The [CH2CHOH.+, CH3CHO] solvated enol radical cation

The bimolecular reaction of the CH₂CHOH^.+ enol ion (m/z 44) with acetaldehyde gives a strongly dominant product,m/z 45, formed mainly by proton transfer from the ion to the molecule. The abundance of the product coming from a H^. abstraction reaction from the neutral, albeit more exothermic, is negligible. In order to explain this result, the long lived [CH₂CHOH^.+, CH₃CHO] solvated ion was generated by reaction of the CH₂CHOH^.+ enol ion with (CH₃CHO) _n in the cell of a Fourier transform ion cyclotron resonance mass spectrometer. The structure of this solvated ion was clearly established. Labeling indicates that [CH₂CHOH^.+, CH₃CHO], upon low energy collisions, reacts by H^. abstraction more rapidly than by H⁺ transfer to the neutral moiety. This shows that the entropic factors are determinant when the enol ion reacts directly with acetaldehyde.     

General access to iminosugar C-glycoside building blocks by means of cross-metathesis: a gateway to glycoconjugate mimetics

[reaction: see text] Cross-metathesis reactions of alpha-1-C-allyl-1-deoxynojirimycin derivatives 7a,b and various functionalized alkenes mediated by Grubbs's catalyst 3 are reported. The reactions showed reasonable to very good yields and excellent E/Z selectivity. This methodology allows the efficient and convergent synthesis of iminosugar C-glycosides with a great degree of structural diversity in the aglycone, opening the way to a variety of new glycoconjugate mimetics of biological interest.     

Probing electrochemical properties of pi-conjugated thienylenevinylenes/fullerene C(60) adducts by ESI/MS: evidence for dimerized cation-radicals

Oligothienylenevinylenes/C(60) dyads n-C and triads n-C(2) are studied by electrospray mass spectrometry. A clear correlation is observed between the nature of the charged species detected by mass spectrometry, i.e. protonated molecule [M + H], (+) cation radical M(+.) and dication M(++), and the oxidation potentials of the molecules. Moreover, under defined solubility conditions, mass spectrometry provides conclusive evidences for the reversible dimerization of cation-radicals of n-C(2) compounds.     

Dialkyl formyl-1 methylphosphonates α-fonctionnels—II : Preparation par voie thermique et transformation en heterocycles α-phosphoniques

The thermal condensation of functional phosphonates bearing strongly withdrawing groups (RO)₂P(O)CH₂Z1 with dimethylformamide dimethyl acetal gives corresponding β-functional, β-phosphonic enamines (RO)₂P(O)C(Z)=CHNMe₂2. Acid or basic hydrolysis of the enamines frequently gives the free aldehyde (RO)₂P(O)CH(Z)—CHO 3. We show that the enamines can be used with success for the synthesis of heterocycles like, pyrazoles 4, pyrimidines 5, benzodiazepine 6 or indole 7, all of them substituted with a phosphonate group.     

All electron calculations of open-shell polyatomic molecules. III. Perturbation treatment of the spin polarization in vinyl and methyl radicals

A first order perturbation treatment starting with SCF-MO 'S in canonical or equivalent quasi-localized form is presented for the hyperfine coupling constants of vinyl and methyl radicals. The spin-polarisation contribution to hyperfine splittings is found to be large, negative for the proton of the radical center in both radicals and positive for the β protons of vinyl.     

Mechanisms and kinetics of polymerization of thermoplastic polyimides. II. Study of “bridged” dianhydride/aromatic amine systems

The aim of the present work was to identify and follow the main and side reactions involved in the ring dehydration of amic acid prepared from “bridged” dianhydrides whose central substituent is an electron acceptor or donor, and an aromatic diamine. Several isomeric structures may appear as a result of the opening reactivity and selectivity of anhydride groups towards the aromatic amine. Reaction mechanisms and kinetics were thus studied in solvent phase with HPLC and ¹³C-NMR and in solid molten phase by FTIR and solid ¹³C-NMR. The experimental conditions (liquid and solid) and the structure of the products (type of central substituent) affecting the mechanisms and kinetics of the reactions were noted. © 1993 John Wiley & Sons, Inc.     

UV spectra and excitation delocalization in DNA: influence of the spectral width.

The singlet excited states of the model DNA duplex (dA)10.(dT)10 are studied. Calculations are performed in the exciton theory framework. Molecular dynamics calculations provide the duplex geometry. The dipolar coupling is determined using atomic transition charges. The monomer transition energies are simulated by Gaussian functions resembling the absorption bands of nucleosides in aqueous solutions. Most of the excited states are found to be delocalized over at least two bases and result from the mixing of different monomer states. Their properties are only weakly affected by conformational changes of the double helix. On average, the highest oscillator strength is carried by the upper eigenstates. The duplex absorption spectra are shifted a few nanometers to higher energies with respect to the spectra of noninteracting monomers. The states with larger spatial extent are located close to the maximum of the absorption spectrum.     

Two-stage Off-Gel isoelectric focusing: protein followed by peptide fractionation and application to proteome analysis of human plasma

This paper presents the recently introduced Off-Gel electrophoresis (OGE) technology as a versatile tool to reproducibly fractionate intact proteins and peptides into discrete liquid fractions. The coupling of two stages of OGE, i.e., the separation of intact proteins in a first-stage followed by fractionation of peptides derived from each protein fraction after proteolysis in a second stage, results in an array of 15 x 15 fractions that are directly amenable to additional peptide fractionation like reverse-phase liquid chromatography (RPC). The analysis of all second-stage peptide fractions from only the first-stage protein fraction representing pH 5.0 -5.15 by on-line reverse-phase LC-tandem mass spectrometry resulted in the identification of 53 proteins (337 peptides), of which 10 were on different immunoglobulin (Ig) chains, with an input of only 1.5 mg human blood plasma proteins. Increasing the protein load to approximately 12 mg increased the number of identified proteins in the same protein fraction to 73 proteins (449 peptides), of which 15 were Ig-related. Immunodepletion of six of the most abundant proteins (albumin, transferrin, haptoglobin, IgG, IgA, and alpha-1-antitrypsin) prior to first-stage OGE with an input of 1.5 mg of protein (equivalent to approximately 10 mg nondepleted plasma) resulted in the identification of 81 proteins (660 peptides), of which three were still Ig fragments. The pI-based separation of peptides appears to be nonuniform based on the theoretically determined pI values of identified peptides. This observation specifically accounts for the neutral zone (pI 5-8) and can be accounted for by the physicochemical properties of the peptides given by their amino acid composition. The power of OGE separation of proteins and peptides is discussed with a focus on the use of the knowledge about the pI of proteins and peptides that assist the validation of correct identifications together with the retention time of peptides on RPC.     

Substitutional carbon defects in silicon: A quantum mechanical characterization through the infrared and Raman spectra

The infrared (IR) and Raman spectra of eight substitutional carbon defects in silicon are computed at the quantum mechanical level by using a periodic supercell approach based on hybrid functionals, an all electron Gaussian type basis set and the CRYSTAL code. The single substitutional C _s case and its combination with a vacancy (C _sV and C _sSiV) are considered first. The progressive saturation of the four bonds of a Si atom with C is then examined. The last set of defects consists of a chain of adjacent carbon atoms C, with i = 1–3. The simple substitutional case, C _s, is the common first member of the three sets. All these defects show important, very characteristic features in their IR spectrum. One or two C related peaks dominate the spectra: at 596 cm⁻¹ for C _s (and C _sSiV, the second neighbor vacancy is not shifting the C _s peak), at 705 and 716 cm⁻¹ for C _sV, at 537 cm⁻¹ for C and C (with additional peaks at 522, 655 and 689 for the latter only), at 607 and 624 cm⁻¹, 601 and 643 cm⁻¹, and 629 cm⁻¹ for SiC, SiC, and SiC, respectively. Comparison with experiment allows to attribute many observed peaks to one of the C substitutional defects. Observed peaks above 720 cm⁻¹ must be attributed to interstitial C or more complicated defects.     

Optimization of spiroimidazolidinone derivatives synthesis on solid phase using SynPhase™ Lanterns

We report the synthesis of 1,4,8-triazaspiro[4.5]decan-2-one derivatives from N-benzyl-4-piperidone and N-protected amino acid amides on solid support. We have translated the chemistry from solution to solid phase using a backbone amide linker (BAL) mimic. Using a parallel combinatorial approach, we performed the optimization of the synthesis on SynPhase™ Lanterns.