Chemical Infiltration during Atomic Layer Deposition: Metalation of Porphyrins as Model Substrates

New uses for ALD : By applying standard metal oxide atomic layer deposition (ALD) to two types of porphyrins, site‐specific chemical infiltration of substrate molecules is achieved: Diethylzinc can diffuse into the interior of porphyrin supramolecular structures and induce metalation of the porphyrin molecules from the vapor phase. A=Ph, p‐HO₃SC₆H₄.

     

Cover Picture: Controlling the Chair Conformation of a Mannopyranose in a Large‐Amplitude [2]Rotaxane Molecular Machine (Chem. Eur. J. 21/2009)

A domino effect from one extremity to the other is observed in a large‐amplitude mannosyl [2]rotaxane molecular machine. In their Communication on page 5186 ff., F. Coutrot and E. Busseron describe the efficient preparation of new [2]rotaxane molecular machines containing anilinium and either mono‐ or disubstituted pyridinium amide stations. In the case of the disubstituted pyridinium amide, the macrocycle shuttles from the anilinium to the pyridinium upon deprotonation and causes an impressive flipping of the chair conformation of the glucidic moiety.

     

Evidence for the cation-pi interaction between Cu2+ and tryptophan

The cation-pi interaction, a noncovalent interaction of electrostatic nature between a cation and an electron-rich pi system, is increasingly recognized as an important force that influences the structures and functions of molecules including proteins. Unlike other metal cations, the transition metal cation Cu2+ is not regarded to take part in a cation-pi interaction because Cu2+ tends to oxidize the pi electron system, in particular that of Trp, and to introduce covalency in the metal-pi electron interaction. This paper reports the first spectral evidence for the cation-pi interaction between Cu2+ and Trp. The Cu2+ ion bound to the amino N-terminal Cu2+/Ni2+ binding motif composed of three amino acid residues interacts with the indole ring of the fourth Trp residue in a noncovalent manner. The Cu2+-Trp interaction produces a distinct negative band at 223 nm in circular dichroism (CD), which disappears upon mutation or depletion of the Trp residue or upon replacement of the Cu2+ ion by Ni2+. In UV absorption, a pair of negative/positive intensity changes is generated at 222/231 nm by the Cu2+-Trp interaction, being consistent with the previous observations on the indole ring interacting with K+ or a cationic His imidazole ring. The negative CD band around 223 nm is characteristic of the Cu2+-Trp pair and may be useful as a marker of the Cu2+-Trp cation-pi interaction. Coordination of negatively charged ligands to Cu2+ is suggested to be important for the cation to be involved in a cation-pi interaction.     

Cationic copolymerization of phenyl propenyl ethers

Ring-substituted phenyl propenyl ethers were found to form homopolymers without any rearrangement by metal halides. Phenyl propenyl ethers were less reactive than the corresponding phenyl vinyl ethers in cationic polymerization. In order to study the electronic effect of a substituent on the reactivity, cis-p-Cl,p-CH₃, and p-CH₃O-phenyl propenyl ethers were copolymerized with phenyl propenyl ether in methylene chloride at ?78°C with stannic chloride–trichloroacetic acid, and their ¹H- and ¹³C-NMR spectra were measured. The reaction constant ρ against Hammett σ_p was ?2.1. The cis-phenyl propenyl ethers were slightly more reactive than the corresponding trans isomers. On the other hand, an o-methyl group decreased the reactivity of phenyl propenyl ether. The low reactivity of o-methyl phenyl propenyl ether was attributed to the steric hindrance between the propagating carbocation and the monomer.     

Application of the ellipsoid method in an interactive procedure for multicriteria linear programming

The research reported in this paper is concerned with an application of the ellipsoid algorithm in the interactive multicriteria linear programming step method (STEM) byBenayoun et al. [1971]. Due to this application we eliminate some drawbacks of the original version of STEM and, moreover, we avoid extra computations connected with sensitivity analysis in every iteration. Specifically, we use the ellipsoid algorithm to minimize the Euclidean norm in the criterion space instead of the Chebyshev norm, which ensures that every solution submitted to the decision maker is efficient. As follows from a computational experiment, in comparison with the application of the simplex method, the proposed modification of STEM shows a smaller increase of the computational effort when the number of criteria increases. However, the absolute computation time becomes worse for problems of larger size.

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Zusammenfassung In dieser Arbeit wird über eine Anwendungsmöglichkeit der Khachiyan-Shor-Algorithmus (Ellipsoid-Algorithmus) im Rahmen des STEM-Verfahrens zur interaktiven Lösung linearer Vektoroptimierungsmodelle berichtet. Auf diese Weise können einige spezifische Nachteile des STEM-Verfahrens in seiner Originalversion vermieden werden. Durch die Verwendung der Euklidischen Norm anstelle der beim STEM-Verfahren üblichen Tschebyscheff-Norm wird garantiert, daß dem Entscheidungsträger nur effiziente Lösungen vorgeschlagen werden. Die numerischen Erfahrungen zeigen, daß der Lösungsaufwand der hier vorgeschlagenen Modifikation des STEM-Verfahrens mit steigender Anzahl von Zielfunktionen weniger stark zunimmt als bei der üblichen Version. Dies gilt jedoch nicht hinsichtlich der allgemeinen Problemgröße.

     

Weighted majority games and the matrix of homogeneity

If a weighted majority game (not necessarily constant sum or super additive) is described by the weights (voting strength) of the players involved and a majority level, then it is desirable to know whether the game is in addition homogeneous. The paper provides a recursive procedure defining a test for homogeneity. This procedure involves the computation of a number theoretical function, the matrix of homogeneity. If this matrix is knownall majority levels with respect to which the given set of weights represents a homogeneous simple weighted majority game are known at once.

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Zusammenfassung Ein gewichtetes Majoritätsspiel (nicht notwendig superadditiv oder mit Konstantsummeneigenschaft) kann beschrieben werden durch die Gewichte (die Abstimmungsstärke) der beteiligten Spieler und durch eine Mehrheitsschranke. Wenn eine solche Darstellung gegeben ist, so ist es wünschenswert, das Spiel zusätzlich auf die Eigenschaft der Homogenität hin zu untersuchen. Die vorliegende Arbeit stellt eine rekursive Prozedur zur Verfügung, die einen Test auf Homogenität einer vorgelegten Darstellung eines Spieles impliziert. Die Prozedur ermöglicht die Berechnung einer zahlentechnischen Funktion, der Homogenitätsmatrix. Wenn diese Matrix bekannt ist, kann man bei einem vorgegebenen Gewichtssatz alle Majoritätsschranken angeben, bezüglich welcher die vorgelegten Gewichte ein homogenes einfaches gewichtetes Majoritätsspiel darstellen.

     

Distribution of values of σ2 (n) in residue classes

IntegersN for which ₂ (n has weak uniform distribution (modN) are determined.     

Ein Algorithmus zur Lösung eines Verteilungsproblems

Zusammenfassung Bei der Lastverteilung eines Elektrizitätsversorgungsunternehmens besteht die Möglichkeit, durch eine Tonfrequenzrundsteueranlage die Last optimal aufzuteilen. Eine Zielsetzung besteht darin, durch Zu- und Wegschalten von Verbrauchergruppen die Lastspitze möglichst klein zu halten. Dabei muß allerdings jedem Verbraucher in einem gewissen Zeitraum eine gewisse Einschaltdauer garantiert sein. Der zur Lösung herangezogene Algorithmus basiert im wesentlichen auf dem Prinzip der dynamischen Optimierung und der Idee von Branch- and-Bound-Verfahren.

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Summary One aim of electric load management is to keep load peaks low by switching on and off water heaters of different groups of customers. There is a restriction that those heaters have to be switched on within a certain period of time for some fixed time. The optimal switching strategy for this distribution problem is computed using dynamic programming and the idea of branch and bound methods.

     

Die Strommer-Zykliden des Flaggenraumes

According to H. BRAUNER a flag space is a three-dimensional affine space with an absolute {,f,F}, wheref is a line in the plane of infinity andF a point onf. A cyclide is a surface of order 4 that intersects only atf. A STROMMER-cyclide is a cyclide generated by translation of a circle in an isotropic plane. In this paper we proof that all STROMMER-cyclides can be generated by translation of an isotropic circle along a divergent Newton-parabola or a conic in a full isotropic plane. We give normal-forms and CAD-pictures of these surfaces. Finaly some geometrical results about STROMMER-cyclides are developed.

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Herrn o.Prof. Dr. Gy. Strommer zum 70. Geburtstag gewidmet.     

On locally optimal nonparametric tests

Summary There is an abundancy of problems in which no parametric model realistically describes the situation and in which, accordingly, we have to resort to nonparametric methods. As the numerical problems connected with nonparametric tests are becoming less and less important, rank tests, permutation tests and the like are becoming more and more part of the standard armatory of applied statisticians. The lack of tabulated critical values, for instance, should no longer be a serious objection against the use of permutation tests in practice; cf. Edgington (1987).The rationale underlying permutation and rank tests has been outlined in quite a number of text books and papers; cf. Fraser (1957), Lehmann (1959), Hájek-Sidák (1967) or Witting (1970). Roughly speaking, permutation tests are constructibel if the data can be condensed by means of a sufficient and complete statistic allowing for the proper kind of conditioning. Rank tests arise if the underlying problem is invariant with respect to (w.r.t.) a large group of transformations which leads to a maximal invariant statistic consisting of (signed) ranks.Most practical nonparametric problems, however, are too complex to be tractable by just one of those approaches. Many of them, however, can be handled by a combination of both techniques. In this paper we outline the logic underlying that combined reduction method and apply it to construct locally most powerful tests. Moreover, we discuss what we label Hoeffding's transfer problem, i.e. the uniformity aspect of locally most powerful tests with respect to the starting point at the boundary. We are concentrating on the discussion of the nonparametric two-sample location and scale problem. Further important problems are mentioned in Section III.This is a written account of an invited lecture delivered by the third author on occasion of the 14th Symposium über Operations Research, Ulm, September 6–8, 1989.