| 1. |
- Al-Khalili, A, et al.
(författare)
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Dissociative recombination cross section and branching ratios of protonated dimethyl disulfide and N-methylacetamide
- 2004
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 121:12, s. 5700-5708
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Tidskriftsartikel (refereegranskat)abstract
- Dimethyl disulfide (DMDS) and N-methylacetamide are two first choice model systems that represent the disulfide bridge bonding and the peptide bonding in proteins. These molecules are therefore suitable for investigation of the mechanisms involved when proteins fragment under electron capture dissociation (ECD). The dissociative recombination cross sections for both protonated DMDS and protonated N-methylacetamide were determined at electron energies ranging from 0.001 to 0.3 eV. Also, the branching ratios at 0 eV center-of-mass collision energy were determined. The present results give support for the indirect mechanism of ECD, where free hydrogen atoms produced in the initial fragmentation step induce further decomposition. We suggest that both indirect and direct dissociations play a role in ECD.
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| 2. |
- Geppert, W D, et al.
(författare)
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Dissociative recombination of nitrile ions : DCCCN+ and DCCCND
- 2004
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Ingår i: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 613:2, s. 1302-1309
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Tidskriftsartikel (refereegranskat)abstract
- Branching ratios and absolute cross sections have been measured for the dissociative recombination of DCCCN+ and DCCCND+ using the CRYRING ion storage ring. In the case of DCCCN+ the dissociation yielding D + C3N and those leading to two fragments containing a pair of heavy atoms dominate, whereas pathways producing a fragment with three heavy atoms play only a minor role. Conversely, for DCCCND+, only those channels preserving the carbon chain or producing two fragments with a pair of heavy atoms each are detected. The cross sections of the reactions are very similar and can be fitted to the expressions sigma = (2.9 +/- 0.5) x 10(-15)E(eV)(-1.05 +/- 0.02) cm(2) and sigma = (2.3 +/- 0.4) x 10(-15)E(eV)(-1.10 +/- 0.02) cm(2) for DCCCN+ and DCCCND+, respectively. From these data, thermal reaction rates of k(T) = (1.5 +/- 0.3) x 10(-6)(T/300 K)(-0.60 +/- 0.02) cm(3) s(-1) and k(T) = (1.5 +/- 0.3) x 10(-6)(T/300 K)(-0.58 +/- 0.02) cm(3) s(-1) were calculated for DCCCN+ and DCCCND+, respectively. These rates and branching ratios are compared with those hitherto used in astrophysical models.
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| 3. |
- Geppert, W D, et al.
(författare)
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Dissociative recombination of (SO2+)-O-18 : Evidence for three-body breakup
- 2004
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Ingår i: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 610:2, s. 1228-1233
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Tidskriftsartikel (refereegranskat)abstract
- Branching ratios and absolute cross sections have been measured for the dissociative recombination of (SO2+)-O-18 using the CRYRING ion storage ring. The branching ratio of the (SO2+)-O-18 + e(-)-->(SO)-O-18+O-18 channel amounts to 61%, while the three-body breakup (SO2+)-O-18 + e(-)-->S+2(18)O accounts for the remaining 39% of the total reaction. The cross section of the reaction could be fitted by the expression sigma=(1.2+/-0.4)x10(-15) E-0.96+/-0.02 cm(2), which leads to a thermal reaction rate of k(T)=(4.6+/-0.2)x10(-7)(T/300 K)(-0.52+/-0.02) cm(3) mol(-1) s(-1).
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| 4. |
- Geppert, W D, et al.
(författare)
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Dissociative recombination of C3H4+ : preferential formation of the C3H3 radical
- 2004
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Ingår i: International Journal of Mass Spectrometry. - : Elsevier BV. - 1387-3806 .- 1873-2798. ; 237:1, s. 25-32
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Tidskriftsartikel (refereegranskat)abstract
- Branching ratios and absolute cross sections have been measured for the dissociative recombination of C3H4+ using the CRYRING ion storage ring. The pre-eminent channel involves the production of C3H3 and H, whereas processes involving rupture of carbon-carbon bonds are clearly disfavoured. The cross section of the reaction could be fitted to the expression sigma = 5.5 +/- 0.2 x 10(-15) E-1.01+/-0.02, which leads to a thermal reaction rate of k(T) = 2.95 +/- 0.1 x 10(-6) (T/300)(-0.67+/-0.02) cm(3) s(-1).
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| 5. |
- Geppert, W. D., et al.
(författare)
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Dissociative recombination of N2H+ : Evidence for fracture of the N-N bond
- 2004
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Ingår i: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 609:1, s. 459-464
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Tidskriftsartikel (refereegranskat)abstract
- Branching ratios and absolute cross sections have been measured for the dissociative recombination of N2H+ using the CRYRING ion storage ring. It has been found that the channel N2H+ + e(-) --> N-2 + H accounts for only 36% of the total reaction and that the branching into the other exoergic pathway, N2H+ + e(-) --> NH + N, consequently amounts to 64%. The cross section of the reaction could be fitted by the expression sigma = (2.4 +/- 0.4) x 10(-16) E-1.04 +/- 0.02 cm(2), which leads to a thermal reaction rate of k(T) = (1.0 +/- 0.2) x 10(-7)(T/300)(-0.51 +/- 0.02) cm(3) s(-1), in favorable agreement with previous flowing afterglow Langmuir probe measurements at room temperature, although our temperature dependence is very different. The implications of these measurements for the chemistry of interstellar clouds are discussed. A standard model calculation for a dark cloud predicts a slight increase of N2H+ in the dark clouds but a five- to sevenfold increase of the NH concentration as steady state is reached.
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| 6. |
- Geppert, W D, et al.
(författare)
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Dissociative recombination of N2OD
- 2004
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 6:13, s. 3415-3419
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Tidskriftsartikel (refereegranskat)abstract
- Branching ratios and absolute cross sections have been measured for the dissociative recombination of N2OD+ using the CRYRING ion storage ring. The most dominating pathways were found to be those eading to N-2 + OD (46%) and the three-body break-up producing N-2 + O + D (40%). The production of N2O is not observed. The cross section of the reaction could be fitted to the expression sigma = 1.25 +/- 0.25 x 10(-15)(E/eV)(-1.24+/-0.02), which leads to a thermal reaction rate of k(T) = 1.4 +/- 0.1 x 10(-6)(T/300)(-0.74+/-0.02) cm(3) s(-1). The findings are compared with those of the related dissociative recombination of DOCO+ as well as with earlier flowing afterglow measurements.
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| 7. |
- Geppert, W D, et al.
(författare)
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Extraordinary branching ratios in astrophysically important dissociative recombination reactions
- 2004
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Ingår i: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 127, s. 425-437
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Tidskriftsartikel (refereegranskat)abstract
- Branching ratios of the dissociative recombination reactions of the astrophysically relevant ions DCO+, N2H+ and DOCO+ ( as substitute for HOCO+) have been measured using the CRYRING storage ring at the Manne Siegbahn Laboratory at the University of Stockholm, Sweden. For DCO+, the channel leading to D and CO was by far the most important one ( branching ratio 0.88), only small contributions of the CD+O and OD+C product pathways ( branching ratios 0.06 each) were recorded. In the case of N2H+ the surprising result of a break-up of the N-N bond to N and NH ( branching ratio 0.64) was found with the branching ratio of the N-2+H product channel therefore displaying a branching ratio of only 0.36. In the case of DOCO+, the three-body break-up into D+O+CO dominated ( branching ratio 0.68), whereas the contribution of the CO2+H channel was only minute (0.05). The remaining share ( branching ratio 0.27) was taken by the pathway leading to OH+CO. For the dissociative recombination of N2H+ and DOCO+ also absolute reaction cross sections were obtained in the collisional energy range between 0 and 1 eV. From these cross sections it was possible to work out the thermal rate constants, which were found to be k(T) = 1.0 +/- 0.1 x 10(-7) (T/300 K)(-0.51 +/- 0.02) cm(3) s(-1) and k(T) = 1.2 +/- 0.1 x 10(-6) (T/300 K)(-0.64 +/- 0.02) cm(3) s(-1) for N2H+ and DOCO+, respectively.
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| 8. |
- Fritioff, K, et al.
(författare)
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Single and double detachment from H-
- 2004
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Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622 .- 2469-9926 .- 2469-9934. ; 69:4, s. 042707-
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Tidskriftsartikel (refereegranskat)abstract
- Absolute cross sections for single and double detachment from H- following electron impact have been measured over a range of collision energies from the thresholds to 170 eV. The measurements were made using a magnetic storage ring. The ions in the ring were merged with a monoenergetic electron beam and neutral and positively charged fragments were detected. We cover larger energy ranges than in many of the previous experiments, and this is the first time both single and double detachment have been measured simultaneously. This allows us to present accurate ratios between the single and double detachment cross sections. On the basis of these ratio measurements we discuss possible mechanisms leading to double detachment.
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| 9. |
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| 10. |
- Voets, T, et al.
(författare)
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Intracellular calcium dependence of large dense-core vesicle exocytosis in the absence of synaptotagmin I.
- 2001
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Ingår i: Proceedings of the National Academy of Sciences of the United States of America. - : Proceedings of the National Academy of Sciences. - 0027-8424 .- 1091-6490. ; 98:20, s. 11680-5
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Tidskriftsartikel (refereegranskat)abstract
- Synaptotagmin I is a synaptic vesicle-associated protein essential for synchronous neurotransmission. We investigated its impact on the intracellular Ca(2+)-dependence of large dense-core vesicle (LDCV) exocytosis by combining Ca(2+)-uncaging and membrane capacitance measurements in adrenal slices from mouse synaptotagmin I null mutants. Synaptotagmin I-deficient chromaffin cells displayed prolonged exocytic delays and slow, yet Ca(2+)-dependent fusion rates, resulting in strongly reduced LDCV release in response to short depolarizations. Vesicle recruitment, the shape of individual amperometric events, and endocytosis appeared unaffected. These findings demonstrate that synaptotagmin I is required for rapid, highly Ca(2+)-sensitive LDCV exocytosis and indicate that it regulates the equilibrium between a slowly releasable and a readily releasable state of the fusion machinery. Alternatively, synaptotagmin I could function as calcium sensor for the readily releasable pool, leading to the destabilization of the pool in its absence.
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