Solid-phase synthesis using a new polyacrylic resin : Synthesis of the fragment 14–21 of the amino acid sequence of histone H4

The solid-phase synthesis of the octapeptide 1 AcGly-Ala-Lys-Arg-His-Arg-Lys-ValOMe, which represents the fragment 14-21 of the amino acid sequence of the chromosomal histone H4, as well as of the structurally related nonapeptide 2 AcGly-Ala-Lys-Leu-Arg-His-Arg-Lys-ValOMe, is described using a new polyacrylic resin containing a glycolamide ester linkage(resin-NHCO-CH₂-OCO-peptide) acting as a labile anchoring moiety between the resin and the peptide.After elongation of the polypeptide chain using classical protecting groups, i.e. t-butyloxycarbonyl for the α-NH₂ function, benzyloxycarbonyl, nitro and 2,4-dinitrophenyl groups for the side-chains of Lys, Arg and His respectively, both peptides 1 and 2 were obtained in good yields and with a high purity as shown by high-pressure liquid chromatography, by amino-acid analysis and by high-field proton NMR spectroscopy.This work demonstrates the ability of the newly introduced polyacrylic resin to act as a convenient support for solid-phase peptide synthesis.     

The standard redox potential of the phenyl radical/anion couple

The voltammogram of aryldiazonium tetrafluoroborates in acetonitrile (ACN), at low concentration, shows a first one-electron wave followed at a more negative potential by a small second wave; this last one corresponds to the reduction of the radical formed at the level of the first wave. Simulation of the voltammogram permits one to determine the standard redox potential of the radical/anion couple Eo(Ph./Ph-) = 0.05 V/SCE and the reduction mechanism of the diazonium cation. An electron transfer concerted with the cleavage of the C-N bond furnishes the aryl radical; this radical undergoes two competitive reactions: reduction at the electrode and H-atom transfer.     

Calcul théorique des énergies de divers arrangements géométriques de la molécule (η5-C5H5)2TiCl2

The molecular energy of the complex (η⁵-C₅H₅)₂TiCl₂ has been calculated for experimental geometry and for several hypothetical forms by a semi-empirical CNDO/2 approach. The energy difference between experimental (quasi-tetrahedral) geometry and a planar geometry is ca. 20 kcal mol^?1. This difference is sufficiently high to explain the difficulty of the inversion process.     

Fluorescence from the second excited singlet state of [18] annulenes

The emission spectra of the second excited singlet state of [18] annulene and of monofluoro [18] annulene (in a 3-methylpentane glass at 4 K) are reported. The large energy gap between the first and second excited singlet states inhibits fast internal conversion and favours the appearance of S₂ → S₀ emission. In addition, fluorescence from the S₁ state can be observed in monofluoro [13] annulene by exciting into the S₂ or directly into the S₁ absorption.     

Third-order nonlinear optical figure of merits for conjugated TTF-quinone molecules

We have revealed a substantial enhancement of third-order optical figure of merits by the synthesis of a compact molecule possessing the tetrathiafulvalene (TTF) group with two backside C=O groups. Addition of the saturated methylene chain substantially suppresses the third-order optical figure of merits and even local optical hyperpolarizabilities at lambda = 532 nm. Another TTF-derivative molecule possessing ethylenic and acetylenic chains demonstrates large hyperpolarizabilities; however, generally, the figure of merit factor decreases due to the increasing optical losses as a consequence of enhanced linear absorption. At the same time, both of the chromophores have a large nonlinear optical response. General approaches for search and design of the third-order optical materials with improved properties are given.     

Pyridazines: (thiényl-2)-3 pyridazine,quelques (thiényl-2)-3 pyridazines substituées en 6 et systèmes à noyaux condensés dérivés

We describe the synthesis of 3-(2-thienyl)pyridazine and of some of its derivatives substituted on the 6 position eg., ethoxy, hydrazino and azido. Some of these compounds have lead to condensed rings systems, namely, triazolo- and tetrazolopyridazines.     

Comportement de LiAlH4 en fonction de la dilution dans la racemisation d'un silane optiquement actif en milieu thf

The optically active methylphenyl-α-naphthylsilane racemises quickly in tetrahydrofuran in the presence of LiAlH₄.Kinetic results show a different behaviour of the hydride depending on its concentration. Activation parameters have been obtained and mechanisms proposed.     

Synthesis of functionalized rab GTPases by a combination of solution- or solid-phase lipopeptide synthesis with expressed protein ligation

Prenylated proteins with non-native functionalities are generally very difficult to obtain by recombinant or enzymatic means. The semisynthesis of preparative amounts of prenylated Rab guanosine triphosphatases (GTPases) from recombinant proteins and synthetic prenylated peptides depends largely on the availability of functionalised prenylated peptides corresponding to the proteins' native structure or modifications thereof. Here, we describe and compare solution-phase and solid-phase strategies for the generation of peptides corresponding to the prenylated C terminus of Rab7 GTPase. The solid-phase with utilisation of a hydrazide linker emerges as the more favourable approach. It allows a fast and practical synthesis of pure peptides and gives a high degree of flexibility in their modification. To facilitate the analysis of semisynthetic proteins, the synthesised peptides were equipped with a fluorescent group. Using the described approach, we introduced fluorophores at several different positions of the Rab7 C terminus. The position of the incorporated fluorescent groups in the peptides did not influence the protein-ligation reaction, as the generated peptides could be ligated onto thioester-tagged Rab7. However, it was found that the positioning of the fluorescent group had an influence on the functionality of the Rab7 proteins; analysis of the interaction of the semisynthetic Rab7 proteins with REP (Rab escort protein) and GDI (guanosine diphosphate dissociation inhibitor) molecules revealed that modification of the peptide side chains or of the C-terminal isoprenoid did not significantly interfere with complex formation. However, functionalisation of the C terminus was found to have an adverse effect on complex formation and stability, possibly reflecting low structural flexibility of the Rab GDI/REP molecules in the vicinity of the lipid-binding site.     

Thermodynamic properties of aqueous organic mixtures near the critical demixing: Cases of 2,6-dimethylpyridine and of 2-isobutoxyethanol

Phase diagrams, volumes and heat capacities of aqueous mixtures of 2,6-dimethylpyridine (2,6-L) and 2-isobutoxyethanol (iBE) and activities of 2,6-L in aqueous mixtures were measured in the monophasic region near the lower critical solution temperature (LCST). With 2,6-L some measurement were also made just above the LCST. From the temperature dependence of these data, partial molar relative enthalpies (2,6-L), expansibilities and the temperature derivative of heat capacities were calculated and show that iBE undergoes a microphase transition at low concentration which is not related to the phase separation. On the other hand, the properties of 2,6-L in the water-rich region at temperatures well below the LCST indicates that this solute has only a slight tendency to associate. The heat capacities of 2,6-L show an important increase near the LCST. Such changes are not observed for iBE and other alkoxyethanols and amines since these systems already exist in the form of microphases; the partial molar properties of iBE near the LCST are nearly equal to the molar values of the pure liquid, and the changes in thermodynamic properties corresponding to the macroscopic phase transition, are therefore too small to be measured by the present techniques.