Magnetic resonance imaging of bone after radiation

Magnetic resonance imaging (MRI) was performed in 22 patients at various times (0-3) years) following radiation therapy to the spine. T1 and T2 weighted images were obtained at 0.5 Tesla. Increased signal was seen after 800-6000 rads (8-60 Gy). Marrow effects corresponded to radiation ports. Recurrent tumor was clearly separated from fatty replacement. This was much better seen on T1 weighted images. Five patients that had MRI during their course of radiotherapy (XRT) did not have increased signal on T1 images of the bone marrow. The earliest fatty marrow change was seen nine days following completion of 3000 rads (30 Gy) XRT over one month's duration. One patient who received 800 rads (8 Gy) to the upper thoracic spine for eosinophilic granuloma had no radiation effects on MRI when imaged 16 days following completion of XRT given over five days. Fatty marrow change was seen in this patient on MRI six months later. MRI was particularly useful in defining the extent of prior radiation effects when repeat therapy was needed.     

Global Optimization Algorithm for the Nonlinear Sum of Ratios Problem

This article presents a branch-and-bound algorithm for globally solving the nonlinear sum of ratios problem (P). The algorithm economizes the required computations by conducting the branch-and-bound search in ^p, rather than in ⁿ, where p is the number of ratios in the objective function of problem (P) and n is the number of decision variables in problem (P). To implement the algorithm, the main computations involve solving a sequence of convex programming problems for which standard algorithms are available.     

Effects of buffer gases on the infrared multiphoton dissociation of C2H4DCl: A chemical clock to explore highly excited molecules

Observations are reported of the effect of the buffer gases He, Ne, and CF₄, in the pressure range of 0–30 torr, on the branching ratio [HCl]/[DCl] of the unimolecular decomposition The ratio R = k_H/k_D has been measured in high-pressure thermal decomposition (670–1100 K) and was shown to give a unique measure of the internal energy of the decomposing molecules and hence, with RRKM theory and pressure fall-off data, a time scale for their decomposition. Applying the thermal data to the photolysis leads to the conclusion that excitation and decomposition are produced by the laser spike (high intensity, 70 ns FWHM) and also at a slower rate by the larger, less intense tail (1.6 μs). Added buffer gases quench the latter, leaving the former which, from measurements of R, is shown to correspond to excitations of 115 ± 15 kcal/mol and lifetimes of ～30 ps. No bond breaking is seen despite the high energies, in accord with theoretical expectations. The results require an enhanced rate of photon absorption by the highly excited molecules, which are about hundredfold greater than that observed for 300 K molecules. Data are also reported for C₂H₂F₂ and the secondary multiphoton photolysis of the ethylenes produced. Effects of beam geometry and wavelength are explored.     

Kinetic studies of the reactions CH2I2 + HI⇄CH3I + I2 and 2 CH3I⇄CH4 + CH2I2 the heat of formation of the iodomethyl radical

The rate of the reaction CH₂I₂ + HI ? CH₃I + I₂ has been followed spectrophotometrically from 201.0 to 311.2°. The rate constant for the reaction fits the equation, log (k₁/M^?1 sec^?1) = 11.45 ± 0.18 - (15.11 ± 0.44)/θ. This value, combined with the assumption that E₂ = 0 ± 1 kcal/mole, leads to ΔH (CH₂I, g) = 55.0 ± 1.6 kcal/mole and DH (H? CH₂I) = 103.8 ± 1.6 kcal/mole. The kinetics of the disproportionation, 2 CH₃I ? CH₄ + CH₂I₂ were studied at 331° and are compatible with the above values.     

VLPR study of the reaction Br + CH3CHO

The reaction \documentclass{article}\pagestyle{empty}\begin{document}${\rm Br} + {\rm CH}_3 {\rm CHO}\buildrel1\over\rightarrow{\rm HBr} + {\rm CH}_3 {\rm CO}$\end{document} has been studied by VLPR at 300 K. We find k₁ = 2.1 × 10¹² cm³/mol s in excellent agreement with independent measurements from photolysis studies. Combining this value with known thermodynamic data gives k_-1 = 1 × 10¹⁰ cm³/mol s. Observations of mass 42 expected from ketene suggest a rapid secondary reaction: in which step 2 is shown to be rate limiting under VLPR conditions and k₂ is estimated at 10^12.6 cm³/mol s from recent theoretical models for radical recombination. It is also shown that 0 ? E₁ ? 1.4 kcal/mol using theoretical models for calculation of A₁ and is probably closer to the lower limit. Reaction ?1 is negligible under conditions used.     

Very-low-pressure pyrolysis of nitroso- and pentafluoronitrosobenzene C?NO bond dissociation energies

The high-pressure absolute rate constants for the decomposition of nitrosobenzene and pentafluoronitrosobenzene were determined using the very-low-pressure pyrolysis (VLPP) technique. Bond dissociation energies of DH⁰(C₆H₅? NO) = 51.5 ± 1 kcal/mole and DH⁰ (C₆F₅? NO) = 50.5 ± 1 kcal/mole could be deduced if the radical combination rate constant is set at log k_r(M^?1·sec^?1) = 10.0 ± 0.5 for both systems and the activation energy for combination is taken as 0 kcal/mole at 298°K. δH_f⁰(C₆H₅NO), δH_f⁰(C₆F₅NO), and δH_f⁰(C₆F₅) could be estimated from our kinetic data and group additivity. The values are 48.1 ± 1, –160 ± 2, and – 130.9 ± 2 kcal/mole, respectively. C–X bond dissociation energies of several perfluorinated phenyl compounds, DH⁰(C₆F₅–X), were obtained from the reported values of δH_f⁰(C₆F₅X) and our estimated δH_f⁰(C₆F₅) [X = H, CH₃, NO, Cl, F, CF₃, I, and OH].