A supramolecular cup-and-ball C60-porphyrin conjugate system

In addition to the ammonium-crown ether recognition, pi-stacking interactions between the C60 sphere and the porphyrin moiety have been evidenced in a supramolecular complex obtained from a porphyrin-crown ether conjugate and a fullerene derivative bearing an ammonium unit.     

Aziridines as a protecting and directing group. Stereoselective synthesis of (+)-bromoxone

[reaction: see text] The directing ability of an aziridine group for the epoxidation of adjacent double bonds is demonstrated. The aziridine group is also used to effectively protect a double bond in a cycloenone system for a short synthesis of the title compound.     

Hermite Interpolation and Sobolev Orthogonality

In this paper, we study orthogonal polynomials with respect to the bilinear form (f, g) _S = V(f) A V(g) ^T + <u, f ^(N) g ^(N)V(f) =(f(c ₀), f "(c ₀), ..., f ^{(n – 1)} ₀(c ₀), ..., f(c _p ), f "(c _p ), ..., f ^{(n – 1)} _p(c _p )) u is a regular linear functional on the linear space P of real polynomials, c ₀, c ₁, ..., c _p are distinct real numbers, n ₀, n ₁, ..., n _p are positive integer numbers, N=n ₀+n ₁+...+n _p , and A is a N × N real matrix with all its principal submatrices nonsingular. We establish relations with the theory of interpolation and approximation.     

Associative and segregative phase separations of poly(N-tert-butylacrylamide)/poly(acrylic acid) mixtures. Effect of solvent

Poly(N-tert-butylacrylamide) (PNtBAm) and poly(acrylic acid) (PAA) form interpolymer complexes in 1- and 2-propanol, blend in ethanol, whereas a segregative phase separation is observed when using methanol as solvent as shown by Fourier transform infrared (FTIR) spectrometry and elemental analysis studies. The composition of PNtBAm/PAA complexes has been determined. Thermal studies demonstrated that all complexes show unique glass transition temperatures, higher than those of the polymer components. Complexation of PAA with PNtBAm results in an improvement of its thermal stability. Solvent effects and specific interactions in the system PNtBAm/PAA have been studied by FTIR, revealing that differences in the polymer–solvent interactions are a decisive factor governing complex formation in solution.     

Stochastic PAC models for vacancy motions with trapping and detrapping

In order to explain PAC data for tetragonal zirconia at temperatures between 900 and 1300oC, we have developed a four-state stochastic model. The model simulates vacancies which trap and detrap at a PAC probe nucleus. While trapped, the vacancies hop around the probe in equivalent sites. The four states in this Winkler–Gerdau stochastic theory are three trapped states with equivalent electric field gradients (EFGs) of different orientations and a detrapped state with a weaker EFG whose axis of symmetry is oriented along the diagonal between the three trapped EFGs. There are three hopping rates in this model: w, the rate a trapped vacancy hops around the probe, w_D, the detrapping rate, and w_t, the trapping rate. We report results of calculations for values of these hopping rates implied by our tetragonal zirconia data, and we report heuristic fitting functions which summarize the computer results and can be used to fit data efficiently for a wide range of parameters. This revised version was published online in August 2006 with corrections to the Cover Date.     

Can density functional theory (DFT) be used as an aid to a deeper understanding of tandem mass spectrometric fragmentation pathways?

Prediction of tandem mass spectrometric (MS/MS) fragmentation for non‐peptidic molecules based on structure is of immense interest to the mass spectrometrist. If a reliable approach to MS/MS prediction could be achieved its impact within the pharmaceutical industry could be immense. Many publications have stressed that the fragmentation of a molecular ion or protonated molecule is a complex process that depends on many parameters, making prediction difficult. Commercial prediction software relies on a collection of general heuristic rules of fragmentation, which involve cleaving every bond in the structure to produce a list of ‘expected’ masses which can be compared with the experimental data. These approaches do not take into account the thermodynamic or molecular orbital effects that impact on the molecule at the point of protonation which could influence the potential sites of bond cleavage based on the structural motif. A series of compounds have been studied by examining the experimentally derived high‐resolution MS/MS data and comparing it with the in silico modelling of the neutral and protonated structures. The effect that protonation at specific sites can have on the bond lengths has also been determined. We have calculated the thermodynamically most stable protonated species and have observed how that information can help predict the cleavage site for that ion. The data have shown that this use of in silico techniques could be a possible way to predict MS/MS spectra. Copyright © 2009 John Wiley & Sons, Ltd.