Elektronenreiche übergangsmetallkomplexe : V. Phosphinsubstituierte wolframdicarbonyle

Chloride-bridged tungsten tricarbonylmetalates [(OC)₃W(Cl)₃W(CO)₃]^3?, obtainable in high yields from tungsten hexacarbonyl and tetraalkylammonium chlorides, with allyl halides give π-allylhalogenotungsten dicarbonyls. With phosphines reductive elimination of allylhalide yields bis- or tris-(phosphine)-tungsten-dicarbonyls L₂W(PR₃)₂(CO)₂, LW(PR₃)P₃(CO)₂ (L = CH₃CN). Substitution reactions of L with various ligands under mild conditions are described. IR and electronic spectra of more than twenty new compouonds are discussed and compared with corresponding compounds of molybdenum.     

Kleine nicht‐kodierende Ribonukleinsäuren. In Eukaryoten

The recently discovered small non coding RNAs like small interfering RNAs, micro RNAs and repeat associated RNAs regulate diverse cellular pathways like differentiation. Even though small RNAs are involved in so many different processes they were ignored for a long time. Now we are just beginning to understand the complexity of this regulation but the exact mechanisms are still unknown. This review provides an insight into the challenging world of small RNAs.     

Jatrophane diterpenoids with multidrug resistance-modulating activity from Euphorbia mongolica Prokh.

Four novel (1–4) and one known (5) diterpene polyesters with the jatrophane skeleton were isolated from a methanol extract of the aerial parts of the East Asian weed Euphorbia mongolica Prokh. The isolated compounds were characterized structurally and evaluated for multidrug resistance (MDR) reversing activity on human MDR gene-transfected L5178 mouse lymphoma cells; all these compounds were found to modulate the intracellular drug accumulation. The results highlighted some aspects of the structural requirements of jatrophane diterpenes as MDR modulators.     

Delamination in visco-elastic materials with thermal effects

This contribution reports on a model describing the evolution of brittle delamination between two visco-elastic bodies Ω₊ and Ω₋, bonded along a prescribed contact surface Γ_C, over a fixed time interval (0, T); a detailed discussion and a rigorous mathematical analysis can be found in [1]. (© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Analysis of the Molecular Weight Distributions of Aminolyzed Poly(Ethylene Terephthalate) by Using Gel Permeation Chromatography

The molecular weight distributions of poly(ethylene terephthalate) fibers aminolyzed with selected primary amines (namely, methylamine, ethylamine, n-butylamine, and ethanolamine) were determined by using gel permeation chromatography. Initially the shape of the differential molecular weight distribution (DMWD) curve did not change although its peak shifted to lower molecular weights. As aminolysis continued, a shoulder appeared on the DMWD curve. Its appearance seemed to coincide with an increase in the density of the product. Ultimately, distinct molecular populations could be identified in the treated polymer depending on the severity of the aminolysis and the selectivity of the particular amine. The lowest is thought to represent primarily crystalline residues and has a peak molecular weight of 3400. The relations between M _n and ultimate tenacity and breaking strain for the aminolyzed products were linear.     

Principle and analytical applications of resonance lonization mass spectrometry

Resonance ionization mass spectrometry (RIMS) is a very sensitive analytical technique for the detection of trace elements. This method is based on the excitation and ionization of atoms with resonant laser light followed by mass analysis. It allows element and, in some cases, isotope selective ionization and is applicable to most of the elements of the periodic table. A high selectivity can be achieved by applying three step photoionization of the elements under investigation and an additional mass separation for an unambiguous isotope assignment.An effective facility for resonance ionization mass spectrometry consists of three dye lasers which are pumped by two copper vapor lasers and of a linear time-of-flight spectrometer with a resolution better than 2500. Each copper vapor laser has a pulse repetition rate of 6.5 kHz and an average output power of 30 W.With such an apparatus measurements with lanthanide-, actinide-, and technetium-samples have been performed. By saturating the excitation steps and by using autoionizing states for the ionization step a detection efficiency of 4 × 10^–6 and 2.5 × 10^–6 has been reached for plutonium and technetium, respectively, leading to a detection limit of less than 10⁷ atoms in the sample. Measurements of isotope ratios of plutonium samples were in good agreement with mass-spectrometric data. The high elemental selectivity of the resonance ionization spectrometry could be demonstrated.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria     

Structural versatility of anion-pi interactions in halide salts with pentafluorophenyl substituted cations

A series of pentafluorophenyl substituted ammonium, iminium, amidinium, and phosphonium halides are presented which show extensive anion-pi interactions. Hereby, the well-known anion-donor-pi-acceptor as well as "eta6" anion-pi-complex type interactions are observed. The latter is supported by fixation of the anion on top of the aromatic system through hydrogen bonding. This arrangement was investigated by theoretical methods showing a highly attractive anion-pi interaction. In addition an eta2-type coordination of the anions to only two C-atoms of the electron-deficient ring system is described.     

ACTION SPECTRUM FOR ERYTHEMA IN HUMANS INVESTIGATED WITH DYE LASERS

Abstract— Erythema reactions of human skin were reevaluated with improved experimental methods: a tunable, highly monochromatic irradiation source as well as an instrumental measurement of skin reactions were used. The irradiation system consisted of an excimer laser pumped dye laser and a U V fiber optic system. The skin color after irradiation was determined with a colorimeter in the three-dimensional norm system of the Commission Internationale d'Eclairage (CIE). The wavelength dependence for delayed erythema was investigated in the UVB and UVA region from 294 nm to 374 nm in skin type II and III individuals. The maximum of the action spectrum in the UVB range was measured at 298.5 nm and an additional maximum was found at 362 nm in the UVA range. The action spectrum is compared with previous spectra from the literature and with the current standard erythema curve of the CIE as well as with other photobiological action spectra. Our results suggest a UVA/UVB boundary at 330 nm.     

New Heteroaromatic Complexing Agents and Luminescence of Their Europium(III) and Terbium(III) Chelates

Twelve heteroaromatic complexing agents 9a–I were synthesized with the purpose to develop suitable labels for time-resolved luminescence-based bioaffinity assays. The relative luminescence yields, excitation maxima, and emission decay constants of their europium(III) and terbium(III) chelates were determined. According to these results, 2,2′,2″,2?-[(2,2′-bipyridine-6,6′-diyl)bis(methylenenitrilo)]tetrakis (acetic acid) ( 9e ) and 2,2′,2″,2?-[(2,2′:6′,2″-terpyridine-6,6″-diyl)bis(methylenenitrilo)] tetrakis(acetic acid) ( 91 ) are the most promising agents.     

High-yield one-step synthesis in water of [Pt3n(CO)6n]2- (n > 6) and [Pt38(CO)44]2-

Carbonylation of Na2PtCl6.6H2O, as well as K2PtCl6, in water under a CO pressure of 900 mm Hg selectively and quantitatively affords [Pt3n(CO)6n]2- (n > 6) salts; conversely, their corresponding carbonylation at reduced CO pressure of 760-800 mm Hg leads to a convenient one-step synthesis of [Pt38(CO)44]2-.