An optical-fibre laser photometer for on-line measurements

An optical-fibre laser photometer is described for measuring on-line the concentration of the different oxidation states of uranium and plutonium. It is based on a dye laser with five exchangeable curvettes containing five different dyes. The dye laser is pumped by a nitrogen laser. To compensate for the influence of the concentration of nitrate on the absorbance of the different species, the conductivity of the solution is measured to give a correction factor. Fibre optics are used to connect the dye laser, the optical flow-through cell and the photometer. The deviation for the plutonium concentration for single-sample analysis is <1 g l^?1 for concentrations up to 50 g l^?1, and in the on-line mode is <0.14 g l^?1 for the same concentration range. For uranium, the deviation is <3.07 g l^?1 for a concentration range up to 77 g l^?1 in the on-line mode.     

Amino acid cluster formation studied by electrospray ionization mass spectrometry

The association properties of natural and non-natural amino acids were studied in detail using electrospray ionization mass spectrometry. The results show a highly diverse cluster formation behavior of amino acids. There are differences regarding the degree of clustering (average cluster size), the presence or absence of one or several 'magic' clusters of special stability and the influence of chirality on cluster stability. Cluster formation does not show a good correlation with simple physico-chemical properties (such as solubility), indicating that it is a specific process and not only a simple aggregation during evaporation/ionization. A systematic study of cluster formation of serine derivatives reveals that all functional groups play a prominent role in the binding of the magic octamer. The results support the idea of the zwitterionic character of the octamer. Electrospray ionization of the side-chain acetylated serine shows the formation of a very stable tetramer with a strong preference for homochirality. The results suggest that Ser8 is made up of two tetramer subunits, held together by hydrogen bonds of the side-chain.     

A new multivariable <Subscript><Emphasis Type="BoldItalic">6</Emphasis></Subscript><Emphasis Type="BoldItalic">ψ</Emphasis><Subscript><Emphasis Type="BoldItalic">6</Emphasis></Subscript> summation formula

By multidimensional matrix inversion, combined with an A _r extension of Jackson’s ₈ φ ₇ summation formula by Milne, a new multivariable ₈ φ ₇ summation is derived. By a polynomial argument this ₈ φ ₇ summation is transformed to another multivariable ₈ φ ₇ summation which, by taking a suitable limit, is reduced to a new multivariable extension of the nonterminating ₆ φ ₅ summation. The latter is then extended, by analytic continuation, to a new multivariable extension of Bailey’s very-well-poised ₆ ψ ₆ summation formula. Partly supported by FWF Austrian Science Fund grants P17563-N13, and S9607 (the second is part of the Austrian National Research Network “Analytic Combinatorics and Probabilistic Number Theory”).     

Laccase Production by the Aquatic Ascomycete Phoma sp. UHH 5-1-03 and the White Rot Basidiomycete Pleurotus ostreatus DSM 1833 During Submerged Cultivation on Banana Peels and Enzyme Applicability for the Removal of Endocrine-Disrupting Chemicals

This work aimed to study the production of laccase from Pleurotus ostreatus DSM 1833 and Phoma sp. UHH 5-1-03 using banana peels as alternative carbon source, the subsequent partial purification and characterization of the enzyme, as well the applicability to degrade endocrine disruptors. The laccase stability with pH and temperature, the optimum pH, the K _m and V _max parameters, and the molar mass were determined. Tests were conducted for assessing the ability of degradation of the endocrine disruptors t-nonylphenol, bisphenol A, and 17??-ethinylestradiol. Laccase production of 752 and 1,117?U?L^?1 was obtained for Phoma sp. and P. ostreatus, respectively. Phoma sp. laccase showed higher stability with temperature and pH. The laccase from both species showed higher affinity by syringaldazine. The culture broth with banana peels induced the production of two isoforms of P. ostreatus (58.7 and 21?kDa) and one of Phoma sp. laccase (72?kDa). In the first day of incubation, the concentrations of bisphenol A and 17??-ethinylestradiol were reduced to values close to zero and after 3?days the concentration of t-nonylphenol was reduced in 90% by the P. ostreatus laccase, but there was no reduction in its concentration by the Phoma sp. laccase.     

The Torsional Barriers of 2‐Hydroxy‐ and 2‐Fluorobiphenyl: Small but Measurable

By making use of a novel diastereotopicity probe, namely C(CF₃)₂OH, it has been possible to measure by very low temperature ¹⁹F NMR spectroscopy the elusive aryl–aryl rotation barriers of biphenyls bearing an OH or F group in one ortho position. The experimental values (5.4 and 4.4 kcal mol^?1, respectively) are matched by those from ab initio calculations (5.3 and 4.3 kcal mol^?1, respectively).     

Biomimetic oxidation of 3,5-di-tert-butylcatechol by dioxygen via Mn-enhanced base catalysis

The 6-coordinate dioximatomanganese(II) complex [Mn(HL)(CH3OH)]+ (2, where H2L is [HON=C(CH3)C(CH3)=NCH2CH2]2NH), formed by instant solvolysis of [Mn2(HL)2](BPh4)2 (1) in methanol, accelerates the triethylamine (TEA)-catalyzed oxidation of 3,5-di-tert-butylcatechol (H2dtbc) by O2 to the corresponding o-benzoquinone. Significantly, 2 alone has no catalytic effect. The observed rate increase can be explained by the interaction of 2 with the hydroperoxo intermediate HdtbcO2- formed from Hdtbc- and O2 in the TEA-catalyzed oxidation. The kinetics of the TEA-catalyzed and Mn-enhanced reaction has been studied by gas-volumetric monitoring of the amount of O2 consumed. The initial rate of O2 uptake (V(in)) shows a first-order dependence on the concentration of 2 and O2 and saturation kinetics with respect to both H2dtbc and TEA. The observed kinetic behavior is consistent with parallel TEA-catalyzed and Mn-enhanced oxidation paths. The 3,5-di-tert-butylsemiquinone anion radical is an intermediate detectable by electron spin resonance (ESR) spectroscopy. The dimeric catalyst precursor has been characterized by X-ray diffraction and electrospray ionization mass spectrometry and the monomeric catalyst by ESR spectroscopy.     

Weight-dependent commutation relations and combinatorial identities

We derive combinatorial identities for variables satisfying specific systems of commutation relations, in particular elliptic commutation relations. The identities thus obtained extend corresponding ones for $q$-commuting variables $x$ and $y$ satisfying $yx=qxy$. In particular, we obtain weight-dependent binomial theorems, functional equations for generalized exponential functions, we derive results for an elliptic derivative of elliptic commuting variables, and finally study weight-dependent extensions of the Weyl algebra which we connect to rook theory.