Dirichletsche Reihen auf arithmetischen Progressionen

A characterisation of all real Δ≠0 is given, such that $$\overline {f(\sigma + i\Delta \mathbb{N})} = \overline {f(\sigma + i\mathbb{R})} $$ holds for all Dirichlet seriesf(s)=Σa _n n ^?s and all σ greater than the abscissa of absolute convergence off. For only countably many Δ relation (*) is not valid. By using transcendental results it is shown, that (*) holds in the special case, Δ=1.     

Die Komplexe von Dioxocyan (OCN)2 mit TiCl4 und ZrCl4

Complexes of Dioxocyanogen (OCN)₂ with TiCl₄ and ZrCl₄ A solution of (OCN)₂ was obtained by reaction of AgOCN with Br₂ in H₂CCl₂ at ?70°C. From this the complexes TiCl₄(NCO)₂ and ZrCl₄(NCO)₂ were obtained by addition of equimolar amounts of TiCl₄ and ZrCl₄, respectively. According to the i.r. and Raman spectra, the (NCO)₂ ligand is bonded via its N atoms to the metal.     

Density fluctuations in amorphous and semicrystalline polymers

Summary The small-angle scattering of amorphous and semicrystalline polymers contains an intensity component due to density fluctuations within the crystalline and amorphous domains.For amorphous polymers, the density fluctuations aboveT _g correspond to the theoretical value for a fluid system in thermodynamic equilibrium. BelowT _g , a temperature dependence proportional to T is observed over a range of about 50°. At lower temperatures, a linear relationship with a smaller slope has been found which extrapolates to a non-zero value at 0 °K. This value corresponds to the frozen-in disorder, the slope at low temperatures is related to thermal vibrations and can be evaluated in terms of photon-phonon scattering.Semicrystalline polymers show a temperature dependence of the density fluctuation similar to that of the amorphous polymers. At constant temperature the density fluctuations vary linearly with crystallinity.Natural rubber shows an increase of the density fluctuations with increasing cross-linking densities from which information on the density changes in the vicinity of a cross-link and on the statistics of the distribution of cross-linking can be obtained.

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Zusammenfassung Die Kleinwinkelstreuung amorpher und teilkristalliner Polymere besitzt eine Intensitätskomponente, die von Dichtefluktuationen innerhalb der kristallinen und amorphen Bezirke herrührt. Für amorphe Polymere entspricht die Dichtefluktuation oberhalb vonT _g dem theoretischen Wert für ein fluides System im thermodynamischen Gleichgewicht. UnterhalbT _g wird eine Temperaturabhängigkeit proportional zuT über einen Bereich von etwa 50° beobachtet. Bei tieferen Temperaturen wird eine lineare Beziehung mit einer geringeren Steigung gefunden, welche zu einem endlichen Wert bei 0 °K extrapoliert werden kann. Dieser Wert bezieht sich auf die eingefrorene Fehlordnung, die Steigung bei tiefen Temperaturen ist auf thermische Schwingungen zurückzuführen und kann als Photon-Phonon-Streuung ausgewertet werden.Teilkristalline Polymere zeigen eine Temperaturabhängigkeit der Dichtefluktuation, die der von amorphen Polymeren ähnlich ist. Bei konstanter Temperatur ändert sich die Dichtefluktuation linear mit der Kristallinität.Naturkautschuk zeigt eine mit der Vernetzungsdichte ansteigende Dichtefluktuation, aus der man Information über die Dichteänderung in der Umgebung eines Netzpunktes und die Statistik der Netzpunktverteilung erhalten kann.

     

Mass spectrometric determination of selenenylsulfide linkages in rat selenoprotein P

The reversible formation of a selenenylsulfide linkage in mammalian thioredoxin reductase was identified as having a key role in its activity. Identification of selenenylsulfide and/or diselenide linkages is therefore critical to the determination of the structure and function of selenoproteins. A selenopeptide, (298)SGSAITUQCAENLPSLCSUQGLFAEEK(324) (U=selenocysteine), was isolated from a tryptic digest of rat selenoprotein P. Its two cysteine residues and two selenocysteine (Sec) residues were determined to be present in oxidized form by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The selenopeptide was subjected to partial reduction by dithiothreitol with immediate alkylation by iodoacetamide. This process was monitored by MALDI-TOFMS to determine the number of alkylations that had taken place. The partially reduced and alkylated peptides were then analyzed by nano-electrospray ionization tandem mass spectrometry and the results indicated that selenenylsulfide linkages Sec304-Cys314 and Cys306-Sec316 were present. It is concluded that selenoprotein P contains these two selenenylsulfide bonds.     

Die IR-Spektren von NH4UO2AsO4·3H2O und NH4UO2PO4·3H2O

The infrared spectra of the title compounds, as well as that of the structurally related mineral meta-autunite, [Ca(UO₂)₂(PO₄)₂·n H₂O], are reported and discussed using the available crystallographic data. The results can be considered as representative for the full group of the so-called torbernite-minerals.     

Inorganic nanocrystal-dynamic porous polymer assemblies with effective energy transfer for sensitive diagnosis of urine copper

Despite their remarkable mechanical, optical, and electrical properties, inorganic particles and dynamic polymer assemblies encounter difficulties in their compatibility with regards to structural order and complexity. Here, covalent organic frameworks (COFs) constructed through reversible coupling reactions were exploited as dynamic porous polymers to prepare inorganic nanocrystal-polymer assemblies. Under an in situ growth process, carbon quantum dots (CDs) were gradually prepared in the COF cavity, with a narrow size distribution (2 ± 0.5 nm). The well-established assemblies achieve effective energy transfer from the inorganic to the organic part (efficiency > 80%), thus rendering a ∼130% increase in quantum yield compared with the pristine COF network. Notably, the hybrid material realizes a simple, selective, and sensitive diagnostic tool for urine copper, surpassing the detection limit of COF solid by 150 times. Beyond the scientific and fundamental interests, such hybrid assemblies are attractive from technological perspectives as well, for example, in energy storage, electronics, catalysis, and optics.

Despite their remarkable mechanical, optical, and electrical properties, inorganic particles and dynamic polymer assemblies encounter difficulties in their compatibility with regards to structural order and complexity.     

Strong Structural and Electronic Binding of Bovine Serum Albumin to ZnO via Specific Amino Acid Residues and Zinc Atoms

ZnO biointerfaces with serum albumin have attracted noticeable attention due to the increasing interest in developing ZnO-based materials for biomedical applications. ZnO surface morphology and chemistry are expected to play a critical role on the structural, optical, and electronic properties of albumin-ZnO complexes. Yet there are still large gaps in the understanding of these biological interfaces. Herein we comprehensively elucidate the interactions at such interfaces by using atomic force microscopy and nanoshaving experiments to determine roughness, thickness, and adhesion properties of BSA layers adsorbed on the most typical polar and non-polar ZnO single-crystal facets. These experiments are corroborated by force field (FF) and density-functional tight-binding (DFTB) calculations on ZnO-BSA interfaces. We show that BSA adsorbs on all the studied ZnO surfaces while interactions of BSA with ZnO are found to be considerably affected by the atomic surface structure of ZnO. BSA layers on the surface have the highest roughness and thickness, hinting at a specific upright BSA arrangement. BSA layers on surface have the strongest binding, which is well correlated with DFTB simulations showing atomic rearrangement and bonding between specific amino acids (AAs) and ZnO. Besides the structural properties, the ZnO interaction with these AAs also controls the charge transfer and HOMO-LUMO energy positions in the BSA-ZnO complexes. This ZnO facet-specific protein binding and related structural and electronic effects can be useful for improving the design and functionality of ZnO-based materials and devices.     

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.

     

N,N′-bis(1-ferrocenyl-1-oxo-3-methyl)propenylethylenediamine and its metal complexes

Summary A new Schiff base ligand, N,N-bis(l-ferrocenyl-1-oxo-3-methyl)propenylethylenediamine (H₂L) and its copper(II), zinc(II), cobalt(II), nickel(II), cadmium(II) and manganese(II) complexes have been prepared, and the structure of the copper complex has been determined by single crystal X-ray techniques and refined to R = 0.041 for 7403 independent reflections. The copper atom is situated in a distorted planar environment. The dihedral angle between planes of two chelating rings which do not contain the metal is 33.5°. Two substituted Cp rings are conjugated with two chelating acacim rings. The iron-centroid forms an angle of 179.4°. The Cp rings are twisted from the eclipsed conformation.     

Structure and Thermal Stability of a Novel 2‐D Layered Copper(II) Coordination Polymer with the Bidentate Ligand 1, 2, 4‐Triazol‐5‐one

Single crystals of {[Cu(TO)₂(H₂O)₂](NO₃)₂}_n (TO: 1, 2, 4‐triazol‐5‐one) were grown by slow evaporation from aqueous solution. It crystallizes in the orthorhombic space group Pbca, with a = 7.082(1), b = 10.285(1), c = 17.911(3)Å, V = 1304.6(3)ų, Z = 4. The Cu^II distorted octahedra are bridged by bidentate TO ligands into infinite 2‐D interlaced rhombic grid‐like network planes, {[Cu(TO)₂(H₂O)₂]²⁺}_n. Hydrogen bonds, electrostatic interactions, and weak van der Waals' forces assemble these planes and the NO₃^— anions to a layered structure. The title compound decomposes at 153.4 °C to the final products, Cu(CN)₂ and CuO.