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According to the IUPAC definition, the interconversion of the two enantiomers is not a true epimerization because two stereocenters change configuration, see
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According to the IUPAC definition, the interconversion of the two enantiomers is not a true epimerization because two stereocenters change configuration, see: http://goldbook.iupac.org/E02167.html.
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79952061815
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note
-
2 at about 2 mbar) serves as the stationary phase and provides a resistance against forward transport. For two isobaric ions of different shape ("potato and cigar"), the more compact one interacts less with the buffer gas and thus reaches the detector before the more extended ion of identical mass.
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21
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79952047054
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note
-
The experiments were performed with a SYNAPT G2 ion-mobility mass spectrometer (Waters, Manchester, UK). In brief, the instrument has an ESI source from which the ions are extracted towards a quadrupole mass filter (Q) for parent-ion selection. In the ion-mobility mode, the ions are first collected in an argon-filled linear ion trap (Trap) and then admitted in pulses through a helium cooling cell into the ion-mobility unit (IM) in which nitrogen is present at an approximate pressure of 2 mbar. Next, the ions pass a transfer cell (Trans) and enter the source region of a reflectron time-of-flight (TOF) mass spectrometer, which continuously records mass spectra with a mass resolution (m/Δm) of approximately 25000.
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22
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39149137577
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For recent reviews of ion-mobility measurements of gaseous ions, see: a
-
For recent reviews of ion-mobility measurements of gaseous ions, see: a) A. B. Kanu, P. Dwivedi, M. Tam, L. Matz, H. H. Hill, Jr., J. Mass Spectrom. 2007, 43, 1-22;
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Kanu, A.B.1
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Hill Jr., H.H.5
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23
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57449100366
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b) B. C. Bohrer, S. I. Mererbloom, S. L. Koeniger, A. E. Hilderbrand, D. E. Clemmer, Annu. Rev. Anal. Chem. 2008, 1, 293-327;
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24
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50149120507
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c) J. Puton, M. Nousiainen, M. Sillanpaa, Talanta 2008, 76, 978-987.
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Puton, J.1
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25
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33845524655
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Aside from gravity, our IM-MS setup does not have any element of asymmetry. Thus, enantiomeric ions cannot be distinguished from each other. Such a separation can be achieved by addition of chiral dopants to the mobility unit, see
-
Aside from gravity, our IM-MS setup does not have any element of asymmetry. Thus, enantiomeric ions cannot be distinguished from each other. Such a separation can be achieved by addition of chiral dopants to the mobility unit, see: P. Dwivedi, C. Wu, L. M. Matz, B. H. Clowers, W. F. Siems, H. H. Hill, Jr., Anal. Chem. 2006, 78, 8200-8206.
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Dwivedi, P.1
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Hill Jr., H.H.6
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26
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34249796694
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For an ESI study on the mechanism of formation of Tröger bases, see
-
For an ESI study on the mechanism of formation of Tröger bases, see: C. A. M. Abella, M. Benassi, L. S. Santos, M. N. Eberlin, F. Coelho, J. Org. Chem. 2007, 72, 4048-4054.
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Coelho, F.5
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27
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33846811132
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The arrival times in the SYNAPT G2 very much depend on the adjustments of the pressures and the voltage settings and can only be compared relative to each other. Also see
-
The arrival times in the SYNAPT G2 very much depend on the adjustments of the pressures and the voltage settings and can only be compared relative to each other. Also see: S. D. Pringle, K. Giles, J. L. Wildgoose, J. P. Williams, S. E. Slade, K. Thalassinos, R. H. Baterman, M. T. Bowers, J. H. Scrivens, Int. J. Mass Spectrom. 2007, 261, 1-12.
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Pringle, S.D.1
Giles, K.2
Wildgoose, J.L.3
Williams, J.P.4
Slade, S.E.5
Thalassinos, K.6
Baterman, R.H.7
Bowers, M.T.8
Scrivens, J.H.9
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28
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54849429587
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For a detailed consideration of the ESI process, see
-
For a detailed consideration of the ESI process, see: W. D. Luedtke, U. Landman, Y.-H. Chiu, D. J. Levandler, R. A. Dressler, S. Sok, M. S. Gordon, J. Phys. Chem. A 2008, 112, 9628-9649.
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34
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79952054817
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note
-
Other types of ESI sources do not apply a cone voltage, but most ESI sources have a device with a similar function to modify the ionization conditions.
-
-
-
-
35
-
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77954248081
-
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For a recent example of probing the interconversion of different conformers using ion mobility, see
-
For a recent example of probing the interconversion of different conformers using ion mobility, see: M. Grabenauer, T. Wyttenbach, N. Sanghera, S. E. Slade, T. J. T. Pinheiro, J. H. Scrivens, M. T. Bowers, J. Am. Chem. Soc. 2010, 132, 8816-8818.
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Pinheiro, T.J.T.5
Scrivens, J.H.6
Bowers, M.T.7
-
36
-
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79952047819
-
-
note
-
i stands for the corresponding ion abundances. The difference between the two compounds is small but was observed reproducibly at five different collision energies.
-
-
-
-
37
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43049141516
-
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The calculations were performed using the M06-2X density functional in conjunction with 6-311++G(2df,2pd) basis sets. Energies refer to 0 K and include zero-point vibrational energy
-
The calculations were performed using the M06-2X density functional (Y. Zhao, D. G. Truhlar, Theor. Chem. Acc. 2008, 120, 215-241) in conjunction with 6-311++G(2df,2pd) basis sets. Energies refer to 0 K and include zero-point vibrational energy.
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Theor. Chem. Acc.
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Zhao, Y.1
Truhlar, D.G.2
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38
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79952064869
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note
-
-1 higher in energy.
-
-
-
-
39
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77956438198
-
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For a recent example, see
-
For a recent example, see: L. Ducháčková, A. Kadlčíková, M. Kotora, J. Roithová, J. Am. Chem. Soc. 2010, 132, 12660-12667.
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Ducháčková, L.1
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41
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R. Imbihl, R. J. Behm, R. Schlögl, Phys. Chem. Chem. Phys. 2007, 9, 3459.
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Imbihl, R.1
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