The synthesis of piperidine nucleoside analogs—a comparison of several methods to access the introduction of nucleobases

This work deals with the synthesis of piperidine and hydroxypiperidine analogs of nucleosides. Starting from commercially available 3-hydroxypiperidine, proline or 4-hydroxyproline, a series of piperidine derivatives of both purine and pyrimidine nucleobases was prepared. Various methods of nucleobase attachment were evaluated. The prepared compounds were tested for cytostatic, antibacterial, and antiviral properties but no significant activity was found.     

Intriguing Differences in the Gas-Phase Dissociation Behavior of Protonated and Deprotonated Gonyautoxin Epimers

The aim of this study was to investigate the unusual gas-phase dissociation behavior of two epimer pairs of protonated gonyautoxins (GTX) following electrospray ionization in comparison to their deprotonated counterparts. The chemical structures of the investigated GTX1-4 variants vary in their substitution pattern at N-1 and the stereochemical orientation of the hydroxysulfate group at C-11 (11α for GTX1/2 versus 11β for GTX3/4). The direct comparison of mass spectra in positive and negative ion modes illustrated two distinct features: first, an intriguing difference between protonated 11α and 11β species, where 11α conformations exhibited almost complete dissociation of [M + H]⁺ ions via facile SO₃ elimination, while 11β species remained mostly intact as [M + H]⁺; and second, the lack of such differences for the deprotonated counterparts. In this study, we propose an acid-catalyzed elimination mechanism from density functional theory calculations, initiated by a proton transfer of a guanidinium proton to the hydroxysulfate group with simultaneous SO₃ release, which is only possible for the 11α conformation based on intramolecular distances. The same mechanism explains the lack of a comparable SO₃ loss in the negative ion mode. CID experiments supported this proposed mechanism for GTX1 and GTX2. Computational modeling of product ions seen in the CID spectra of GTX3 and GTX4 established that the lowest energy dissociation pathway for the 11β epimers is elimination of water with the possibility for further SO₃ release from the intermediate product. Experimental data for structurally analogous decarbamoyl gonyautoxins confirmed the evidence for the GTX compounds as well as the proposed elimination mechanisms.     

Absorption properties of commercial lead chromates

For the cyanide determination in waste waters containing more than 2.5×10^?6 Mol of CN^?/l a conductometric method has been proposed. The sulphuric acid containing samples were distilled and the obtained HCN was passed into a 5×10^?4 Mol/l AgNO₃ solution, of which the conductivity was measured. The method offers the possibility of a precise observation of the completion of the HCN distillation and also the direct measurement of the cyanide concentration by the change of conductivity. The analysis time is about 40 min.     

Homoclinic orbits in the dynamics of resonantly driven coupled pendula

We present a plethora of homoclinic and heteroclinic orbits that exist in the phase space of a weakly nonlinear model describing small oscillations of two resonantly driven coupled pendula. These orbits connect equilibria in a resonance band, which is contained in an invariant plane, and is born under perturbation out of a circle of equilibria. Their existence is shown by using a combination of the Melnikov method and singular perturbation techniques.     

On a quadrature formula of Micchelli and Rivlin

Micchelli and Rivlin (1972) obtained a quadrature formula of highest algebraic degree of precision for the Fourier-Chebyshev coefficients A_n(f), which is based on the divided differences of f′ at the zeros of the Chebyshev polynomial T_n(x). We give here a simple approach to questions of this type, which applies to the coefficients in arbitrary orthogonal expansion of f. As an auxiliary result we obtain a new interpolation formula and a new representation of the Turán quadrature formula.     

Indazoles in organic synthesis: Formation of some fused heterocycles

Derivatives of pyrimido(1,2-b)indazole and s-triazino(1,2-b)indazole were prepared by several different routes and some transformations are described.