Semiempirical Pm3 Quantum Mechanics Calculations of Carbohydrate Crystals

ABSTRACT

Miniature crystal models of six small carbohydrates were examined using the PM3 semiempirical quantum mechanics method. The minicrystal structures, consisting of 27 sugar residues, were optimized by the combined procedure of partial optimization and reconstruction of the model, while maintaining the original crystal symmetries. All of the minicrystals were successfully optimized without exhibiting a great increase in an energy at any reconstruction step. Some minicrystals showed a prolonged behavior of optimization cycles. A major source of structure change appeared to arise from hydroxyl group rotations wherein the largest movements mostly occurred in an early optimization stage. No significant deformations in geometry of either residues or hydrogen bonds were observed in the final minicrystal structures. The thermodynamic values calculated for the optimized minicrystals were in reasonably good agreement with the literature data. The present study indicated that the PM3 semiempirical method successfully predicted the basic features of intermolecular hydrogen bonding involved in a condensed system.     

A modified Ortega method to evaluate the activation energies of solid state reactions

The application of the average linear integral isoconversional method developed by Ortega for evaluating the activation energies of solid state reactions may be hindered by experimental noise and the uncertainties associated with selecting appropriate reaction segments. This paper suggests a procedure, called the modified Ortega method, which can avoid or minimize these hindrances. By applying the modified Ortega method to the kinetic analyses of both simulated and experimental data, a more consistent dependence of the activation energy on the extent of reaction conversion was found with those calculated from the modified Vyazovkin method and the Friedman method.     

Reactions of Sterically Protected 1-Halo- and 1-Pseudohalo-2-Phosphaethenyl-Lithiums

Abstract

Phosphorus analogs of alkylidenecarbenoid, Ar-P=C(X)Li, where X equals halogen or pseudohalogen atom, such as C1, Br, or SPh, have been generated by use of the 2,4,6-tri-t-butylphenyl group (abbreviated to Ar in the Scheme) as a protecting group for low coordinated organophosphorus compounds. The reaction with methyl iodide and with some aldehydes or ketones, at low temperature, gave the corresponding alkylation products^[l]. The reaction with copper salts gave 1,4-diphosphabutadiene (1) or 1,4-diphosphabutatriene (2), depending upon the substituent X^[2,3], as well as reaction conditions, such as reaction tenlperature and time, solvent, presence or absence of oxygen. Upon warming the phosphaethenyllithiun1s, thus generated, the chloro derivative of E-configuration gave a phosphaalkyne (3) via [1,2]-aromatic migration^[4], whereas the bromo derivative of Z-configuration gave a l-phospha-3,4-dihydronaphthalene derivative (4), that is a formal C-H insertion product of a phosphinidenecarbene intermediate^[5].     

Accurate position detection of targets in noise image

Targets at various positions in a noise image were detected by the optical matched filtering technique. In this case the thermoplastic optical recorder was used as a matched filter recorder. High accuracy of position detection was obtained, i.e. the position error was 2% or less.     

Infrared seed inspection system (IRSIS) on painted car shells

This paper describes a newly-developed automated thermal system for detection of seeds on newly painted car shells. The system’s novel approach is to use thermal emission; previously applied techniques relied on light reflection strategies. The system is described beginning with analytical modeling of the underlying detection theory to verification on a pilot run in an automotive production line. Parker’s flash procedure, using a thermal detector, was performed to extract the thermal properties of inspected panels. New computer logic developed in-house for processing the acquired thermograms is also presented.     

Microradiographic strain measurement using markers

A method for measuring strain on interior planes of some real structural materials is presented. X-ray images are formed of small (10–40 micron) gold markers placed on selected interior planes of optically opaque X-ray transparent materials. The use of well collimated monochromatic synchrotron radiation makes possible high contrast images of the small markers. Images of the particles before and after straining are recorded photographically. Photographs are enlarged 33X and measured using a simple electro-optical setup. In calibration experiments using approximately a 300-micron gage length, the strain measured by this method agreed with extensometer measured strains to within 100 microstrain. Example applications in a graphite-epoxy composite are presented, including measurement of the strain drop off near the free edge, strain concentration around a hole, and the strain field on a particular plane near a hole after local delamination. The technique is currently limited to materials no less X-ray transparent than titanium.Paper was presented at the 1992 SEM Spring Conference on Experimental Mechanics held in Las Vegas, NV on June 8–11.     

The first x-ray structure determination of a -phosphaethylene: -2-phenyl-1-(2,4,6-tri-t-butylphenyl)phosphaethylene

The sterically protected -phosphaethylene, -2-phenyl-1-(2,4,6-tri-t-butylphenyl)phosphaethylene (1-Z), was analyzed by X-ray crystallography.