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.     

A formula periodic table for benzenoid hydrocarbons and the aufbau and excised internal structure concepts in benzenoid enumerations

The genesis of the aufbau and excised internal structure concepts is traced. These concepts were pivotal to the first published enumerations of the strictly peri-condensed, non-Kekuléan, and essentially strain-free total resonant sextet benzenoid groups. Aperiodic table set is defined as a partially ordered set forming a two-dimensional array which complies with thetriad principle where a central element has a metric property that is the arithmetic mean of two adjacent surrounding member elements.     

Mass spectral fragmentation of functionalized lanostanes-I

Mass spectra of various functionalized lanostanes and their deuterated analogs are compared. It is proposed that the transfer of a hydrogen from the 18-methyl group to the 11-oxo group via a McLafferty rearrangement is made geometrically possible by prior ionization of the 13,14 bond which allows an optimum interatomic distance between the oxygen and hydrogen to be acquired; the 8,9 double bond is a requisite for electronic induction of this specific process. Transfer of the hydrogen from the 7β-hydroxy group to position 14 is implicated in the mass spectrum of 3β-acetoxy-7β-hydroxy-5α-lanostan-11-one.     

Substituted m-phenylene bridges as strong ferromagnetic couplers for Cu(II)-bridge-Cu(II) magnetic interactions: new perspectives

Based on a combined theoretical-experimental study, we propose that substituted m-phenylene ligands (m-N-Phi-N) can act as tuneable strong ferromagnetic couplers connecting Cu(II) ions; a new complex presenting that bridge with J close to +15 cm(-1) has been suggested and synthesized.     

A theoretical study of π-hydrocarbon-iron tricarbonyl complexes

The molecular orbital parameters for tricarbonyl(tetrahapto-unsaturated-hydrocarbon)iron complexes are computed using graph-theoretical methods. The results are in agreement with their experimental properties.     

The effect of sampling conditions on the thermal decomposition of electrolytic manganese dioxide

The effect of sampling conditions on the decomposition of electrolytic manganese dioxide using thermal methods is reported. Significant differences were observed in the mechanism of the decomposition by simply changing the reaction environment from a closed pan to an open pan configuration. The purge gas atmosphere was also observed to influence the decomposition mechanism. As a product of the decomposition is oxygen, the change in the mechanism observed between the experimental conditions may be explained in terms of the ease of removal of oxygen from the reaction site. This revised version was published online in August 2006 with corrections to the Cover Date.     

Application of thermal analysis to study smelting reduction kinetics

A thermal analysis study on the reduction of iron oxide rich slags under different conditions is presented in this paper. The effects of important process variables such as time, temperature, lime-silica ratio, FeO level in slag etc. are discussed. It is shown that the mechanism of reduction by externally added graphite is different from that by a carbon saturated bath although the activation energy values are similar.     

On the maximum of the minimum of a sum

LetB denote the closure of a bounded open set of points inE ⁿ with Jordan content |B|>0 and letc>0 be constant. Typical of the expressions considered is $$M(N,c) = \max _{\left\{ {x_j } \right\}} \min _{x \in B} \sum\limits_{j = 1}^N {\left| {x - x_j } \right|^{ - c} } ,x_j \in E^n$$ Together with its analogs and extensions, the problem forc has a long history, associated with the names of Fekete, Leja, Pólya, Szegö, Frostman and Carleson, to mention just a few. It involves the notions of generalized capacity, transfinite diameter, and equilibrium potential. Here we consider the casec≧n and its extensions, for which the prior history seems less comprehensive. Illustrative of the results obtained are the three equations $$\mathop {\lim }\limits_{N \to \infty } \frac{{M(N,n)}}{{N\log N}} = \frac{{\omega (n)}}{{\left| B \right|}},\mathop {\lim }\limits_{N \to \infty } \frac{{M(N,c)}}{{N^{{c \mathord{\left/ {\vphantom {c n}} \right. \kern-\nulldelimiterspace} n}} }} = \frac{{L(n,c)}}{{\left| B \right|^{{c \mathord{\left/ {\vphantom {c n}} \right. \kern-\nulldelimiterspace} n}} }},\mathop {\lim }\limits_{c \to \infty } L(n,c)^{{1 \mathord{\left/ {\vphantom {1 c}} \right. \kern-\nulldelimiterspace} c}} = \mathop {\lim }\limits_{N \to \infty } \frac{{\left( {\left| B \right|/N} \right)^{{1 \mathord{\left/ {\vphantom {1 n}} \right. \kern-\nulldelimiterspace} n}} }}{{\varrho (N)}}$$ In the firstc=n and ω (n) is the volume of the unit ball. In the secondc>n and existence of the limit is asserted, 0<L(n,c)<∞. In the third, ? (N) is the smallest value such thatN spheres of radius ? (N) can coverB. The results would be unchanged if we requiredx _j ∈B instead ofx _j ∈E ⁿ in the definition ofM(N, c).