Zur Elektronenstruktur metallorganischer Komplexe der f‐Elemente. 64 Äußert sich die zwitterionische Natur des Triphenylphosphanoxid‐Liganden auch in seinen spektrochemischen Eigenschaften?

Electronic Structures of Organometallic Compounds of f Elements. 64 Does the Zwitterionic Nature of the Triphenylphosphine Oxide Ligand Manifest itself in its Spectrochemical Properties? The triphenylphosphine oxide mono adducts of the moiety tris(η⁵‐cyclopentadienyl)lanthanide(III) (Ln(Cp)₃; Ln = Pr ( 1 ), La ( 2 )) were synthesized and structurally characterized. The Ln–O distances of these compounds are noticeably shorter than those of the corresponding THF adducts. A crystal field (CF) analysis of the optical spectra of 1 leads to a low absolute value of the quadratic CF parameter which is comparable with those of [Pr(Cp)₃(L)]^? adducts with anionic bases but not with [Pr(Cp)₃(MeTHF)]. Reasons for the latter finding are presented.     

Über Antimon-haltige Heterocyclen. I. Molekül- und KristallStruktur von 2-Chlor- 1,3,6-trithia-2-stibaocan

On Antimony Containing Heterocyclic Systems. I. Molecular and Crystal Structure of 2-Chloro-1,3,6-trithia-2-stibaocane 2-Chloro-1,3,6-trithia-2-stibaocane crystallizes in the orthorhombic space group P2₁2₁2₁ with cell dimensions a = 9.054, b = 22.610, c = 9.097 Å and Z = 8. The crystal structure has been determined from single crystal X-ray data and refined to a conventional R of 0.038. The eight-membered ring has deformated boat-conformation with 1,5-intraannular Sb? S-interaction. The coordination of the Sb-atom is ψ-trigonal-bipyramidal with axial distances Sb? Cl 2.51 Å, Sb? S 2.86 Å and equatorial distances Sb? S 2.44 and 2.45 Å. The Sb? S-bond is discussed. The structure consists of 14-coordinated molecules densest packed parallel to the x? y-plane and less densely packed perpendicular to this plane.     

FLUORESCENCE STUDIES WITH HUMAN EPIDERMAL GROWTH FACTOR

Steady-state and time-resolved fluorescence studies have been performed with human epidermal growth factor, a small globular protein having two adjacent tryptophan residues near its C-terminus. Based on the relatively red fluorescence and accessibility to solute quenchers, the two tryptophan residues are found to be exposed to solvent. Anisotropy decay measurements show the dominant depolarizing process to have a sub-nanosecond rotational correlation time indicating the existence of rapid segmental motion of the fluorescing tryptophan residues. From an analysis of the low-temperature excitation anisotropy spectrum of the protein (and in comparison with that of tryptophan, the peptide melittin, and the dipeptide trp-trp), it is concluded that homo-energy transfer and/or exciton interaction occurs between the adjacent tryptophan residues. A thermal transition in the structure of the protein, which is observed by circular dichroism measurements, is not sensed by the steady-state fluorescence of the protein. This result, in conjunction with the anisotropy decay results, indicates that the two tryptophan residues are in a highly flexible C-terminus segment, which is not an integral part of the three-dimensional structure of the protein. Fluorescence measurements with three site-directed mutants also show very little variation.     

Response Characteristics of Arsenic-Sensitive Bioreporters Expressing the gfp Reporter Gene

This paper describes the development of an analytical technique for arsenic analyses that is based on genetically-modified bioreporter bacteria bearing a gene encoding for the production of a green fluorescent protein (gfp). Upon exposure to arsenic (in the aqueous form of arsenite), the bioreporter production of the fluorescent reporter molecule is monitored spectroscopically. We compared the response measured as a function of time and concentration by steady-state fluorimetry (SSF) to that measured by epi-fluorescent microscopy (EFM). SSF is a bulk technique; as such it inherently yields less information, whereas EFM monitors the response of many individual cells simultaneously and data can be processed in terms of population averages or subpopulations. For the bioreporter strain used here, as well as for the literature we cite, the two techniques exhibit similar performance characteristics. The results presented here show that the EFM technique can compete with SSF and shows substantially more promise for future improvement; it is a matter of research interest to develop optimized methods of EFM image analysis and statistical data treatment. EFM is a conduit for understanding the dynamics of individual cell response vs. population response, which is not only a matter of research interest, but is also promising in the practical terms of developing micro-scale analysis.     

Über Chalkogenolate. LVIII. Untersuchungen über Thiomeiensäuren 6. Cyandithioameisensäure und Azidodithioameisensäure

Polymeric cyanodithioformic acid has been prepared by interaction between a solution of Na[NCCS₂]. 3 DMF and HCl(aq). In the gaseous state there exists [NCCS(SH)]_x with x = 1 and 2. The instable crystalline acidodithioformic acid is formed on reaction of Na[N₃CS₂] with HCl(aq). In the gaseous state there exists the monomeric acid N₃CS(SH).     

Zum mechanismus des strahlenchemischen abbaus von polytetrafluorethylen

The present work studies the changes in polymer structure and the mechanism of the decomposition of polytetrafluoroethylene resin (PTFE) exposed to high energy radiation (electron beam). Spectroscopic and kinetic observations are used to interpret the degradation process. For the first time the decomposition of PTFE has been carried out on a preparative scale and new results obtained by analysing the degradation products. The radiation-induced degradation of PTFE is accompanied by thermal degradation under certain irradiation conditions. This is due to an increase in temperature of the polymer caused by retardation of highly accelerated electrons (heat accumulation effect).The kinetics are discussed in terms of the reactions and recombination of radicals produced by high-energy radiation both in the polymer melt and the polymer surface. These are related to the overall rate of decomposition.The primary radicals formed by decomposition of PTFE in an inert atmosphere (N₂, Ar) react to produce perfluorinated alkanes and alkenes. In the presence of reactive gases the decomposition fragments originated will react rapidly; e.g. if oxygen is present in the reactive area the radicals form perflourinated peroxyl and oxyl radicals which finally stabilize themselves by CC-scission to perfluorocarbon acid fluorides and carbonyldifluorides.     

Effect of Groundwater Composition on Arsenic Detection by Bacterial Biosensors

A luminescent bacterial biosensor was used to quantify bioavailable arsenic in artificial groundwater. Its light production above the background emission was proportional to the arsenite concentration in the toxicologically relevant range of 0 to 0.5 μM. Effects of the inorganic solutes phosphate, Fe(II) and silicate on the biosensor signal were studied. Phosphate at a concentration of 0.25 g L⁻¹ phosphate slightly stimulated the light emission, but much less than toxicologically relevant concentrations of the much stronger inducer arsenite. No effect of phosphate was oberved in the presence of arsenite. Freshly prepared sodium silicate solution at a concentration of 10 mg L⁻¹ Si reduced the arsenite-induced light production by roughly 37%, which can be explained by transient polymerization leading to sequestration of some arsenic. After three days of incubation, silicate did not have this effect anymore, probably because depolymerization occurred. In the presence of 0.4 mg L⁻¹ Fe(II), the arsenite-induced light emission was reduced by up to 90%, probably due to iron oxidation followed by arsenite adsorption on the less soluble Fe(III) possibly along with some oxidation to the stronger adsorbing As(V). Addition of 100 μM EDTA was capable of releasing all arsenic from the precipitate and to transform it into the biologically measurable, dissolved state. The biosensor also proved valuable for monitoring the effectiveness of an arsenic removal procedure based on water filtration through a mixture of sand and iron granules.     

High-spin to low-spin relaxation kinetics in the [Fe(TRIM)2]Cl2 complex

A quasi-quantitative photo-induced low-spin (LS)-->high-spin (HS) conversion of FeII ions has been observed in the [Fe(TRIM)2]Cl2 complex by irradiating the sample with blue light (488 nm) at 10 K. The time dependence of the HS-->LS relaxation has been studied between 10 K and 44 K by means of magnetic susceptibility measurements. These relaxation curves could be satisfactorily fitted by mono-exponential decays including tunnelling effect except for temperatures below 30 K. The introduction of a distribution of vibrational frequencies into this model improved significantly the fits in the low-temperature range and gave a good agreement with the experimental data in the whole temperature range suggesting a multi-rate relaxation process in this complex.