Some salts of bile acids increase the size of their micellar aggregates in aqueous solutions by varying parameters such as pH or ionic strength and give rise to transitions: aqueous micellar solution --> gel --> fiber --> crystal. Helical fibers of sodium and rubidium salts of glycodeoxycholic and taurodeoxycholic acids (NaGDC, RbGDC, NaTDC, and RbTDC, respectively) were drawn from aqueous solutions and investigated by means of X-ray diffraction analysis to clarify the structure of their micellar aggregates and to verify whether the micellar structures of the sodium and rubidium salts were similar. In this case, the rubidium salts can be studied in place of the sodium ones by extended X-ray absorption fine structure spectroscopy. The X-ray patterns of the NaGDC, RbGDC, NaTDC, and RbTDC fibers showed a close resemblance and were interpreted by means of very similar unit cell parameters and helical structures, formed by trimers arranged in 7/1 helices. Calculations of interatomic distances provided a model of the 7/1 helix which satisfactorily packs into the unit cells of the fibers. Quasi-elastic light-scattering measurements carried out on aqueous micellar solutions up to a concentration of NaCl or RbCl of about 0.3 M supported the similarity among the structures of the NaGDC, RbGDC, NaTDC, and RbTDC micellar aggregates. Oligomers of small size were observed without NaCl or RbCl. The extent of micellar growth increased upon increasing NaCl or RbCl concentration. The micellar size, which seemed to be dependent on the peculiar cation-anion Coulombic interaction starting from a NaCl or RbCl concentration of about 0.2 M, was in the following order: NaGDC > NaTDC approximate to RbTDC > RbGDC. Electromotive force measurements accomplished on NaTDC solutions at constant ionic medium provided the distribution of micellar sizes. Most of the aggregates have aggregation numbers that are a multiple of 3. The fraction of bound Na+ ions is high in accordance with an ordered structure like that of the 7/1 helix. Further support for the 7/1 helix came from the calculation of mean hydrodynamic radii using the helical model. The agreement with quasi-elastic light-scattering measurements at low bile salt concentration and within a wide range of ionic strength was satisfactory. The helical structure of the anions seems to be similar in the micellar aggregates of NaGDC, RbGDC, NaTDC, RbTDC, and tetramethylammonium taurodeoxycholate

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Sodium glycocholate (NaGC) and taurocholate (NaTC) have been studied by means of X-ray and circular dichroism (CD) measurements, using bilirubin-lXa (BR) as probe molecule, together with potential-energy calculations. Helical models for the micellar aggregates of NaGC and NaTC were inferred from crystal structures solved by X-ray analysis. Since it is known that chiral molecules, micellar aggregates and macromolecules select preferentially or exclusively one of the two enantiomeric conformers of BR, CD spectra of BR in submicellar and micellar aqueous solutions of NaGC and NaTC were recorded as a function of pH and BR concentration in order to verify these helical models and the enantioselective ability of the bile salt monomers and micellar aggregates. Potential-energy calculations supported the CD experimental results and provided reasonable bile salt-BR interaction models. The behaviour of NaGC and NaTC is compared with that of sodium deoxycholate (NaDC), previously studied. The CD spectra of the bile salt-BR systems seem to allow characterisation of the typical structure of the bile salt micellar aggregates.

supported on alumina. The appearance of all of the products and the disappearance of one of the reactants (OH-) can be simultaneously followed by FTIR.RhC13 has been shown to react with surface O H groups on alumina at 180 "C. The product of this reaction is believed to be Rh3+ bonded to a surface oxygen on alumina. This species is an intermediate in the room-temperature oxidation of CO listed above.Removal of the surface O H groups by reaction with RhC1, dramatically suppresses the reaction of COz with alumina.Acknowledgment. This work has been funded in part by the Office of Naval Research, and the University of Richmond Faculty Research Committee. We thank Dr. John Yates for his helpful comments and for his assistance in designing the experimental setup and Hampton Rexrode for his work on the apparatus construction. Previously a helical model was satisfactorily verified for sodium (NaDC) and rubidium (RbDC) deoxycholate micelles in aqueous solutions by means of SAXS, EXAFS, NMR, ESR, and CD measurements. Here we report the beginning of an analogous study carried out on sodium glycodeoxycholate (NaGDC) and taurodeoxycholate (NaTDC) following the strategy applied to NaDC and RbDC. The crystal structure of NaGDC sesquihydrate, solved by X-ray analysis, provides again a helical model that is compared with those of NaDC, RbDC, and NaTDC. Since it was previously observed that bilirubin-IXa (BR) exhibits a bisignate CD Cotton effect in NaDC aqueous solutions, and it was suggested that the chiral micelles of NaDC interact preferentially or exclusively with one of the two enantiomeric conformers of BR, we have recorded CD spectra of BR in aqueous micellar solutions of the bile salts in order to check the helical models. The spectra show in all cases two large and proximate bands of opposite sign between 400 and 500 nm, which support both our chiral models and the selection of the BR left-handed enantiomer. Moreover, we have accomplished van der Waals energy calculations for the system formed by a NaGDC helix and the left-or right-handed BR molecule to test if the interaction energy is lower for one of the two BR enantiomeric conformers. The results of the calculations seem to indicate that the NaGDC helix binds preferentially the BR molecule with left-handed chirality. Interaction models are proposed. IntroductionStudies carried out on sodium and rubidium deoxycholate (NaDC and RbDC, respectively) following a strategy previously reported' showed that a helical model, observed in the crystal structures of NaDC and RbDC,2v3 describes very satisfactorily the behavior of their micellar aggregates in aqueous solutions.'*e7 The helical structure of the NaDC and RbDC micelles was verified unambiguously by nuclear magnetic resonan~e,'.~ circular dichroism! electron spin resonance! small-angle X-ray scattering,6 and extended X-ray absorption fine structure7 measurements.Subsequently, the investigation of the structure of the sodium taurodeoxycholate (NaTDC) micellar aggregates was undert a k e~? +~ and other helical models were...

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