Trends in the CNDO/2 molecular orbital study of electronic structure in some neurotransmitter drugs

An investigation of electronic structure in some neurotransmitter drugs has been made using the CNDO/2 semi-empirical molecular orbital method.The electronic structure has been conveniently characterized by the electronic parameters nett atomic population (NAP) and bond index (BI). A variation of these electronic parameters with respect to conformation has been studied and has been found unlikely to exceed 0.1 e in most. cases. Further, the useful extent to which the electronic parameters of some commonly occurring functional groups may be regarded as conformationally invariant has been demonstrated. Also presented are (i) a discussion on the intramolecular close-approach of functional groups — the interaction between terminal —COO^? and ?NH₃⁺ groups of α-ω anaino acids is explicitly considered; (ii) an enquiry into the extension of ‘standard’ (idealized) geometry models in the elucidation of electronic structure.The implication of the results and observations presented here are briefly discussed with reference to classical and quantum structure-activity studies of drug molecules.     

DETECTION OF DNA-PSORALEN PHOTOADDUCTS in situ

Abstract— An immunological method, with the use of specific immune serum, has been developed for detection of 8-methoxypsoralen (8-MOP) photoadducts to DNA, formed in situ in cell nuclei, after combined treatment with 8MOP and UV-A irradiation (Zarçbska et al. , 1978). Lymphocytes fixed on slides or in suspension, and cryostat sections of different mammalian tissues, served as antigenic substrate, after treatment with 8-MOP and UV-A in vitro. Specific fluorescence in these substrates was detected in the nuclei after treatment with 30 ˜ 140 kJ/m² UV-A in the presence of 0.1-0.3 μg/cm² 8-MOP. PHA-stimulated-lymphocytes appeared to be the most sensitive substrate.
However, hairless mice treated with high doses of UV-A in vivo , 70 ˜ 360 kJ/m² did not reveal a specific fluorescence of epidermal nuclei, unless a high local concentration of 8-MOP was attained.
The apparent discrepancy in the level of photoadduct detection between the in vitro and in vivo treated specimens was explained by the low number of DNA-8-MOP-photoadducts formed in vivo under these experimental conditions. The relevance of these findings to the role of DNA-8-MOP-photoadducts formed during PUVA photochemotherapy is discussed.     

The Spectral Density Function for the Laplacian on High Tensor Powers of a Line Bundle

For a symplectic manifold with quantizing line bundle, a choice of almost complex structure determines a Laplacian acting on tensor powers of the bundle. For high tensor powers Guillemin–Uribe showed that there is a well-defined cluster of low-lying eigenvalues, whose distribution is described by a spectral density function. We give an explicit computation of the spectral density function, by constructing certain quasimodes on the associated principle bundle.     

A CNDO/2 molecular orbital study of the electronic and conformational modes of ibotenic acid

CNDO/2 molecular orbital calculations on the non-ionic molecule, zwitterion and mono-anion of ibotenic acid are reported. Internal energy surfaces have been calculated from which minimum energy conformations are predicted. The relative internal energies, dipole moments and net atomic populations at the minimum-energy conformations are given. The importance of using a free energy rather than internal energy approach in the construction of energy surfaces is also discussed.     

Upper and Lower Bounds on Resonances for Manifolds Hyperbolic Near Infinity

For a conformally compact manifold that is hyperbolic near infinity and of dimension n + 1, we complete the proof of the optimal O(r ⁿ⁺¹) upper bound on the resonance counting function, correcting a mistake in the existing literature. In the case of a compactly supported perturbation of a hyperbolic manifold, we establish a Poisson formula expressing the regularized wave trace as a sum over scattering resonances. This leads to an r ⁿ⁺¹ lower bound on the counting function for scattering poles.     

ON QUOTIENTS OF BRAID GROUPS

ABSTRACT.

Let G be the group ?[t, t ^?1] x ?. By studying the action of the braid group B_n on the set Gⁿ , we obtain representations of B_n into a wreath product of the symmetric group and the general linear group over ?[t, t ^?1]. This in particular recovers the Burau representation of the braid group. Furthermore, some quotients of the braid group are obtained by using the representations found.     

Microcalorimetry of O2 and NO on flat and stepped platinum surfaces

Using the single-crystal adsorption calorimeter (SCAC), coverage-dependent heats of adsorption and sticking probabilities are reported for O₂ and NO on Pt{1 1 1}, Pt{2 1 1} and Pt{4 1 1} at 300 K. At low coverage, oxygen adsorption is dissociative for all Pt surfaces. The highest initial heat of adsorption is found on Pt{2 1 1}, with a value of 370 kJ/mol, followed by those on Pt{4 1 1} (310 kJ/mol) and Pt{1 1 1} (300 kJ/mol). We attribute this relatively large difference in the dissociative heat of adsorption at low coverage to the step character of the {2 1 1} surface. Initial sticking probabilities, s_o, are similar for the three surfaces, 0.22 on Pt{1 1 1}, 0.17 on Pt{2 1 1} and 0.18 on Pt{4 1 1}, rapidly decreasing as the oxygen coverage increases. For nitric oxide, the initial heats of adsorption are very similar and consistent with either dissociative or molecular adsorption, with values of 182 kJ/mol on Pt{1 1 1}, 192 kJ/mol on Pt{2 1 1} and 217 kJ/mol on Pt{4 1 1}. The s_o value is virtually identical for all three systems, with values ranging from 0.82 to 0.85, suggesting that the initial sticking probability is insensitive to the surface structure and adsorption is intrinsically precursor mediated. SCAC data are also used to evaluate pre-exponential factors, ν, for first-order desorption at high coverage where adsorption is non-dissociative. Values of 3 × 10¹⁸, 6 × 10¹⁸ and 2 × 10¹⁸ s^?1 for O₂, and 4 × 10¹⁹, 6 × 10¹⁷ and 2 × 10²⁰ s^?1 for NO on Pt{1 1 1}, Pt{2 1 1} and Pt{4 1 1}, respectively, are found. These unexpectedly high values are rationalised in terms of conventional transition state theory entropy changes.     

Cell-cell contact and membrane spreading in an ultrasound trap

An ultrasonic standing wave trap [Langmuir 19 (2003) 3635] in which the morphologies of 2-D latex–microparticle aggregates, forming a pressure node plane, were characterised has been applied here to different cell suspensions with increasing order of specificity of cross-linking molecule, i.e. polylysine with chondrocytes; wheat germ agglutinin (WGA) with erythrocytes and surface receptors on neural cells. The outcome of initial cell–cell contact, i.e. whether the cells stuck at the point of contact (collision efficiency=1) or rolled around each other (collision efficiency=0), was monitored in situ by video-microscopy. The perimeter fractal dimensions (FD) of 2-D hexagonally symmetric, closely packed aggregates of control erythrocytes and chondrocytes were 1.16 and 1.18, respectively while those for the dendrititc aggregates formed initially by erythrocytes in 0.5 μg/ml WGA and chondrocytes in 20 μg/ml polylysine were 1.49 and 1.66. The FDs for control and molecularly cross-linked cells were typical of reaction-limited aggregation (RLA) and transport diffusion-limited aggregation (DLA), respectively. The FDs of the aggregates of cross-linked cells decreased with time to give more closely packed aggregates without clear hexagonal symmetry. Suspensions of neural cells formed dendritic aggregates. Spreading of inter-cellular membrane contact area occurred over 15 min for both erythrocyte and neural cell dendritic aggregates. The potential of the technique to characterise and control the progression of cell adhesion in suspension away from solid substrata is discussed.     

The shallow flow equations solved on adaptive quadtree grids

This paper describes an adaptive quadtree grid‐based solver of the depth‐averaged shallow water equations. The model is designed to approximate flows in complicated large‐scale shallow domains while focusing on important smaller‐scale localized flow features. Quadtree grids are created automatically by recursive subdivision of a rectangle about discretized boundary, bathymetric or flow‐related seeding points. It can be fitted in a fractal‐like sense by local grid refinement to any boundary, however distorted, provided absolute convergence to the boundary is not required and a low level of stepped boundary can be tolerated. Grid information is stored as a tree data structure, with a novel indexing system used to link information on the quadtree to a finite volume discretization of the governing equations. As the flow field develops, the grids may be adapted using a parameter based on vorticity and grid cell size. The numerical model is validated using standard benchmark tests, including seiches, Coriolis‐induced set‐up, jet‐forced flow in a circular reservoir, and wetting and drying. Wind‐induced flow in the Nichupté Lagoon, México, provides an illustrative example of an application to flow in extremely complicated multi‐connected regions. Copyright © 2001 John Wiley & Sons, Ltd.