Comparison of 17beta-estradiol structures from x-ray diffraction and solution NMR

The NMR-derived structure of estrogen (17beta-estradiol, E2), the drug of choice for postmenopausal women, was compared with a recent literature crystal x-ray structure of Fab-bound E2. 1H and 13C NMR spectra of E2 were acquired in DMSO-d6. Assignments were obtained from an analysis of DQF-COSY, TOCSY, HETCOR, HMQC and HMBC 2D NMR spectra. The 1H and 13C NMR assignments are the first reported for E2 in DMSO-d6. Two solution structures, S1 and S2, were obtained with molecular modeling using NOE constraints. S1 overlaps with the crystal structure for all rings. S2 shows prominent differences in the C-ring (C9--C11--C12--C13) segment, which deviates from a chair conformation, and excellent overlap in the A-, B- and D-rings of E2. The C-ring in S2 adopts a boat conformation as opposed to a chair conformation in the x-ray and S1 structures. The S2 structure is about 6 degrees more twisted than the bound x-ray and S1 models. The S1, S2 and x-ray structures had ring bowing values of 10.1 +/- 0.3, 11 +/- 1 and 10.37 degrees , respectively. Of the 100 solution conformers generated, 83 had S1 conformation and 17 had S2 conformation, with average internal energies of 112 +/- 2 and 141 +/- 2 kcal mol(-1), respectively. The 100 S1- and S2- derived conformers showed a r.m.s.d. of 0.72 A for all atoms. The x-ray, S1 and S2 C18--O17 distances were 2.93, 2.92 +/- 0.01 and 2.93 +/- 0.01 A, respectively, and the O3--O17 distances were 11.06, 11.18 +/- 0.12, and 10.89 +/- 0.05 A, respectively.     

Supramolecular hydrogels and organogels based on novel l-valine and l-isoleucine amphiphiles

New low-molecular-weight gelators based on l-valine and l-isoleucine gelators, which have a positively charged terminal group, can gel not only pure water and aqueous solutions containing inorganic acids and salts but also some organic solvents and oils.     

Acid-catalyzed reaction of pyrazolo[1,5-a]pyridines with aldehydes: Formation of bis(pyrazolo[1,5-a]pyrid-3-yl)methane

Reaction of pyrazolo[1,5-a]pyridines with aldehydes in the presence of trifluoroacetic acid gave bis[pyrazolo[1,5-a]pyrid-3-yl)methanes in high yields.     

Comparison of the phytoestrogen trans-resveratrol (3,4',5-trihydroxystilbene) structures from x-ray diffraction and solution NMR

The NMR-derived solution structure of trans-3,4',5-trihydroxystilbene (resveratrol) was compared with two recent literature crystal x-ray structures, resveratrol in complex with human transthyretin (TTR-RES) from 1DVS.pdb and resveratrol bound to chalcone synthase (CHS-RES) from 1CGZ.pdb. 1H and 13C NMR spectra of resveratrol were acquired in DMSO-d6. Assignments were obtained from an analysis of DQF-COSY, TOCSY, DEPT, HMQC/HSQC, HMBC and INADEQUATE NMR spectra. Past 1H and 13C NMR literature assignments are corrected. The dihedral angle 2-1-1'-2' provides an indication of the relative spatial orientation of the two phenolic rings. Values of 1.62, - 54.10 and 12.6 +/- 1.1 degrees were found for the 1DVS.pdb, 1CGZ.pdb and NMR resveratrol structures, respectively. The 1DVS.pdb resveratrol structure is 'flat' with the two phenolic rings along the same plane. The 1CGZ.pdb structure has these two rings almost orthogonal to each other, and the NMR structure has these two rings much closer to being along the same plane. The angles 1-alpha--alpha' and 1'-alpha'--alpha are along the same trace and of similar magnitude for the 1CGZ.pdb and NMR resveratrol structures. For the 1DVS.pdb resveratrol structure, these angles are about 7-10 degrees greater, with alpha and alpha' being 180 degrees out-of-phase from the other two structures. The alpha rings did not overlap, with the NMR result representing a 'median model' of the two x-ray structures.     

Relative nullity distributions, an affine immersion from an almost product manifold and a para-pluriharmonic isometric immersion

We give a characterization for an affine immersion from an almost product manifold the almost product structure of which is adjoint or skew-adjoint with respect to its affine fundamental form by the relative nullity distribution.     

Study by XPS of the chlorination of proteins aggregated onto tin dioxide during electrochemical production of hypochlorous acid

In solution, hypochlorous acid (HOCl) reacts with organic matter and notably with protein side-chains. In this study, HOCl was produced by an electrochemical way, by oxidation of chloride ions at a transparent tin dioxide electrode in the presence of a protein, the bovine serum albumin (BSA). A thick irregular layer is formed at the electrode when HOCl is produced at the SnO₂ surface. Indeed, SEM analyses show that an important deposit is formed during the anodic polarization of SnO₂ in the presence of chloride ions and proteins. Actually, two phenomena take place on the one hand the chlorination of the proteins due to the reaction of HOCl with some protein side-chains and on the other hand the aggregation of proteins onto the SnO₂ surface. The present X-ray photoelectron spectroscopy study points out the cross-linking of BSA molecules via formation of inter molecular sulfonamide groups. It also shows that the BSA chlorination is due on the one hand to the formation of sulfonyl chloride groups (-SO₂Cl) and on the other hand to formation of chloramine groups (N-Cl). The Cl2p and S2p photo-peak intensities allowed us to quantify the chloramines. It is found that, one BSA entity immobilized onto the SnO₂ surface contains about 50 chloramine groups.     

Light attenuation in a semitransparent foam sheet-Thickness measurement for industrial use

An optical method for measuring the thickness of heterogeneous materials has been studied. The method is based on the light attenuation theory. A complete system has been constructed in order to demonstrate the applicability of the present method for industrial use. The experimental set-up consists of semiconductor lasers, focusing lenses, photo-diodes serving as a power meter and a personal computer with an A/D converter for data acquisition. Averaging of numerous measurements is required in the present method because the heterogeneous cell structure of the foam material yields large fluctuations in transmitted light levels. The fluctuations can be reduced to below 1% of the transmitted light power by 80 times averaging. The error of the measurement is considered to be a few tens of micrometers in thickness. The present system is capable of sampling data at a rate of 400 Hz and has been successfully applied to a manufacturing process.