Bis(PheOH) maleic acid amide-fumaric acid amide photoizomerization induces microsphere-to-gel fiber morphological transition: the photoinduced gelation system

The photoinduced gelation system based on 1 (non-gelling) to 2 (gelling) molecular photoisomerization in water results by microspheres (1) to gel fibers (2) transformation at the supramolecular level.     

Oscillating autoxidation reaction of p-xylene in the liquid phase, catalyzed by metal oxides

Oscillatory reaction was observed during liquid-phase oxidation of p-xylene in the presence of certain transition metal oxides as catalysts. Experimental conditions under which oscillations occur and parameters influencing this behavior are described.

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Hybridization in some macrocyclic polyacetylenes

The hybridization in several cyclic polyacetylene compounds has been calculated by the maximum overlap method, assuming planar and non-planar geometries of the molecules. In the planar configuration the hybrids describing the molecular skeleton deviate from the corresponding bond directions. We have a few “bent” bonds, but in contrast to the situation in small rings, here the deviation angles are negative, i.e., the hybrids point toward the inside of the ring. Non-planar structures in which acetylene groups are kept in a plane and CCH₂ or CH₂ groups are displaced out of the plane show less deviation from the bond directions of bent bonds. Furthermore, the deviation angles decrease with an increase in the out-of-plane displacement of methylene groups. Finally, when the angle of bending of the molecules approaches 50°, the deviation vanishes, predicting a puckered conformation for the molecules. Correlation between CC stretching vibration frequencies and the corresponding CC bond overlap is discussed.     

Generalized bond orders

We introduce generalized bond orders defined in terms of weighted Kekule valence structures. The weights were determined by the contributions of linearly independent and minimal conjugated circuits in individual Kekule valence structure. When special values for the contributions of conjugated circuits of different size are assumed, one obtains quantities that show considerable similarity to the Pauling and the Clar's bond orders. Pauling bond orders are obtained when one assumes that all conjugated circuits make equal contribution to bond orders. © 1994 John Wiley & Sons, Inc.     

Eigenmobilities in background electrolytes for capillary zone electrophoresis: III. Linear theory of electromigration

A mathematical model of capillary zone electrophoresis (CZE) based on the conception of eigenmobilities, which are the eigenvalues of a matrix M tied to the linearized governing equations is presented. The model considers CZE systems, where constituents, either analytes or components of the background electrolyte (BGE), are weak electrolytes--acids, bases, or ampholytes. There is no restriction on the number of components nor on the valence of the constituents nor on pH of the BGE. An electrophoretic system with N constituents has N eigenmobilities. In most BGEs one or two eigenmobilities are very close to zero so their corresponding eigenzones move very slowly. However, there are BGEs where no eigenmobility is close to zero. The mathematical model further provides: the transfer ratio, the molar conductivity detection response, and the relative velocity slope. This allows the assessment of the indirect detection, conductivity detection and peak broadening (distortion) due to electromigration dispersion. Also, we present a spectral decomposition of the matrix M to matrices allowing the assessment of the amplitudes of system eigenpeaks (system peaks). Our model predicted the existence of BGEs having no stationary injection zone (or water zone, gap, peak, dip). A common practice of using the injection zone as a marker of the electroosmotic flow must fail in such electrolytes.     

Graph-theoretical analysis of molecular properties. Isomeric variations in nonanes

Paths of length two and three appear to dominate variations in isomers of alkanes when various physical and chemical molecular properties are compared. The regularities previously observed for octanes have been fully examined for the set of 35 nonane isomers C₉H₂₀. Such examinations are facilitated by construction of appropriate grid graphs with paths of length two and three, respectively, representing molecules and connecting such points along the grid axes. By ordering structures in the two-dimensional coordinate plane, various trends and regular changes in the relative magnitudes for the selected thermodynamic properties have been traced to molecular connectivity and topology.     

Surface tension in Ising systems with Kac potentials

We consider an Ising spin system with Kac potentials in a torus of ^d,d>-2, and fix the temperature below its Lebowitz-Penrose critical value. We prove that when the Kac scaling parameter vanishes, the log of the probability of an interface becomes proportional to its area and the surface tension, related to the proportionality constant, converges to the van der Waals surface tension. The results are based on the analysis of the rate functionals for Gibbsian large deviations and on the proof that they -converge to the perimeter functional of geometric measure theory (which extends the notion of area). Our considerations include nonsmooth interfaces, proving that the Gibbsian probability of an interface depends only on its area and not on its regularity.     

Survey of structural regularities in molecular properties. I. Carbon-13 chemical shifts in alkanes

Many regularities in properties among structurally related compounds are known but a systematic approach to investigate all such cases is rare. A plan is outlined for a systematic study of structural regularities that is based on use of selected graph invariants as prime auxiliary quantities. In this paper carbon-13 chemical shifts in alkanes are examined. Since NMR spectra of paraffins are well understood, the example provides a useful illustration of the approach, introduces basic concepts, and illustrates the kind of the results that the graph-theoretical scheme generates. Differences and similarities between graph-theoretical viewing of the problem of structural regularities and customary direct use of additivities are discussed in some detail.     

Selective additions of polyhalogenated compounds to chloro substituted ethenes catalyzed by a copper complex

The Cu complex Cu(L)_nCl (L=2-propylamine) has been found to be an advantageous catalyst for the addition of polyhalogenated compounds to chloro substituted ethenes; the 11 adducts were formed almost exclusively in up to 71% yield.

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, , Cu(L)_nCl (L=2-), ; 71% 11.