Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.     

The Problem of the Pointwise Fourier Inversion for Piecewise Smooth Functions of Several Variables

We study the pointwise convergence problem for the inverse Fourier transform of piecewise smooth functions, i.e., whether S_rD f (\bx) ? f (\bx)S_{\rho D} f (\bx) \to f (\bx) as r? ￥\rho \to \infty . r? ￥\rho \to \infty . Here for \bx,\bxi ? \Rn\bx,\bxi \in \Rn S_rDf(\bmx)=\dsf1(2p)^n/2\intli_rD [^(f)](\bxi) e^{\dst iá\bmx,\bxi?} d\bxi . S_{\rho D}f(\bm{x})=\dsf1{(2\pi)^{n/2}}\intli_{\rho D} \widehat{f}(\bxi) e^{\dst i\langle\bm{x},\bxi\rangle} d\bxi~. is the partial sum operator using a convex and open set DD containing the origin, and rD={ r\bxi:\bxi ? D }\rho D=\left\{ \rho \bxi:\bxi\in D \right\}.     

Sub-bundles of the complexified tangent bundle

We study embeddings of complex vector bundles, especially line bundles, in the complexification of the tangent bundle of a manifold. The aim is to understand implications of properties of interest in partial differential equations.

     

Advances in constant-velocity Mössbauer instrumentation

A prototype of a programmable constant-velocity scaler is presented. This instrument allows the acquisition of partial Mössbauer spectra in selected energy regions using standard drivers and transducers. It can be fully operated by a remote application, thus data acquisition can be automated. The instrument consists of a programmable counter and a constant-velocity reference. The reference waveform generator is amplitude modulated with 13-bit resolution, and is programmable in a wide range of frequencies and waveforms in order to optimize the performance of the transducer. The counter is compatible with most standard SCA, and is configured as a rate-meter that provides counts per selectable time slice at the programmed velocity. As a demonstration of the instrument applications, a partial Mössbauer spectrum of a natural iron foil was taken. Only positive energies were studied in 512 channels, accumulating 20 s per channel. A line width of 0.20 mm/s was achieved, performing with an efficiency of 80%.     

Vinyl‐terminated side‐chain liquid‐crystalline polyethers containing mesogenic benzylideneaniline moieties

The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P₄ and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and ¹H and ¹³C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C₂ mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006     

Determination of N-nitrosamines by HPTLC with Fluorescence Detection — Use of Non-Ionic Surfactants as Enhancing Agents

JPC – Journal of Planar Chromatography – Modern TLC - The dansyl derivatives of N-nitrosodimethylamine, N-nitrosodi-ethylamine, and N-nitrosodibuthylamine have been separated by HPTLC...     

Application of preparative high-speed counter-current chromatography for the separation of flavonoids from the leaves of Byrsonima crassa Niedenzu (IK)

The methanolic extract of the leaves of the medicinal plant Byrsonima crassa (Malpighiaceae) contain flavonoids with antioxidant activity. They were separated in a preparative scale using high-speed counter-current chromatography. The optimum solvent system used was composed of a mixture of ethyl acetate-n-propanol-water (140:8:80 (v/v/v)) and led to a successful separation between monoglucosilated flavonoids (quercetin-3-O-alpha-L-arabinoside, quercetin-3-O-beta-D-galactoside) and the biflavonoid amentoflavone in only 3.5 h. The purities of quercetin-3-O-alpha-L-arabinoside (95 mg), quercetin-3-O-beta-D-galactoside (16 mg) and the biflavonoid amentoflavone (114 mg) were all isolated at purity over 95%. Identification was performed by 1H NMR, 13C NMR and UV analyses.