First total synthesis of cichorine and zinnimidine

The first total synthesis of the phytotoxins cichorine and zinnimidine is described. The synthetic tactics involve the sequential connection of the dense and diverse functionalities on the aromatic nucleus followed by a Parham cyclization process, giving rise to the lactam unit embedded in the title compound framework.     

A Semi-exclusive study of heavy-residue production in the40Ar + Ag reaction at 35 MeV/u incident energy

Heavy residues created in the reaction Ar + Ag at 35 MeV/u have been detected at various forward angles. Their velocity spectra (quite different from the corresponding spectra measured at 27 MeV/u) show that these events result both from central and peripheral reactions and that the fusion component has dramatically decreased. Coincident light charged particles spectra have been obtained in a large solid angle forward hodoscope. The analysis of these spectra allows to differentiate peripheral and central collisions. The proton spectra are analysed in terms of emitting sources. There is no need for a participant zone in peripheral reactions. Instead protons are emitted either from the target like or from the projectile like fragments. However projectile sequential emission is not sufficient to explain all the high energy protons.     

Experimental evidence of highly energy relaxed products in the 35 MeV/u84Kr+197Au reaction

The Q_β-values of⁹⁹Rb,^99,100Sr and¹⁰⁰Y have been measured for the first time at the mass separator OSTIS of the ILL; for⁹⁹Y,^99,100Zr and¹⁰⁰Nb, the results of earlier experiments were confirmed with reduced experimental errors. The two-neutron binding energies derived from the experimental Q_β-values clearly indicate that the nuclei¹⁰⁰Sr and¹⁰⁰Y are strongly deformed.     

Flow Measurements with Gundestrup Probe: Problems and Solutions

Electrical probes are an excellent tool for local measurements of basic plasma parameters, fluctuations and plasma flow studies. However, the application of a probe diagnostics is usually accompanied by theoretical restrictions, practical limitations and problems. In this paper we describe the new probe system recently developed for the TOMAS toroidal device (Forschungszentrum Jülich, Germany). This system comprises multi-collector Gundestrup probe for flow measurements and Langmuir probe for plasma characterization. During development of such a system, several physical and technical issues, which are common for probe applications, were solved or essentially suppressed.     

Neutral pion production in subthreshold heavy ion collision with16O (38 MeV/u) and20Ne (200 MeV/u) beams

Inclusive production of neutral pions has been studied in¹⁶O +²⁷Al,¹⁹⁷Au reactions at 38 MeV/u and²⁰Ne +²⁷Al reaction at 200 MeV/u. A setup of 10 Pb glass Cherenkov detector telescopes was used to detect the twoγ rays from theπ ⁰ decay.     

Lanthanide(III) Complexes with Two Hexapeptides Incorporating Unnatural Chelating Amino Acids: Secondary Structure and Stability

Unnatural metal‐chelating amino acids bearing aminodiacetate side‐chains have been introduced into two hexapeptides to obtain efficient lanthanide‐binding peptides. The synthesis of the enantiopure Fmoc‐Ada_n(tBu)₂‐OH synthons is described with overall yields of 32 and 50 % for n=2 and n=3 side‐chain carbon atoms, respectively. The two peptides AcWAda_nPGAda_nGNH₂ ( P ⁿ ) were synthesized from the protected synthons by standard solid‐phase peptide synthesis. Studies of the lanthanide complexes of the two peptides P ⁿ by luminescence titrations, mass spectrometry, circular dichroism, and solution NMR spectroscopy demonstrate that the Ada_n chain length has a dramatic effect on the complexation properties. Indeed, the flexible compound P³ forms a mononuclear complex of moderate stability (β₁₁=10^9.9), which tends to transform into a binuclear species in the presence of excess of the metal ion. Interestingly, the more compact peptide P² provides stable Ln³⁺ complexes with the exclusive formation of the mononuclear Ln P² adduct. The stability constant of Tb P² is two orders of magnitude higher (β₁₁=10^12.1) than that measured for P³ . The 800 MHz NMR spectrum of the La³⁺ complex of P² evidences a well‐defined type II β‐turn as well as a hydrophobic Trp(indole)–Pro interaction. These interactions exemplify the non‐innocent character of the peptide spacer in the complex La P² as well as the role of a peptide secondary structure in the stabilization of metal complexes.     

Phosphoester Hydrolysis: The Incoming Substrate Turns the Bridging Hydroxido Nucleophile into a Terminal One

Identifying the active nucleophile in hydrolysis reactions catalyzed by binuclear hydrolases is a recurrent problem and a matter of intense debate. We report on the phosphate ester hydrolysis by a Fe^IIIFe^II complex of a binucleating ligand. This complex presents activities in the range of those observed for similar biomimetic compounds in the literature. The specific electronic properties of the Fe^IIIFe^II complex allowed us to use ¹H NMR and Mössbauer spectroscopies to investigate the nature of the various species present in the solution in the pH range of 5–10. Both techniques showed that the hydrolysis activity is associated to a μ‐hydroxido Fe^IIIFe^II species. Further ¹H NMR experiments show that binding of anions or the substrate changes this bonding mode suggesting that a terminal hydroxide is the likely nucleophile in these hydrolysis reactions. This view is further supported by the structure determination of the hydrolysis product.     

Thiazole‐Based γ‐Building Blocks as Reverse‐Turn Mimetic to Design a Gramicidin S Analogue: Conformational and Biological Evaluation

This paper describes the ability of a new class of heterocyclic γ‐amino acids named ATCs (4‐amino(methyl)‐1,3‐thiazole‐5‐carboxylic acids) to induce turns when included in a tetrapeptide template. Both hybrid Ac‐Val‐(R or S)‐ATC‐Ile‐Ala‐NH₂ sequences were synthesized and their conformations were studied by circular dichroism, NMR spectroscopy, MD simulations, and DFT calculations. It was demonstrated that the ATCs induced highly stable C₉ pseudocycles in both compounds promoting a twist turn and a reverse turn conformation depending on their absolute configurations. As a proof of concept, a bioactive analogue of gramicidin S was successfully designed using an ATC building block as a turn inducer. The NMR solution structure of the analogue adopted an antiparallel β‐pleated sheet conformation similar to that of the natural compound. The hybrid α,γ‐cyclopeptide exhibited significant reduced haemotoxicity compared to gramicidin S, while maintaining strong antibacterial activity.