Recognition and quantification of binary and ternary mixtures of isomeric peptides by the kinetic method: metal ion and ligand effects on the dissociation of metal-bound complexes

The kinetic method is applied to differentiate and quantify mixtures of isomeric tripeptides based on the competitive dissociations of divalent metal ion-bound clusters in an ion trap mass spectrometer. This methodology is extended further to determine compositions of ternary mixtures of the isomers Gly-Gly-Ala (GGA), Ala-Gly-Gly (AGG), and Gly-Ala-Gly (GAG). This procedure also allows to perform chiral quantification of a ternary mixture of optical isomers. The divalent metal ion Ca(II) is particularly appropriate for isomeric distinction and quantification of the isobaric tripeptides Gly-Gly-Leu/Gly-Gly-Ile (GGL/GGI). Among the first-row transition metal ions, Cu(II) yields remarkably effective isomeric differentiation for both the isobaric tripeptides, GGI/GGL using GAG as the reference ligand, and the positional isomers GAG/GGA using GGI as the reference ligand. This is probably due to agostic bonding: alpha-agostic bonding occurs between Cu(II) and GAG and beta-agostic bonding between Cu(II) and GGI, each produces large but different steric effects on the stability of the Cu(II)-bound dimeric clusters. These data form the basis for possible future quantitative analyses of mixtures of larger peptides such as are generated, for example, in combinatorial synthesis of peptides and peptide mimics.     

Die Mikrobestimmung der Oxyäthylengruppe

Zusammenfassung Es wurde eine Mikromethode für die Bestimmung von Oxyäthylengruppen ausgearbeitet. Das Prinzip der Methode beruht darauf, daß Äthylenoxydverbindungen beim Sieden mit Jodwasserstoffsäure neben anderen Produkten eine äquivalente Menge Jod liefern, die durch Titration mit Natriumthiosulfat bestimmt wird.Es wurde eine einfache Apparatur erprobt, die selbst geringe Jodverluste verhindert.

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Summary A micromethod has been worked out for the determination of oxyethylene groups. Its principle is based on the fact that on boiling with hydriodic acid, the ethylene oxide compounds yield, along with other products, an equivalent quantity of iodine, which can be measured by titration with sodium thiosulfate.A simple apparatus has been tested, which prevents the loss of even slight amounts of iodine.

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Résumé On a mis au point une microméthode pour doser les groupes oxéthyles. Le principe de la méthode repose sur le fait que les composés de l'oxyde d'éthylène, portés à l'ébullition avec de l'acide iodhydrique, libèrent, à côté d'autres produits, une quantité équivalente d'iode que l'on titre par le thiosulfate de sodium.On a expérimenté un appareil simple qui empêche les pertes en iode, même faibles.

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Herrn Dipl.-Ing.J. Simandl danken wir für die anregende Diskussion und die Überlassung von oxyäthylierten Aminen. Herrn Dipl.-Ing.J. Kami danken wir für die Überlassung von Proben reiner Polyglykoläther. Die Wasserbestimmung nachK. Fischer führte HerrZ. Netuil aus.     

Approximation algorithms for scheduling unrelated parallel machines

We consider the following scheduling problem. There arem parallel machines andn independent jobs. Each job is to be assigned to one of the machines. The processing of jobj on machinei requires timep _ij . The objective is to find a schedule that minimizes the makespan.Our main result is a polynomial algorithm which constructs a schedule that is guaranteed to be no longer than twice the optimum. We also present a polynomial approximation scheme for the case that the number of machines is fixed. Both approximation results are corollaries of a theorem about the relationship of a class of integer programming problems and their linear programming relaxations. In particular, we give a polynomial method to round the fractional extreme points of the linear program to integral points that nearly satisfy the constraints.In contrast to our main result, we prove that no polynomial algorithm can achieve a worst-case ratio less than 3/2 unlessP = NP. We finally obtain a complexity classification for all special cases with a fixed number of processing times.A preliminary version of this paper appeared in theProceedings of the 28th Annual IEEE Symposium on the Foundations of Computer Science (Computer Society Press of the IEEE, Washington, D.C., 1987) pp. 217–224.     

Nonlinear theory of the compressible gas flows over a nonuniform boundary in the gravitational field in the shallow-water approximation

A set of equations is derived for the motion of a compressible ideal gas over a nonuniform boundary in the gravitational field in the shallow-water approximation. Classical simple waves are shown not to be the solutions to this set of equations. Generalized simple waves are found to exist only in the case of a linear underlying-surface profile. All continuous and discontinuous solutions are obtained in an explicit form for the case of the boundary in the form of an inclined plane, and an analytical solution is found for the problem of the decay of an arbitrary discontinuity. This solution consists of four wave configurations. Necessary and sufficient conditions are determined for the existence of each configuration.     

An aperiodic set of 13 Wang tiles

A new aperiodic tile set containing only 13 tiles over 5 colors is presented. Its construction is based on a recent technique developed by Kari. The tilings simulate the behavior of sequential machines that multiply real numbers in balanced representations by real constants.     

Linearly polarized, 3.35 W narrow-linewidth, 1150 nm fiber master oscillator power amplifier for frequency doubling to the yellow

A high-power linearly polarized Yb-doped silica fiber master oscillator power amplifier at 1150 nm is reported. It produced 3.35 W cw and 2.33 W of average power in 1 micros pulses at a 100 kHz repetition rate, both with 8 pm linewidth. This is the first report, to the best of our knowledge, of a high-power Yb-doped fiber amplifier at a wavelength longer than 1135 nm. The pulsed output was frequency doubled in a bulk periodically poled near-stoichiometric LiTaO(3) chip to generate 976 mW of average power at 575 nm with an overall system optical-to-optical efficiency of 9.8% with respect to launched pump power.     

Breakdown magnetic field in an inductively coupled plasma

The Paschen curve shows that the breakdown voltage over a gap is a non-linear function of the product of the gas pressure and the gap distance for plasmas which are generated inside an electric field driven source. The Paschen breakdown relationship does not depend on the applied frequency and covers secondary emission at the electrodes of the discharge. Adapting the Paschen curve, a breakdown curve for a time-dependent magnetic field, typical for inductively coupled plasmas which sources are without electrodes, is examined here. It is shown that in this case the magnetic field breakdown curve does depend on the applied frequency.     

Diamond/graphite content and biocompatibility of DLC films fabricated by PLD

Biocompatibility and physicochemical properties of diamond-like carbon (DLC) thin layers prepared by pulsed laser deposition method were studied. The films of high and low diamond/graphite content were prepared by changing the laser energy density on the graphite target from 4 to 11 J cm⁻². The bonds and surface properties as roughness, atomic force microscopy topology, contact angle parameters, and zeta potential were measured. The cell adhesion/proliferation on DLC layers was tested using normal human fibroblasts and keratinocytes.