SUPPORTING INFORMATION
MS/MS sequencing in the negative mode to read binary information encoded in
sequence-defined poly(alkoxyamine amide)s
Laurence Charles,1* Chloé Laure,2 Jean-François Lutz2* and Raj Kumar Roy2
Aix-Marseille Université – CNRS, UMR 7273, Institut de Chimie Radicalaire, Marseille
Cedex 20, France – Email: laurence.charles@univ-amu.fr
2
Precision Macromolecular Chemistry, Institut Charles Sadron, UPR22-CNRS, BP84047, 23
rue du Loess, 67034 Strasbourg Cedex 2, France. Email: jflutz@unistra.fr
1
Content
page
Scheme S1. Dissociation of protonated oligo(alkoxyamine amide)s in the positive mode …...
S2
Table S1. Exact mass measurement of product ions from [α-1-T-1-T-1-T-1-T-1-T-1-Br –H]–
S2
Figure S1. MS3 experiments performed for [α-(1-T)5-1- – H]– …………………….………..
S3
Scheme S2. Formation of secondary fragments during CID of [α-(1-T)n-1- – H]– ………….
S4
Table S2. Exact mass measurement of product ions from [α-1-T-1-T-0-T-1-T-1-T-0-Br –H]–
S4
–
S4
Table S3. Exact mass measurement of product ions from [α-1-T-1-T-0-T-1-T-0-T-1-Br –H]
Figure S2. ESI-MS/MS of the deprotonated α-0-T-1-T-1- oligomer ………………………..
S5
Table S4. Exact mass measurement of product ions from [α-1-T-1-T-1-T-1-T-NH2 –H]– ……
S5
S1
Scheme S1. MS/MS dissociation of protonated oligo(alkoxyamine amide)s in the positive mode and
nomenclature of product ions generated upon homolysis of each C–ON bond between a coding unit (0
when R = H, 1 when R = CH3) and a TEMPO nitroxide moiety. Product ions containing the α
termination were named c (i.e., the third letter of the alphabet) since the cleaved C–ON bond is the
third one in any X-T moieties (with X=0 or 1) considered as the building blocks of the oligomers from
a dissociation viewpoint. Similarly, product ions containing the  termination were named y (i.e., the
second letter starting from the end of the alphabet) since the cleaved C–ON bond is the second one in
any X-T moieties when numbering bonds from right to left and not counting bonds involved in the T
cycle. Superscripted "•" and "+" signs added to this letter account for the distonic character of these
protonated radicals, while the number of partial or entire X-T building blocks is indicated as a
subscript.
composition
m/zth
Main product ions
C71H129N11O13Br–
1422.8960
•–
1103.7939
C58H105N9O11
863.6101
C45H81N7O9•–
•–
623.4263
C32H57N5O7
383.2426
C19H33N3O5•–
•–
143.0588
C6H9NO3
–
C6H8NO3
142.0510
Secondary product ions
1033.7520
C54H99N9O10•–
•–
793.5683
C41H75N7O8
553.3845
C28H51N5O6•–
–
C45H82N7O10
880.6129
C32H58N5O8–
640.4291
C19H34N3O6–
400.2453
m/zexp
assignment
I.S.
1103.7965
863.5994
623.4273
383.2405
143.0601
142.0518
[M – H]– : [α-1-T-1-T-1-T-1-T-1-T-1- – H]–
c5•–: [α-1-T-1-T-1-T-1-T-1• – H]–
c4•–: [α-1-T-1-T-1-T-1• – H]–
c3•–: [α-1-T-1-T-1• – H]–
c2•–: [α-1-T-1• – H]–
c1•–: [α-1• – H]–
1033.7531
793.5607
553.3857
880.5972
640.4225
400.2460
c5•– – O=C=C(CH3)2
c4•– – O=C=C(CH3)2
c3•– – O=C=C(CH3)2
[α-1-T-1-T-1-T-1-OH – H]–
[α-1-T-1-T-1-OH – H]–
[α-1-T-1-OH – H]–
Table S1. Mass measurements of product ions generated from [α-1-T-1-T-1-T-1-T-1-T-1- –H]– (with
 = 79Br) at m/z 1422.9 (Figure 2a). I.S.: internal standard.
S2
Figure S1. Left: Negative mode ESI. a1) MS/MS of [α-(1-T)5-1- – H]– at m/z 1422.9 and MS3
spectra obtained after activation of b1) c5•– at m/z 1103.8, c1) c4•– at m/z 863.6, and d1) c3•– at m/z
623.4. Symbols designate the same secondary fragments observed in Figure 2, while peaks annotated
with italicized m/z values were specifically observed in MS3 experiments. Right: Positive mode ESI.
a2) MS/MS of [α-(1-T)5-1- + H]+ at m/z 1424.9 and MS3 spectra obtained after activation of b2) c5•+
at m/z 1105.8, c2) c4•+ at m/z 865.6, and d2) c3•+ at m/z 625.4. Peaks designated by open diamonds
correspond to internal fragments, formed after ci•+ have eliminated the α-1 moiety as a radical to
generate protonated cyclic (T-1)x species (with x>1).
S3
Scheme S2. Secondary fragments designated by open squares (a) and open triangles (b) in MS/MS
spectra of Figure 2 are proposed to arise from dissociation of primary ci•– product ions, as exemplified
here with the case of c4•–.
composition
m/zth
Main product ions
C69H125N11O13Br–
1394.8647
1089.7783
C57H103N9O11•–
•–
849.5945
C44H79N7O9
609.4107
C31H55N5O7•–
•–
383.2426
C19H33N3O5
143.0588
C6H9NO3•–
–
C6H8NO3
142.0510
Secondary product ions
1019.7364
C53H97N9O10•–
•–
779.5526
C40H73N7O8
C44H80N7O10–
866.5972
C31H56N5O8–
626.4134
m/zexp
assignment
I.S.
1089.7741
849.5965
609.4072
383.2398
143.0550
142.0537
[M – H]– : [α-1-T-1-T-0-T-1-T-1-T-0- – H]–
c5•–: [α-1-T-1-T-0-T-1-T-1• – H]–
c4•–: [α-1-T-1-T-0-T-1• – H]–
c3•–: [α-1-T-1-T-0• – H]–
c2•–: [α-1-T-1• – H]–
c1•–: [α-1• – H]–
1019.7392
779.5531
866.5986
640.4225
c5•– – O=C=C(CH3)2
c4•– – O=C=C(CH3)2
[α-1-T-1-T-0-T-1-OH – H]–
[α-1-T-1-T-0-OH – H]–
Table S2. Mass measurements of product ions generated from [α-1-T-1-T-0-T-1-T-1-T-0- – H]–
(with  = 79Br) at m/z 1394.9 (Figure 2a). I.S.: internal standard.
composition
m/zth
Main product ions
C69H125N11O13Br–
1394.8647
1075.7626
C56H101N9O11•–
•–
849.5945
C44H79N7O9
•–
609.4107
C31H55N5O7
383.2426
C19H33N3O5•–
•–
143.0588
C6H9NO3
C6H8NO3–
142.0510
Secondary product ions
1005.7207
C52H95N9O10•–
779.5526
C40H73N7O8•–
–
C31H56N5O8
626.4134
m/zexp
assignment
I.S.
1075.7581
849.5955
609.4086
383.2444
143.0571
142.0545
[M – H]– : [α-1-T-1-T-0-T-1-T-0-T-1- – H]–
c5•–: [α-1-T-1-T-0-T-1-T-0• – H]–
c4•–: [α-1-T-1-T-0-T-1• – H]–
c3•–: [α-1-T-1-T-0• – H]–
c2•–: [α-1-T-1• – H]–
c1•–: [α-1• – H]–
1005.7200
779.5558
626.4138
c5•– – O=C=C(CH3)2
c4•– – O=C=C(CH3)2
[α-1-T-1-T-0-OH – H]–
Table S3. Mass measurements of product ions generated from [α-1-T-1-T-0-T-1-T-0-T-1- – H]–
(with  = 79Br) at m/z 1394.9 (Figure 2b). I.S.: internal standard.
S4
Figure S2. ESI-MS/MS of the deprotonated α-0-T-1-T-1- oligo(alkoxyamine amide) recorded at a
1.20 eV energy (center-of-mass frame).
composition
m/zth
m/zexp
assignment
Main product ions
C54H100N9O10–
1034.7599
I.S.
[M – H]– : [α-1-T-1-T-1-T-1-T-NH2 – H]–
863.6101
863.6089 c4•–: [α-1-T-1-T-1-T-1• – H]–
C45H81N7O9•–
•–
623.4263
623.4219 c3•–: [α-1-T-1-T-1• – H]–
C32H57N5O7
•–
383.2426
383.2413 c2•–: [α-1-T-1• – H]–
C19H33N3O5
•–
143.0588
143.0592 c1•–: [α-1• – H]–
C6H9NO3
–
C6H8NO3
142.0510
142.0520
Secondary product ions
793.5683
793.5662 c4•– – O=C=C(CH3)2
C41H75N7O8•–
–
C32H58N5O8
640.4291
640.4252 [α-1-T-1-T-1-OH – H]–
C19H34N3O6–
400.2453
400.2460 [α-1-T-1-OH – H]–
Table S4. Mass measurements of product ions generated from [α-1-T-1-T-1-T-1-T-NH2 – H]– at m/z
1034.8 (Figure 4). I.S.: internal standard.
S5