Optimale Bestelltermine bei zufallsveränderlichen Lieferfristen

Zusammenfassung Ermittlung des günstigsten Bestellzeitpunktes, wenn die Zeitspanne zwischen der Bestellung und der Lieferung eine Zufallsveränderliche mit bekannter Verteilung ist.

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Summary Determination of the optimal time for placing orders in those cases where the time interval between order and supply is a random variable with known distribution.

     

N,N′-dialkylsubstituted Imidazolidine-2-thionecopper(I) complexes. X-ray analysis of chloro-bis(N,N′-dimethylimidazolidine-2-thione)copper(I)

Summary New complexes of copper(I) withN,N-dialkylsubstituted imidazolidine-2-thione ligands were prepared by reduction of CuX₂ (X = Cl or Br). The i.r. spectra show that in all the complexes the ligand coordinates through the sulphur atom. The crystal structure of chloro-bis(N,N-dimethylimidazolidine-2-thione)copper(I) has been determined from x-ray diffraction data. Crystals are monoclinic. space groupC ₂, with unit cell dimensions:a = 16.022(15),b = 9.942(10),c = 15.112(15) A, = 139.84(10)², Z = 4. The final R index is 5.2%. The copper coordination is trigonal, involving sulphur atoms of the two ligands and One chlorine atom. The steric effect of the two methyls imposes a rotation of the imidazolidine rings with respect to the coordination plane. The dihedral angle between the mean plane of thiourea moieties. parallel one with the other. and the coordination plane is 119.3°.This work was supported by the National Research Council (C.N.R.) of Rome.     

A new tricyclic triketone from tandem condensation reactions

Perhydrophenanthrene-1,5,10-trione (6) was isolated from the reaction of methyl 3-(carboxymethyl)cyclohexanone and cyclohexenone in a tandem Michael-Claisen reaction. NMR and X-ray analysis confirmed the structure of the product.     

Atomic force microscopy study of early morphological changes during apoptosis

Apoptosis is defined by a distinct set of morphological changes observed during cell death including loss of focal adhesions, the formation of cell membrane buds or blebs, and a decrease in total cell volume. Recent studies suggest that these dramatic morphological changes, particularly apoptotic volume decrease (AVD), are an early prerequisite to apoptosis and precede key biochemical time-points. Here we use atomic force microscopy to observe early stage AVD of KB cells undergoing staurosporine-induced apoptosis. After a 3-h exposure to 1 microM staurosporine, a 32% decrease in total cell height and a 50% loss of total cell volume is observed accompanied by only a 15% change in cell diameter. The observed AVD precedes key biochemical hallmarks of apoptosis such as loss of mitochondrial membrane potential, phosphatidyl serine translocation, nuclear fragmentation, and measurable caspase-3 activity. This suggests that morphological volume changes occur very early in the induction of apoptosis.     

Metabolic profile of lettuce leaves by high-field NMR spectra

A detailed analysis of the proton high-field NMR spectra of aqueous and organic extracts of lettuce leaves is reported for the first time. A combination of COSY, TOCSY, (1)H-(13)C HSQC, (1)H-(13)C HMBC bidimensional sequences and DOSY was used to assign each spin system and to separate the components of the complex patterns. A large number of water-soluble metabolites belonging to different classes such as carbohydrates, polyols, organic acids and amino acids were fully assigned. Moreover, the complex spectra of metabolites extracted in organic solvents belonging to sterols, fatty acids, diacylglycerophospholipids, galactosyldiacylglycerols, sulpholipids, pheophytins, carotenoids and hydrocarbons were also assigned.     

Measurement of coupling constants in symmetrical spin systems using a full multiple-step cross-polarization-driven NMR pulse scheme

New NMR pulse schemes completely driven under homonuclear and heteronuclear cross-polarization conditions are proposed for the study and the measurement of coupling constants in symmetrical molecules in solution. The appropriate superimposition of independent magnetization components can afford several spin-selective multiplet patterns that are suitable for the determination of the magnitude and the sign of proton-proton and proton-carbon coupling constants with optimum sensitivity levels. A detailed product operator formalism analysis for the proposed doubly selective 1D and nonselective 2D HCP-TOCSY versions is provided and experimental verification for the configurational analysis of symmetric olefinic systems having chemical equivalence is demonstrated.     

Tuning of redox properties for the design of ruthenium anticancer drugs: part 2. Syntheses, crystal structures, and electrochemistry of potentially antitumor [Ru III/II Cl6-n(Azole)n]z(n = 3, 4, 6) complexes

A series of mixed chloro-azole ruthenium complexes with potential antitumor activity, viz., mer-[RuIIICl3(azole)3] (B), trans-[RuIIICl2(azole)4]Cl (C), trans-[RuIICl2(azole)4] (D), and [RuII(azole)6](SO3CF3)2 (E), where azole = 1-butylimidazole (1), imidazole (2), benzimidazole (3), 1-methyl-1,2,4-triazole (4), 4-methylpyrazole (5), 1,2,4-triazole (6), pyrazole (7), and indazole (8), have been prepared as a further development of anticancer drugs with the general formula [RuCl4(azole)2]- (A). These compounds were characterized by elemental analysis, IR spectroscopy, electronic spectra, electrospray mass spectrometry, and X-ray crystallography. The electrochemical behavior has been studied in detail in DMF, DMSO, and aqueous media using cyclic voltammetry, square wave voltammetry, and controlled potential electrolysis. Compounds B and a number of C complexes exhibit one RuIII/RuII reduction, followed, at a sufficiently long time scale, by metal dechlorination on solvolysis. The redox potential values in organic media agree with those predicted by Lever's parametrization method, and the yet unknown EL parameters were estimated for 1 (EL = 0.06 V), 3 (EL = 0.10 V), 4 (EL = 0.17 V), and 5 (EL = 0.18 V). The EL values for the azole ligands 1-8 correlate linearly with their basicity (pK(a) value of the corresponding azolium acid H2L+). In addition, a logarithmic dependence between the homogeneous rate constants for the reductively induced stepwise replacement of chloro ligands by solvent molecules and the RuIII/RuII redox potentials was observed. Lower E(1/2) values (higher net electron donor character of the ligands) result in enhanced kinetic rate constants of solvolysis upon reduction. The effect of the net charge on the RuIII/RuII redox potentials in water is tentatively explained by the application of the Born equation. In addition, the pH-dependent electrochemical behavior of trans-[RuCl2(1,2,4-triazole)4]Cl is discussed.     

Modeling the morphology and mechanical properties of sheared ternary mixtures

Through a combination of simulation techniques, we determine both the structural evolution and mechanical properties of blends formed from immiscible ternary mixtures. In this approach, we first use the lattice Boltzmann method to simulate the phase separation dynamics of A/B/C fluid mixtures for varying compositions within the spinodal region. We also investigate the effect of an imposed shear on the phase ordering of the mixture. We assume that the fluid is quenched sufficiently rapidly that the phase-separated structure is preserved in the resultant solid. Then, the output from our morphological studies serves as the input to the lattice spring model, which is used to simulate the elastic response of solids to an applied deformation. These simulations reveal how the local stress and strain fields and the global Young's modulus depend on the composition of the blend and the stiffness of the components. By comparing the results for the sheared and unsheared cases, we can isolate optimal processing conditions for enhancing the mechanical performance of the blends. Overall, the findings provide fundamental insight into the relationship between structure, processing, and properties for heterogeneous materials and can yield guidelines for formulating blends with the desired macroscopic mechanical behavior.     

Analytic gradients for the spin-conserving and spin-flipping equation-of-motion coupled-cluster models with single and double substitutions

Analytic gradient expressions for the spin-conserving and spin-flipping equation-of-motion coupled-cluster models with single and double substitutions are derived using a Lagrangian approach for the restricted and unrestricted Hartree-Fock references, both for the case of all orbitals being active in correlated calculations and for the frozen core and/or virtual orbitals. Details of the implementation within the Q-CHEM electronic structure package are discussed. The capabilities of the new code are demonstrated by application to cyclobutadiene.     

A modified analytical method for total antioxidant potential assay using RP-HPLC with electrochemical detection and its application for pro- and antioxidative properties of dopamine measurement

Total antioxidant potential (TAP) is usually measured using photometric or fluorometric assays. Preliminary results of a reversed-phase high-performance liquid chromatography--electrochemical detection assay are given. The method is based on the generation of hydroxyl radicals in a Fenton reaction and analysis of the product of their interaction with p-hydroxybenzoic acid (3,4-dihydroxybenzoic acid). The method is applied to estimate the TAP of dopamine. As a result, depending on the concentration, dopamine is pro- or antioxidant. The results are compared with TAP measurements using a standard photometric method.