Conformational flexibility of the 1,4-dihydropyridine ring in calcium channel agonists and antagonists molecules

Conformational flexibility of the 1,4-dihydropyridine ring in 4-aryl derivatives of the 2,6-dimethyl-3,5-dicarbmethoxy-1,4-dihydropyridine has been studied using the MM3 molecular mechanics method. Change of the C=C---C---C= endocyclic torsion angle of dihydrocycle in the range of 35° entails an increase of energy less than 1 kcal mol⁻¹. The energy levels below 99% of the molecular population for each molecule were estimated. The interval of the torsion angle change for these regions is about 60°.     

Direct Photocontrol of Peptidomimetics: An Alternative to Oxygen‐Dependent Photodynamic Cancer Therapy

Conventional photodynamic treatment strategies are based on the principle of activating molecular oxygen in situ by light, mediated by a photosensitizer, which leads to the generation of reactive oxygen species and thereby causes cell death. A diarylethene‐derived peptidomimetic is presented that is suitable for photodynamic cancer therapy without any involvement of oxygen. This light‐sensitive molecule is not a mediator but is itself the cytotoxic agent. As a derivative of the cyclic amphiphilic peptide gramicidin S, the peptidomimetic exists in two thermally stable photoforms that are interconvertible by light of different wavelengths. The isomer generated by visible light shows much stronger toxicity against tumor cells than the UV‐generated isomer. First in vivo applications are demonstrated on a tumor animal model to illustrate how the peptidomimetic can be administered in the less toxic form and then activated locally in a solid tumor by visible light.     

Design,Synthesis, and Application of an Optimized Monofluorinated Aliphatic Label for Peptide Studies by Solid‐State 19F NMR Spectroscopy

A conformationally restricted monofluorinated α‐amino acid, (3‐fluorobicyclo[1.1.1]pentyl)glycine (F‐Bpg), was designed as a label for the structural analysis of membrane‐bound peptides by solid‐state ¹⁹F NMR spectroscopy. The compound was synthesized and validated as a ¹⁹F label for replacing natural aliphatic α‐amino acids. Calculations suggested that F‐Bpg is similar to Leu/Ile in terms of size and lipophilicity. The ¹⁹F NMR label was incorporated into the membrane‐active antimicrobial peptide PGLa and provided information on the structure of the peptide in a lipid bilayer.     

Assessment of performance of the general purpose polarizable force field QMPFF3 in condensed phase

The recently introduced force field (FF) QMPFF3 is thoroughly validated in gas, liquid, and solid phases. For the first time, it is demonstrated that a physically well-grounded general purpose FF fitted exclusively to a comprehensive set of high level vacuum quantum mechanical data applied as it is to simulation of condensed phase provides high transferability for a wide range of chemical compounds. QMPFF3 demonstrates accuracy comparable with that of the FFs explicitly fitted to condensed phase data, but due to high transferability it is expected to be successful in simulating large molecular complexes.     

New antimony-capped iron(II) and cobalt(III) clathrochelate precursors of the polytopic hybrid cage complexes: Synthesis,X-ray structures and electrochemistry

Direct template macrocyclization of the three dimethylglyoxime molecules on the iron(II) ion and the capping of nonmacrocyclic K₃CoDm₃ tris-dimethylglyoximate with triethylantimony(V) derivatives led to the formation of triethylantimony-capped iron(II) and cobalt(III) clathrochelates. The complexes obtained have been characterized using elemental analysis, MALDI-TOF mass, IR, UV–Vis, ⁵⁷Fe Mössbauer and ¹H and ¹³C NMR spectroscopies, and X-ray crystallography. The influence of the nature of an encapsulated metal ion, the capping groups and the chelate fragments on a clathrochelate framework geometry is discussed. The cyclic voltammograms show oxidation and reduction waves assignable to Fe^2+/3+ and Co^2+/3+ couples of the encapsulated metal ion.     

A highly anisotropic cobalt(II)-based single-chain magnet: exploration of spin canting in an antiferromagnetic array

In this article we report for the first time experimental details concerning the synthesis and full characterization (including the single-crystal X-ray structure) of the spin-canted zigzag-chain compound [Co(H2L)(H2O)]infinity [L = 4-Me-C6H4-CH2N(CPO3H2)2], which contains antiferromagnetically coupled, highly magnetically anisotropic Co(II) ions with unquenched orbital angular momenta, and we also propose a new model to explain the single-chain magnet behavior of this compound. The model takes into account (1) the tetragonal crystal field and the spin-orbit interaction acting on each Co(II) ion, (2) the antiferromagnetic Heisenberg exchange between neighboring Co(II) ions, and (3) the tilting of the tetragonal axes of the neighboring Co units in the zigzag structure. We show that the tilting of the anisotropy axes gives rise to spin canting and consequently to a nonvanishing magnetization for the compound. In the case of a strong tetragonal field that stabilizes the orbital doublet of Co(II), the effective pseudo-spin-1/2 Hamiltonian describing the interaction between the Co ions in their ground Kramers doublet states is shown to be of the Ising type. An analytical expression for the static magnetic susceptibility of the infinite spin-canted chain is obtained. The model provides an excellent fit to the experimental data on both the static and dynamic magnetic properties of the chain.