Solvent effect on the conformational behaviour of amino acid and oligopeptide derivatives

The solvent effect on acetyl amino acid methyl esters and C- and N-protected di- and tripeptide derivatives has been studied in deuterium oxide (D₂O), 1.1.1.3.3.3-hexafluoroisopropanol (HFiP), dimethyl sulfoxide (DMSO) and methylene chloride (CH₂Cl₂). The interpretation is based on the amide I region. For the amino acid derivatives the relative shift of the amide I signal clearly indicates the strength of the interaction with the solvent molecules. However, in HFiP and DMSO solutions the occurrence of two overlapping signals for the amide I and the ester carbonyl signal, respectively, indicates the existence of two major conformers. Knowing the solvent effects on the small amino acid esters allows the assignment of the signals in di- and tripeptide derivatives. Although the identification of turn structures in these flexible molecules is not possible, the band positions and intensity of the deconvoluted amide I region clearly shows that certain conformers can be stabilised. It can be concluded that the band profile in the amide I region is determined by the number of amino acid residues linked in the molecule, the bulkiness of the side chains and their sequence and to a major extend by the solvent properties.     

Determination of catechin and epicatechin in the peel of apple varieties resistant and non-resistant to apple scab

Catechin and epicatechin were analysed in the peel of six apple cultivars (three resistant and three non-resistant to apple scab). Two methods of analytical sample preparation following extraction were tested: solid phase extraction and column separation with Sephadex LH-20 coupled to a differential refractometric detector. Prior to GC and GC-MS analyses, these compounds were silylized. This permitted co-injection with standards and the comparison of retention values and mass spectra with those recorded for standards. The content of catechin and epicatechin in apple peel is discussed in relation to the resistance of apple trees to scab.     

Low-Temperature TLC-MS of Essential Oils from Five Different Sage (Salvia) Species

JPC – Journal of Planar Chromatography – Modern TLC - In a previous paper we discussed the possibility of fractionating the essential oils of different sage species by low-temperature...     

The effect of cholesterol on the adsorption of phenyltin compounds onto phosphatidylcholine and sphingomyelin liposome membranes

Organometallic compounds are widely spread in the human environment sometimes, causing a substantial health risk. Their amphiphilic character enables them to intercalate and penetrate cell membranes, potentially affecting various vital cell functions. Compound adsorption onto the membrane depends on the compound properties, as well as on the membrane composition and state. When adsorbing onto the lipidic surface, phenyltins localize at areas where lipid bilayer organization is compatible with compound spatial requirements. The lipid bilayer is a dynamic and laterally nonuniform structure with complex local and global architecture correlated with a variety of cell functions. The selective binding of a toxic compound to selected membrane areas may, therefore, interfere with some types of cellular process. We present experimental results concerning phenyltin adsorption onto the lipid bilayer surface measured with the fluorescent probe fluorescein‐PE. Model lipid bilayers were formed from lipid mixtures mimicking various plasma membrane regions. The adsorption of Ph₃SnCl and P₂SnCl₂ onto the phosphatidylcholine–cholesterol bilayer was qualitatively different from sphingomyelin–cholesterol. The results presented indicate that phenyltins are likely to accumulate in areas containing phosphatidylcholine, outside of lipid rafts. Copyright © 2004 John Wiley & Sons, Ltd.     

Microwave‐assisted synthesis,characterization, biotoxicity and antispermatogenic activity of some antimony(III) complexes with N∩O and N∩S donor ligands

New series of phenylantimony chloride and antimony chloride with Schiff base ligands, L¹H and L²H having N^∩S and N^∩O donor systems were synthesized under microwave irradiation using a domestic microwave oven. The reaction time was brought down from hours to a few seconds with improved yield as compared with conventional heating. All the ligands and their antimony(III) derivatives were characterized on the basis of microanalysis, elemental analyses, molecular weight determinations and spectral studies including IR, NMR (¹H and ¹³C) and electronic spectral studies. A distorted trigonal bipyramidal and pseudo‐octahedral geometry around the antimony atom was tentatively proposed for these derivatives. The compounds were screened in vitro against bacteria and fungi to test their antimicrobial property and in vivo in male albino rats to test their antifertility properties. The treatment with the ligands and their phenylantimony derivatives at dose levels of 20 mg per rat per day did not cause any significant change in body weight, but a significant reduction in the weights of reproductive organs was observed. Arrest of spermatogenesis was noted at various stages with production of primary spermatocytes (preleptotene and pachytene), secondary spermatocytes and step‐19 spermatids found to be decreased. Biochemical parameters of tissues, i.e. protein, sialic acid, cholesterol content of testes and seminal vesicular fructose also showed significant reduction. Further, the serum testosterone concentrations were also decreased after treatment with ligands and their antimony(III) derivatives. Copyright © 2008 John Wiley & Sons, Ltd.