α‐Peptide–Oligourea Chimeras: Stabilization of Short α‐Helices by Non‐Peptide Helical Foldamers

Short α‐peptides with less than 10 residues generally display a low propensity to nucleate stable helical conformations. While various strategies to stabilize peptide helices have been previously reported, the ability of non‐peptide helical foldamers to stabilize α‐helices when fused to short α‐peptide segments has not been investigated. Towards this end, structural investigations into a series of chimeric oligomers obtained by joining aliphatic oligoureas to the C‐ or N‐termini of α‐peptides are described. All chimeras were found to be fully helical, with as few as 2 (or 3) urea units sufficient to propagate an α‐helical conformation in the fused peptide segment. The remarkable compatibility of α‐peptides with oligoureas described here, along with the simplicity of the approach, highlights the potential of interfacing natural and non‐peptide backbones as a means to further control the behavior of α‐peptides.     

Phase Behavior of a Designed Cyclopropyl Analogue of Monoolein: Implications for Low‐Temperature Membrane Protein Crystallization

Lipidic cubic phases (LCPs) are used in areas ranging from membrane biology to biodevices. Because some membrane proteins are notoriously unstable at room temperature, and available LCPs undergo transformation to lamellar phases at low temperatures, development of stable low‐temperature LCPs for biophysical studies of membrane proteins is called for. Monodihydrosterculin (MDS) is a designer lipid based on monoolein (MO) with a configurationally restricted cyclopropyl ring replacing the olefin. Small‐angle X‐ray scattering (SAXS) analyses revealed a phase diagram for MDS lacking the high‐temperature, highly curved reverse hexagonal phase typical for MO, and extending the cubic phase boundary to lower temperature, thereby establishing the relationship between lipid molecular structure and mesophase behavior. The use of MDS as a new material for LCP‐based membrane protein crystallization at low temperature was demonstrated by crystallizing bacteriorhodopsin at 20 °C as well as 4 °C.     

Synthesis and luminescence properties of new red-shifted absorption lanthanide(III) chelates suitable for peptide and protein labelling

The synthesis and photo-physical properties of an original bis-pyridinylpyrazine chromophore efficiently sensitising europium(III) and samarium(III) are described. The corresponding lanthanide(III) complexes display in aqueous solutions a maximum excitation wavelength which is significantly red-shifted compared to the usual terpyridine-based chelates, and a valuable luminescence brightness above 2,000 dm(3) mol(-1) cm(-1) at 345 nm was obtained with a europium(III) derivative. Further functionalisation with three different bioconjugatable handles was also investigated and their ability to efficiently label a model hexapeptide was evaluated and compared. Finally, the best bioconjugatable europium(III) chelate was used in representative labelling experiments involving monoclonal antibodies and the luminescence features of the corresponding bioconjugates remained satisfactory.     

Synthesis and reactivity of a phosphine-stabilized monogermanium analogue of alkynes

The synthesis of the first isolable C-phosphino-Ge-aminogermyne, stabilized by a phosphine ligand, has been achieved. X-ray diffraction analysis indicates a quite long Ge-C bond whose length is between that of a single and a double bond but consistent with the theoretically predicted values for a germyne bearing π-donating substituents. The isomerization of this germyne derivative affords a new stable N-heterocyclic germylene through migration of the original phosphine ligand from germanium to the carbon center.     

Crystallization and characterization of an inflammatory lectin purified from the seeds of Dioclea wilsonii

DwL, a lectin extracted from the seeds of Dioclea wilsonii, is a metalloprotein with strong agglutinating activity against rabbit and ABO erythrocytes, inhibited by glucose and mannose. DwL was purified by affinity chromatography on a Sephadex G-50 column and ion exchange chromatography on a HiTrap SP XL column. SDS-PAGE revealed three electrophoretic bands corresponding to the α (25,634 ± 2 Da), β (12,873 ± 2 Da) and γ (12,779 ± 2 Da) chains. Protein sequencing was done by Tandem Mass Spectrometry. The primary sequence featured 237 amino acids and was highly homologous to other reported Diocleinae lectins. A complete X-ray dataset was collected at 2.0 ? for X-Man-complexed DWL crystals produced by the vapor diffusion method. The crystals were orthorhombic and belonged to the space group I222, with the unit-cell parameters a = 59.6, b = 67.9 and c = 109.0 ?. DWL differed in potency from other ConA-like lectins and was found to induce neutrophil migration in rats, making it particularly useful in structural/functional studies of this class of proteins.     

A novel ruthenium(II) complex for two-photon absorption-based optical power limiting in the near-IR range

In this article, the synthesis of a novel high-conjugated ligand and its corresponding Ru(II) complex PTFTF:Ru is reported, along with the linear and nonlinear optical characterizations. Two-photon absorption based optical power limiting properties (OPL), especially in the near infrared, are described and compared to those of the analogous complexes previously published. Combined with a preliminary theoretical approach, this allows us to highlight several key parameters for OPL optimization in such molecular systems and more particularly the spectral overlap between TPA and excited-state absorption.     

Die Zerfälle des Rh97g und des Rh97m

The decays of Rh^97g and Rh^97m were investigated using Ge(Li)- and Si(Li)-detectors and a Ge(Li)—Ge(Li)-coincidence circuit. The isomeric transition with an energy of 259 keV was identified by its conversion electrons and decays with a half-life of (48.0±0.8) min. Therefore, the half-lives (30.3±0.9) min and (47.9±0.6) min obtained from theγ-studies were attributed to the decays of Rh^97g and Rh^97m respectively. The proposed decay schemes have 31 excited states of Ru⁹⁷ and account for 84 of the 110 observedγ-transitions, especially for the 37 strongest ones. Twelve of the proposed levels having spins and parities 1/2^? or 3/2^? and excitation energies between 2200 keV and 3600 keV are interpreted as being due to 2p _1/2-neutron-hole-states.     

Semiempirical determination of the atom-surface interaction

We discuss three methods of determining V(z), the lateral average (G = 0 Fourier component) of the atom-surface interaction, from the bound state spectrum found in beam scattering. One method uses the Rydberg-Klein-Rees technique, which yields the width of the potential (i.e., separation of classical turning points) as a function of energy. This method incorporates also the known asymptotic form V ～ ?C₃z^?3, whereC₃ is derived from the polarizability and dielectric function of atom and solid, respectively. The second method uses a hybrid potential, constructed from a Morse potential with shifted zero of energy connected to the asymptotic form,?C₃z^?3, requiring continuity of V and $\text{d}\text{V}\text{d}\text{z}$. The third potential is a Lennard-Jones 3–9 interaction. Results are presented for H and He scattering from LiF and NaF.