THE PHOTOADDITION OF NUCLEOPHILES TO URACIL

Abstract— Quantum yields for 254 nm ultraviolet photoaddition of the nucleophiles hydrazine, HCN, HSO₃^-, methyl amine, and BH₄^- to uracil have been measured; the quantum yields for hydrazine, HCN, and HSO₃^- additions are pH-dependent. The nucleophiles sulfide, azide, chloride, bromide, iodide, nitrite and thiocyanate failed to photo–add under similar conditions. These reactions are interpreted as 1,4-additions to the conjugated enone system of the anti-aromatic compound, uracil; as suggested by S. Y. Wang (Wang and Nnadi, 1968). The nuclear magnetic resonance (NMR) spectrum of the photohydrate of uracil-5-d-showed that the proton was added to the 5-position in a stereochemically random manner. The photoaddition of HSO₃^- takes place at much lower concentrations than required for the thermal addition of this anion and is also stereochemically random.     

INTERACTION OF DIBUCAINEHCl LOCAL ANESTHETICS WITH BACTERIORHODOPSIN IN PURPLE MEMBRANE: A SPECTROSCOPIC STUDY

Several spectroscopic techniques (absorption, emission, transient absorption and differential scanning calorimetry--DSC) were used to investigate the deprotonation of dibucaine.HCl in a hydrophobic environment, and the interaction sites and mechanisms of the local anesthetic dibucaine.HCl on bacteriorhodopsin (bR) in purple membrane. The important results are summarized as follows: (1) the visible absorption features of native (lambda max = 568 nm) and deionized (lambda max = 608 nm) bR are sensitive to the amount of dibucaine.HCl added; (2) the emission spectrum of dibucaine.HCl embedded in the retinal-free mutant bR is similar to that of dibucaine free base in Triton X-100 micellar solutions; (3) the phosphorescence emission of dibucaine at 77 K is completely quenched by bR and the fluorescence quenching rate for the incorporated dibucaine.HCl in bR was determined as kq = 4.09 x 10(13) M-1 s-1; (4) the incorporation of dibucaine.HCl in bR inhibits the slow component rate of formation of M412 and decreases the amount of M412 formation in the photochemical cycle of bR; and (5) the thermal stability of native bR was measured by DSC in the presence and absence of dibucaine and yielded an endothermic transition at 95.9 +/- 1.0 degrees C with 13.6 J/g (3.25 +/- 0.12 cal/g) of enthalpy changes. All observations suggest that the action site of the local anesthetic, dibucaine.HCl, is near or at the chromophore, i.e. the retinal Schiff base of bR. The anesthetic action on bR purple membrane is probably via a specific site binding, but not a conformational mechanism.     

Heavy-ion fusion: Comparison of experimental data with classical trajectory models

Currently available data on fusion excitation functions for heavy-ion induced reactions over a wide mass range are compared to results calculated with a classical dynamical model based on the proximity nuclear potential of Blocki et al., the Coulomb potential of Bondorf et al., and one-body nuclear friction in the proximity formalism of Randrup. With these conservative and dissipative forces and the radial parameters of Myers, overall good agreement is obtained between the theoretical excitation functions and most of the available data. Extensive calculations have been performed to test the sensitivity of the calculated fusion cross-sections to a number of parameters, including the radial dependence of the Coulomb and nuclear potentials, the radial and tangential friction form factors as well as the projectile and target radii. The theoretical excitation functions for the lighter heavy-ion systems are rather insensitive to changes in either the conservative or dissipative forces. The calculations show that tangential friction sufficient to produce the rolling condition is necessary to explain the magnitude of the fusion cross-sections at high energies, which are also sensitive to the magnitude of the radial friction component. This is in contrast to the fusion cross-sections at low energies which are determined by the nuclear potential at larger separations, and to a lesser extent by tangential friction. The low energy fusion data are most sensitive to the nuclear radii. The calculations reveal the importance of more experimental measurements of fusion cross-sections at high energies, especially for heavy systems where the magnitudes of the fusion cross-sections are the most sensitive to the assumed forces. However, even for these cases the effects of the conservative and dissipative forces are similar and difficult to separate. These studies indicate, however, that it is possible to construct a conservative potential that will give calculated fusion excitation functions which are in good agreement with all experimental data over the entire mass range. The maximum fusion cross-sections as defined here exceed considerably the liquid-drop limiting value for heavy systems.     

Modelling,simulation, animation,and real-time control (MoSART) for a class of electromechanical systems: a system-theoretic approach

This paper describes an interactive modelling, simulation, animation, and real-time control (MoSART) environment for a class of ‘cart-pendulum’ electromechanical systems that may be used to enhance learning within differential equations and linear algebra classes. The environment is useful for conveying fundamental mathematical/systems concepts through computer-aided analysis, design, graphical visualization, and 3D animation. Referred to as Cart-Pendulum Control3D-Lab1Control3D-Lab-short for control 3D animation laboratory. The author to whom correspondence should be addressed., the environment is based on Microsoft Windows/Visual C++/Direct-3D and MATLAB/Simulink2MATLAB and Simulant are trademarks of The Masterworks, Inc.. Pull-down menus provide access to systems/models/control laws, exogenous signals, parameters, animation models and visual indicators, a suite of (easy-to-modify) Simulant diagrams containing models and control laws, MATLAB m-files for detailed analysis and design, and detailed documentation for each of the above. Three blocks enable animation, joystick inputs, and real-time animation within Simulant. Examples are presented to illustrate the utility of the environment as a valuable tool for analysing/visualizing the above class of electromechanical systems and for enhancing mathematics instruction.     

The Saffman-Taylor problem for an extremely shear-thinning fluid

We consider a steady flow driven by pushing a finger of gasinto a highly shear-thinning power-law fluid, with exponentn, in a Hele-Shaw channel. We formulate the problem in termsof the streamfunction , which satisfies the p-Laplacian equation (with ), and investigate travelling wave solutions in the large-n (extreme shear-thinning) limit.We take a Legendre transform of the free-boundary problem for, which reduces it to a linear problem on a fixed domain. The solution to this problem is foundby using matched asymptotic expansions and the resulting shapeof the finger deduced (being, to leading order, a semi-infinitestrip). The nonlinear problem for the streamfunction is alsotreated using matched asymptotic expansion in the physical plane.The finger-width selection problem is briefly discussed in termsof our results.     

HUMIC MACROMOLECULES IN NATURAL WATERS

Abstract

Humic substances are the major organic constituents of soils and sediments. They also occur in small concentrations in natural surface waters and groundwaters. They form through the breakdown of plant and animal tissues by chemical and biological processes that tend to produce complex chemical structures that are more stable than the original material from which they were derived. One of the more important characteristics of humic substances is their ability to form water-soluble and water-insoluble complexes with metal ions and hydrous oxides and to interact with clay minerals and various organic compounds such as alkanes, fatty acids, and toxic organic substances such as pesticides.