Mass spectra of bile acid methyl ester acetate derivatives

Deuterium labeling in the acetate derivatives of cholic acid demonstrates that electron impact induced consecutive loss of HOAc from the molecular ion occurs in the following order of decreasing preference: 12α-OAc > 7α-OAc > 3α-OAc. Numerous examples are presented showing that consecutive loss of HOAc from a common ion generally increases progressively with relative intensity. In the acetate pregnan-20-one derivatives of cholic acid, loss of 43 mass units from the molecular ion comes from the 12α-OAc and not the 17β-acetyl sidechain. Ketene is ejected from an acetoxy group located in an α position to a carbonyl on which an ion-radical charge is localized.     

Studies directed toward synthesis of quassinoids. VI—mass spectral fragmentation of D-ring seco esters and δ-lactone derivatives of cholic acid

Analogy and deuterium labeling demonstrate that considerable remote group interaction occurs between functional groups at positions 7 and 16 in 16, 17-secosteroids. It is proposed that ion-dipole interact?ions separations of distances of 10 to 2 Å will involve energies of 1–30 kcal mol^?1 and can play a significant role in fragmentation processes. Successive loss of one, two and three HOAc molecules from a milecular or daughter ion increase progressively in relative intensity; irregularity in this pattern indicates the operation of special factors or multiple genesis of daughter ions having the same m/e. Evidence is presented which suggests that facile ketene ejection from the acetate functional group only occurs from a radical ion and must be preceded by transfer of a hydrogen radical from the acetate group to the site of charge localization.     

Risk externalities and too big to fail

This paper establishes the case for a fallacy of economies of scale in large aggregate institutions and the effects of scale risks. The problem of rogue trading and excessive risk taking is taken as a case example. Assuming (conservatively) that a firm exposure and losses are limited to its capital while external losses are unbounded, we establish a condition for a firm not to be allowed to be too big to fail. In such a case, the expected external losses second derivative with respect to the firm capital at risk is positive. Examples and analytical results are obtained based on simplifying assumptions and focusing exclusively on the risk externalities that firms too big to fail can have.     

Radiosynthesis and biological evaluation of 166Ho labeled methoxylated porphyrins as possible therapeutic agents

¹⁶⁶Ho labeled 5,10,15,20-tetrakis(3,4-dimethoxyphenyl) porphyrin, and 5,10,15,20-tetrakis(3,4,5-trimethoxyphenyl) porphyrin ([¹⁶⁶Ho]–TDMPP and [¹⁶⁶Ho]–TTMPP respectively) were prepared with acceptable radiochemical purity and specific activities. Stability and partition coefficient of the complexes were determined in the final formulations and biodistribution studies in mouse demonstrated high accumulation of [¹⁶⁶Ho]–TDMPP in the lung and liver and less excretion through the kidney. while [¹⁶⁶Ho]–TTMPP was mostly excreted into intestines and kidneys while lungs were a minor accumulation site. In contrast to other reported radiolanthanide labeled porphyrins these two complexes showed less liver accumulation. Further investigation of their potential therapeutic properties is of interest.     

Scattering amplitude of absorbing and nonabsorbing spheroidal particles in the WKB approximation

This work is devoted to a theoretical study of scattering of light by absorbing and nonabsorbing oriented spheroidal particles in the Wentzel-Kramers-Brillouin (WKB) approximation. Within the framework of the scattering theory, we investigate the form factor and the scattering amplitude for this approximation. The Rayleigh-Gans-Debye theory (RGD), the diffraction approximation (DA), and the anomalous diffraction (AD) are treated as particular cases for nonabsorbing spheroids. To illustrate our formalism, we analyze some numerical examples.     

Plasma-Catalytic Dry Reforming of CH4 over Calcium Oxide: Catalyst Structural and Textural Modifications

Plasma Chemistry and Plasma Processing - The coupling of catalyst and nonthermal plasma for the dry reforming of methane was investigated with a special attention to the textural and structural...     

A self-tuning guidance and control system for marine surface vessels

An integrated guidance and control system has been developed to enable underactuated marine surface vessels to operate autonomously and yield robust tracking performance in spite of significant external disturbances and modeling imprecision. A nonlinear ship model, accounting for all six degrees-of-freedom of the ship, has been used as a test bed to assess the performance of the proposed scheme. The controller combines the advantages of the variable structure systems (VSS) theory with the self-tuning fuzzy logic scheme. It does not require an accurate dynamic model of the ship or the construction of a rule-based expert system. Its asymptotic stability is ensured by knowing the upper bounds on modeling imprecision and external disturbances and by forcing the tuning parameters to satisfy the sliding conditions. The guidance system is based on the concepts of the variable radius line-of-sight (LOS) and the acceptance circle around the waypoints. The current system varies the LOS radius exponentially with the cross track error in order to achieve a fast convergence rate of the ship to its desired trajectory. The simulation results demonstrate the robust tracking characteristic of the integrated guidance and control system in spite of significant modeling uncertainties and environmental disturbances.