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A new derivative of racemic gossypol with 2-thiophenecarbohydrazide (GHHT) and its complexes with monovalent cations have been synthesized and studied by electrospray ionization-mass spectroscopy (ESI-MS), multinuclear nuclear magnetic resonance (NMR), as well as by the Parametric Method 5 (PM5) methods. It is demonstrated that GHHT forms stable complexes of 1:1 stoichiometry with monovalent metal cations. The structures of the complexes are stabilized by three types of intramolecular hydrogen bonds. The spectroscopic methods have provided clear evidence that GHHT and its complexes exist in the DMSO-d6 solution in the N-imine-N-imine tautomeric forms. The structures of the GHHT and its complexes with Li+, Na+, K+, Rb+, and Cs+ cations are visualized and discussed in detail., (Copyright (c) 2006 Wiley Periodicals, Inc.)

Monensin A is an ionophore able to carry protons and cations through the cell membrane. Its methyl ester (MON1) and its hydrates have been studied in acetonitrile, and its deuterated analogue by Fourier transform infrared (FTIR) and (1)H and (13)C NMR spectroscopies as well as by vapor pressure osmotic and PM5 semiempirical methods. Interestingly, these hydrates show new and unexpected biophysical and biochemical properties. The formation of the hydrates starts with a transfer of a proton from the O(IV)-H hydroxyl group of MON1 to an oxygen atom of a water molecule, which is subsequently hydrated by other water molecules forming the (MON1 + 3H(2)O) species. This hydrate exhibits a ringlike structure in which the water molecules form an almost linear hydrogen-bonded chain. Within this chain, the excess proton fluctuates very fast inside the water cluster as indicated by a continuous absorption in the FTIR spectra. The formation of the (MON1 + 3H(2)O) species is accompanied by a self-assembly process, leading to the formation of a proton channel made up of eight (MON1 + 3H(2)O) units with a length of 60 A, in which the proton can fluctuate over the whole distance. Semiempirical calculations suggest that due to the hydrophobic surface the channel can be incorporated readily in a lipid bilayer. This hypothetical new channel is thought to be able to transport protons through the cell membrane. Thus it is a suitable model for studying proton-transfer processes, and in addition, it may open interesting new fields of application.

A new Schiff base of gossypol with 5-methoxytryptamine (GSTR) and a new hydrazone of gossypol with dansylhydrazine (GHDH) have been synthesized and studied by Fourier transform infrared (FTIR), 1H and 13C nuclear magnetic resonance (NMR), ultraviolet-visible (UV-VIS), electrospray ionization-mass spectroscopy (ESI-MS) as well as the parametric method PM5. The spectroscopic methods have provided clear evidence that GSTR exists in chloroform solution as an enamine-enamine tautomer, whereas GHDH is present in chloroform as a N-imine-N-imine tautomer. The fluorescence spectra of both compounds indicate that their quantum yield of fluorescence is increased by one or two orders of magnitude compared to that of pure gossypol. The ESI-MS spectra of the 1:1 mixtures of GSTR or GHDH with formic acid have demonstrated that both compounds exist as protonated monomers in the gas phase, whereas GHDH can also exist in a stable protonated dimeric structure. The structures of the stable tautomers are calculated and visualized using the PM5 semiempirical method. The intra- and intermolecular hydrogen bonds within these structures are discussed., ((c) 2006 Wiley Periodicals, Inc.)

A new ester of Monensin A with ethylene glycol (MON2) has been synthesized by a new method and its ability to form complexes with Li+, Na+, and K+ cations has been studied by ESI MS, 1H and 13C NMR, FT-IR, and PM5 semiempirical methods. It is demonstrated that MON2 forms stable complexes of 1:1 stoichiometry with monovalent metal cations. The structures of the complexes are stabilized by intramolecular hydrogen bonds in which the OH groups are always involved. In the structure of MON2 the oxygen atom of the C=O ester group is involved in very weak bifurcated intramolecular hydrogen bonds with two hydroxyl groups, whereas in the complexes of MON2 with monovalent metal cations the C=O ester group is not engaged in any intramolecular hydrogen bonds. The structures of the MON2 and its complexes with Li+, Na+, and K+ cations are visualized and discussed in detail., ((c) 2006 Wiley Periodicals, Inc.)

A new Schiff base of gossypol with 3,6,9-trioxo-decylamine (GSTB) forms stable complexes with monovalent cations. This process of complex formation was studied by electrospray ionization mass spectrometry, (1)H-NMR and FTIR spectroscopy, and the PM5 (parametric method 5) semiempirical method. It is found that GSTB forms 1 : 1 and 1 : 2 complexes with Li(+) and Na(+) and 1 : 1 complexes with K(+), Rb(+), or Cs(+) cations and exists in all these complexes in the enamine-enamine tautomeric form. Moreover, within these complexes only Li(+) cations can fluctuate between the oxygen atoms of trioxo-alkyl chains. All other cations are strongly localized. In the complex of GSTB with two protons localized on the N atoms of the Schiff base, the imine-imine tautomeric form is realized. The complexes of the Schiff base with K(+), Rb(+), or Cs(+) cations are the 1 : 1 type with the oxygen atoms of the trioxo-alkyl chains, as well as the O(1)H or O(1')H group coordinating the cation. The structures of the complexes are calculated by the PM5 semiempirical method and discussed., (Copyright 2004 Wiley Periodicals, Inc.)

Three Schiff bases of racemic gossypol with L-amino acid methyl esters are synthesized and studied by FTIR and (1)H-NMR spectroscopy, and their structures are calculated by the PM3 semiempirical method. The Schiff bases in the study exist in the solid state and in solutions as enamine forms. The existence of diastereoisomers is very visible in the (1)H-NMR spectra. The amount of the diastereoisomers depends on the amount of time the solutions are rested in diffused light. The epimerization from D,L-isomer to L,L-isomer is very slow. The structures of the Schiff bases and the hydrogen bonds within these structures are discussed., (Copyright 2002 John Wiley & Sons, Inc.)