TY - JOUR
T1 - Ion trap tandem mass spectrometry applied to small multiply charged oligonucleotides with a modified base
AU - McLuckey, Scott A.
AU - Habibi-Goudarzi, Sohrab
N1 - Funding Information:
Thisw ork was supported by the National Institutes of Health under grant ROl GM45372 Oak Ridge National Laboratory is managed for the U.S. Department of Energy under Contract DE-AC05-84OR21400 by Martin Marietta Energy Systems, Inc. SHG acknowledges support through an appointment to the Oak Ridge National Laboratory Postdoctoral Research Associates Prc-gram administered jointly by the Oak Ridge Institute for Science and Education and Oak Ridge National Laboratory.
PY - 1994/8
Y1 - 1994/8
N2 - Two isomeric oligodeoxynucleotide hexamers, 5′-d(N-6meATGCAT)-3′ and 5′-d(ATGSmeCAT)-3′, were subjected to analysis by electrospray and ion trap mass spectrometry. In the case of the isomer with a modified adenine, location of the modified base in the sequence was straightforward and a triple mass spectrometry experiment provided information on the identity of the modification. In contrast, the isomer with the methylated cytosine did not yield definitive information on the location or identity of the modification. Tandem mass spectrometry data in this case could indicate that the modification was present on either the third or fourth nucleoside. The two isomers represent extremes in the facility with which modified bases can be identified and located in a small oligonucleotide via multiple mass spectrometry of multiply charged anions. A preference for loss of particular bases strongly influences which structurally diagnostic ions are formed upon collisional activation. The likelihood for locating and identifying a modified base is dependent, therefore, upon the likelihood that the base is lost directly from the parention.
AB - Two isomeric oligodeoxynucleotide hexamers, 5′-d(N-6meATGCAT)-3′ and 5′-d(ATGSmeCAT)-3′, were subjected to analysis by electrospray and ion trap mass spectrometry. In the case of the isomer with a modified adenine, location of the modified base in the sequence was straightforward and a triple mass spectrometry experiment provided information on the identity of the modification. In contrast, the isomer with the methylated cytosine did not yield definitive information on the location or identity of the modification. Tandem mass spectrometry data in this case could indicate that the modification was present on either the third or fourth nucleoside. The two isomers represent extremes in the facility with which modified bases can be identified and located in a small oligonucleotide via multiple mass spectrometry of multiply charged anions. A preference for loss of particular bases strongly influences which structurally diagnostic ions are formed upon collisional activation. The likelihood for locating and identifying a modified base is dependent, therefore, upon the likelihood that the base is lost directly from the parention.
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U2 - 10.1016/1044-0305(94)80006-5
DO - 10.1016/1044-0305(94)80006-5
M3 - Article
C2 - 24222001
AN - SCOPUS:0001678484
VL - 5
SP - 740
EP - 747
JO - Journal of the American Society for Mass Spectrometry
JF - Journal of the American Society for Mass Spectrometry
SN - 1044-0305
IS - 8
ER -