Tandem mass spectrum of a farnesyl transferase inhibitor--gas-phase rearrangements involving imidazole

Compound 1 (1-(3-chlorophenyl)-4-[1-(4-cyanobenzyl)imidazolylmethyl]-2-piperazinone hydrochloride) is a farnesyl transferase inhibitor intended for treatment of cancer. A detailed analysis of the electrospray ionization mass spectrometry and tandem mass spectrometry data of protonated 1 shows that in the gas phase, upon collision-induced dissociation, this ion undergoes complicated rearrangement and fragmentation. These processes include a novel two-step rearrangement. The first step involves a gas-phase intramolecular S(N)2 reaction that forms an intermediate. The second step consists of three competitive rearrangement/fragmentation pathways of the intermediate, giving rise to protonated 2, protonated methylene-imidazole, and a distonic methylimidazole radical cation. Deuterated 1 was studied under the same experimental conditions, and the results strongly support the proposed two-step rearrangement process. It is noted that the unique structure of 1, especially the imidazole ring of 1, plays a critical role in the rearrangement of protonated 1.     

Heat transfer in polymer composites filled with inorganic hollow micro-spheres: A theoretical model

The heat transfer mechanisms in inorganic hollow micro-spheres filled polymer composites are analyzed in the present paper. This heat transfer includes mainly three mechanisms: (1) thermal conduction between solid and gas; (2) thermal radiation between the hollow micro-sphere surfaces; and (3) natural thermal convection of the gas in the micro-hollow spheres. A theoretical model of heat transfer in polymer/inorganic hollow micro-sphere composites is established based on the law of minimal thermal resistance and the equal law of the specific equivalent thermal conductivity, and a corresponding equation of effective thermal conductivity is derived. The effective thermal conductivity (k_eff) of hollow glass bead-filled polypropylene composites is estimated by using this equation, and is compared with the numerical simulations by means of a finite element method. The results show that the variation of the theoretical estimations of k_eff are similar to the numerical simulations at lower filler volume fraction (φ_f20%). Moreover, k_eff decreases linearly with increasing φ_f, and reduces somewhat with increase of filler size.     

Symmetrically bifurcate hydrogen bonding—IV : Steric requirements in symmetrically hydrogen-bonded bis(β-acylvinyl)amines and their isomers

The effect of the size and branching of alkyl substituents R¹ and R² on the formation of all possible stereoisomers of bis(β-acylvinyl)amines, [R¹COCR²CH]₂NH, has been investigated. IR and NMR data show that steric requirements of these substituents and resonance stabilization of the s-trans system are the main factors determining the position of the dynamic equilibrium.     

Incoherent subharmonic light scattering in isotropic media

Incoherent subharmonic light scattering in isotropic media is a new kind of nonlinear light scattering, which involves single input photon and multiple output photons of equal frequency. We investigate theoretically the dependence of the subharmonic scattering intensity on the hyperpolarizability of molecules and the incident intensity using nonlinear optics theory similar to that used for Hyper-Rayleigh scattering and degenerate optical parametric oscillators. It is derived that the subharmonic scattering intensities grow exponentially or superexponentially with the hyperpolarizability of molecules and the incident intensity.     

H3PW12O40 and its cesium salts as pentane isomerization catalysts at ambient temperature

The activity of Mg−Al basic heterogeneous catalysts in the reactions of alcohols with ethylene oxide was studied. The kinetics of alcohol oxyethylation was examined. The kinetic equation of the reaction was determined and the structure of products was studied. The distribution coefficients of the oxyethylation reaction products were calculated. A comparison of the catalytic activity of Mg−Al hydroxides and products of their thermal treatment was made.     

A New Setting for Polynomial Continuous-Time Systems, and a Realization Theorem

The paper deals with polynomial continuous time systems on algebraicmanifolds. The main result states that a nonlinear system maybe regularly immersed into a polynomial algebraically observablesystem ifi its observation algebra is finitely generated andregular. We also indicate some perspectives for future workin this direction.     

A Ramsey-Sperner theorem

Letn≥k≥1 be integers and letf(n, k) be the smallest integer for which the following holds: If ℱ is a family of subsets of ann-setX with |ℱ|<f(n,k) then for everyk-coloring ofX there existA B ∈ ℱ,A∈B, A⊂B such thatB-A is monochromatic. Here it is proven that for a fixedk there exist constantsc _k andd _k such that and ask→∞. The proofs of both the lower and the upper bounds use probabilistic methods.     

Magnetic structures of R(Cu,Ni)2 compounds (R = heavy rare earth) studied by neutron diffraction

Magnetics structures of powdered orthorhombic R(Cu, Ni)₂ compounds (R = heavy rare earth) determined by neutron diffraction are described. The influence of magnetocrystalline anisotropy and exchange interactions on the type of magnetic ordering is discussed.Dedicated to Academician Vladimír Hajko on the occasion of his 65th brithday.We would like to express our thanks to Professor P. Luká for continual interest and encouragement and to . Zajac and V. Sechovský for many fruitfull discussions.     

A study of fast neutron production in p20Ne and pp interactions at 300 GeV/c

Data on the multiplicity, momentum and angular spectra of fastp _n1 GeV/c) neutrons produced in inelastic interactions of protons with neon nuclei and protons at 300 GeV/c are presented. The experimental results obtained for p²⁰Ne interactions are compared with predictions of the additive quark model in which the intranuclear cascading of slow particles is taken into account.We thank V. G. Grishin and R. J. Loveless for valuable discussions.