Metallkomplexe mit biologisch wichtigen Liganden. CXLVII [1] Struktur und Eigenschaften von Pfeiffers Nickel(II)‐Schiff‐Base‐Komplex aus Salicylaldehyd und Glycinester

Metal Complexes with Biological Important Ligands. CXLVII [1] Structure and Properties of Pfeiffer's Nickel(II) Schiff Base Complex from Salicylaldehyde and Glycine Ester. The structure of the planar nickel(II) complex reported by Paul Pfeiffer with two Schiff base ligands from salicylaldehyde and glycine ethylester and with trans‐NiO₂N₂ arrangement was determined by X‐ray diffraction. The finding by Pfeiffer that this complex reacts with oxygen to give the bis(O, N‐imine) complex Ni(OC₆H₄CH=NH)₂ under C‐N cleavage could be confirmed by spectroscopic data, and a reaction path is suggested.     

Nonlinear analysis of dynamic binding in affinity capillary electrophoresis demonstrated for inclusion complexes of beta-cyclodextrin

The stability of the molecular host-guest inclusion complexes of beta-cyclodextrin with benzoate and four different hydroxybenzoates is investigated. For the measurement of the binding constants an experimental method is devised that is based on affinity capillary electrophoresis (ACE) with indirect UV absorbance detection. We derive an explicit equation for effective mobilities in ACE experiments without violation of rigorous mass balance. This equation is employed in the nonlinear least-squares analyses of the experimental data yielding binding constants of 48+/-2 M(-1) for benzoate, 299+/-38 M(-1) for 2-hydroxybenzoate, 37+/-1 M(-1) for 3-hydroxybenzoate, 228+/-9 M(-1) for 4-hydroxybenzoate, and 895+/-110 M(-1) in the case of 2,4-dihydroxybenzoate.     

Y16I19C8B4 – ein Yttriumboridcarbidhalogenid mit B2C4-Einheiten

Y₁₆I₁₉C₈B₄ – a Yttrium Boride Carbide Halide Containing B₂C₄ Units The new compound Y₁₆I₁₉C₈B₄ was prepared from Y, YI₃, C and B at 1050–1150 °C. The structure of a twinned crystal was determined by means of X-ray diffraction (space group P 1¯, a = 12.311(2) Å, b = 13.996(3) Å, c = 19.695(3) Å, α = 74.96(2)°, β = 89.51(2)°, γ = 67.03(2)°, Z = 2). Y₁₆I₁₉C₈B₄ is a semiconductor and contains nearly planar B₂C₄ units which are located in cages built up by 12 yttrium atoms. Assuming (B₂C₄)^12–, these units can be regarded as isoelectronic with B₂F₄. The yttrium cages are connected via faces to form rods, which are surrounded by iodine atoms. Bridging iodine atoms connect the rods so that layers are formed. The characteristic twinning observed can be understood from the geometry of the crystal structure.     

A versatile toolbox for variable DNA functionalization at high density

To broaden the applicability of chemically modified DNAs in nano- and biotechnology, material science, sensor development, and molecular recognition, strategies are required for introducing a large variety of different modifications into the same nucleic acid sequence at once. Here, we investigate the scope and limits for obtaining functionalized dsDNA by primer extension and PCR, using a broad variety of chemically modified deoxynucleotide triphosphates (dNTPs), DNA polymerases, and templates. All natural nucleobases in each strand were substituted with up to four different base-modified analogues. We studied the sequence dependence of enzymatic amplification to yield high-density functionalized DNA (fDNA) from modified dNTPs, and of fDNA templates, and found that GC-rich sequences are amplified with decreased efficiency as compared to AT-rich ones. There is also a strong dependence on the polymerase used. While family A polymerases generally performed poorly on "demanding" templates containing consecutive stretches of a particular base, family B polymerases were better suited for this purpose, in particular Pwo and Vent (exo-) DNA polymerase. A systematic analysis of fDNAs modified at increasing densities by CD spectroscopy revealed that single modified bases do not alter the overall B-type DNA structure, regardless of their chemical nature. A density of three modified bases induces conformational changes in the double helix, reflected by an inversion of the CD spectra. Our study provides a basis for establishing a generally applicable toolbox of enzymes, templates, and monomers for generating high-density functionalized DNAs for a broad range of applications.     

Screening for library-assisted identification and fully validated quantification of 22 beta-blockers in blood plasma by liquid chromatography-mass spectrometry with atmospheric pressure chemical ionization

A liquid chromatographic-mass spectrometric assay with atmospheric pressure chemical ionization (LC-APCI-MS) is presented for screening for, library-assisted identification (both in scan mode) and quantification (selected-ion mode) of the beta-blockers acebutolol, diacetolol, alprenolol, atenolol, betaxolol, bisoprolol, bupranolol, carazolol, carteolol, carvedilol, celiprolol, esmolol, labetalol, metoprolol, nadolol, nebivolol, oxprenolol, penbutolol, propranolol, sotalol, talinolol and timolol in blood plasma after mixed-mode (HCX) solid-phase extraction (SPE) and separation by reverse-phase liquid chromatography with gradient elution. The validation data were within the required limits. The assay was successfully applied to authentic plasma samples allowing confirmation of diagnosis of overdose situations as well as monitoring of patients' compliance.     

Electron capture negative ion (ECNI) mass spectrometry of complex mixtures of chlorinated decanes and dodecanes: An approach to ECNI mass spectra of chlorinated paraffins in technical mixtures

The electron capture negative ion (ECNI) mass spectra of two complex mixtures of polychlorinated decanes (PCDe) and polychlorinated dodecanes (PCDo) are presented. The number of isomers in these mixtures is still high but is drastically reduced in comparison to technical products of chlorinated paraffins (CP), due to their fixed chain length. As a result, the mass spectra are simplified and less complex. Different modes of negative ion formation were observed in the spectra of the PCDe and PCDo. [M+Cl]^– adduct ions were the most abundant ions in the spectra of lower chlorinated molecules. Higher chlorinated isomers formed prominently [M-Cl]^– and [M-HCl]^– fragments besides [M+Cl]^–. Possible consequences for the determination of chlorinated paraffins by ECNI-MS that result from the variation in ion formation are addressed. Received: 18 August 1997 / Revised: 26 January 1998 / Accepted: 31 January 1998     

Position-specific isotope analysis of the methyl group carbon in methylcobalamin for the investigation of biomethylation processes

In the environment, the methylation of metal(loid)s is a widespread phenomenon, which enhances both biomobility as well as mostly the toxicity of the precursory metal(loid)s. Different reaction mechanisms have been proposed for arsenic, but not really proven yet. Here, carbon isotope analysis can foster our understanding of these processes, as the extent of the isotopic fractionation allows to differentiate between different types of reaction, such as concerted (S_N2) or stepwise nucleophilic substitution (S_N1) as well as to determine the origin of the methyl group. However, for the determination of the kinetic isotope effect the initial isotopic value of the transferred methyl group has to be determined. To that end, we used hydroiodic acid for abstraction of the methyl group from methylcobalamin (CH₃Cob) or S-adenosyl methionine (SAM) and subsequent analysis of the formed methyl iodide by gas chromatography (GC) isotope ratio mass spectrometry (IRMS). In addition, three further independent methods have been investigated to determine the position-specific δ ¹³C value of CH₃Cob involving photolytic cleavage with different additives or thermolytic cleavage of the methyl-cobalt bonding and subsequent measurement of the formed methane by GC-IRMS. The thermolytic cleavage gave comparable results as the abstraction using HI. In contrast, photolysis led to an isotopic fractionation of about 7 to 9 ‰. Furthermore, we extended a recently developed method for the determination of carbon isotope ratios of organometal(loid)s in complex matrices using hydride generation for volatilization and matrix separation before heart-cut GC and IRMS to the analysis of the low boiling partly methylated arsenicals, which are formed in the course of arsenic methylation. Finally, we demonstrated the applicability of this methodology by investigation of carbon fractionation due to the methyl transfer from CH₃Cob to arsenic induced by glutathione.

Second-harmonic generation in an optically poled azo-dye/polymer film

The power dependence of the optical poling process of a new azo chromophore in the polymethylmethacrylate matrix at room temperature has been investigated. The existing theory is found to be inconsistent with the experiment. A simple model based on the rate equation is proposed to describe the writing process of the chromophore/polymer system. The measured growth rate and the plateau second-harmonic generation intensity as induced by all optical poling are found to be in good agreement with the prediction of the simple model.