Properties of updating methods for the multipliers in augmented Lagrangians

The convergence properties of different updating methods for the multipliers in augmented Lagrangians are considered. It is assumed that the updating of the multipliers takes place after each line search of a quasi-Newton method. Two of the updating methods are shown to be linearly convergent locally, while a third method has superlinear convergence locally. Modifications of the algorithms to ensure global convergence are considered. The results of a computational comparison with other methods are presented.This work was supported by the Swedish Institute of Applied Mathematics.     

A combined penalty function and gradient projection method for nonlinear programming

A new programming algorithm for nonlinear constrained optimization problems is proposed. The method is based on the penalty function approach and thereby circumyents the necessity to maintain feasibility at each iteration, but it also behaves much like the gradient projection method. Although only first-order information is used, the algorithm converges asymptotically at a rate which is independent of the magnitude of the penalty term; hence, unlike the simple gradient method, the asymptotic rate of the proposed method is not affected by the ill-conditioning associated with the introduction of the penalty term. It is shown that the asymptotic rate of convergence of the proposed method is identical with that of the gradient projection method.Dedicated to Professor M. R. HestenesThis research was supported by the National Science Foundation, Grant No. GK-16125.     

Structure determination of Ls-threonine by neutron diffraction

The structure of the aminoacid, L_s-threonine [NH ₃ ⁺ CH(CHOHCH₃)COO^?], space groupP2₁2₁2₁,a=13.630(5),b=7.753(1),c=5.162(2) Å,z=4, has been determined from neutron diffraction data using direct methods. The intensities of 1148 neutron Bragg reflections were measured from a single crystal. The structural parameters were refined by the method of least squares using anisotropic temperature factors. The finalR(F ²) is 0.068. The structure was also refined from the x-ray data of Shoemakeret al (1950J. Am. Chem. Soc. 72 2328); there is good agreement between the two sets of heavy atom parameters. The parameters of hydrogen atoms are of course more precisely determined in our neutron study. The molecular conformation and the hydrogen bonding scheme are discussed. Weighted average values of bond distances and angles from 14 aminoacid structures with ionized carboxylic groups studied by neutron diffraction at Brookheven and Trombay are also presented.     

Generalized nonlinear master equations for local fluctuations: Dimensionality expansions and augmented mean field theory

By application of a projection operator technique we derive a formally exact generalization of the nonlinear mean field master equation introduced recently for the study of local fluctuations in a reacting medium. Our starting point is a phenomenological cell master equation. The results of our theory are applicable to the theory of a fluctuating hydrodynamic reacting system. The mean field equation is placed on a firm theoretical foundation by showing it to be the lowest order approximation in an expansion in the dimensionality of the physical space keeping the product of the number of nearest neighbors (an increasing function of dimensionality) and the typical diffusion coefficient constant. A more accurate nonlinear master equation that allows for the correlation and fluctuations in the environment of a given volume element is derived in the form of an augmented mean field equation.Work supported in part by a grant from the National Science Foundation.     

Intramolecular Ene Reactions in Organic Synthesis

Thermal cyclizations of appropriate dienes, enynes and related unsaturated systems, some of them carried out on an industrial scale, demonstrate increasingly the preparative power of the intramolecular ene reaction. A variety of substituted, fused and bridged ring systems, including natural products, are thus easily accessible in a regio- and stereo-selective manner. Numerous examples are discussed systematically illustrating the possibilities, limitations, and common features of this cyclization reaction and its reverse ring-opening process.     

Zum Fließverhalten kurzglasfasergefüllter Thermoplastschmelzen im stationären und instationären Bereich

Zusammenfassung Durch Zugabe von Glasfasern wird das rheologische Verhalten von Kunststoffschmelzen verändert. Kurzglasfasergefüllte Styrol-Acrylnitril-Copolymere mit verschiedenen Füllgraden wurden mit dem Rotations-und dem Kapillarrheometer untersucht. Sowohl im stationären Bereich als auch im instationären Bereich (Anlauf- und Abklingverhalten) sind Unterschiede zum ungefüllten Material festzustellen: Mit Zunahme des Faseranteils steigt der Schubmodul, und das viskoelastische Überschwingen wird geringer als bei ungefüllten Systemen. Erhöhung von Temperatur, Schergeschwindigkeit und Faseranteil führen zu einer Verkürzung der Relaxationszeiten, Steigerung des hydrostatischen Druckes erwartungsgemäß zu deren Verlängerung.

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Summary The rheological behaviour of polymer melts is changed by addition of glass fibres. Experiments were conducted with styrene-acrylonitrile copolymers filled with various amounts of short fibres on a rotational and a capillary rheometer, both under steadystate and transient conditions. It is observed that by adding fibres the shear modulus increases but the stress overshoot decreases. With increase of temperature, shear rate and fibre content relaxation times become shorter whereas with higher hydrostatic pressures they grow longer, as is to be expected.

Mit 9 Abbildungen und 2 Tabellen     

Solvent Relaxation in Phospholipid Bilayers: Principles and Recent Applications

Although there exist a number of methods, such as NMR, X-ray, e.g., which explore the hydration of phospholipid bilayers, the solvent relaxation (SR) method has the advantage of simple instrumentation, easy data treatment and possibility of measuring fully hydrated samples. The main information gained from SR by the analysis of recorded “time-resolved emission spectra” (TRES) is micro-viscosity and micro-polarity of the dye microenvironment. Based on these parameters, one can draw conclusions about water structure in the bilayer. In this review, we focus on physical background of this method, on all the procedures that are needed in order to obtain relevant parameters, and on the requirements on the fluorescence dyes. Furthermore, a few recent applications (the effect of curvature, binding of antibacterial peptides and phase transition) illustrating the versatility of this method are mentioned. Moreover, limitations and potential problems are discussed.     

Four complementary theoretical approaches for the analysis of NMR paramagnetic relaxation

Four theoretical and computational approaches used at the University of Michigan to analyze NMR paramagnetic relaxation enhancement (NMR-PRE) are described. The primary objective of the theory is to describe the relationship of the NMR-PRE phenomenon to the electron spin hamiltonian and the spin energy level structure when zero field splitting interactions are significant. Four formulations of theory are discussed: (1) spin dynamics simulation; (2) the laboratory frame "constant H(S)" formulation; (3) the Molecular Frame "constant H(S)" formulation; and (4) the zfs-limit "constant H(S)" formulation. No single theoretical approach describes all important aspects of the relaxation mechanism in a fully satisfactory way. We use the four formulations in a complementary manner to provide as complete a picture of the relaxation mechanism as possible. We also discuss the integration of NMR-PRE theory and recently developed theory of electron spin relaxation which accounts for effects of the permanent zfs hamiltonian.     

Multicanonical Monte Carlo simulations on intramolecular micelle formation in copolymers

The formation of intramolecular micelles in copolymers with periodic sequence, where hydrophobic units (stickers) are periodically placed along the chain, is studied by using multicanonical Monte Carlo computer simulations for an off-lattice bead-rod model in three dimensions. With decreasing the temperature, a transition from random-coil conformations to micelles occurs and flower-type micelles are formed via the transition. The number of stickers forming a micelle core is limited by the excluded-volume effect of loop chains around micelle cores. By this effect, two intramolecular micelles are formed for long polymer chains with 60 bonds via the coil-to-micelle transition. By further decreasing the temperature, we find that another transition, i.e., a micelle-to-micelle transition, takes place. At this transition point, the two intramolecular micelles merge into one micelle. Furthermore, we extend the multicanonical MC method to study elastic properties of single polymer chains with strong attractive interactions under external force fields, and study how the intramolecular micellization affects the elastic property of single polymer chains.     

Influence of the Brownian step size in off-lattice Monte Carlo simulations of irreversible particle aggregation

The influence of the Brownian step size in off-lattice Monte Carlo simulations of the aggregation and gelation of spheres is studied. It is found that the kinetics are strongly influenced if the step size is larger than the mean smallest distance between the sphere surfaces. The structure of the clusters and the gels is influenced, but only over length scales smaller than the step size. Using large step sizes leads to a narrower size distribution of the clusters. Implications of the present results are discussed for simulations reported in the literature in which the Brownian step size was chosen equal to the sphere diameter.