.54 -6.00 -3.74 -3.44 -7.35 -5.58 -14.35 -7.69 -2.88 0.00 -2.70 -4.65 -0.48 -13.41 -1.87 5.31 -7.10 1.60 -2.00 -3.24 -8.02 -5.61 -12.36 -3.67 -1.18 -9.60 -1.93 -3.03 -4.06 -3.11 -2.86 -4.14 -5.60 -3.68 -2.66 -2.86 -3.55 -8.00
14
Proposed formula C22H45Cl5O13P3 C19H40Cl4O13P3 C16H32Cl3O9P2 C13H28Cl3O9P2 C13H27Cl2O9P2 C10H22ClO9P2 C10H20Cl2O5P C9H18Cl2O4P C7H15ClO5P C6H13ClO4P C7H14O5P C4H10O5P C3H8O4P C2H6O4P C19H39Cl4O10P2 C13H28Cl3O9P2 C10H23Cl2O9P2 C7H18ClO9P2 C4H13O9P2 C7H15ClO5P C4H10O5P C2H6O4P C17H35Cl4O10P2 C14H30Cl3O10P2 C11H25Cl2O10P2 C10H20Cl2O5P C8H17ClO6P C7H15ClO5P C4H10O5P C2H6O4P C16H33Cl4O9P2 C13H28Cl3O9P2 C10H23Cl2O9P2 C10H20Cl2O5P C7H15ClO5P C4H10O5P C2H6O4P C14H29Cl2O10P2 C11H24ClO10P2 C7H15ClO5P C4H10O5P C2H6O4P
Proposed neutral loss C3H5Cl C6H13Cl2O4P C9H17Cl2O4P C9H18Cl3O4P C12H23Cl4O4P C12H25Cl3O8P2 C13H27Cl3O9P2 C15H30Cl4O8P2 C16H32Cl4O9P2 C15H31Cl5O8P2 C18H35Cl5O8P2 C19H37Cl5O9P2 C20H39Cl5O9P2 C6H11ClO C9H16Cl2O C12H21Cl3O C15H26Cl4O C12H24Cl3O5P C15H29Cl4O5P C17H33Cl4O6P C3H5Cl C6H10Cl2 C7H15Cl2O5P C9H18Cl3O4P C10H20Cl3O5P C13H25Cl4O5P C15H29Cl4O6P C3H5Cl C6H10Cl2 C6H13Cl2O4P C9H18Cl3O4P C12H23Cl4O4P C14H27Cl4O5P C3H5Cl C7H14ClO5P C10H19Cl2O5P C12H23Cl2O6P
Table S6. (Continued) Constituent name DEGBDCIPP-IM5
DEGBDCIPP-IM6
DEGBDCIPP-IM7
Observed m/z 357.0179 281.0098 205.0021 174.9915 107.0260 98.9844 63.0001 327.0070 250.9995 174.9920 98.9844 245.0329 169.0257 124.9993
Theoretical m/z 357.0192 281.0112 205.0033 174.9927 107.0264 98.9847 63.0002 327.0087 251.0007 174.9927 98.9847 245.0346 169.0266 125.0004
Error (ppm) -3.64 -4.98 -5.85 -6.86 -3.74 -3.03 -1.59 -5.20 -4.78 -4.00 -3.03 -6.94 -5.32 -8.80
15
Proposed formula C10H21Cl3O5P C7H16Cl2O5P C4H11ClO5P C3H9ClO4P C4H8ClO H 4O 4P C2H4Cl C9H19Cl3O4P C6H14Cl2O4P C3H9ClO4P H 4O 4P C7H15ClO5P C4H10O5P C2H6O4P
Proposed neutral loss C3H5Cl C6H10Cl2 C7H12Cl2O C6H13Cl2O4P C10H17Cl3O C8H17Cl2O5P C3H5Cl C6H10Cl2 C9H15Cl3 C3H5Cl C5H9ClO
Figure S1. Total and extracted ion chromatograms of constituents in CR-733S using atmospheric pressure photoionization-quadrupole time-of-flight mass spectrometry compatible with gel permeation chromatography. Constituent names are shown in Table 1. Intensity 3236908
TIC
0 14912
m/z 1319.1740
0 109688
m/z 1071.1502
0 527635
m/z 823.1263
0 4937
m/z 591.0974
PBDPP-IM1
0 1693059
m/z 575.1025
PBDPP-O1
PBDPP-O4
PBDPP-O3
PBDPP-O2
0 m/z 343.0735
PBDPP-IM2
4485 0 17077
m/z 327.0786
PBDPP-IM3
0 0
2
4
6
8
10
Retention time (min)
16
Figure S2. Total and extracted ion chromatogram of constituents in CR-741 by an atmospheric pressure photoionization-quadrupole time-of-flight mass spectrometry compatible with gel permeation chromatography. Constituent names are shown in Table 1. Intensity TIC
4727066
0 7652
m/z 1425.3849
0 226768
m/z 1059.2828
BPABDPP-O3
BPABDPP-O2
0 2327
m/z 827.2539
BPABDPP-IM1
0 2252911
m/z 693.1807
BPABDPP-O1
0 10962
m/z 461.1518
0 10506
m/z 327.0786
BPABDPP-IM2
BPABDPP-IM3
0 0
2
4
6
8
10
Retention time (min)
17
Figure S3. Total and extracted ion chromatogram of constituents in PX-200 by an atmospheric pressure photoionization-quadrupole time-of-flight mass spectrometry compatible with gel permeation chromatography. Constituent names are shown in Table 1. Intensity 4993753
TIC
0 10121
m/z 963.2828
0 2422997
m/z 687.2277
PBDMPP-O2
PBDMPP-O1
0 m/z 399.1361
PBDMPP-IM1
m/z 411.1725
PBDMPP-IM2
18424 0 17933 0 0
2
4
6
8
10
Retention time (min)
18
Figure S4. Total and extracted ion chromatogram of constituents in CR-504L by an atmospheric pressure photoionization-quadrupole time-of-flight mass spectrometry compatible with gel permeation chromatography. Constituent names are shown in Table 1. Intensity TIC
2820360
0 7212
m/z 1303.1156
DEGBDCIPP-O4
0 49810
m/z 1059.0889
DEGBDCIPP-O3
0 197425
m/z 815.0621
DEGBDCIPP-O2
0 6507
m/z 785.0516
DEGBDCIPP-IM1
0 2168
m/z 629.0773
0 3360
m/z 601.0460
DEGBDCIPP-IM3
0 696472
m/z 571.0354
DEGBDCIPP-O1
0 2346
m/z 489.0613
DEGBDCIPP-IM4
0 5255
m/z 357.0192
DEGBDCIPP-IM5
0 7374
m/z 327.0087
DEGBDCIPP-IM2
DEGBDCIPP-IM6
0 m/z 245.0346
DEGBDCIPP-IM7
3947 0 0
2
4
6
8
10
Retention time (min)
19
Figure S5. Chromatograms of (a) CR-733S, (b) CR-741, (c) PX-200, and (d) CR-504L by a refractive index detector compatible with gel permeation chromatography. Constituent names are shown in Table 1. 100000
a) CR-733S
150000
CR-733S_RI - CH2
PBDPP-O12
PX-200_RI - CH2
c) PX-200
PBDMPP-O1
Intensity [µV]
Intensity [µV]
100000
50000
PBDPP-O2 PBDPP-IM2
PBDPP-O3
PBDPP-IM1 PBDMPP-O2
PBDMPP-IM2
0
0
6.0
150000
50000
PBDPP-IM3
PBDPP-O4
6.2
6.4
6.6
6.8 7.0 7.2 Retention Time [min]
7.4
7.6
7.8
6.0
CR-741_RI - CH2
b) CR-741 BPABDPP-O1
6.2
6.4
6.6
6.8 7.0 7.2 Retention Time [min]
7.4
7.6
7.8
CR-504L_RI - CH2
d) CR-504L DEGBDCIPP-O1 30000
50000
Intensity [µV]
Intensity [µV]
100000
BPABDPP-O2
20000
DEGBDCIPP-O2 DEGBDCIPP-O3
10000
BPABDPP-O3
BPABDPP-IM3
DEGBDCIPP-IM6
DEGBDCIPP-O4 0
0
6.0
6.2
6.4
6.6
6.8 7.0 7.2 Retention Time [min]
7.4
7.6
7.8
6.0
6.2
20
6.4
6.6
6.8 7.0 7.2 Retention Time [min]
7.4
7.6
7.8
Figure S6. Proposed fragmentation pathways of constituents in CR-733S. Constituent names are shown in Table 1. -H2 O
m/z 1225
-HPO3
m/z 1163
PBDPP-O4 -C6 H4 m/z 1243 [M+H]+ = 1319
-C6 H4
-C6 H4
PBDPP-O3 -C6 H4 [M+H]+ = 1071
m/z 1149
-HPO3
m/z 1087
-H2 O
m/z 1069 -C6 H4 O -H2 O
-H2 O
m/z 977
-HPO3
m/z 915
-C6 H4 PBDPP-IM3 (TPHP) [M+H]+ = 327 -H3 PO4
m/z 251
m/z 229
-C6 H4
m/z 233
m/z 228
-H2 O
-HPO3 -C6 H4 m/z 153
H
m/z 901
-C6 H4
-C6 H4
-H2 O
m/z 839
-C6 H4 O
-H2 O
m/z 729
-HPO3
m/z 667
m/z 635
-H2 O
-C6 H4
m/z 653
m/z 747 -C6 H4
m/z 591
m/z 215
-H2 O PBDPP-O1 (PBDPP) -C6 H4 [M+H]+ = 575
-HPO3 m/z 573 -H2 O
m/z 481
-HPO3
m/z 419
H -C6 H4
-C6 H4 O PBDPP-IM1 (HP-PHP-HP-DPHP) [M+H]+ = 591
m/z 499
-C6H5 PO3
m/z 435
-HPO3
-C6 H4 O
m/z 481
m/z 419
-C6 H4
m/z 387
-C6 H4
m/z 405
m/z 343
-HPO3 m/z 325
-C6H4 O
m/z 251
-H2 O
-CO
m/z 311
m/z 307 -H2 O
m/z 215
-HPO3
m/z 153
m/z 233
m/z 141
-C6 H4
m/z 65
m/z 231 m/z 141
-HPO3 -C6 H4
m/z 93
m/z 151 m/z 65
m/z 169 -C6 H4
m/z 405
-C6 H4
m/z 343
m/z 251
m/z 169
m/z 251
-C6H7 PO4
-H2O
-H2O
-CO
-C6 H7 PO4
m/z 249
-C6 H4
-H2 O
-C6 H4 -C6 H6 O
-H2 O
-C6 H4
m/z 387
-HPO3 m/z 325 -H2 O
m/z 93
21
-C6 H4
m/z 77
-H2 O
-C6 H4
-H2 O
m/z 311
m/z 307
-H2 PO3
m/z 226
-C6 H4 O
-C6 H4 O
m/z 152
-H2 O
-C6 H4 O
m/z 499
m/z 77
-H2 O
PBDPP-IM2 (HP-DPHP) [M+H]+ = 343
m/z 883 -HPO3 m/z 821
m/z 995
PBDPP-O2 [M+H]+ = 823
-H2 O
-C6 H4
-H2 O
m/z 215
-HPO3
m/z 153
m/z 233 -C6 H4
m/z 77
Figure S7. Proposed fragmentation pathways of constituents in CR-741. Constituent names are shown in Table 1. BPABDPP-O3 - C18 H15 PO4 m/z 1099 -C3 H4 m/z 1059 [M+H]+ = 1425 - C18 H15 PO4
- C6 H4
BPABDPP-O2 - C18 H15 PO4 m/z 733 [M+H]+ = 1059
-C3 H4
-H2 O
m/z 809
m/z 693
- C18 H15 PO4
- C6 H4
BPABDPP-O1 (BPA-BDPP) - C18H15 PO4 m/z 367 [M+H]+ = 693 - C18 H15 PO4 m/z 135
-C6 H4
m/z 251
BPABDPP-IM3 (TPHP) [M+H]+ = 327 -H3 PO4
m/z 229
-H2 O
-C6 H4
H m/z 228
m/z 233
-H2 O
-HPO3 -C6 H4 m/z 153
BPABDPP-IM1 (BPA-PHP-BPA-DPHP) [M+H]+ = 827
-C3 H4
-C3 H4
m/z 443
-H2 O
BPABDPP-IM2 (BPA-DPHP) [M+H]+ = 461
m/z 327
m/z 107
m/z 215
m/z 77
H -C6 H4
m/z 152
22
Figure S8. Proposed fragmentation pathways of constituents in PX-200. Constituent names are shown in Table 1. -C8 H10
m/z 857
-C8 H10 O
PBDMPP-O2 [M+H]+ = 963
-C8 H9 PO3
-C8 H10 O
-C8 H10 O -C6 H6 O2 -HPO3
m/z 305
PBDMPP-IM2 (TDMPP) [M+H]+ = 411 m/z 289
-C6 H4 O -HPO3
m/z 565
-C8 H10
-C8 H10
m/z 675
m/z 581
-C8 H9 PO3
PBDMPP-IM1 (HP-DDMPP) [M+H]+ = 399
m/z 737
-C8 H8
m/z 779
-C8 H10
PBDMPP-O1 (PBDMPP) [M+H]+ = 687
-C8 H8
m/z 841
m/z 503
m/z 293
m/z 277
- H3 PO4
- HPO3
-C8 H8
m/z 399
m/z 195
m/z 197
-C6 H6 O2 -HPO3
-C6 H4 O
-CH3
m/z 209
m/z 103
-C2 H2
-CH3
m/z 194
-CH3
m/z 179
m/z 77
m/z 182 -C6 H4 O
m/z 209
- H3 PO4
- HPO3
-CH3
m/z 207
m/z 209
-CH3
-CH3
m/z 194
-CH3
m/z 192
m/z 194
-CH3
-CH3
m/z 179
-C6 H2
m/z 177
m/z 179
-C6 H2
-C6 H2
m/z 105
-C2 H2
m/z 103
m/z 105
-C2 H2
-C2 H2
m/z 79
m/z 77
m/z 79
-C8 H10 O
23
-C6 H2
m/z 105
-C2 H2
m/z 79
Figure S9. Proposed fragmentation pathways of constituents in CR-504L. Constituent names are shown in Table 1. DEGBDCIPP-O4 -C3 H5 Cl -C3 H5 Cl m/z 1227 m/z 1151 [M+H]+ = 1303 -H3 PO4 -C3 H5 Cl m/z 1053 m/z 977 -C4 H6 O DEGBDCIPP-O3 -C3 H5 Cl -C3 H5 Cl m/z 907 m/z 983 [M+H]+ = 1059 DEGBDCIPP-IM4 -H3 PO4 [M+H]+ = 489 -C3 H5 Cl -C3 H5 Cl m/z 809 m/z 733 m/z 657 -C3 H5 Cl -C4 H6 O -C4 H6 O -C3 H5 Cl DEGBDCIPP-O2 -C3 H5 Cl DEGBDCIPP-IM7 m/z 739 m/z 663 [M+H]+ = 815 [M+H]+ = 245 -H3 PO4 -C H Cl -C H Cl -C3 H5 Cl m/z 565 3 5 m/z 489 3 5 m/z 413 -C4 H6 O -C4 H6 O -C4 H6 O DEGBDCIPP-O1 (DEG-BDCIPP) -C3 H5 Cl -C H Cl -C H Cl m/z 495 3 5 m/z 419 3 5 m/z 343 [M+H]+ = 571 -H3 PO4 -H3 PO4 -C2 H4 O -C H Cl -C H Cl m/z 321 3 5 m/z 245 3 5 m/z 169 m/z 125 -C4 H10 ClPO5 -C4 H10 ClPO5 -C4 H7 ClO -C3H 8ClPO4 DEGBDCIPP-IM3 -C3 H5 Cl -C H Cl m/z 525 3 5 m/z 449 m/z 275 [M+H]+ = 601
DEGBDCIPP-IM2 -C6 H11 ClO [M+H]+ = 629 -C3 H4 -C3H 8ClPO4 -C3H 8ClPO4 DEGBDCIPP-IM1 -C3 H5 Cl -C H Cl -C H Cl m/z 709 m/z 535 3 5 m/z 459 3 5 m/z 383 m/z 209 [M+H]+ = 785 -C4 H9 PO5 -C4 H9 PO5 -C4 H6 O -C H Cl -C H Cl m/z 291 3 5 m/z 215 3 5 m/z 139
DEGBDCIPP-IM6 (TCIPP) -C3 H5 Cl -C H Cl -C H Cl m/z 99 m/z 251 3 5 m/z 175 3 5 [M+H]+ = 327 -C4 H7 ClO
-C4 H7 ClO
DEGBDCIPP-IM5 -C3 H5 Cl -H3 PO4 -C H Cl -C2 H4 O m/z 107 m/z 281 3 5 m/z 205 m/z 63 [M+H]+ = 357
24
