Dissociative recombination of water cluster ions with free electrons: cross sections and branching ratios.

Dissociative recombination (DR) of water cluster ions H(+)(H(2)O)(n) (n=4-6) with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, branching ratios have been determined for the dominating product channels and absolute DR cross sections have been measured in the energy range from 0.001 to 0.7 eV. Dissociative recombination is concluded to result in extensive fragmentation for all three cluster ions, and a maximum number of heavy oxygen-containing fragments is produced with a probability close to unity. The branching ratio results agree with earlier DR studies of smaller water cluster ions where the channel nH(2)O+H has been observed to dominate and where energy transfer to internal degrees of freedom has been concluded to be highly efficient. The absolute DR cross sections for H(+)(H(2)O)(n) (n=4-6) decrease monotonically with increasing energy with an energy dependence close to E(-1) in the lower part of the energy range and a faster falloff at higher energies, in agreement with the behavior of other studied heavy ions. The cross section data have been used to calculate DR rate coefficients in the temperature range of 10-2000 K. The results from storage ring experiments with water cluster ions are concluded to partly confirm the earlier results from afterglow experiments. The DR rate coefficients for H(+)(H(2)O)(n) (n=1-6) are in general somewhat lower than reported from afterglow experiments. The rate coefficient tends to increase with increasing cluster size, but not in the monotonic way that has been reported from afterglow experiments. The needs for further experimental studies and for theoretical models that can be used to predict the DR rate of polyatomic ions are discussed.

Dissociative recombination of H+(H2O)3 and D+(D2O)3 water cluster ions with electrons: cross sections and branching ratios.

Dissociative recombination (DR) of the water cluster ions H(+)(H(2)O)(3) and D(+)(D(2)O)(3) with electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, absolute DR cross sections have been measured for H(+)(H(2)O)(3) in the energy range of 0.001-0.8 eV, and relative cross sections have been measured for D(+)(D(2)O)(3) in the energy range of 0.001-1.0 eV. The DR cross sections for H(+)(H(2)O)(3) are larger than previously observed for H(+)(H(2)O)(n) (n=1,2), which is in agreement with the previously observed trend indicating that the DR rate coefficient increases with size of the water cluster ion. Branching ratios have been determined for the dominating product channels. Dissociative recombination of H(+)(H(2)O)(3) mainly results in the formation of 3H(2)O+H (probability of 0.95+/-0.05) and with a possible minor channel resulting in 2H(2)O+OH+H(2) (0.05+/-0.05). The dominating channels for DR of D(+)(D(2)O)(3) are 3D(2)O+D (0.88+/-0.03) and 2D(2)O+OD+D(2) (0.09+/-0.02). The branching ratios are comparable to earlier DR results for H(+)(H(2)O)(2) and D(+)(D(2)O)(2), which gave 2X(2)O+X (X=H,D) with a probability of over 0.9.

Dissociative recombination of protonated methanol.

The branching ratios of the different reaction pathways and the overall rate coefficients of the dissociative recombination reactions of CH3OH2+ and CD3OD2+ have been measured at the CRYRING storage ring located in Stockholm, Sweden. Analysis of the data yielded the result that formation of methanol or deuterated methanol accounted for only 3 and 6% of the total rate in CH3OH2+ and CD3OD2+, respectively. Dissociative recombination of both isotopomeres mainly involves fragmentation of the C-O bond, the major process being the three-body break-up forming CH3, OH and H (CD3, OD and D). The overall cross sections are best fitted by sigma = 1.2 +/- 0.1 x 10(-15) E(-1.15 +/- 0.02) cm2 and sigma = 9.6 +/- 0.9 x 10(-16) E(-1.20 +/- 0.02) cm2 for CH3OH2+ and CD3OD2+, respectively. From these values thermal reaction rate coefficients of k(T) = 8.9 +/- 0.9 x 10(-7) (T/300)(-0.59 +/- 0.02) cm3 s(-1) (CH3OH2+) and k(T) = 9.1 +/- 0.9 x 10(-7) (T/300)(-0.63 +/- 0.02) cm3 s(-1) (CD3OD2+) can be calculated. A non-negligible formation of interstellar methanol by the previously proposed mechanism via radiative association of CH3+ and H2O and subsequent dissociative recombination of the resulting CH3OH2+ ion to yield methanol and hydrogen atoms is therefore very unlikely.

Branching ratios and absolute cross sections of dissociative recombination processes of N2O+.

We have investigated the dissociative recombination of the N2O+ ion using the CRYRING heavy-ion storage ring at the Manne Siegbahn laboratory in Stockholm, Sweden. The dissociative recombination branching ratios were determined at minimal (approximately 0 eV) collision energy, showing that the dominating pathways involved two-body fragmentation: N2 + O (48%) and NO + N (36%). The branching ratio of the three-body break-up 2N + O was 16%. The overall thermal rate coefficient of the title reaction follows the expression k(T) = 3.34 +/- 0.75 x 10(-7) (T/300) (-0.57+/- 0.03 cm3 s(-1)), which correlates perfectly with earlier flowing afterglow studies on the same process.

Dissociative recombination cross section and branching ratios of protonated dimethyl disulfide and N-methylacetamide.

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.

Dissociative recombination of NH4+ and ND4+ ions: storage ring experiments and ab initio molecular dynamics.

The dissociative recombination (DR) process of NH4+ and ND4+ molecular ions with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). The absolute cross sections for DR of NH4+ and ND4+ in the collision energy range 0.001-1 eV are reported, and thermal rate coefficients for the temperature interval from 10 to 2000 K are calculated from the experimental data. The absolute cross section for NH4+ agrees well with earlier work and is about a factor of 2 larger than the cross section for ND4+. The dissociative recombination of NH4+ is dominated by the product channels NH3+H (0.85+/-0.04) and NH2+2H (0.13+/-0.01), while the DR of ND4+ mainly results in ND3+D (0.94+/-0.03). Ab initio direct dynamics simulations, based on the assumption that the dissociation dynamics is governed by the neutral ground-state potential energy surface, suggest that the primary product formed in the DR process is NH3+H. The ejection of the H atom is direct and leaves the NH3 molecule highly vibrationally excited. A fraction of the excited ammonia molecules may subsequently undergo secondary fragmentation forming NH2+H. It is concluded that the model results are consistent with gross features of the experimental results, including the sensitivity of the branching ratio for the three-body channel NH2+2H to isotopic exchange.

Recombination of simple molecular ions studied in storage ring: dissociative recombination of H2O+

Dissociative recombination of vibrationally relaxed H2O+ ions with electrons has been studied in the heavy-ion storage ring CRYRING. Absolute cross-sections have been measured for collision energies between 0 eV and 30 eV. The energy dependence of the cross-section below 0.1 eV is found to be much steeper than the E-1 behaviour associated with the dominance of the direct recombination mechanism. Resonant structures found at 4 eV and 11 eV have been attributed to the electron capture to Rydberg states converging to electronically excited ionic states. Complete branching fractions for all dissociation channels have been measured at a collision energy of 0 eV. The dissociation process is dominated by three-body H + H + O breakup that occurs with a branching ratio of 0.71.

Nitrogen Utilization in Lemna: II. Studies of Nitrate Uptake Using NO(3).

(13)N-labeled nitrate was used to trace short-term nitrate influx into Lemna gibba L. G3 in experiments where disappearance of both radioactivity and total nitrate from the incubation medium was measured continuously and simultaneously. In plants performing net nitrate uptake from an initial nitrate concentration of 40 to 60 micromolar, there was no discrepancy between net uptake and influx, irrespective of the N status of the plants, indicating that concomitant nitrate efflux was low or nil. Plants treated with tungstate to inactivate nitrate reductase were able to take up nitrate following induction of the uptake system by exposure to a low amount of nitrate. Also, in this case, net uptake was equivalent to influx. In tungstate-treated plants preloaded with nitrate, both net uptake and influx were nil. In contrast to these observations, a clear discrepancy between net uptake and influx was observed when the plants were incubated at an initial nitrate concentration of approximately 5 micromolar, where net uptake is low and eventually ceases. It is concluded that plasmalemma nitrate transport is essentially unidirectional in plants performing net uptake at a concentration of 40 to 60 micromolar, and that transport is nil when internal nitrate sinks (vacuole, metabolism) are eliminated. The efflux component becomes increasingly important when the external concentration approaches the threshold value for net nitrate uptake (the nitrate compensation point) where considerable exchange between internal and external nitrate occurs.

Nitrogen Utilization in Lemna: III. Short-Term Effects of Ammonium on Nitrate Uptake and Nitrate Reduction.

The effects of ammonium application on nitrate utilization were studied in N-limited cultures of Lemna gibba L. G3. Addition of ammonium instantaneously inhibited net nitrate uptake by at least 60%, followed by a slight recovery. The inhibition was equally clear after near-complete inactivation of glutamine synthetase by application of l-methionine-d,l-sulfoximine. Experiments where (13)N-labeled nitrate was used as an influx tracer revealed that ammonium specifically inhibited influx, but did not promote nitrate efflux. Nitrate accumulation was relatively more inhibited than nitrate reduction and net uptake. Nitrate reductase, extracted and assayed in vitro in the presence of the thiol proteinase inhibitor leupeptin, was unaffected by short-term treatment of the plants with either nitrate, ammonium, or ammonium nitrate. Nitrate reductase activity recovered in the absence of leupeptin was considerably lower; however, it was enhanced by all the nitrogen sources, with ammonium as the most potent. It is argued that the effect of ammonium on nitrate utilization in Lemna is due to inhibition of nitrate influx, and that the effect should be attributed to ammonium itself, not to a newly formed nitrogen derivative. The decreased nitrate flux caused a decrease in nitrate reduction, whereas the activity of nitrate reductase per se rather is stabilized by presence of ammonium.

Short-term studies of NO 3 (-) uptake in Pisum using (13)NO 3 (-).

Influx, efflux and net uptake of NO 3 (-) was studied in Pisum sativum L. cv. Marma in short-term experiments where (13)NO 3 (-) was used to trace influx. The influx rate in N-limited plants was similar both during net uptake at external concentrations of around 50 µM, and at low external NO 3 (-) concentrations (4-6 µM) when net uptake was practically zero. Efflux could be inferred from discrepancies between influx and net uptake but was never very high in the N-limited plants during net uptake. Close to the threshold concentration for not NO 3 (-) uptake, efflux was high and equalled influx. Thus, the threshold concentration can be regarded as a NO 3 (-) compensation point. The inclusion of NH 4 (+) in the outer medium decreased influx by about 40% but did not significantly affect efflux. The roles of NO 3 (-) fluxes and nitrate-reductase activity in regulating/limiting NO 3 (-) utilization are discussed.

C-11-labeled glucose and its utilization in positron-emission tomography.

Carbon-11-labeled glucose was prepared photosynthetically using the green alga Scenedesmus obtusiusculus Chod. The carbohydrates were extracted from the cells with dilute HCI and the glucose was isolated and purified using high-performance liquid chromatography. The manipulations in the hot cell are described. Analysis of the material (gas liquid chromatography and HPLC) showed that the glucose obtained was radiochemically pure. The total incorporation of the 11CO2 added to the algae was 60-80%. The radiochemical yield of pure carrier-added glucose was approximately 25%, at 40 min after E.O.B. including the HPLC purification and sterile filtration. The C-11 glucose uptake in rat brain was compared with that of commercial D[U-14C]glucose, and preliminary PET studies with D-[11C]glucose in a patient with a brain infarct are presented.