Zinn und Antimon in Legierungen

Ohne Zusammenfassung     

L-Curve and Curvature Bounds for Tikhonov Regularization

The L-curve is a popular aid for determining a suitable value of the regularization parameter when solving linear discrete ill-posed problems by Tikhonov regularization. However, the computational effort required to determine the L-curve and its curvature can be prohibitive for large-scale problems. Recently, inexpensively computable approximations of the L-curve and its curvature, referred to as the L-ribbon and the curvature-ribbon, respectively, were proposed for the case when the regularization operator is the identity matrix. This note discusses the computation and performance of the L- and curvature-ribbons when the regularization operator is an invertible matrix.     

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.     

Chemistry of Succinylsuccinic Acid Derivatives. Part II. The crystal and molecular structure of diethyl succinylsuccinate

X-ray structure analysis of the title compound (I) is reported. The results are interpreted to predict formation of anti-tricyclo[4.4.0^1,6.0^7,12]-1,4,7,10-tetraethoxycarbonyl-3,6,9,12-tetrahydroxy-dodeca-3,9-diene on UV.-irradiation of solid (I).     

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.     

Buchbesprechungen

Ohne Zusammenfassung     

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 .     

Equational partiality

A special kind of partiality of heterogeneous algebraic structures is introduced. Every operator of a heterogeneous operator domain is associated with a set of term equations as necessary and sufficient domain condition.It is shown that some kind of hierarchy condition for the system of domain equations is equivalent to the condition that every injective weak homomorphism is a strong homomorphism which is equivalent to the statement that every bijective weak homomorphism is an isomorphism.On the base of this result the notions of a quasi-variety and of a variety of equationally partial heterogeneous algebras are suggested. The class of all small categories becomes a standard example of a variety of equational partial heterogeneous algebras.Presented by V. Trnková.     

Reaction properties of the trans-hyponitrite complex [Ru2(CO)4(mu-H)(mu-PBu(t)2)(mu-Ph2PCH2PPh2)(mu-eta2-ONNO)

The protonation of [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNO)] (1) with HBF(4) occurs at the oxygen of the noncoordinating side of the trans-hyponitrite ligand to give [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNOH)][BF(4)] (2) in good yield. The monoprotonated hyponitrite in 2 is deprotonated easily by strong bases to regenerate 1. Furthermore, 1 reacts with the methylating reagent [Me(3)O][BF(4)] to afford [Ru(2)(CO)(4)(mu-H)(mu-PBu(t)()(2))(mu-dppm)(mu-eta(2)-ONNOMe)][BF(4)] (3). The molecular structures of 2 and 3 have been determined crystallographically, and the structure of 2 is discussed with the results of the DFT/B3LYP calculations on the model complex [Ru(2)(CO)(4)(mu-H)(mu-PH(2))(mu-H(2)PCH(2)PH(2))(mu-eta(2)-ONNOH)](+) (2a). Moreover, the thermolysis of 2 in ethanol affords [Ru(2)(CO)(4)(mu-H)(mu-OH)(mu-PBu(t)()(2))(mu-dppm)][BF(4)] (4) in high yield, and the deprotonation of 4 by DBU in THF yields the novel complex [Ru(2)(CO)(4)(mu-OH)(mu-PBu(t)()(2))(mu-dppm)] (5).