AUTOMATED MECHANICAL STIMULATION AND MEASUREMENT OF BIOLUMINESCENCE IN MARINE DINOFLAGELLATES

A new integrated system for reproducible, automated mechanical stimulation and measurement of bioluminescence (BL) in multiple samples of marine dinoflagellate cell suspensions is described. The system was designed to allow the application of standardized experimental routines to parallel test vials for the purpose of toxicity testing. A sample tray delivered test vials to the position of mechanical stimulation and BL measurement. Mechanical stimulation of BL was applied as sharp rotation-onset of the test vial about its vertical axis. Thus, any direct chemical or physical perturbation of the cell suspension was avoided. A silicon photovoltaic cell measured the emitted light. Stimulation, measurement and recording of BL were integrated and controlled by specially developed software, which runs on a personal computer in the graphic environment of MS-Windows. Precise scheduling, flexible programming and identical repetition of experimental routines are possible in practice. For Gonyaulax polyedra, details of BL, as stimulated and measured with the new system, are presented and discussed. We conclude that the system exhibits specific features that offer wide potential of application in several fields of research on dinoflagellate BL, particularly for toxicity testing.     

Kinetics of the photodissociation iodine laser with slow pumping

Systematic calculations of maximum inversion were performed for iodine photodissociation laser in dependence on the mixture composition. The flash-lamp radiation was modelled as emanating from an optically thin Xe plasma. Duration of the pumping pulse is about 300 s. The sensitivity of the model to the values of kinetic constants was also tested.     

Thermal analysis of anhydrous and hydrated Cholesterol

Cholesterol constitutes the major component of most gallstones. It was identified and determined, in gallstones, issued from eleven patients, by thermal analysis: differential scanning calorimetry (DSC), with the use of the melting temperature and enthalpy, thermogravimetry (TG), with the mass loss of water. Anhydrous cholesterol (ChA) was characterized by two endothermic peaks (polymorphic, melting) and cholesterol monohydrate (ChH) by two endothermic peaks (dehydration, melting), too. Cha needle and Chh plate crystals were observed under polarizing light microscopy. The numerous stones obtained from nine patients were cholesterol stones: the ChA was higher 45 and lower 96%. ChH was present in stones of three patients. This revised version was published online in July 2006 with corrections to the Cover Date.     

Carbohydrate chain of ganglioside GM1 as a ligand: identification of the binding strategies of three 15 mer peptides and their divergence from the binding modes of growth-regulatory galectin-1 and cholera toxin

The branched pentasaccharide chain of ganglioside GM1 is a prominent cell surface ligand, for example, for cholera toxin or tumor growth-regulatory homodimeric galectins. This activity profile via protein recognition prompted us to examine the binding properties of peptides with this specificity. Our study provides insights into the mechanism of molecular interaction of this thus far unexplored size limit of the protein part. We used three pentadecapeptides in a combined approach of mass spectrometry, NMR spectroscopy and molecular modelling to analyze the ligand binding in solution. Availability of charged and hydrophobic functionalities affected the intramolecular flexibility of the peptides differently. Backfolding led to restrictions in two cases; the flexibility was not reduced significantly by association of the ligand in its energetically privileged conformations. Major contributions to the interaction energy arise from the sialic acid moiety contacting Arg/Lys residues and the N-terminal charge. Considerable involvement of stacking between the monovalent ligand and aromatic rings could not be detected. This carbohydrate binding strategy is similar to how an adenoviral fiber knob targets sialylated glycans. Rational manipulation for an affinity enhancement can now be directed to reduce the flexibility, exploit the potential for stacking and acquire the cross-linking capacity of the natural lectins by peptide attachment to a suitable scaffold.     

Counterion Exchange Selectivity in Detergent–Polymer Aggregates

In aqueous solution, the interaction between sodium dodecyl sulfate (SDS) and poly(ethylene glycol) (PEG) results in the formation of small aggregates or clusters of SDS attached to the PEG polymer chain. Selectivity coefficients for exchange of two monovalent (N-methyl-4-cyanopyridinium cation and Tl⁺) and two divalent (methylviologen cation and Cu²⁺) counterions at the surface of SDS–PEG clusters, determined employing photophysical techniques, are similar, but not identical, to those for exchange at the surface of SDS micelles in the absence of PEG. The principal factor affecting ion exchange selectivity in SDS–PEG clusters does not appear to be aggregate size or surface charge density but rather the presence of poly(oxyethylene) subunits at the aggregate surface.     

On kinetics of the photodissociation iodine laser

The kinetics of iodine laser amplifiers is examined by solving the time evolution equations of chemical kinetics during optical pumping. The pumping radiation intensity is modelled by a black body of the temperature varying in time (corresponding to the flash lamp pulse). A brief comparison is made of pumping effects by long and short light pulses. Pumping by the long pulse is studied in more detail and it is found that there exists an optimum pulse strength beyond which the inversion in the laser mixture no longer grows appreciably, only its lifetime is shortened. In this connection the effect of pyrolysis of the alkyliodide molecule is also discussed. The pyrolysis is found to occur under very strong illumination, but it does not interfere with the photolytic decomposition and the optimum laser action. Finally, the influence of the reaction rate constants is studied in a systematic way and only few of them are found to carry real weight.The authors are obliged to Drs. S. V. Kuznetsova and A. I. Maslov who were consulted on the values of the reaction constants and who also drew our attention to some of the references.     

Über den Einfluß von Temperatur und Fremdionen auf Eigenschaften und Bau der Natriumwasserglaslösungen

The Influence of Temperature and Impurities Addition on the Properties and the Constitution of Sodium Water Glass Solutions Sodium water glass (NaWG-)solutions of constant composition (SiO₂/Na₂O = 3,3; C_SiO2 = 6,2 M) and different concentration of impurities (Fe, Al, Ti, Cu, chloride, sulfate) were investigated in dependence on temperature by means of the dye absorption method, ¹H- and ²³Na-NMR spectroscopy. It is shown, that the differences in the dye absorption spectra of normalized technical NaWG-solutions, mainly depend on the Fe-concentration in the solutions and their thermal history. From the results follow a crosslinking of polymeric silicate species by Fe? O? Si bonds and/or hydrogen bridges and a fully or partially degradation of these bonds at higher temperatures (150°C).     

Conformations of the ten-membered ring in 5,10-secosteroids I. X-ray and NMR. Analysis of (E)-3 β-hydroxy-5,10-seco-1(10)-cholesten-5-one esters

X-ray structure determination of the p-bromobenzoate 2b of one of the (E/Z)-isomeric 3β-hydroxy-5,10-seco-1(10)-cholesten-5-ones confirmed the (E)-configuration proposed previously and showed the cyclodecenone ring to adopt an extended crown conformation of type A ₁ (Fig. 9). Analysis of the ¹H- and ¹³C-NMR. spectra of acetate 2a revealed that in solution the ten-membered ring of this steroid exists in at least two distinct forms, the predominant (about 85%) corresponding to the solid-state conformation of 2b (= A ₁), and the minor most likely to B ₂ (Fig. 9). From NMR. data the energy difference between the two species and the relevant activation energy were estimated. A number of conformational force field calculations using a simplified partial structural model was performed; but the computed energy differences between the various possible conformations do not reproduce the effective situation, neither in solution nor in the crystal lattice, indicating that additional effects such as the transannular interaction of the double bond with the carbonyl group may strongly influence the thermodynamic stability of the system. The conformations deduced were used to rationalize the stereochemical course of different chemical reactions of 2a .     

Accurate values for the nonrelativistic energies of the lowest singlet and triplet S-states of the4He-Isotop

Accurate lower and upper bounds for the nonrelativistic lowest energies¹ E ₀ and³ E ₀ of the singlet and triplet-system of the⁴He-Isotop are calculated with the linearized method of variance minimization. The same was done for¹ E ₁ the energy of the first excitedS-state 2¹ S. The results especially for¹ E ₀ and³ E ₀ in a.u. are −2.9033076997₅ ≤¹ E ₀ ≤ −2.9033076921₈ −2.1749324263₇ ≤³ E ₀ ≤ −2.1749324245₉ i.e. the values are determined with an absolute error smaller than 0.00167 cm⁻¹ for¹ E ₀ and 0.00039 cm⁻¹ for³ E ₀.