Spectroscopic characterization of 6-hydroxy and 1-methyl-6-hydroxybicyclo[2.2.2]octan-2-one ethylene acetals and ethylene dithioacetals

6-endo- and 6-exo-Hydroxybicyclo[2.2.2]octan-2-one and 1-methyl-6-endo- and 6-exo-hydroxybicyclo[2.2.2]octan-2-one ethylene acetals and ethylene dithioacetals 1-4 have been characterized by 1D and 2D NMR methods.     

Gradient bounds for the horizontal <Emphasis Type="Italic">p</Emphasis>-Laplacian on a Carnot group and some applications

In a Carnot group we prove a new priori bound for the right-invariant horizontal gradient of smooth solutions of a class of quasilinear equations which are modeled on the so-called horizontal p-Laplacian. Exploiting such bound and a regularization procedure based on difference quotients we obtain the C^1,a_loc{C^{1,\alpha}_{loc}} regularity of weak solutions which possess some special symmetries. For instance, in the first Heisenberg group \mathbbH¹{\mathbb{H}^{1}} we obtain such regularity for all weak solutions of the horizontal p-Laplacian, with p ≥ 2, which are of the form u(z, t) = u(|z|, t).     

Non-steroidal antiinflammatory agents. VI. Synthesis of 10-oxo-5H-pyrrolo[1,2-b]isoquinoline-3-acetic Acid,a conformationally restricted analogue of tolmetin

The synthesis of 10-oxo-5H-pyrrolo[1,2-b]isoquinoline-3-acetic acid 4 , a tricyclic analogue of tolmetin which might show significant analgesic-antiinflammatory activity, has been accomplished in four steps. Alkylation of ethyl 2-pyrrolylglyoxylate ( 15 ) with 2-cyanobenzyl bromide afforded derivative 16 , which was transformed by the Huang-Minion reaction into the dicarboxylic acid 6 . Cyclization of this key intermediate to 17 , followed by alkaline hydrolysis, afforded 10-oxo-5H-pyrrolo[1,2–6]isoquinoline-3-acetic acid ( 4 ). Various attempted syntheses of 6 are also discussed.     

Elusive 6-exo-Hydroxybicyclo[2.2.2]octan-2-ones from the corresponding acetates by methanolysis in the presence of CH(3)ONa/La(OTf)(3)

[reaction: see text] A series of 6-exo-acetoxybicyclo[2.2.2]octan-2-ones were converted into the corresponding 6-exo-hydroxybicyclo[2.2.2]octan-2-ones by methanolysis in the presence of CH(3)ONa/La(OTf)(3). Under the given conditions, epimerization at C(6) of the latter led in the least favorable cases only to traces of the more stable 6-endo-hydroxybicyclo[2.2.2]octan-2-ones. This procedure, when combined with the described conversion of easily available 6-endo-hydroxybicyclo[2.2.2]octan-2-ones into the corresponding 6-exo-acetoxy derivatives, provides a convenient route to elusive 6-exo-hydroxybicyclo[2.2.2]octan-2-ones. Applications to total synthesis are shown and envisaged.     

Evaluation of mobile phase, ion pairing, and temperature influence on an HILIC-MS/MS method for L-arginine and its dimethylated derivatives detection

Asymmetric N(G),-N(G)-dimethylarginine (ADMA) increases in diseases such as renal failure, diabetes mellitus, and hypercholesterolemia. The feasibility and utility of a hydrophilic interaction chromatography (HILIC) method for the separation of free L-arginine (Arg), ADMA, and symmetric N(G),-N(G')-dimethylarginine (SDMA) on a typical silica column were explored and the impact of some experimental parameters on the chromatographic behavior of these analytes was investigated. The effect of water and TFA content in mobile phase and of column temperature was investigated during the development of a fast and simple HILIC-MS/MS method that might be suitable for the quantification of free Arg, ADMA, and SDMA in plasma for routine analysis. Our results show that a good compromise between efficiency and peak shape with acceptable retention and total chromatographic run time is achieved using an ACN/water (90:10) mobile phase with TFA% as additive ranging from 0.015 to 0.025% and column temperature ranging from 25 to 30 degrees C.     

Schrödinger operators on manifolds, essential self-adjointness, and absence of eigenvalues

Suppose thatM ⁿ is a complete, noncompact, Riemannian manifold. If Δ denotes the Laplace operator ofM, one has associated Schrödinger operators ? Δ +V. Conditions onV are formulated, which ensures the essential self-adjointness of ? Δ +V. In particular, ifV ∈ Q_α,loc (M ⁿ), the local Stummel class, andV ≥ ? c outside of a compact set, then ? Δ +V is essentially self-adjoint on C ₀ ^∞ (M ⁿ). In addition, essential self-adjointness is proved for potentials which are strongly singular at a point. The absence of eigenvalues of ?Δ +V is also studied. This relies upon Rellich-type identities. The results on strongly singular potentials make use of a generalization of the classical uncertainty principle, inR ⁿ, to Riemannian manifolds with a pole.