Synthesis and crystallographic characterization of a dicyclopentadienylvanadium alkynide complex: (C5H5)2VCCC(CH3)3

(C₅H₅)₂VCl reacts with LiCCC(CH₃)₃ to form (C₅H₅)₂VCCC(CH₃)₃ which was characterized by spectroscopic, analytical, and crystallographic methods. The complex crystallizes from pentane at 0°C as a monomer in the orthorhombic space group Pnma with four molecules in a unit cell of dimensions a 9.075(3), b 9.807(3), c 16.444(5) Å. Full-matrix least-squares refinement based upon 1300 nonzero intensity data converged to a final conventional R factor of 0.060. The molecule has a mean VC₅H₅-ring centroid distance of 1.941 Å with 146.6° ring centroid-V-ring centroid angle. The vanadium alkynide carbon distance is 2.075(5) Å.     

Rapid quantitative capillary zone electrophoresis method for monitoring the micro-heterogeneity of an intact recombinant glycoprotein

A simple high-resolution capillary zone electrophoresis (CZE) method capable of rapidly assessing the micro-heterogeneity of a 24 kDa molecular weight glycoprotein, has been developed. Separation is carried out using a bare silica capillary at a pH of 2.5 in a commercially available electrophoresis buffer system composed of triethanolamine and phosphoric acid. Over 30 peaks were detected within a run time of 15 min using a 27 cm capillary and approximately 60 peaks were detected using a 77 cm capillary. Although most of the peaks arise from differences in the oligosaccharide structures present on the one glycosylation site on this molecule, other forms of micro-heterogeneity due to the presence of the nonglycosylated form of this glycoprotein and various types of chemical degradation, e.g., deamidation, are also responsible for the multitude of peaks observed. Although the exact chemical identity of each peak in the resulting electropherogram of this glycoprotein is not known, useful information can be obtained for assessing comparability, stability, and batch consistency. Factors impacting the resolution, precision, accuracy, and robustness of the assay are also discussed along with inherent advantages and limitations associated with measuring the micro-heterogeneity of intact glycoproteins.     

Evaluation of multidimensional (ion-exchange/reversed-phase) protein separations using linear and step gradients in the first dimension

The performance characteristics of multidimensional liquid chromatographic protein separations were evaluated using on-line electrospray mass detection, and a novel workflow for automated LC/MS data processing. Two-dimensional ion exchange/reversed-phase LC separations of Escherichia coli cytosol were conducted using either a continuous linear or discontinuous step gradient in the first dimension. Chromatographic profiles of the top 100 most abundant components were characterized to assess overall separation reproducibility within each mode, and to characterize differences in component distribution between the two modes of operation. Analysis of the resulting data indicates that multidimensional separations of complex protein mixtures can be done reproducibly. Furthermore, under the conditions employed within this study, a linear first dimension gradient was more effective at fractionating the protein mixture, distributing fewer major components to multiple second dimension cycles than an equivalent step gradient. The application of on line mass spectrometry, and automated processing of the resulting data, proved valuable for producing component level analysis of multidimensional protein separations.     

Absolute infrared intensities of hydrocarbons

Dipole-moment derivatives, calculated by both the CNDO/2 method with different parameterizations and the INDO method, are compared to the experimental values determined from absolute infrared intensity measurements for the IR active modes of methane, ethane, ethylene and acetylene. A parameter refinement procedure is introduced in which the CNDO/2 molecular orbital parameters are adjusted through a damped least-squares treatment to give best agreement with the observed dipole-moment derivatives. It is found that the refinement does not substantially improve the agreement obtained with the original CNDO/2 parameterization. The INDO method gives somewhat poorer agreement than the CNDO/2 calculations. As an example of the applicability of the molecular orbital methods toward reproducing relative infrared intensities, the spectrum of cyclopropane in the gasphase is examined.

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Zusammenfassung Die Ableitungen des Dipol-Moments, die nach der CNDO/2-Methode mit verschiedenen Parametrisierungen sowie der INDO-Methode berechnet wurden, werden mit den experimentellen Ergebnissen aus Messungen der absoluten Infrarot-Intensitäten für die IR-aktiven Schwingungen von Methan, Äthan, Äthylen und Azetylen verglichen. Die CNDO/2-Parameter werden mit einer Methode der kleinsten Quadrate den beobachteten Dipol-Moment-Ableitungen angepaßt. Die Ergebnisse sind jedoch nicht wesentlich von denen der ursprünglichen CNDO/2-Methode verschieden. Die INDO-Ergebnisse sind nicht so gut wie die CNDO/2-Ergebnisse. Als Beispiel der Anwendbarkeit der MO-Methoden zur Berechnung von relativen IR-Intensitäten wird das Spektrum des Cyclopropans in der Gasphase untersucht.

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Résumé Les dérivées du moment dipolaire, calculées par la méthode CNDO/2 avec différentes paramétrisations et par la méthode INDO, sont comparées aux valeurs expérimentales déterminées à partir de mesures d'intensité absolue pour les modes actifs dans l'infra-rouge dans le méthane, l'éthane, l'éthylène et l'acétylène. Les paramètres sont ajustés de manière à donner le meilleur accord avec les dérivées du moment dipolaire. Cet ajustement n'améliore pas sensiblement l'accord obtenu avec la paramétrisation CNDO/2 originale. La méthode INDO donne des résultats moins bons que les calculs CNDO/2. Le spectre du cyclopropane en phase gazeuse est étudié comme exemple de l'applicabilité de la méthode des orbitales moléculaires au calcul des intensités relatives infra-rouge.

     

Aromatic polyethers,polysulfones, and polyketones as laminating resins. IV. Polymers with p-cyclophane units for crosslinking

1,3-Bis(p-phenoxybenzenesulfonyl)benzene, 4,4′-bis(p-phenoxybenzenesulfonyl)diphenyl ether, and 4,4′-diphenoxydiphenyl sulfone were polymerized with isophthaloyl or terephthaloyl chlorides in Friedel-Crafts type polymerizations. These polymers had [2,2]p-cyclophane units in the backbone, introduced by employing 3,9-bis(p-phenoxybenzoyl) [2.2]p-cyclophane as part of the polyaryl ether component. Thermolysis of the dimethylene bridge of the [2.2]p-cyclophane monomer produced diradicals which combined across polymer chains to provide crosslinks. p-Cyclophane polymers with 1,3-bis-(p-phenoxybenzenesulfonyl)benzene showed potential as high performance, thermally stable laminating resins.     

Untersuchung verschiedener Lebensmittel

Ohne Zusammenfassung     

An Efficient Approach to Spirosesquiterrenes. Synthesis of (±)β-Vetivone.

(±)β-Vetivone and (±) 10-epi-β-vetivone have been synthesized in 6 steps via an efficient spiroannelation-functionalization sequence.     

The run-up of nonlinearly deformed sea waves on the coast of a bay with a parabolic cross-section

The run-up of long waves on the coast of a bay with a parabolic cross-section, where the region of constant depth along the principal axis of the bay is connected with the linearly inclined segment, is considered. The study is carried out analytically in the framework of the nonlinear shallow-water theory under the approximation that the height of the initial wave is small compared to the basin depth, and the reflection from the inflection point of the bottom is negligibly small. Three types of incident waves, viz., a sinusoidal wave and solitary waves of positive and negative polarities, are considered in detail. It is shown that a sinusoidal wave undergoes nonlinear deformation at a segment of constant depth faster than solitary waves of positive and negative polarities. Solitary waves of negative polarity steepen somewhat faster than solitary waves of positive polarity. Waves of positive polarity steepen at wave front, while waves of negative polarity steepen at wave rear. These differences in steepness may become crucial at the wave run-up stage, since the wave run-up height on the coast of a bay with a parabolic cross-section is directly proportional to the steepness of a wave that arrives at the slope and can lead to the anomalous run-up of waves on the coast.     

A priori error estimates for nonstationary optimal control problems with gradient state constraints

We are concerned with the discretization of semilinear parabolic optimization problems subject to constraints on the first derivative of the solution of the PDE. Constructing sequences of feasible controls for the dG(0)-cG(1) discretization of the problem and relying on a quadratric growth condtion, we show convergence orders as temporal and spatial mesh tends to zero. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)