Structures of Lithiated Lysine and Structural Analogues in the Gas Phase: Effects of Water and Proton Affinity on Zwitterionic Stability †
ABSTRACT The structures of lithiated lysine, ornithine, and related molecules, both with and without a water molecule, are investigated using both density functional theory and blackbody infrared radiative dissociation experiments. The lowest-energy structure of lithiated lysine without a water molecule is nonzwitterionic; the metal ion interacts with both nitrogen atoms and the carbonyl oxygen. Structures in which lysine is zwitterionic are higher in energy by more than 29 kJ/mol. In contrast, the singly hydrated clusters with the zwitterionic and nonzwitterionic forms of lysine are more similar in energy, with the nonzwitterionic form more stable by only approximately 7 kJ/mol. Thus, a single water molecule can substantially stabilize the zwitterionic form of an amino acid. Analogous molecules that have methyl groups attached to either the N-terminus (NMeLys) or the side-chain amine (Lys(Me)) have proton affinities greater than that of lysine. In the lithiated clusters with a water molecule attached, the zwitterionic forms of NMeLys and Lys(Me) are calculated to be approximately 4 and approximately 11 kJ/mol more stable than the nonzwitterionic forms, respectively. Calculations of the potential-energy pathway for interconversion between the different forms of lysine in the lithiated complex indicate multiple stable intermediates with an overall barrier height of approximately 83 kJ/mol between the lowest-energy nonzwitterionic form and the most accessible zwitterionic form. Experimentally determined binding energies of water are similar for all these complexes and range from 57 to 64 kJ/mol. These results suggest that loss of a water molecule from the lysine complexes is both energetically and entropically favored compared to interconversion between the nonzwitterionic and zwitterionic structures. Comparisons to calculated binding energies of water to the various structures show that the experimental results are most consistent with the nonzwitterionic forms.
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ABSTRACT: We propose a distributed rate control scheme for throughput maximization and different QoS support of each user in the 3GPP WCDMA system using the variable spreading factor of physical channel specification. We focus on the uplink rather than downlink for the reason that the uplink resource is not used effectively by the multiple access. The base station transmits rate command bits and persistence value p considering current load and number of users with each transmission rate. And each mobile station performs the persistence test and changes transmission rate. The performance of the proposed scheme is compared with other conventional methods by simulation. The simulation results show that the proposed scheme has high throughput and supports proper differentiation according to the user's QoSVehicular Technology Conference, 2001. VTC 2001 Fall. IEEE VTS 54th; 02/2001
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ABSTRACT: In aqueous solution, amino acids (AA) and peptides are known to exist as zwitterions over a large pH range. However, in the gas phase, i.e. in electrospray (ESI), the zwitterionic form becomes unfavorable owing to the absence of stabilizing effects from intermolecular solvation. Nevertheless, during mass spectrometry experiments, the presence of a metallic cation can reinforce the zwitterionic character of the molecule and thus influence its fragmentation under low energy collision-induced dissociation (CID) conditions. The [M + Cu(II)](2+) complexes of six pentapeptides (YGGFL, YGGFL(NH(2)), YGGFK, YGGFQ, KYGGF and QYGGF) were analyzed by collision to highlight the presence of zwitterions. The experiments were performed on a 3D-ion trap equipped with an orthogonal ESI source. For each peptides studied, negative-charge driven fragmentations on globally positively charged ions were observed. These fragmentation mechanisms, generally observed in the negative mode, suggest the competitive deprotonation of the C-terminal carboxylic acid or of the tyrosine side-chain residue for each peptide studied and thus a zwitterionic form to preserve the charge balance. Moreover, the specific loss of (CH(3)--C(6)H(4)--O)(*) characterizes YGGFK compared to YGGFQ and the specific loss of styrene characterizes KYGGF compared to QYGGF. These results allow the differentiation of the two couples of isobaric pentapeptides. An unusual loss of NH(4) (+), which occurred from the N-terminus, was also observed for YGGFL, YGGFL(NH(2)), YGGFK and YGGFQ. Finally, the reduction of Cu(II) to Cu(I), concomitant with the (CH(3)--C(6)H(4)--O)(*) release, was pointed out for YGGFK.Journal of Mass Spectrometry 01/2007; 42(1):25-35. DOI:10.1002/jms.1127 · 2.38 Impact Factor
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ABSTRACT: The gas-phase structures of protonated and alkali metal cationized arginine (Arg) and arginine methyl ester (ArgOMe) are investigated with infrared spectroscopy and ab initio calculations. Infrared spectra, measured in the hydrogen-stretch region, provide compelling evidence that arginine changes from its nonzwitterionic to zwitterionic form with increasing metal ion size, with the transition in structure occurring between lithium and sodium. For sodiated arginine, evidence for both forms is obtained from spectral deconvolution, although the zwitterionic form is predominant. Comparisons of the photodissociation spectra with spectra calculated for low-energy candidate structures provide additional insights into the detailed structures of these ions. Arg*Li+, ArgOMe*Li+, and ArgOMe*Na+ exist in nonzwitterionic forms in which the metal ion is tricoordinated with the amino acid, whereas Arg*Na+ and Arg*K+ predominately exist in a zwitterionic form where the protonated side chain donates one hydrogen bond to the N terminus of the amino acid and the metal ion is bicoordinated with the carboxylate group. Arg*H+ and ArgOMe*H+ have protonated side chains that form the same interaction with the N terminus as zwitterionic, alkali metal cationized arginine, yet both are unambiguously determined to be nonzwitterionic. Calculations indicate that for clusters with protonated side chains, structures with two strong hydrogen bonds are lowest in energy, in disagreement with these experimental results. This study provides new detailed structural assignments and interpretations of previously observed fragmentation patterns for these ions.Journal of the American Chemical Society 03/2007; 129(6):1612-22. DOI:10.1021/ja066335j · 12.11 Impact Factor