Atmospheric Solid Analysis Probe â Ion Mobility Mass Spectrometry of ...
Atmospheric Solid Analysis Probe – Ion Mobility Mass Spectrometry of Polypropylene
Caroline BARRERE1,2,3, Florian MAIRE1,2,3, Carlos AFONSO1,2,3*, Pierre GIUSTI4.
1
2
INSA de Rouen, avenue de l’Université, 76801 Saint Etienne du Rouvray, France. 3
4
Université de Rouen, IRCOF, rue Tesnière, 76130 Mont-Saint-Aignan, France.
CNRS UMR 6014, COBRA, rue Tesnière, 76130 Mont-Saint-Aignan, France.
TOTAL Refining & Chemicals, European Research and Technical Center, Rogerville, France.
Supplementary Information Contribution of TWIM We can note that TWIM is important to facilitate mass spectrometry data treatment. For example, the ASAP-MS mass spectrum of PP1 is presented Figure S1. In this case, a large difference of intensity between stabilizers and pyrolysis residues indicates, the apparent absence of pyrolysis residues signals.
1
Figure S1: ASAP-MS spectrum (without TWIM separation) obtained for PP1. The most important advantage of TWIM is the post-ionization separation the ions. Indeed, without any ion mobility separation, certain signals from stabilizers and pyrolysis residues were overlapped, as shown Figure S2(a). In this case, the use of TWIM allow the different signals to be easily attributed to PP pyrolysis residues Figure S2(b) and to Irganox 1010 Figure S2(c). This separation will be essential in the case of isomers.
2
Figure S2: Expanded view of (a) ASAP-MS spectrum (without TWIM separation), (b) pyrolysis residues signal and Irganox 1010 signal in ASAP-TWIM-MS mode obtained for PP1.
Identification of Stabilizers Identification of all stabilizers was supported by accurate mass measurements. They have been realized from the ASAP-MS spectrum using background ion of ASAP source at m/z 277.0777 as internal reference (see Table S1).
Table S1: Accurate mass measurements supporting identification of stabilizers detected for PP1 and PP2
Sample PP1 PP2
Detected stabilizers Irganox 1010 Irganox 1076 Irganox PS 802 Irganox 1010
Elemental composition C73H108O12 C35H62O3 C42H82O4S C73H108O12
m/z theo (M+•) 1176.7835 530.4693 682.5928 1176.7835
m/z exp (M+•) 1176.7760 530.4700 682.5901 1176.7777
Error (ppm) -6.4 +1.3 -4.0 -4.9
3
Irgafos 168 Oxidized Irgafos 168
C42H63O3P C42H63O4P
646.4509 662.4458
646.4495 662.4446
-2.2 -4.9
MS/MS of m/z 530.5 ion The identification of several ions observed on ASAP-TWIM-MS spectrum of PP1 was supported by MS/MS experiment of molecular ion of Irganox 1076 at m/z 530.5. This ion was selected and fragmented using collision induced dissociation activation (see spectrum Figure S2).
Figure S3: MS/MS spectrum of Irganox 1076 ion at m/z 530.5 (PP1 sample) obtained with energy in center-of-mass frame of 1.75 eV. Moreover, accurate mass measurement of the different fragments ions were done using precursor ion as an internal reference. The results were given in Table S2. Briefly, fragment ion at m/z 515.4 could be produced through a CH3● loss from the precursor ion. The fragment ion at m/z 474.4 corresponds to a loss of 2-methyl propene from tert-butyl group of precursor ion.
4
Moreover, the fragment ion at m/z 459.4 could be explained by a combination of CH3● and 2methyl propene losses from the precursor ion. The ion at m/z 263.2 could be explained by a loss of the alkyl group (C18H36) from the m/z 515.4 ion. The ions at m/z 232.2 and 219.2 could correspond to dissociation, respectively in alpha and beta position of the carbonyl group. Table S2: Accurate mass measurements supporting identification of ions obtained for Irganox 1076 fragmentation. The precursor ion was used as an internal reference. Elemental composition C34H59O3 C31H54O3 C30H51O3 C16H23O3 C16H24O C15H23O
m/z theo (M+•) 515.4459 474.4067 459.3833 263.1642 232.1822 219.1743
m/z exp 515.4456 474.4060 459.3828 263.1638 232.1823 219.1743
Error (ppm) -0.6 -1.5 -1.1 -1.5 +0.4 +0.0
MS/MS of ion at m/z 646.5 The identification of several ions observed on ASAP-TWIM-MS spectrum of PP2 was supported by MS/MS experiment of molecular ion of Irgafos 168 at m/z 646.5. This ion was selected and fragmented using collision-induced dissociation activation (see spectrum Figure S3).
5
Figure S4: MS/MS spectrum of Irgafos 168 ion at m/z 646.5 (PP2 sample) obtained with energy in center-of-mass frame of 0.58 eV. We can note that Figure S3 shows a mixture of molecular ion (M+●) and protonated molecule (MH+) of Irgafos 168. The [M+H]+ ion is present only as a minor species in the mass spectrum (overlapped with the 13C isotope of the molecular ion) but as it is more stable than the M+● it is reinforced in terms of relative intensity in the CID spectrum. Moreover, only one fragment ion was observed at m/z 441.3 produced through a loss of a stabilizer arm, as supported by accurate mass measurement given in Table S3.
6
Table S3: Accurate mass measurements supporting identification of ions obtained for Irgafos 168 fragmentation. The precursor ion was used as an internal reference. Elemental composition C28H42O2P
m/z theo (M+•) 441.2917
m/z exp 441.2922
Error (ppm) +1.1
7
Caroline BARRERE1,2,3, Florian MAIRE1,2,3, Carlos AFONSO1,2,3*, Pierre GIUSTI4.
1
2
INSA de Rouen, avenue de l’Université, 76801 Saint Etienne du Rouvray, France. 3
4
Université de Rouen, IRCOF, rue Tesnière, 76130 Mont-Saint-Aignan, France.
CNRS UMR 6014, COBRA, rue Tesnière, 76130 Mont-Saint-Aignan, France.
TOTAL Refining & Chemicals, European Research and Technical Center, Rogerville, France.
Supplementary Information Contribution of TWIM We can note that TWIM is important to facilitate mass spectrometry data treatment. For example, the ASAP-MS mass spectrum of PP1 is presented Figure S1. In this case, a large difference of intensity between stabilizers and pyrolysis residues indicates, the apparent absence of pyrolysis residues signals.
1
Figure S1: ASAP-MS spectrum (without TWIM separation) obtained for PP1. The most important advantage of TWIM is the post-ionization separation the ions. Indeed, without any ion mobility separation, certain signals from stabilizers and pyrolysis residues were overlapped, as shown Figure S2(a). In this case, the use of TWIM allow the different signals to be easily attributed to PP pyrolysis residues Figure S2(b) and to Irganox 1010 Figure S2(c). This separation will be essential in the case of isomers.
2
Figure S2: Expanded view of (a) ASAP-MS spectrum (without TWIM separation), (b) pyrolysis residues signal and Irganox 1010 signal in ASAP-TWIM-MS mode obtained for PP1.
Identification of Stabilizers Identification of all stabilizers was supported by accurate mass measurements. They have been realized from the ASAP-MS spectrum using background ion of ASAP source at m/z 277.0777 as internal reference (see Table S1).
Table S1: Accurate mass measurements supporting identification of stabilizers detected for PP1 and PP2
Sample PP1 PP2
Detected stabilizers Irganox 1010 Irganox 1076 Irganox PS 802 Irganox 1010
Elemental composition C73H108O12 C35H62O3 C42H82O4S C73H108O12
m/z theo (M+•) 1176.7835 530.4693 682.5928 1176.7835
m/z exp (M+•) 1176.7760 530.4700 682.5901 1176.7777
Error (ppm) -6.4 +1.3 -4.0 -4.9
3
Irgafos 168 Oxidized Irgafos 168
C42H63O3P C42H63O4P
646.4509 662.4458
646.4495 662.4446
-2.2 -4.9
MS/MS of m/z 530.5 ion The identification of several ions observed on ASAP-TWIM-MS spectrum of PP1 was supported by MS/MS experiment of molecular ion of Irganox 1076 at m/z 530.5. This ion was selected and fragmented using collision induced dissociation activation (see spectrum Figure S2).
Figure S3: MS/MS spectrum of Irganox 1076 ion at m/z 530.5 (PP1 sample) obtained with energy in center-of-mass frame of 1.75 eV. Moreover, accurate mass measurement of the different fragments ions were done using precursor ion as an internal reference. The results were given in Table S2. Briefly, fragment ion at m/z 515.4 could be produced through a CH3● loss from the precursor ion. The fragment ion at m/z 474.4 corresponds to a loss of 2-methyl propene from tert-butyl group of precursor ion.
4
Moreover, the fragment ion at m/z 459.4 could be explained by a combination of CH3● and 2methyl propene losses from the precursor ion. The ion at m/z 263.2 could be explained by a loss of the alkyl group (C18H36) from the m/z 515.4 ion. The ions at m/z 232.2 and 219.2 could correspond to dissociation, respectively in alpha and beta position of the carbonyl group. Table S2: Accurate mass measurements supporting identification of ions obtained for Irganox 1076 fragmentation. The precursor ion was used as an internal reference. Elemental composition C34H59O3 C31H54O3 C30H51O3 C16H23O3 C16H24O C15H23O
m/z theo (M+•) 515.4459 474.4067 459.3833 263.1642 232.1822 219.1743
m/z exp 515.4456 474.4060 459.3828 263.1638 232.1823 219.1743
Error (ppm) -0.6 -1.5 -1.1 -1.5 +0.4 +0.0
MS/MS of ion at m/z 646.5 The identification of several ions observed on ASAP-TWIM-MS spectrum of PP2 was supported by MS/MS experiment of molecular ion of Irgafos 168 at m/z 646.5. This ion was selected and fragmented using collision-induced dissociation activation (see spectrum Figure S3).
5
Figure S4: MS/MS spectrum of Irgafos 168 ion at m/z 646.5 (PP2 sample) obtained with energy in center-of-mass frame of 0.58 eV. We can note that Figure S3 shows a mixture of molecular ion (M+●) and protonated molecule (MH+) of Irgafos 168. The [M+H]+ ion is present only as a minor species in the mass spectrum (overlapped with the 13C isotope of the molecular ion) but as it is more stable than the M+● it is reinforced in terms of relative intensity in the CID spectrum. Moreover, only one fragment ion was observed at m/z 441.3 produced through a loss of a stabilizer arm, as supported by accurate mass measurement given in Table S3.
6
Table S3: Accurate mass measurements supporting identification of ions obtained for Irgafos 168 fragmentation. The precursor ion was used as an internal reference. Elemental composition C28H42O2P
m/z theo (M+•) 441.2917
m/z exp 441.2922
Error (ppm) +1.1
7
