Reactivity of a σ,σ,σ,σ-tetraradical: the 2,4,6-tridehydropyridine radical cation

The 2,4,6-tridehydropyridine radical cation, an analogue of the elusive 1,2,3,5-tetradehydrobenzene, was generated in the gas phase and its reactivity examined. Surprisingly, the tetraradical was found not to undergo radical reactions. This behavior is rationalized by resonance structures hindering fast radical reactions. This makes the cation highly electrophilic, and it rapidly reacts with many nucleophiles by quenching the N-C ortho-benzyne moiety, thereby generating a relatively unreactive meta-benzyne analogue.     

Capillary electrophoresis-mass spectrometry of a new cross-linker with acrylic functionality

Analytical characterization of dimethacrylate-tyrosine-lysine-tyrosine (DMTLT, a new biodegradable acrylic cross-linker synthesized at our laboratory) is carried out using CE-MS. DMTLT is a pseudopeptide composed by tyrosine-lysine-tyrosine amino acids linked through urea bonds with two methacrylic groups, one at each end of the molecule, making this compound an excellent cross-linker for polymerization reactions and for obtaining new biodegradable materials. A new CE-MS method is developed for the characterization of DMTLT and its products of degradation after basic hydrolysis. In order to carry out an exhaustive examination of such degradation products methods based on CE coupled to IT and TOF-MS are employed. Based on CE-IT-MS results and the elemental composition of the degradation products obtained by CE-TOF-MS, conclusions on the mechanism and kinetic of hydrolysis of DMTLT are obtained confirming both the usefulness of CE-MS to characterize new biomaterials and the applicability of DMTLT for preparing new biodegradable polymers. These results are corroborated through the CE-MS detection of the identified products of degradation in a dimethyl acrylamide polymer cross-linked with DMTLT.     

On even (unitary) perfect polynomials over F2

We give all even perfect (resp. unitary perfect) polynomials over the prime field ${\mathbb{F}}_2$ of the form $x^a{(x+1)}^b{M}_1^{h_1}?M_r^{h_r}$, where each $M_i$ is a Mersenne irreducible polynomial, $h_i=2^{n_i}?1$ (resp. $h_i=2^{n_i}$) and $a,b,r,n_i\in \mathbb{N}$. In particular, we characterize nine of the eleven known “sporadic” even perfect polynomials over ${\mathbb{F}}_2$ that have the above form.     

Lifetimes and transition probabilities in Kr V

Weighted oscillator strengths (gf), weighted transition probabilities (gA) and lifetimes are presented for all experimentally known dipole transitions and levels of Kr V. Values were determined by four methods. Three of them are based on the Hartree–Fock method, including relativistic corrections and core-polarization effects, with electrostatic parameters optimized by a least-squares procedure in order to obtain energy levels adjusted to the corresponding experimental values. The fourth method is based on a relativistic multiconfigurational Dirac–Fock approach. In addition, 47 new classified lines belonging to the Kr V spectrum are presented.