Four isomers of [C3H8O]+˙ distinguished by collisional activation

Collisional activation of the molecular ions of 1-propanol, 2-propanol and methyl ethyl ether, and of the m/z 60 ion from 1,2-dimethoxyethane provides evidence for four distinct forms of [C₃H₈O]^+˙. Collision induced decompositions may be explained either by simple cleavages, by cyclic processes involving adjacent substituents, or by bicyclic processes of adjacent substituents. Evidence for a form of [C₃H₈O]^+˙ in which charge and radical site are separate is assembled from the spectra.     

Strain relaxation in the epitaxy of La2/3Sr1/3MnO3 grown by pulsed-laser deposition on SrTiO3(001)

With a Curie point at 370?K, the half-metal (La_0.7Sr_0.3)MnO₃ (LSMO) is one of the most interesting candidates for electronic devices based on tunnel magnetoresistance. SrTiO₃ (STO) is up to now the best substrate for the epitaxy of suitable thin films of LSMO. The pseudocubic unit cell of rhombohedral LSMO has a parameter a _LSMO such that (a _STO ? a _LSMO)/a _LSMO = +?0.83% (where a _STO is the parameter of cubic STO) and an angle of 90.26°. As strained growth is tetragonal, relaxation implies recovery of both the pseudocubic parameter and of the original angle. In the LSMO layers that we prepare by pulsed-laser deposition, we show that these two processes are quite independent. The angular distortion is partially recovered by twinning in films 25?nm thick, while recovery of the parameter never occurs in the thickness range that we explored (up to 432?nm). A relaxation, however, takes place above a thickness of 100?nm, associated with a transition from two-dimensional to three-dimensional columnar growth. It is accompanied by chemical fluctuations. Our magnetic measurements exhibit Curie temperatures and magnetic moments very close to the bulk values in those layers where the crystal parameter is strained but the angle partially relaxed.     

Synthesis and Complexation Studies of Various Precursors Based on Calix[4]arene-crown-5 and -6 for the Immunoanalysis of Potassium and Caesium Ions

In an attempt to generate antibodies for the development of an immunoanalysis method for potassium and caesium ions, new 1,3-alternate calix[4]arenes-crown-5 and -6 bearing either carboxylic or hydroxyl functions were synthesized in good yields. Their complexation properties towards potassium and caesium ions were investigated using ¹H NMR spectroscopy and the usual properties proved to be preserved in the presence of the anchoring arms.     

Degeneracy of the Antithrombin Binding Sequence in Heparin: 2-O-Sulfated Iduronic Acid Can Replace the Critical Glucuronic Acid

Heparin binds to and activates antithrombin (AT) through a specific pentasaccharide sequence, in which a trisaccharide subsite, containing glucuronic acid (GlcA), has been considered as the initiator in the recognition of the polysaccharide by the protein. Recently it was suggested that sulfated iduronic acid (IdoA2S) could replace this “canonical” GlcA. Indeed, a heparin octasaccharidic sequence obtained by chemoenzymatic synthesis, in which GlcA is replaced with IdoA2S, has been found to similarly bind to and activate antithrombin. By using saturation-transfer-difference (STD) NMR, NOEs, transferred NOEs (tr-NOEs) NMR and molecular dynamics, we show that, upon binding to AT, this IdoA2S unit develops comparable interactions with AT as GlcA. Interestingly, two IdoA2S units, both present in a ¹C₄-²S₀ equilibrium in the unbound saccharide, shift to full ²S₀ and full ¹C₄ upon binding to antithrombin, providing the best illustration of the critical role of iduronic acid conformational flexibility in biological systems.     

Solid‐state tautomeric structure and invariom refinement of a novel and potent HIV integrase inhibitor

The conformation and tautomeric structure of (Z)‐4‐[5‐(2,6‐difluorobenzyl)‐1‐(2‐fluorobenzyl)‐2‐oxo‐1,2‐dihydropyridin‐3‐yl]‐4‐hydroxy‐2‐oxo‐N‐(2‐oxopyrrolidin‐1‐yl)but‐3‐enamide, C₂₇H₂₂F₃N₃O₅, in the solid state has been resolved by single‐crystal X‐ray crystallography. The electron distribution in the molecule was evaluated by refinements with invarioms, aspherical scattering factors by the method of Dittrich et al. [Acta Cryst. (2005), A 61 , 314–320] that are based on the Hansen–Coppens multipole model [Hansen & Coppens (1978). Acta Cryst. A 34 , 909–921]. The β‐diketo portion of the molecule exists in the enol form. The enol –OH hydrogen forms a strong asymmetric hydrogen bond with the carbonyl O atom on the β‐C atom of the chain. Weak intramolecular hydrogen bonds exist between the weakly acidic α‐CH hydrogen of the keto–enol group and the pyridinone carbonyl O atom, and also between the hydrazine N—H group and the carbonyl group in the β‐position from the hydrazine N—H group. The electrostatic properties of the molecule were derived from the molecular charge density. The molecule is in a lengthened conformation and the rings of the two benzyl groups are nearly orthogonal. Results from a high‐field ¹H and ¹³C NMR correlation spectroscopy study confirm that the same tautomer exists in solution as in the solid state.     

Studies on the Synthesis of Eremophilane Sesquiterpenes. A Novel Entry into the Aristolane Ring System

Readily available tricyclo[3.2.2.0^2,4]non-6-en-8-one is converted into the tricyclo ring system of the aristolane sesquiterpenes via an alkoxide accelerated [3, 3]-sigmatropic rearrangement.     

An Experimentally Convenient Preparation of Highly Substituted Pyridines

A four step sequence is described for the conversion of α,β-unsaturated carboxylic acids into highly substituted pyridines.