On the Heterogeneous Nature of Cisplatin-1-Methyluracil Complexes: Coexistence of Different Aggregation Modes and Partial Loss of NH3 Ligands as Likely Explanation

The conversion of the 1 : 1-complex of Cisplatin with 1-methyluracil (1MeUH), cis-[Pt(NH₃)₂(1MeU-N3)Cl] ( 1 a ) to the aqua species cis-[Pt(NH₃)₂(1MeU-N3)(OH₂)]⁺ ( 1 b ), achieved by reaction of 1 a with AgNO₃ in water, affords a mixture of compounds, the composition of which strongly depends on sample history. The complexity stems from variations in condensation patterns and partial loss of NH₃ ligands. In dilute aqueous solution, 1 a , and dinuclear compounds cis-[(NH₃)₂(1MeU-N3)Pt(μ-OH)Pt(1MeU-N3)(NH₃)₂]⁺( 3 ) as well as head-tail cis-[Pt₂(NH₃)₄(μ-1MeU-N3,O4)₂]²⁺ ( 4 ) represent the major components. In addition, there are numerous other species present in minor quantities, which differ in metal nuclearity, stoichiometry, stereoisomerism, and Pt oxidation state, as revealed by a combination of ¹H NMR and ESI-MS spectroscopy. Their composition appears not to be the consequence of a unique and repeating coordination pattern of the 1MeU ligand in oligomers but rather the coexistence of distinctly different condensation patterns, which include μ-OH, μ-1MeU, and μ-NH₂ bridging and combinations thereof. Consequently, the products obtained should, in total, be defined as a heterogeneous mixture rather than a mixture of oligomers of different sizes. In addition, a N₂ complex, [Pt(NH₃)(1MeU)(N₂)]⁺ appears to be formed in gas phase during the ESI-MS experiment. In the presence of Na⁺ ions, multimers n of 1 a with n=2, 3, 4 are formed that represent analogues of non-metalated uracil quartets found in tetrastranded RNA.     

M-matrix asymptotics for Sturm–Liouville problems on graphs

We consider a system formulation for Sturm–Liouville operators with formally self-adjoint boundary conditions on a graph. An M-matrix associated with the boundary value problem is defined and related to the matrix Prüfer angle associated with the system boundary value problem, and consequently with the boundary value problem on the graph. Asymptotics for the M-matrix are obtained as the eigenparameter tends to negative infinity. We show that the boundary conditions may be recovered, up to a unitary equivalence, from the M-matrix and that the M-matrix is a Herglotz function. This is the first in a series of papers devoted to the reconstruction of the Sturm–Liouville problem on a graph from its M-matrix.     

Phosphorylated serine and threonine residues promote site‐specific fragmentation of singly charged,arginine‐containing peptide ions

In order to investigate gas‐phase fragmentation reactions of phosphorylated peptide ions, matrix‐assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI) tandem mass (MS/MS) spectra were recorded from synthetic phosphopeptides and from phosphopeptides isolated from natural sources. MALDI‐TOF/TOF (TOF: time‐of‐flight) spectra of synthetic arginine‐containing phosphopeptides revealed a significant increase of y ions resulting from bond cleavages on the C‐terminal side of phosphothreonine or phosphoserine. The same effect was found in ESI‐MS/MS spectra recorded from the singly charged but not from the doubly charged ions of these phosphopeptides. ESI‐MS/MS spectra of doubly charged phosphopeptides containing two arginine residues support the following general fragmentation rule: Increased amide bond cleavage on the C‐terminal side of phosphorylated serines or threonines mainly occurs in peptide ions which do not contain mobile protons. In MALDI‐TOF/TOF spectra of phosphopeptides displaying N‐terminal fragment ions, abundant b–H₃PO₄ ions resulting from the enhanced dissociation of the pSer/pThr–X bond were detected (X denotes amino acids). Cleavages at phosphoamino acids were found to be particularly predominant in spectra of phosphopeptides containing pSer/pThr–Pro bonds. A quantitative evaluation of a larger set of MALDI‐TOF/TOF spectra recorded from phosphopeptides indicated that phosphoserine residues in arginine‐containing peptides increase the signal intensities of the respective y ions by almost a factor of 3. A less pronounced cleavage‐enhancing effect was observed in some lysine‐containing phosphopeptides without arginine. The proposed peptide fragmentation pathways involve a nucleophilic attack by phosphate oxygen on the carbon center of the peptide backbone amide, which eventually leads to cleavage of the amide bond. Copyright © 2009 John Wiley & Sons, Ltd.     

Two-, three-, and four-interval forced-choice staircase procedures: estimator bias and efficiency

Threshold estimates for multiple-interval forced-choice staircase procedures were studied using computer simulations. A sigmoidal psychometric function shape governed the hypothetical subject's responses in the simulations. Parameters varied included the number of trials, the step size for stimulus level change, and decision rules that targeted 70.7% and 79.4% correct performance. Each threshold estimate was calculated by averaging the stimulus levels at which a reversal a stimulus level direction occurred. The results of the simulations suggest that, as the number of alternatives is increased from 2 to 4, the variability of repeated threshold estimates decreases or remains constant, and the accuracy of the estimator, in most cases, improves. A subset of the simulations was compared with data obtained in a detection-in-noise task. The behavioral data were consistent with the simulation results. Two major conclusions were reached. First, 3- and 4-interval forced-choice (IFC) procedures are more efficient than a 2IFC procedure with a decision rule that targets 70.7% correct performance even when the additional time required to complete 3- and 4IFC trials is considered. Second, the accuracy of 2IFC procedures can be improved by fitting the trial history of a staircase run using probit analysis.     

Simplified formulas for non-normal reflection from monoclinic crystals

Based on Berreman's 4 × 4 matrix formalism [W. Berreman, J. Opt. Soc. Am. 62, 502 (1972)] we derive simplified expressions for the reflection formulas from the a-c crystal surface for non-normal incidence. The computational effort to apply the formulas was found to be only insignificantly higher than those for normal incidence, but considerably lower than for the general expressions. Consequently, the simplified formulas can be readily applied for dispersion analysis of spectra gained by spectroscopic ellipsometry or attenuated total reflection.