Functional Binding Surface of a β‐Hairpin VEGF Receptor Targeting Peptide Determined by NMR Spectroscopy in Living Cells

In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast ¹⁵N‐edited NMR spectroscopic experiments. To this aim, ¹⁵N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including ¹⁵N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2.     

Convexity of Domains of Riemannian Manifolds

In this paper the problem of the geodesic connectedness and convexity ofincomplete Riemannian manifolds is analyzed. To this aim, a detailedstudy of the notion of convexity for the associated Cauchy boundary iscarried out. In particular, under widely discussed hypotheses,we prove the convexity of open domains (whose boundaries may benondifferentiable) of a complete Riemannian manifold. Variationalmethods are mainly used. Examples and applications are provided,including a result for dynamical systems on the existence oftrajectories with fixed energy.     

A generalization of an example by V. Ya. Ivrii

A well-known example by Ivrii concerning the operatorP=D _t ² −t^2lD _x ² +at^kD_x (a≠0), shows that there exists a delicate relation amongl, k and the Gevrey index of well-posedness of the Cauchy problem. In this paper we give a generalization to a class of pseudo-differential operators includingP.

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Sunto Un famoso esempio di Ivrii riguardante l'operatoreP=D _t ² −t^2lD _x ² +at^kD_x (a≠0), mostra che c'è una relazione sottile tral, k e l'indice di Gevrey di buona positura del problema di Cauchy. In questo articolo viene data una generalizzazione ad una classe di operatori pseudodifferenziali che comprendeP.

     

The extended loop group: An infinite dimensional manifold associated with the loop space

A set of coordinates in the non-parametric loop-space is introduced. We show that these coordinates transform under infinite dimensional linear representations of the diffeomorphism group. An extension of the group of loops in terms of these objects is proposed. The enlarged group behaves locally as an infinite dimensional Lie group. Ordinary loops form a subgroup of this group. The algebraic properties of this new mathematical structure are analyzed in detail. Applications of the formalism to field theory, quantum gravity and knot theory are considered.     

Synthesis of 4H-3,1-benzoxazines, quinazolin-2-ones, and quinoline-4-ones by palladium-catalyzed oxidative carbonylation of 2-ethynylaniline derivatives

An effective and straightforward approach to the synthesis of 4H-3,1-benzoxazines 3 and 4, quinazolin-2-ones 5, and quinoline-4-one derivatives 6 and 7 is provided by palladium-catalyzed cyclization-alkoxycarbonylation of variously substituted 2-(trimethylsilanyl)ethynylaniline amide or urea derivatives 2. Reactions are carried out in 7:1 MeCN/MeOH at 65 or 75 degrees C in the presence of catalytic amounts of 10% Pd/C in conjunction with Bu(4)NI and KF and under 2.4 MPa of a 3:1 mixture of CO and air. Anti and syn 6-exo-dig cyclization modes account for the formation of the two stereoisomers. Isomerization of the vinylpalladium intermediate may occur as well. Formation of a double carbonylation product 7r and of a gem-dimethoxycarbonylation product 6s, whose structures have been determined by X-ray diffraction analysis, is justified through an unusual type of rearrangement.     

Conformational mobility of thianthrene-5-oxide

[reaction: see text] Data on the apparent dipole moment of thianthrene-5-oxide (1) and (1)H NMR spectra in different solvents support the conformational mobility of 1, which flaps between two limit boat conformations with the sulfinyl group in pseudoequatorial and pseudoaxial positions, respectively. The conformational equilibrium of 1 occurs too fast for the (1)H NMR (500 MHz) time-scale even at -130 degrees C, and the equilibrium constant has not been determined. The apparent dipole moments of 1 in n-hexane and 1,4-dioxane and the (1)H NMR spectra of 1 and the model compounds cis- and trans-thianthrene-5,10-dioxides (2) and thianthrene (5) in different solvents and at various temperatures confirm that the relative position of the conformational equilibrium of 1 is solvent-dependent, and more polar solvents favor the conformation with the sulfoxide group in the pseudoaxial position (1(')(ax)). Variable-temperature (1)H NMR spectra have established the interconversion barrier of trans-2 and confirmed that the conformational equilibrium of cis-2 is strongly displaced toward the conformation with both sulfinyl groups in the pseudoequatorial position. The (1)H NMR data support the transannular interaction of the functional groups in 1 and trans-2.     

Baeyer-Villiger oxidation with potassium peroxomonosulfate supported on acidic silica gel

[reaction: see text] Potassium peroxomonosulfate deposited onto silica SiO2 x KHSO5 efficiently reacts with ketones in dichloromethane at room temperature to give the corresponding esters or lactones in quantitative yields. This method avoids hydrolysis of the reaction products. The Baeyer-Villiger reaction is catalyzed by potassium hydrogensulfate present in the supported reagent.