Orientation Of Hydroxy Group Research Articles

Влияние структуры стероидной молекулы на направление гидроксилирования грибомCurvularia lunata

The main and side products of hydroxylation by the C. lunata VKPM F-981 mycelium of fourteen delta(4)-3-ketosteroids of the estrane, androstane, and pregnane series and six of their delta(5)-3beta-hydroxy analogues were identified by H1 PMR spectroscopy and comparison with standard samples. The obtained experimental data are considered in terms of the triangular model of the enzyme-substrate interaction. The dependence of the direction of hydroxylation of steroid molecules and the orientation of hydroxy groups on the structure of the initial substrate was revealed.

Fast chromatographic determination of the bile salt critical micellar concentration

In a line of research focused on the design, synthesis and development of new bile acid-based compounds, the physico-chemical profile of the molecules must be thoroughly explored and analyzed. In this scenario, a fast and reliable information on the critical micellar concentration (CMC) of specific compounds through a profitable chromatographic parameter can be of aid to rationally direct the synthesis of new molecular entities, mainly during the early stages of the drug-discovery process. The derived 'chromatographic hydrophobicity index' (CHI), usually employed for a fast access to the log P/log D value of physico-chemically diverse compounds and obtained via RP-gradient elution, was for the first time engaged in the bile acid field. Accordingly, 14 unconjugated bile acids harboured with a different number, position and orientation of hydroxy groups, as well as other substituents onto the steroidal backbone and side chain, were selected to build up a calibration curve. Such a collection of compounds was rationally assembled in order to manage an almost continuous range of CMC values (spanning the spectrophotometrically obtained CMCs between 5 and 25 mM). A high degree of correlation between CMC and CHI values was obtained (R(2) and cross-validated R(xv)(2) of the pCMC vs CHI plot equal to 0.975 and 0.966, respectively). A selected new subset of five confidential research bile acids with experimental CMCs in the range 6-19 mM was finally recruited to validate the proposed method. The high statistical quality of the established mathematical model turned out into a very appreciable predictive power.

Inclusion complexes of β-cyclodextrin with dihydroxyphenols of various nature

The ways for the practical preparation of stable inclusion complexes of β-cyclodextrin with dihydroxyphenols of various nature are developed. Mutual orientation of hydroxy groups and the nature of the bridge in the bisphenols are shown to affect considerably their ability to the complex formation.

A study on the influence of bile acid chemical structure on dissolution of insoluble calcium salts: Anin vitro study of the use of bile acid-phosphatidylcholine-cholesterol model bile solution

The influence of bile acid chemical structure on dissolution of insoluble calcium salts and the reducing effect of ionized calcium was studied. Various bile acids were used to compound model bile acid-phosphatidylcholine-cholesterol model bile solutions. After CaCO3 was added to these solutions, both total calcium solubility and ionized calcium concentration in the solutions were measured. Dihydroxy bile acid is more effective than trihydroxy bile acid and 7 alpha-hydroxy bile acid is more effective than 7 beta-hydroxy bile acid, with regard to calcium solubility and the reducing effect of ionized calcium in model bile solution. Glutamic or asparaginic acid conjugates are more effective than glycine or taurine conjugates. Therefore, calcium solubility and the reducing effect of ionized calcium in model bile solutions are dependent on the number and orientation of hydroxy groups on the steroid nucleus as well as electrical charge of conjugating amino acid of bile acid. Chenodeoxycholic acid conjugated with glutamic or asparginic acid possesses high calcium solubility and large binding capacity with ionized calcium.

A rapid method for the structural characterization of sulphated phlorotannins by negative ion fast atom bombardment mass spectrometry and acetylation on the target

A method for a rapid and direct structural determination of sulphated phlorotannins has been developed by using a combination of negative ion fast atom bombardment mass spectrometry and acetylation on the target. The structural variations of sulphated phlorotannins include: (i) the number of monomeric phloroglucinol units involved; (ii) the mode of their connectivity; (iii) the orientation of hydroxy groups on aromatic carbon atoms; (iv) the presence of the substituents other than hydroxy groups on aromatic carbon atoms; and (v) the number of sulphate esters on the hydroxy groups. Additionally, the acidic protons on the sulphate groups can be easily substituted by sodium or potassium cations, depending on the mode of isolation. In the negative ion mode, several ions were observed and a determination of molecular size and molecular parameters (i)–(v) appeared to be rather speculative. After adding diluted hydrochloric acid to the sample in order to substitute alkali ions for protons, the hydrolysis of sulphate groups has been observed. The acetylation on the target, however, represents a rapid method to observe the molecular ions, and from the mass differences the molecular parameters can be easily calculated. This procedure also demonstrates the general possibility of studying rapid chemical reactions by fast atom bombardment mass spectrometry.