Untersuchungen an Tetramethylantimonderivaten verschiedener phosphorhaltiger Säuren

Studies on Tetramethyl Antimony Derivatives of Various Phosphorus-containing Acids The preparation and the properties of tetramethyl antimony derivatives of HOOPF₂, HOOPCl₂, HOOPH₂, HOOP(CH₃)₂ and HOSP(CH₃)₂ are described. Infrared, Raman, ¹H-. ³¹P- and ¹⁹F-NMR studies of the difluorophosphat, the dichlorophosphat and the hypophosphite point to ionic structures with (partly distorted) tetrahedral Sb(CH₃)₄⁺ cations and F₂POO^?, Cl₂POO^? and H₂POO^? anions, respectively. The spectroscopic data of the dimethylphosphinate and the dimethylthiophosphinate prove non-ionic structures in the solid, the melt and the solutions in non-polar solvents.     

Birefringence induite dans les directions remarquables d'une suspension de particules rigides en ecoulement

A theoretical formula is derived for the flow birefringence exhibited along the streamlines and in the direction of the shear rate (G) by dilute suspensions of rigid spheroid-like macromolecules; numerical values are computed up to σ = G/D = 900 (D = rotary diffusion coefficient). These results provide two tests for identifying prolate and oblate particles; when combined with the data for observation perpendicular to the plane of flow, they confirm the connection between non-Newtonian viscosity and the Maxwell effect for monodisperse samples; for vanishing rate of shear, they allow a mixture of particles to be characterized by means of a mean rotary diffusion constant ($\text{D}$) and a mean shape coefficient ($\text{R}$).     

Chromophore production in lignin model compounds — Anaerobic reactions

The anaerobic photochemistry of a number of plausible lignin model compounds (i.e. I: 3,4-Dimethoxy-α-(2-methoxyphenoxy)-β-hydroxypropiophenone;II: 1-(3,4-Dimethoxyphenyl)-2-(2-methoxyphenoxy)-propan-1,3-diol;Pol A: Poly(4-methoxyacrylophenone);Pol B: Poly(3,4-dimethoxyacrylophenone);St 1: 3,5-Dimethoxy-4-hydroxystilbene; andSt 2: 3,5,3′,5′-Tetramethoxy-4-hydroxystilbene) was studied, thin films of these materials being exposed to long-wave (λ≥300 nm) radiation under high vacuum conditions (10^?6 torr). In all cases, the only low molecular weight products formed were methane and ethane, and quantum yields were estimated for these reactions. All materials underwent colouration (yellow) and a number of changes were also observed in both the absorbing and emitting characteristics. The colouration was attributed to the presence ofo-quinones which were formed (by further photolysis) from the phenoxy radicals, which were, in turn, produced by O?CH₃ fission, the resulting methyl radicals being the precursors of methane and ethane. The stilbenes were in all cases much more reactive (by a factor of about 100); however, they also absorbed higher intensities of radiation in the 300<λ<350 nm region on account of the greater extent of red-shifting of the longest-wave π-π′ aromatic transitions. Gel permeation data indicate the formation of products of cyclization and isomerization of stilbenes and the dimerization of phenoxy radicals while new absorbances in the infrared and¹³C NMR confirm the presence ofo-quinones in all the models.     

Verwendung schneller Reaktorneutronen zur raschen und zerst?rungsfreien Spurenanalyse, insbesondere von Sauerstoff

Zusammenfassung Der intensive Fluß schneller Neutronen, wie er von Kernreaktoren geliefert wird, kann für eine rasche und zerstörungsfreie, aktivierungs-analytische Bestimmung einer Vielzahl von Elementen verwendet werden. Bei manchen Elementen läßt sich sogar bei der Aktivierung mit schnellen Reaktorneutronen eine im Vergleich zur Aktivierungsanalyse mit thermischen Neutronen tiefere Erfassungsgrenze erreichen. Werden die Proben in einem schnellen, halbautomatischen Rohrpostsystem zum Reaktorkern befördert, können auch sehr kurzlebige Radionuklide gemessen werden. Besonders Sauerstoff läßt sich über die Kernreaktion ¹⁶O(n, p)¹⁶N sehr empfindlich bestimmen, wobei die hochenergetischen -Quanten des 7,2 sec Stickstoff-16 gemessen werden. Es können so bis zu 10 ppm Sauerstoff in vielen Arten von Analysenproben erfaßt werden. Das halbautomatische Analysensystem, das mit Hilfe einer schnellen Rohrpost die Durchführung rascher und zerstörungsfreier Aktivierungs-analysen im Forschungsreaktor München erlaubt, wird beschrieben. Die Verwendung des Systems zur Sauerstoffanalyse und die damit zusammenhängenden Probleme werden genauer besprochen.

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Summary The intense fast-neutron fluxes, which are available in nuclear reactors, can be used for rapid and non-destructive activation analysis of many elements. Some elements have even superior detection limits for activation with fast reactor neutrons compared to reactor thermal-neutron activation. Short-lived radionuclides can also be measured using a fast pneumatic tube system. Oxygen can be determined by the nuclear reaction ¹⁶O(n, p)¹⁶N initiated by fast reactor neutrons counting the high-energy gamma rays of the 7.4 sec nitrogen-16. The method is suitable for determining as little as 10 ppm of oxygen in many types of analytical samples. The fast transfer system, which is used in the Munich research reactor for rapid and non-destructive activation analysis is described. The use of the transfer-system for oxygen activation analysis and problems associated with oxygen analysis are discussed.

     

A field theoretical approach to calculate electronic Born-Oppenheimer coupling terms

In this paper we suggest to consider the spatial distribution of the Born-Oppenheimer nonadiabatic coupling terms as fields which are created by sources, located at degeneracy points, and which can be derived using the ordinary mathematical tools of field theory. It is shown that the curl-divergence equations as formed within a given Hilbert space [M. Baer, Chem. Phys. Lett. 35, 112 (1975)] can be converted into a set of inhomogeneous coupled Poisson equations which are solved for a given set of boundary conditions. The method is applied to the three-state Hilbert subspace of the H(3) system. The numerical results are compared with ab initio calculations for which a very encouraging fit is found.     

Plutonium Activity Ratios in Plankton: New Evidence of Hold-Up Time in Irish Sea Sediments

The determination of activity ratios for radioisotopes of different half-lives can be used to estimate transit times from a point source to locations further away. For conservative elements, this time is approximately equivalent to the net hydrological transport. However, for non-conservative elements such as plutonium, the additional influence of biogeochemical processes decreases the net transport time. In this study, ²⁴¹Pu and ^239,240Pu concentrations in Irish Sea plankton samples, collected in May 1994, were determined and the ²⁴¹Pu/^239,240Pu ratios calculated. Plutonium-239,240 was measured using a standard method by ion exchange chromatography and alpha counting, and ²⁴¹Pu was determined by liquid scintillation counting using the disk-supported technique. The latter showed some methodological problems, which are briefly discussed. The ²⁴¹Pu/^239,240Pu ratios gave an estimate of the "transit time" from Sellafield to the different sampling points. In fact, this time represents the age of plutonium in plankton, i.e., the time lag between release from Sellafield and detection at the different sampling stations. The mean plutonium age was 17±2 years (n = 10) and 18.6±0.8 years (n = 13) in phytoplankton and zooplankton, respectively. The spatial distribution was reasonably homogeneous over the Irish Sea. The assimilation-elimination processes of plutonium in plankton are rather rapid. Therefore, it may be assumed that, in this time scale, the plutonium concentrations were in equilibrium with surrounding waters. Thus, it is concluded that plutonium was rather old because resuspension-sedimentation processes had occurred that delayed its transport within the Irish Sea. Therefore, the age of plutonium in plankton represented the hold-up time of plutonium in the sediments from the Irish Sea.     

Competitive formation of helical cycloocta- and cyclododecapyrroles

In connection with a study aimed at the evaluation of electronic effects in spiro-dicorrole (1a) and its binuclear Ni(II) complex (1b) we became interested in gem-dimethyl-substituted cyclotetrapyrrole (2a) and the corresponding Ni(II) complex (2b). Attempts to prepare 2a as the 12,13,16,17-tetraethyl-2,3,7, 8-tetramethyl derivative (5) by an acid-catalyzed (1 + 1) condensation of dimethyldipyrrylmethane 3 and diformylbipyrrole 4 resulted in the formation of the (2 + 2) and (3 + 3) condensation products, i.e., the cyclooctapyrrole 6 and the cyclododecapyrrole 7, respectively, rather than in that of the desired gem-dimethyl cyclotetrapyrrole. The cyclododecapyrrole 7, isolated as the major product, is among the largest cyclopolypyrroles known to date. These two new macrocycles have been structurally characterized by variable temperature 1D and 2D NMR experiments, as well as by single-crystal X-ray diffraction analysis. In solution both the cyclooctapyrrole 6 and cyclododecapyrrole 7 exhibit dynamic behavior. At 337 K 6 adopts a D(2)-symmetric conformation, whereas at 196 K two equivalent C(2) conformers that interconvert through the D(2)-symmetric intermediate are observed. The energy barrier for the interconversion process between these two degenerate conformers is found to be 10.6 kcal mol(-)(1). The solution dynamics of 7 could be described in an analogous manner, with the time-averaged conformation at 378 K displaying D(3)(h)() symmetry. X-ray analyses showed that for both macrocycles, 6 and 7, the solid state structures were nearly identical to the low-temperature solution conformers.     

Umpolung of the allylpalladium reactivity: mechanism and regioselectivity of the electrophilic attack on bis-allylpalladium complexes formed in palladium-catalyzed transformations

The structure and reactivity of various bis-allylpalladium complexes occurring as catalytic intermediates in important synthetic transformations have been studied by applying density functional theory at the B3PW91(DZ + P) level. It was found that n1,n3 coordinated bis-allylpalladium complexes are readily formed from the corresponding n3,n3 complexes, especially in the presence of pi-acceptor phosphine ligands. The theoretical calculations indicate dsigma-->pi type hyperconjugative interactions occurring in the n1-coordinated allyl moiety of the n3,n3 coordinated complexes. These hyperconjugative interactions influence the structure of the complexes and dramatically increase the reactivity of the double bond in the n1-moiety. The DFT results indicate a remarkably low activation barrier for the electrophilic attack on the n1-allyl functionality. In bridged n1,n3 complexes, the electrophilic attack occurs with a very high regioselectivity, which can be explained on the basis of d-pi type hyperconjugative interactions.     

Determination of in-core power in low energy research reactors by measurement of16N and18F in the primary coolant

The measurement of¹⁶N and¹⁸F activity in the primary coolant of the JASON Argonaut reactor has been used to monitor in-core reactor power. The¹⁶N is produced by the¹⁶O(n, p)¹⁶N reaction and the 6.1 MeV photopeak was measured on-line using a BGO detector adjacent to the primary coolant circuit. These data provided a relative measure of power stability during steady state operation and a measure of linearity at different power levels. The¹⁸F is produced in the primary coolant by the¹⁸O(p, n)¹⁸F reaction and aliquots of primary coolant were sampled from the reactor dump tank for off-line radiochemical analysis. The¹⁸F was separated as trimethylfluorosilane and the activity was determined by measurement of the 0.511 MeV annihilation photopeak using a NaI(TI) detector. The measured¹⁸F activity was used to determine actual in-core reactor power using both ab-initio calculations and by comparison of results with a calibrated power reactor. The¹⁸F data also provided a method of nomalising the¹⁶N data for direct monitoring of in-core reactor power in JASON.     

THE EFFECTS OF PORPHYRIN STRUCTURE AND AGGREGATION STATE ON PHOTOSENSITIZED PROCESSES IN AQUEOUS AND MICELLAR MEDIA

The efficiency of several porphyrins at 10 μM and 83 μM as sensitizers of the photooxidation of 0.1 mM tryptophan and histidine via a singlet oxygen-mechanism was studied in pH 7.4-buffered aqueous solutions and in aqueous dispersions of Triton X-100 micelles. The porphyrins were either solubilized in the bulk aqueous medium or associated with the micellar phase, whereas the amino acids were always located in the aqueous phase. With those porphyrins, such as uroporphyrin I, meso-tetra (4-sulfonatophenyl)porphine, meso-tetra(4-carboxyphenyl)porphine and meso-tetra)N,N,N-trimethylanilinium)porphine, which are > 98% monomeric in both media, the efficiency of histidine photooxidation was independent of the site of O₂(¹Δ_g) generation, as shown by the closely similar values for the photooxidation rate constant and oxygen-consumption quantum yield in the presence and absence of Triton micelles; the same indications were provided by photokinetic experiments with tryptophan. Actually, laser flash photolysis studies showed that the micelle-incorporation of the above mentioned porphyrins brought about only minor changes in their photophysical properties, including the relative yield of O₂(¹Δ_g) generation. On the other hand, hematoporphyrin IX, its Zn²⁺-complex, and coproporphyrin III are largely aggregated in homogeneous aqueous solution; their incorporation into Triton micelles caused an increase of the triplet quantum yield and an enhancement of the oxygen-consumption quantum yield and photooxidation rate constant for both histidine and tryptophan. The lower photosensitizing efficiency of aggregated porphyrin species in comparison with the corresponding monomeric porphyrin was confirmed by measuring the initial rate and quantum yield of oxygen consumption upon irradiation of 1 mM histidine and tryptophan in the presence of different hematoporphyrin concentrations within the 0.3-100μM range.