Conformational Analysis of Sulfated α-(1→3)-Linked D-Galactobioses Using the Mm3 Force-Field

Abstract

The conformational maps of eight derivatives of the disaccharide α-D-Galp-(1→3)-β-D-Galp sulfated in different positions were obtained using the MM3 force-field specially parameterized for sulfate ester groups. As occurred with MM2, the conformational flexibility of the glycosidic linkage is only slightly hindered by sulfation. A substantial effect of sulfation of the β-D-galactose unit on position 4 shifts the global minimum to positive Ψ_H (C1′-O3-C3-H3) angles, while sulfation at position 2 of the same unit deepens the well at negative Ψ^H angles. On the other hand, sulfation on the α-D-galactose unit has a lesser effect, which in any case tends to stabilize the minimum at negative Ψ_H angles.     

Synthesis of pentabromopseudilin and other arylpyrrole derivatives via Heck arylations

Pentrabromopseudilin and other 2 and 3-arylpyrrole derivatives were synthesized through the Heck–Matsuda reaction involving endocyclic enecarbamates and N-protected 3-pyrrolines, respectively. The overall processes permitted an easy and efficient access to these structural motifs present in several bioactive compounds. Attempts to synthesize the compound isopentabromopseudilin led to a tribromo aryl maleimide. We hypothesize that this latter compound is the putative product arising from the unusual thermal instability of isopentabromopseudilin.     

Studies on crude oil‐water biphasic mixtures by low‐field NMR

Low‐field ¹H NMR was used in this work for the analysis of mixtures involving crude oils and water. CPMG experiments were performed to determine the transverse relaxation time (T₂) distribution curves, which were computed by the inverse Laplace transform of the echo decay data. The instrument's ability of quantifying water and petroleum in biphasic mixtures following different methodologies was tested. For mixtures between deionized water and petroleum, one achieved excellent results, with root mean squared error of cross‐validation (RMSECV) of 0.8% for a regression between the water content (wt %) and the relative area of the water peak in the T₂ distribution curve, or a standard deviation of 0.9% for the relationship between the water content and the relative water peak area, corrected by the relative hydrogen index of the crude. In the case of biphasic mixtures of Mn²⁺‐doped water and crude oils, the best result of RMSECV = 1.6% was achieved by using the raw magnetization decay data for a partial least squares regression. Copyright © 2012 John Wiley & Sons, Ltd.     

The prediction of the behaviour of Λ-hyperon electromagnetic form factors

The behaviour of the -hyperon electric and magnetic form factors is predicted within the modified three resonance ((783), (1020), (1680)) vector-meson dominance (VMD) model with correct analytic properties and the asymptotic behaviour predestinated by the quark model for baryons. The resonance couplings to are evaluated from the known couplings to nucleons by utilizing theSU(3) symmetry and normalization conditions for Dirac and Pauli form factors. The masses and widths of the considered vector mesons are fixed at the world averaged values. The optimal position of the effective inelastic threshold, common for Dirac and Pauli form factors, is determined from the fit of the only existing Orsay DM2 point on the cross section att=5·693 GeV². The mean square charge and magnetic radii of the -hyperon are found to be r _E ² =0·018 F² and r _M ² =–0·027 F², respectively.The authors are very much indebted to Prof. R. Baldini-Ferroli for calling their attention to the problem of -hyperon e.m. ff 's in connection with the FENICE experiment.     

Optically detected nuclear magnetic resonance at the sub-micron scale

Nuclear magnetic resonance is arguably one of the most powerful techniques available today to characterize diverse systems. However, the low sensitivity of the standard detection method constrains the applicability of this technique to samples having effective dimensions not less than a few microns. Here, we propose a novel scheme and device for the indirect detection of the nuclear spin signal at a submicroscopic scale. This approach--for which the name Dipolar Field Microscopy is suggested--is based on the manipulation of the long-range nuclear dipolar interaction created between the sample and a semiconductor tip located close to its surface. After a preparation interval, the local magnetization of the sample is used to modulate the nuclear magnetization in the semiconductor tip, which, in turn is determined by an optical inspection. Based on results previously reported, it is shown that, in principle, images and/or localized high-resolution spectra of the sample can be retrieved with spatial resolution proportional to the size of the tip.     

Two-dimensional high-resolution NMR spectra in matched B(0) and B(1) field gradients

In a recent publication we presented a method to obtain highly resolved NMR spectra in the presence of an inhomogeneous B(0) field with the help of a matched RF gradient. If RF gradient pulses are combined with "ideal" 90 degrees pulses to form inhomogeneous z rotation pulses, the line broadening caused by the B(0) gradient can be refocused, while the full chemical shift information is maintained. This approach is of potential use for NMR spectroscopy in an inhomogeneous magnetic field produced by an "ex-situ" surface spectrometer. In this contribution, we extend this method toward two-dimensional spectroscopy with high resolution in one or both dimensions. Line narrowing in the indirect dimension can be achieved by two types of nutation echoes, thus leading to depth-sensitive NMR spectra with full chemical shift information. If the nutation echo in the indirect dimension is combined with a stroboscopic acquisition using inhomogeneous z-rotation pulses, highly resolved two-dimensional correlation spectra can be obtained in matched field gradients. Finally, we demonstrate that an INEPT coherence transfer from proton to carbon spins is possible in inhomogeneous B(0) fields. Thus, it is possible to obtain one-dimensional (13)C NMR spectra with increased sensitivity and two-dimensional HETCOR spectra in the presence of B(0) gradients of 0.4 mT/cm. These schemes may be of some value for ex-situ NMR analysis of materials and biological systems.