Theory of oscillatory experiments with a coaxial cylinder viscometer

Equations are derived for the coaxial cylinder system in the combined oscillatory and steady-state shear mode. The limitations of the use of the various equations are presented. If the usual linear equations are used, the main limitation, in the case of oscillatory shear only, is that the frequency of measurement should be below 0.016 | ^*|/(r ₂ –r ₁ )². Here | ^*| is the modulus of the complex viscosity, is the density of the liquid andr ₁ andr ₂ are the radii of the cylinders. Furthermore it is shown that there is a small error in the numerical factor of the usually applied equations. The calculations are set up in such a way that extension to higher harmonics follows in a natural way. An experimental example illustrates the use of the derived equations.     

The fast multipole boundary element method for molecular electrostatics: An optimal approach for large systems

We propose a fast implementation of the boundary element method for solving the Poisson equation, which approximately determines the electrostatic field around solvated molecules of arbitrary shape. The method presented uses computational resources of order O(N) only, where N is the number of elements representing the dielectric boundary at the molecular surface. The method is based on the Fast Multipole Algorithm by Rokhlin and Greengard, which is used to calculate the Coulombic interaction between surface elements in linear time. We calculate the solvation energies of a sphere, a small polar molecule, and a moderately sized protein. The values obtained by the boundary element method agree well with results from finite difference calculations and show a higher degree of consistency due to the absence of grid dependencies. The boundary element method can be taken to a much higher accuracy than is possible with finite difference methods and can therefore be used to verify their validity. © 1995 by John Wiley & Sons, Inc.     

The inclusion of electrostatic hydration energies in molecular mechanics calculations

Summary The problem of including solvent effects in molecular mechanics calculations is discussed. It is argued that the neglect of charge-solvent (solvation) interactions can introduce significant errors. The finite difference Poisson-Boltzmann (FDPB) method for calculating electrostatic interactions is summarized and is used as a basis for introducing a new pairwise energy term which accounts for charge-solvent interactions. This term acts between all pairs of atoms usually considered in molecular mechanics calculations and can be easily incorporated into existing force fields. As an example, a parameterization is developed for the CHARMm force field and the results compared to the predictions of the FDPB method. An approach to the realistic incorporation of solvent screening into force fields is also outlined.     

THE 'OPSIN SHIFT' IN BACTERIORHODOPSIN: STUDIES WITH ARTIFICIAL BACTERIORHODOPSINS

Abstract— The difference (in cm⁻¹) in absorption maxima between the protonated Schiff base of retinals and the pigment derived therefrom has been defined as the opsin shift. It represents the influence of the opsin binding site on the chromophore. The analysis of the opsin shifts of a series of dihydrobacteriorhodopsins has led to the external point-charge model, which in addition to a counter anion near the Schiff base ammonium, carries another negative charge in the vicinity of the β-ionone ring. This is in striking contrast to the external point-charge model proposed earlier for the bovine visual pigment. The absorption maxima of rhodopsins formed from bromo- and phenyl retinals support the two models. A retinal carrying a photoaffinity label has yielded a nonbleachable bacteriorhodopsin.     

Crystal growth of Ln2NiO4 (Ln = La,Pr, Nd) by skull melting

Growth of large single crystals of quasi-two-dimensional Ln₂NiO₄ (Ln = La, Pr, Nd) has been accomplished using the radio frequency technique of skull melting under controlled oxygen partial pressures. No evidence of intergrowth of other phases such as Ln₃Ni₂O₇ or higher homologs was observed. Determination of the Ni³⁺ content indicates that the crystals are cation deficient.     

Gödel axiom mappings in special relativity and quantum-electromagnetic theory

Exponential mappings into an imaginary space or number field for the axioms of a theory, which are in the form of propositional constants and variables, make possible: (a) an understanding of the meaning and differences between the Lorentz transformation constants, such that their product is still equal to one, but the axioms at each end of the transformations are logically inverse and separately consistent; (b) an interpretation of the psi function phase factor which is part of the axiomE=hf; (c) the unification of the quantum-mechanical psi function and the electromagnetic wave function. Thus, those statements whose mechanisms are unknown (the axioms of the theory) are to be assigned the axiom propositional number symbol and are to be associated with the complex probability eⁱ, which is a uniform factor of the energy equations expressing the physical state. Such probabilistic axiom functions can be associated with both the special theory of relativity and the quantum-electromagnetic theory.     

Ellipsometric investigation of the skeletonization process of langmuir-blodgett films

When Langmuir-Blodgett films, consisting of a mixture of a long chain carboxylic acid and its salt are immersed in benzene, the acid dissolves, while the salt remains as a skeleton. The density of the film is lowered in this way and so is the refractive index. The process can thus be followed by performing ellipsometric measurements as a function of time of skeletonization. It is established that skeletonization is, in first instance, a diffusion-controlled process with a diffusion coefficient of about $\text{5 × 10}{}^{\mathrm{?14}}\text{cm}{}^2\text{sec}$ at room temperature. The salt also slowly dissolves at a rate of about $\text{1.6 × 10}{}^{10}\text{molecules}\text{/}\text{sec}\text{cm}{}^2$.