Oligodeoxynucleotide fragmentation in MALDI/TOF mass spectrometry using 355-nm radiation
Oligodeoxynucleotide fragmentation in MALDI/TOF mass spectrometry using 355-nm radiation
复制标题
使用 355 nm 辐射进行 MALDI/TOF 质谱分析中的寡脱氧核苷酸断裂
DOI：
10.1021/ja00127a018
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发表时间：
1995
影响因子：
15
通讯作者：
Lloyd M. Smith
中科院分区：
文献类型：
--
作者：
Lin;G. Parr;M. Fitzgerald;C. M. Nelson;Lloyd M. Smith
The fragmentation of small oligodeoxynucleotides using matrix-assisted laser desorption/ionization (MAL DI) mass spectrometry with 355-nm radiation from the matrix 2,5-dihydroxybenzoic acid is studied. Negative ion mass spectra of the homopolymer oligodeoxynucleotides d(A){sub n}, d(C){sub n}, and d(G){sub n} (n = 4, 6, 8, and 10) show substantial cleavage at N-glycosidic and phosphodiester bonds, in contrast to d(T){sub n} which shows little fragmentation. The number and intensity of the fragment peaks increase significantly with the length of the parent molecules. A series of asymmetric oligodeoxynucleotides were synthesized to study this fragmentation in greater detail. In dT{sub 4}GT{sub 10}, dT{sub 4}G{sub 4}T{sub 7}, and dT{sub 7}G{sub 4}T{sub 4}, the primary fragmentation pathway is loss of a base followed by backbone cleavage at the 3{prime} C-O bond of the corresponding deoxyribose. Similar fragmentation patterns were observed with dT{sub 4}N{sub 4}T{sub 7} samples where N = C or A. A statistical cleavage model described the observed patterns of fragmentation well; the model yields fractions of backbone cleavage at A, C, and G of 0.13, 0.26, and 0.27, respectively. In contrast to the fragmentation observed using 2,5-dihydroxybenzoic acid as a matrix, little or no fragmentation is observed with the matrix 3-hydroxypicolinic acid. Fragmentation of oligodeoxynucleotidesmore » in UV/MALDI is thus both nucleobase and matrix dependent. 35 refs., 9 figs., 5 tabs.« less
The fragmentation of small oligodeoxynucleotides using matrix-assisted laser desorption/ionization (MAL DI) mass spectrometry with 355-nm radiation from the matrix 2,5-dihydroxybenzoic acid is studied. Negative ion mass spectra of the homopolymer oligodeoxynucleotides d(A){sub n}, d(C){sub n}, and d(G){sub n} (n = 4, 6, 8, and 10) show substantial cleavage at N-glycosidic and phosphodiester bonds, in contrast to d(T){sub n} which shows little fragmentation. The number and intensity of the fragment peaks increase significantly with the length of the parent molecules. A series of asymmetric oligodeoxynucleotides were synthesized to study this fragmentation in greater detail. In dT{sub 4}GT{sub 10}, dT{sub 4}G{sub 4}T{sub 7}, and dT{sub 7}G{sub 4}T{sub 4}, the primary fragmentation pathway is loss of a base followed by backbone cleavage at the 3{prime} C-O bond of the corresponding deoxyribose. Similar fragmentation patterns were observed with dT{sub 4}N{sub 4}T{sub 7} samples where N = C or A. A statistical cleavage model described the observed patterns of fragmentation well; the model yields fractions of backbone cleavage at A, C, and G of 0.13, 0.26, and 0.27, respectively. In contrast to the fragmentation observed using 2,5-dihydroxybenzoic acid as a matrix, little or no fragmentation is observed with the matrix 3-hydroxypicolinic acid. Fragmentation of oligodeoxynucleotidesmore » in UV/MALDI is thus both nucleobase and matrix dependent. 35 refs., 9 figs., 5 tabs.« less