Tandem Mass Spectrometry of Trimethylsilyl-Terminated Poly(Dimethylsiloxane) Ammonium Adducts Generated by Electrospray Ionization

被引:31
作者
Fouquet, Thierry [1 ,2 ,3 ,4 ]
Humbel, Stephane [5 ]
Charles, Laurence [1 ,2 ,3 ]
机构
[1] Univ Aix Marseille 1, CNRS, UMR 6264, Lab Chim Provence, Marseille, France
[2] Univ Aix Marseille 2, CNRS, UMR 6264, Lab Chim Provence, F-13284 Marseille 07, France
[3] Univ Aix Marseille 3, CNRS, UMR 6264, Lab Chim Provence, Marseille, France
[4] CRPHT, Dept Adv Mat & Struct, Esch Sur Alzette, Luxembourg
[5] Aix Marseille Univ, CNRS, UMR 6263, Inst Sci Mol Marseille, Marseille, France
关键词
Synthetic polymers; Tandem mass spectrometry; PDMS; Ammonium adducts; Dissociation pathways; Ab initio calculation; COLLISION-INDUCED DISSOCIATION; MOLECULAR-ORBITAL METHODS; BASIS-SET; STRUCTURAL INFORMATION; OXIDATIVE ADDITION; GAS-PHASE; FRAGMENTATION; OLIGOMERS; IONS; PERFORMANCE;
D O I
10.1007/s13361-010-0073-9
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
Ammonium adducts of trimethylsilyl-terminated poly(dimethylsiloxane) (CH3-PDMS) produced by electrospray ionization were submitted to collision induced dissociation and revealed a particular MS/MS behavior: the same three main product ions at m/z 221, 295, and 369 were always generated in very similar relative abundances regardless of the size of the precursor ion. Combining accurate mass measurements and ab initio calculation allowed very stable cyclic geometries to be obtained for these ionic species. Dissociation mechanisms were proposed to account for the three targeted ions to be readily generated in a two-step or a three-step reaction from any CH3-PDMS ammonium adducts. A second set of three product ions was also observed with low abundance at m/z 207, 281, and 355, which were shown in MS3 experiments to be formed in secondary reactions. An alternative dissociation process was shown to consist of a concerted elimination of ammonia and methane and the need for a methyl of an end-group to be involved in the released methane molecule would account for this reaction to mainly proceed from the smallest precursor ions.
引用
收藏
页码:649 / 658
页数:10
相关论文
共 30 条
[1]   Protonating Polymer Oligomers in the Gas Phase to Change Fragmentation Pathways [J].
Alhazmi, Abdulrahman M. ;
Mayer, Paul M. .
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 2009, 20 (01) :60-66
[2]   MALDI-TOF MS coupled with collision-induced dissociation (CID) measurements of poly(methyl methacrylate) [J].
Baumgaertel, Anja ;
Becer, C. Remzi ;
Gottschaldt, Michael ;
Schubert, Ulrich S. .
MACROMOLECULAR RAPID COMMUNICATIONS, 2008, 29 (15) :1309-1315
[3]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[4]   Extension of Gaussian-2 (G2) theory to molecules containing third-row atoms K and Ca [J].
Blaudeau, JP ;
McGrath, MP ;
Curtiss, LA ;
Radom, L .
JOURNAL OF CHEMICAL PHYSICS, 1997, 107 (13) :5016-5021
[5]   Evidence for the low thermal stability of poly(methyl methacrylate) polymer produced by atom transfer radical polymerisation [J].
Borman, CD ;
Jackson, AT ;
Bunn, A ;
Cutter, AL ;
Irvine, DJ .
POLYMER, 2000, 41 (15) :6015-6020
[6]   Insights in Molecular Structure of Organosilicon Plasma Polymer Produced by Means of Atmospheric Pressure Dielectric Barrier Discharge Process [J].
Bour, Jerome ;
Charles, Laurence ;
Petersen, Julien ;
Michel, Marc ;
Bardon, Julien ;
Ruch, David .
PLASMA PROCESSES AND POLYMERS, 2010, 7 (08) :687-694
[7]   Influence of internal standard charge state on the accuracy of mass measurements in orthogonal acceleration time-of-flight mass spectrometers [J].
Charles, Laurence .
RAPID COMMUNICATIONS IN MASS SPECTROMETRY, 2008, 22 (02) :151-155
[8]   Endgroup-assisted siloxane bond cleavage in the gas phase [J].
Chen, HP .
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 2003, 14 (09) :1039-1048
[9]   Oxidative addition of the fluoromethane C-F bond to Pd. An ab initio benchmark and DFT validation study [J].
de Jong, GT ;
Bickelhaupt, FM .
JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (42) :9685-9699
[10]   DFT benchmark study for the oxidative addition of CH4 to Pd.: Performance of various density functionals [J].
de Jong, GT ;
Geerke, DP ;
Diefenbach, A ;
Bickelhaupt, FM .
CHEMICAL PHYSICS, 2005, 313 (1-3) :261-270