Peptide late-stage C(sp3)–H arylation by native asparagine assistance without exogenous directing groups

There is a strong demand for novel native peptide motifs for post-synthetic modifications of peptides without pre-installation and subsequent removal of directing groups. Herein, we report an efficient method for peptide late-stage C(sp³)–H arylations assisted by the unmodified side chain of asparagine (Asn) without any exogenous directing group. Thereby, site-selective arylations of C(sp³)–H bonds at the N-terminus of di-, tri-, and tetrapeptides have been achieved. Likewise, we have constructed a key building block for accessing agouti-related protein (AGRP) active loop analogues in a concise manner.

An efficient method for peptide late-stage C(sp³)-H arylations assisted by unmodified side chain of asparagine (Asn) without any exogenous directing group has been reported.     

Substrate-reagent complexation ability in enantioselective 1,4 addition reactions

Hydrogen-aarbonyl chelation and magnesium-arene π coordination are proposed to aooount for enhanced enantioselectivïty in 1,4-addition reactions of chiral cuprates.     

Production of fast evaporation residues by the reaction20Ne+208Pb at projectile energies of 8.6, 11.4 and 14.9 A.MeV

Velocity distributions and production cross sections of evaporation residues have been measured in the reaction²⁰Ne+²⁰⁸Pb at projectile energies of 8.6, 11.4, 14.9 A.MeV. Essential deviations from statistical model of deexcitation have been observed. Monte Carlo simulations involving emission of non-equilibrium particles have been used in order to reproduce experimental velocity, charge and mass distributions of evaporation residues and to estimate indirectly multiplicities of pre-equilibrium particles. Communicated by V. Metag     

Systematic study of muon transfer to sulphur dioxide

In a systematic study of the transfer process to sulphur dioxide, in seven different H₂ + SO₂ gas mixtures, the time spectra of the muonic sulphur X-rays yield muon transfer rates to the SO₂ molecule, deduced from the lifetimes of the p atoms, which agree all well with each other. The muonic oxygen time spectra show an additional structure as if p atoms of another kind were present. Reduced transfer rates_O are reproducible if one uses the model of ephemeral p atoms. The intensity ratios between the different kinds of p atoms are also discussed in the framework of this model and the one of black and white p atoms.     

Electrospray/mass spectrometric identification and analysis of 4-hydroxy-2-alkylquinolines (HAQs) produced by <Emphasis Type="Italic">Pseudomonas aeruginosa</Emphasis>

The opportunistic pathogen Pseudomonas aeruginosa produces a large array of 4-hydroxy-2-alkylquinolines (HAQs). These compounds were analyzed by LC/MS, using positive electrospray ionization, in the culture supernatant of strain PA14. Fifty-six HAQs and related compounds were detected and their [M + H](+) ions were further analyzed by collision induced dissociation (CID). These HAQs were grouped into five different series based on the presence of an hydrogen or hydroxyl group at the 3 position, an N-oxide group in place of the quinoline nitrogen, and an unsaturation on their alkyl side chain. Two new analogs of 3,4-dihydroxy-2 heptylquinoline, the Pseudomonas quinolone signal (PQS), were found with an alkyl chain longer by one and two methylene groups. Moreover, two additional series of compounds were identified in which a saturated or unsaturated alkyl side chain is located at the 3 position along with an hydroxyl group at the 3 position and a ketone at the 2 position. No HAQ N-oxides, nor any compounds from the latter two series, were detected in a pqsL mutant derivative of PA14, indicating that this gene is involved in the biosynthesis of these compounds. This work demonstrates the large repertoire of HAQ and HAQ-related compounds produced by P. aeruginosa, and provides insight into N-oxides biosynthesis and confirm the hypothesis that N-oxides are the precursors of compounds from Series 6 and 7.     

Spectrophotometric examination of redox equilibria by use of logarithmic transformations

For the spectrophotometric characterization of redox reactions, a logarithmic transformation is proposed by which it is possible to analyse indirectly the functions E = f (pH) and E = f (C) derived from experimental data. Besides the mechanism of the reaction the equilibrium constant can also be calculated. The method is generally usable for equimolar redox systems and also for non-equimolar ones if a single equilibrium exists in the range under examination. References to the evaluation are given and the practicability is demonstrated with the system Fe(3+)/SO(2-)(3).     

Multichannel digital transmission in an optical network of communicating molecules

In present telecommunication networks, information transfer relies on the interplay of optical and electrical signals. Data are communicated optically but processed electronically. Methods to maintain the propagating signals solely at the optical level must be developed to overcome the transmission capacities and speed limits imposed by the electronic components. We have demonstrated that molecular switches can be used to gate optical signals in response to optical signals. We have realized a simple optical network consisting of three light sources, one cell containing a solution of three fluorescent molecules, one cell containing a solution of a three-state molecular switch and a detector. The light emitted by the three fluorophores is absorbed by the three states of the molecular switch. Using this simple operating principle, we have shown that multichannel digital transmission can be implemented on an ensemble of communicating molecules relying exclusively on the interplay of optical inputs and optical outputs.     

Very general formation of tetrahydropterin cation radicals during reaction of iron porphyrins with tetrahydropterins: model for the corresponding NO-synthase reaction

Electron transfer from tetrahydropterins to iron porphyrins, with formation of intermediate tetrahydropterin cation radicals, is a very general reaction that was shown to occur not only with tetrahydrobiopterin, as originally found in NO-synthases, but also with another important biological cofactor, tetrahydrofolate, and various iron porphyrins, either in their ferric state, or in the Fe(II)O(2) state, as in the first model of the corresponding NO-synthase reaction described in this paper.