Neuere Methoden zum Nachweis, zur Isolierung und quantitativen Bestimmung des Eiwei?es sowie seiner h?heren und tieferen Abbauprodukte

Ohne Zusammenfassung     

Die Destillation von Ammoniak bei der Stickstoffbestimmung

Ohne Zusammenfassung     

The competing roles of topology and spin density in the magnetic behavior of spin-delocalized radicals: Donor–acceptor annelated nitronyl nitroxides

The effects of acceptor–donor interactions in thienyl substituted benzimidazole-nitronyl nitroxides (TBNN) on the absorption spectroscopy, spin density distribution, magnetic behavior, and crystallographic packing were explored through spectroscopy, computation, and characterization of structure and magnetic properties in the crystalline phase. The electronic spectra of the radicals exhibit a strong broad absorption in the NIR (λ_max ～ 1000 nm) that exhibits solvatochromism consistent with charge transfer between the thienyl (donor) and benzonitronyl nitroxide (acceptor) dyads. Computational analysis allowed assignment of the transition as a HOMO–SOMO transition (TD-DFT UB3LYP/6-31G7). The TBNN radicals form highly disordered slipped π-stacks in the solid state that give rise to antiferromagnetic interactions consistent with 1D chain interactions. The magnetic behavior was well-fit to a Bonner–Fisher model to give exchange parameters of J = ?2 to ?10 cm^?1 depending on substitution. The weak exchange parameters are attributed to the degree of solid-state disorder, and the observed properties can be rationalized by the effects of substitution on the electronic structure and topology of the radicals.     

On the approximation of local efflux/influx bed discharge in the shallow water equations based on a wave propagation algorithm

In cities, flood waves may propagate over street surfaces below which lie complicated pipe networks used for storm drainage and sewage. The flood and pipe flows can interact at connections between the underground pipes and the street surface. The present paper examines this interaction, using the shallow water equations to model the flood wave hydrodynamics. Sources and sinks in the mass conservation equation are used to model the pipe inflow and outflow conditions at bed connections. We consider the problem reduced to one dimension. The shallow water equations are solved using a Godunov‐type wave propagation scheme. Wave speeds are modified in the wave propagation algorithm to enable flows to be simulated over nearly dry beds and dry states. First, the model is used to simulate vertical flows through finite gaps in the bed. Next, the interaction of the vertical flows with a dam break flow is considered for both dry and wet beds. An efflux number, En, is defined based on the vertical efflux velocity and the gap length. Comparisons are made with numerical predictions from STAR‐CD, a commercial Navier–Stokes solver that models the free‐surface motions, and a parameter study is undertaken to investigate the effect of the one‐dimensional approximation of the present model, for a range of non‐dimensional efflux numbers. It is found that the shallow flow model gives sensible predictions at all time provided En<0.5, and for long durations for En>0.5. Dam break flow over an underground connecting pipe is also considered. Copyright © 2010 John Wiley & Sons, Ltd.     

Isolation of Elusive HAsAsH in a Crystalline Diuranium(IV) Complex

The HAsAsH molecule has hitherto only been proposed tentatively as a short‐lived species generated in electrochemical or microwave‐plasma experiments. After two centuries of inconclusive or disproven claims of HAsAsH formation in the condensed phase, we report the isolation and structural authentication of HAsAsH in the diuranium(IV) complex [{U(Tren^TIPS)}₂(μ‐η²:η²‐As₂H₂)] ( 3 , Tren^TIPS=N(CH₂CH₂NSiPrⁱ₃)₃; Prⁱ=CH(CH₃)₂). Complex 3 was prepared by deprotonation and oxidative homocoupling of an arsenide precursor. Characterization and computational data are consistent with back‐bonding‐type interactions from uranium to the HAsAsH π*‐orbital. This experimentally confirms the theoretically predicted excellent π‐acceptor character of HAsAsH, and is tantamount to full reduction to the diarsane‐1,2‐diide form.     

Extreme red shifted SERS nanotags

Surfaced enhanced Raman scattering (SERS) nanotags operating with 1280 nm excitation were constructed from reporter molecules selected from a library of 14 chalcogenopyrylium dyes containing phenyl, 2-thienyl, and 2-selenophenyl substituents and a surface of hollow gold nanoshells (HGNs). These 1280 SERS nanotags are unique as they have multiple chalcogen atoms available which allow them to adsorb strongly onto the gold surface of the HGN thus producing exceptional SERS signals at this long excitation wavelength. Picomolar limits of detection (LOD) were observed and individual reporters of the library were identified by principal component analysis and classified according to their unique structure and SERS spectra.     

Concerning time and length scale estimates made from burst-mode LDA autocorrelation measurements

 An investigation was performed in grid-generated turbulence to highlight the difficulties in estimating integral and microscales from discrete autocorrelation measurements made using a burst-mode laser Doppler anemometer (LDA). Comparison was made to hot-wire results and the theoretical growth laws determined by the decay of turbulent energy. The chief concern was the presence of a spike in the measured autocorrelation coefficient functions at t=0. It was found that renormalizing the autocorrelation to a value at t=0 determined by “backfitting” a quadratic equation to the slots near t=0 led to microscale estimates that showed the same trend as the decay law and were in agreement with those determined using a hot-wire. Additionally, practical guidelines are presented for making accurate autocorrelation measurements by LDA. Received: 12 January 1995/Accepted: 9 June 1997     

Characterization of a Defined Cellulolytic and Xylanolytic Bacterial Consortium for Bioprocessing of Cellulose and Hemicelluloses

Diminishing fossil fuel reserve and increasing cost of fossil hydrocarbon products have rekindled worldwide effort on conversion of lignocellloloses (plant biomass) to renewable fuel. Inedible plant materials such as grass, agricultural, and logging residues are abundant renewable natural resources that can be converted to biofuel. In an effort to mimic natural cellulolytic–xylanolytic microbial community in bioprocessing of lignocelluloses, we enriched cellulolytic–xylanolytic microorganisms, purified 19 monocultures and evaluated their cellulolytic–xylanolytic potential. Five selected isolates (DB1, DB2, DB7, DB8, and DB13) were used to compose a defined consortium and characterized by 16S ribosomal RNA gene sequence analysis. Nucleotide sequence blast analysis revealed that DB1, DB2, DB7, DB8, and DB13 were respectively similar to Pseudoxanthomonas byssovorax (99%), Microbacterium oxydans (99%), Bacillus sp. (99%), Ochrobactrum anthropi (98%), and Klebsiella trevisanii (99%). The isolates produced an array of cellulolytic–xylanolytic enzymes (filter paper cellulase, β-glucosidase, xylanase, and β-xylosidase), and significant activities were recorded in 30 min. Isolates DB1 and DB2 displayed the highest filter paper cellulase: 27.83 and 31.22 U mg⁻¹, respectively. The highest β-glucosidase activity (18.07 U mg⁻¹) was detected in the culture of isolate DB1. Isolate DB2 produced the highest xylanase activity (103.05 U mg⁻¹), while the highest β-xylosidase activity (7.72 U mg⁻¹) was observed with DB13. Use of microbial consortium in bioprocessing of lignocelluloses could reduce problems such as incomplete synergistic enzymes, end-product inhibition, adsorption, and requirement for high amounts of enzymes in direct use of enzymes.     

The nature of unsupported uranium-ruthenium bonds: a combined experimental and theoretical study

Four new uranium-ruthenium complexes, [(Tren(TMS))URu(η(5)-C(5)H(5))(CO)(2)] (9), [(Tren(DMSB))URu(η(5)-C(5)H(5))(CO)(2)] (10), [(Ts(Tolyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (11), and [(Ts(Xylyl))(THF)URu(η(5)-C(5)H(5))(CO)(2)] (12) [Tren(TMS)=N(CH(2)CH(2)NSiMe(3))(3); Tren(DMSB)=N(CH(2)CH(2)NSiMe(2)tBu)(3)]; Ts(Tolyl)=HC(SiMe(2)NC(6)H(4)-4-Me)(3); Ts(Xylyl)=HC(SiMe(2)NC(6)H(3)-3,5-Me(2))(3)], were prepared by a salt-elimination strategy. Structural, spectroscopic, and computational analyses of 9-12 shows: i) the formation of unsupported uranium-ruthenium bonds with no isocarbonyl linkages in the solid state; ii) ruthenium-carbonyl backbonding in the [Ru(η(5)-C(5)H(5))(CO)(2)](-) ions that is tempered by polarization of charge within the ruthenium fragments towards uranium; iii) closed-shell uranium-ruthenium interactions that can be classified as predominantly ionic with little covalent character. Comparison of the calculated U-Ru bond interaction energies (BIEs) of 9-12 with the BIE of [(η(5)-C(5)H(5))(3)URu(η(5)-C(5)H(5))(CO)(2)], for which an experimentally determined U-Ru bond disruption enthalpy (BDE) has been reported, suggests BDEs of approximately 150 kJ mol(-1) for 9-12.