High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene

A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings.     

Nondipolar electron angular distributions from fixed-in-space molecules

The first indication of nondipole effects in the azimuthal dependence of photoelectron angular distributions emitted from fixed-in-space molecules is demonstrated in N (2). Comparison of the results with angular distributions observed for randomly oriented molecules and theoretical derivations for the nondipole correction first order in photon momentum suggests that higher orders will be needed to describe distributions measured in the molecular frame.     

Thermal aqueous liquid chromatography—the TALC technique

Thermal Aqueous Liquid Chromatography (TALC) using pure water as a mobile phase should be a very attractive technique promoting the use of liquid chromatography in routine analysis, either in the laboratory or in future on-line process control. This simple form of chromatography, the selectivity of which depends on the fixed phase only, would allow the use of flame ionization as an almost universal, low-cost detector in liquid chromatography. The potential of the TALC technique is illustrated by selected examples.     

Codimension one symplectic foliations and regular Poisson structures

In this short note we give a complete characterization of a certain class of compact corank one Poisson manifolds, those equipped with a closed one-form defining the symplectic foliation and a closed two-form extending the symplectic form on each leaf. If such a manifold has a compact leaf, then all the leaves are compact, and furthermore the manifold is a mapping torus of a compact leaf. These manifolds and their regular Poisson structures admit an extension as the critical hypersurface of a b-Poisson manifold as we will see in [9].     

Polypeptide composition of an adenovirus type 5 used in cancer gene therapy.

For cancer gene therapy, a recombinant adenovirus serotype 5 named RPR/INGN201 has been constructed by susbtitution of the E1 region with human tumor suppressor gene p53. The protein components of RPR/INGN201 virions were separated by reversed-phase HPLC and were individually identified by electrospray time-of-flight mass spectrometry and N-terminal sequencing, both on intact proteins and on their proteolytic fragments after trypsin digestion. Twenty-five peptide components of the proteome (including fiber) with greater than 0.25-0.5% contribution to the protein content of the virus were identified and characterized. Fiber was confirmed to be partially glycosylated (both the non-glycosylated and the monoglycosylated states were identified), and two proteins were isolated and identified as phosphorylation derivatives, namely protein V (non-phosphorylated and monophosphorylated) and protein IIIa (mono- and diphosphorylated). This new analytical tool proved to be very useful not only for refining our current knowledge of the polypeptide repertoire of purified infectious virions but also for monitoring and very rapidly identifying structural modifications resulting from changes in the manufacturing process. It was also used successfully for the characterization of various adenoviral constructs.     

Gas‐Phase Infrared Spectra of Three Compounds of Astrochemical Interest: Vinyl,Allenyl, and Propargyl Isocyanides

Isocyanides, isomers of the cyanides detected in the interstellar medium, are also possible components of this medium. The infrared spectra (5000–500 cm^?1) of gaseous vinyl isocyanide, allenyl isocyanide, and propargyl isocyanide have been recorded at 0.1 cm^?1 resolution. When prepared on a gram scale to produce a partial pressure of 10 mbar after evaporation in the cell, these three isocyanides, which have previously been reported to be kinetically unstable, do not display any sign of decomposition when recording the spectra. Geometry optimizations and harmonic and anharmonic vibrational frequencies were calculated using the LCCSD(T) method with the cc‐pVTZ basis set. Anharmonic frequencies of fundamental, overtone, and combination transitions were calculated using a variational approach implemented in the P Anhar.v2.0 code, to assign the experimental data for each compound. These results improve our knowledge of these under‐investigated compounds and pave the way for other physicochemical studies on functionalized isocyanides.     

Resonant inelastic x-ray scattering at the limit of subfemtosecond natural lifetime

We present measurements of the resonant inelastic x-ray scattering (RIXS) spectra of the CH(3)I molecule in the hard-x-ray region near the iodine L(2) and L(3) absorption edges. We show that dispersive RIXS spectral features that were recognized as a fingerprint of dissociative molecular states can be interpreted in terms of ultrashort natural lifetime of ～200 attoseconds in the case of the iodine L-shell core-hole. Our results demonstrate the capacity of the RIXS technique to reveal subtle dynamical effects in molecules with sensitivity to nuclear rearrangement on a subfemtosecond time scale.     

Synthesis, microwave spectrum, and dipole moment of allenylisocyanide (H2C═C═CHNC), a compound of potential astrochemical interest

An improved synthesis of a compound of potential astrochemical interest, allenylisocyanide (H(2)C═C═CHNC), is reported together with its microwave spectrum, which has been investigated in the 8-120 GHz spectral range to facilitate a potential identification in interstellar space. The spectra of the ground vibrational state and of five vibrationally excited states belonging to three different vibrational modes have been assigned for the parent species. A total of 658 transitions with a maximum value of J = 71 were assigned for the ground state and accurate values obtained for the rotational and quartic centrifugal distortion constants. The spectra of five heavy-atom ((13)C and (15)N) isotopologues were also assigned. The dipole moment was determined to be μ(a) = 11.93(16) × 10(-30) C m, μ(b) = 4.393(44) × 10(-30) C m, and μ(tot) = 12.71(16) × 10(-30) C m. The spectroscopic work has been augmented by theoretical calculations at the CCSD/cc-pVTZ and B3LYP/cc-pVTZ levels of theory. The theoretical calculations are generally in good agreement with the experimental results.