F/Si distance determination in fluoride-containing octadecasil by Hartmann–Hahn cross-polarization under fast magic-angle spinning

¹⁹F/²⁹Si Hartmann–Hahn continuous wave cross-polarization (CP) has been applied under fast magic-angle spinning (MAS) to a powder sample of octadecasil. Strong oscillations occur during CP on a sideband matching condition between the isolated ²⁹Si–¹⁹F spin pairs formed by the silicons in the D4R units and the fluoride anions. The magnitude of the dipolar coupling constant was deduced directly from the line-splitting between the intense singularities of the Pake-like patterns obtained by Fourier transformation of the oscillatory polarization transfer. The corresponding Si–F internuclear distance, r=2.62±0.05 Å, is found to be in very good agreement with the X-ray crystal structure and the value of 2.69±0.04 Å recently reported from rotational echo double resonance (REDOR) and transferred echo double resonance (TEDOR) nuclear magnetic resonance (NMR) experiments. Furthermore, the CP technique is still reliable under fast MAS where both REDOR and TEDOR sequences suffer from severe artefacts due to finite pulse lengths. In octadecasil, a spinning frequency of 14 kHz is shown to be necessary for an effective suppression of ¹⁹F–¹⁹F spin diffusion. The influences of experimental missettings and radiofrequency (RF) field inhomogeneity are taken into account.     

Gauge Invariance of a Critical Number of Flavours in QED3

The fermion propagator in an arbitrary covariant gauge can be obtained from the Landau gauge result via a Landau–Khalatnikov–Fradkin transformation. This transformation can be written in a practically useful form in both configuration and momentum space. It is therefore possible to anticipate effects of a gauge transformation on the propagator’s analytic properties. These facts enable one to establish that if a critical number of flavours for chiral symmetry restoration and deconfinement exists in noncompact QED3, then its value is independent of the gauge parameter. This is explicated using simple forms for the fermion–photon vertex and the photon vacuum polarisation. The illustration highlights pitfalls that must be avoided in order to arrive at valid conclusions. Landau gauge is seen to be the covariant gauge in which the propagator avoids modification by a non-dynamical gauge-dependent exponential factor, whose presence can obscure truly observable features of the theory.     

The Incorporation of Indigo Molecules in Sepiolite Tunnels

Evidence for access of molecules the size of acetone or pyridine to the intracrystalline tunnels of nanofibre clay (sepiolite) has indicated formation of a new type of organic–inorganic nanocomposites. However, the introduction of larger molecules has been a recurring problem. It is now agreed that for indigo, the molecules are located on the external surface and at the ends of the fibres, thus blocking access to internal tunnels. We claim, however, that it is possible for indigo molecules to access the internal channels of sepiolite. FTIR and XRD analyses have provided evidence for folding of the sepiolite structure preheated at high temperature (above 350 °C). By comparison, we have shown that for indigo/sepiolite mixtures treated in the same conditions, no change in the crystalline structure of the sepiolite is observed, and that blue samples, related to Maya blue, with indigo molecules incorporated deeply enough into sepiolite to prevent folding of the tunnels, can be obtained. NMR, FTIR and thermal analysis confirm the interaction of indigo with the water coordinated to magnesium(II) and located inside the internal and external channels of sepiolite. Two other hypotheses are excluded; we show both that zeolitic water is not blocked in the tunnels by indigo, and that if thermal decomposition products of indigo can be formed, they are in a minority.     

High spin states in102Ag

High spin states are populated in¹⁰²Ag using the reaction¹⁶O+⁸⁹Y with projectile energies in the energy range 60–80 MeV. Gamma multipolarities are inferred from DCO ratios and coincidence relationships are established among the gamma rays assigned to¹⁰²Ag. A comprehensive level scheme is constructed with four band systems, two of positive parity and the other two of negative parity. The present study extended spins upto 19^– in the main negative parity band. A new band is populated in the present work and is similar to the one observed in¹⁰⁶Ag.The authors wish to thank and record their appreciation to Dr. S.K. Parthasaradhi, VECC, Calcutta for preparing the target used in this experiment. The authors gratefully acknowledge useful discussions with Dr. Rakhesh Popli. The authors record their grateful thanks to Prof. A.P. Patro and Prof. G.K. Mehta, former and present directors of the Nuclear Science Centre, for their interest in this work, helpful discussions and providing excellent facilities. The authors also thank Dr. S.K. Datta of the Nuclear Science Centre for his continued interest and helpful discussions and accelerator staff of N.S.C. for their efficient services in delivering the beam. Grateful thanks are also due to the University Grants Commission for providing financial support.     

Multistep synthesis of 2,5-diketopiperazines on different solid supports monitored by high resolution magic angle spinning NMR spectroscopy

The solid-phase synthesis of 2,5-diketopiperazines containing the trans-4-hydroxy-L-proline amino acid residue (Hyp) was performed on Ellman polystyrene, polyoxyethylene-polyoxypropylene (POEPOP), polystyrene-polyoxyethylene NovaSyn, and Wang resins, respectively. The reaction pathway allowed the introduction of different functional groups around the bicyclic scaffold in a combinatorial approach, and it generated mixtures of isomers. A detailed characterization of the single reaction steps by high resolution magic angle spinning (HRMAS) NMR spectroscopy was performed. The NMR spectral resolution of the resin-bound intermediates and final products was greatly influenced by the polymer matrix. The POEPOP resin permitted to obtain HRMAS NMR spectra with a resolution comparable with that of the spectra of the molecules in solution. Moreover, configurational and conformational isomers formed during the solid-phase reaction steps could be detected and easily assigned. Therefore, the combination of the HRMAS NMR technique with the use of nonaromatic resins may become an extremely powerful tool in solid-phase organic synthesis. This approach will allow the monitoring of multistep reactions and the conception of on-bead structural studies either on small molecules or on natural and/or synthetic oligomers.     

Highly efficient, enantioselective synthesis of (+)-grandisol from a C2-symmetric bis(alpha,beta-butenolide)

[reaction: see text] A new, very efficient, enantioselective synthesis of the sexual attracting insect pheromone (+)-grandisol has been developed, in which the key step is the double [2 + 2] photocycloaddition of ethylene to a bis(alpha,beta-butenolide) readily available from D-mannitol. The C2 symmetry of the substrate and the appropriate protection of the central diol unit are the crucial features for the high diastereofacial discrimination during the cycloaddition process.     

The influence of electron donor and electron acceptor groups on the electronic structure of the anti‐inflammatory tripeptide Cys‐Asn‐Ser

It has been discussed in the literature that electron delocalization along the peptide backbone and side chain modulates the physical and chemical features of peptides and proteins. The structure and properties of peptides are determined by their charge‐density distribution, such that the modification of its side chain plays an important role on its electronic structure and physicochemical properties. Research on Entamoeba histolytica soluble factors led to the identification of the pentapeptide Met‐Gln‐Cys‐Asn‐Ser, with anti‐inflammatory in vivo and in vitro effects. A synthetic pentapeptide, Met‐Pro‐Cys‐Asn‐Ser, maintained the same anti‐inflammatory actions in experimental assays. A previous theoretical study allowed proposing the Cys‐Asn‐Ser tripeptide (CNS tripeptide) as the pharmacophore group of both molecules. This theoretical hypothesis was recently confirmed experimentally. The objective of this work was to study the influence of the electron donor and electron withdrawing substituent groups on the electronic structure and physicochemical properties of the CNS tripeptide derivatives through a theoretical study at the density functional theory level of theory. Our results in deprotonation energies showed that the relative acidity of hydrogen atom (H2) of the serine‐amide group increases with the electron withdrawing groups. This result was confirmed by means of a study of bond order. The proton affinities illustrated that the electron donor groups favored the basicity of the amino group of the cysteine amino acid. Atomic charges, Frontier molecular orbitals (HOMO–LUMO), and electrostatic potential isosurface and its geometric parameters permitted to analyze the effect that provoked the electron donor and electron attractor groups on its electronic structure and physicochemical features and to identify some reactive sites that could be associated with the anti‐inflammatory activity of tripeptide CNS derivatives. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2398–2410, 2010     

Insertion of indigo molecules in the sepiolite structure as evidenced by 1H-29Si heteronuclear correlation spectroscopy

Despite the numerous studies of the famous indigo-based pigment Maya Blue, there are still many questions regarding the elucidation of its structure. Here, two-dimensional (2D) (1)H-(29)Si heteronuclear correlation (HETCOR) spectroscopy with frequency-switched Lee-Goldburg (FSLG) homonuclear decoupling is applied to sepiolite and sepiolite-indigo complexes. Owing to the high resolution in the (1)H dimension of the 2D (1)H-(29)Si HETCOR spectrum obtained by FSLG homonuclear decoupling, the assignment of the (29)Si cross-polarization magic-angle spinning (CPMAS) spectrum of sepiolite is clearly confirmed. Moreover, 2D (1)H-(29)Si FSLG-HETCOR spectroscopy gives the first direct evidence that some indigo molecules are inserted in the sepiolite structure whereas no interaction between indigo and the external side surface (silanol groups) is observed in the (29)Si CPMAS spectra. These results are consistent with the fact that indigo molecules interact with water coordinated to magnesium and suggest that Maya Blue made from sepiolite is not a surface complex.     

Spectral, structural and DFT studies of platinum group metal 3,6-bis(2-pyridyl)-4-phenylpyridazine complexes and their ligand bonding modes

Reactions of 3,6-bis(2-pyridyl)-4-phenylpyridazine (L^ph) with [(η⁶-arene)Ru(μ-Cl)Cl]₂ (arene = C₆H₆, p-ⁱPrC₆H₄Me and C₆Me₆), [(η⁵-C₅Me₅)M(μ-Cl)Cl]₂, (M = Rh and Ir) and [(η⁵-Cp)Ru(PPh₃)₂Cl] (Cp = C₅H₅, C₅Me₅ and C₉H₇) afford mononuclear complexes of the type [(η⁶-arene)Ru(L^ph)Cl]PF₆, [(η⁵-C₅Me₅)M(L^ph)Cl]PF₆ and [(Cp)Ru(L^ph)(PPh₃)]PF₆ with different structural motifs depending on the π-acidity of the ligand, electronic properties of the central metal atom and nature of the co-ligands. Complexes [(η⁶-C₆H₆)Ru(L^ph)Cl]PF₆1, [(η⁶-p-ⁱPrC₆H₄Me)Ru(L^ph)Cl]PF₆2, [(η⁵-C₅Me₅)Ir(L^ph)Cl]PF₆5, [(η⁵-Cp)Ru(PPh₃)(L^ph)]PF₆, (Cp = C₅H₅, 6; C₅Me₅, 7; C₉H₇, 8) show the type-A binding mode (see text), while complexes [(η⁶-C₆Me₆)Ru(L^ph)Cl]PF₆3 and [(η⁵-C₅Me₅)Rh(L^ph)Cl]PF₆4 show the type-B binding mode (see text). These differences reflect the more electron-rich character of the [(η⁶-C₆Me₆)Ru(μ-Cl)Cl]₂ and [(η⁵-C₅Me₅)Rh(μ-Cl)Cl]₂ complexes compared to the other starting precursor complexes. Binding modes of the ligand L^ph are determined by ¹H NMR spectroscopy, single-crystal X-ray analysis as well as evidence obtained from the solid-state structures and corroborated by density functional theory calculations. From the systems studied here, it is concluded that the electron density on the central metal atom of these complexes plays an important role in deciding the ligand binding sites.     

Application of Rotor-Synchronized Amplitude-Modulated Cross-Polarization in aC–H Spin Pair under Fast Magic-Angle Spinning

Rotor-synchronized amplitude-modulated Hartmann–Hahn cross-polarization has been applied under fast magic-angle spinning to a powder sample of ferrocene. The influence on the cross-polarization process of the heteronuclear double quantum (flop–flop) transitions induced by the amplitude modulation for low ratios of the radiofrequency-field strength to the spinning speed is studied in details. The experimental data are in good agreement with theoretical calculations for a two-spinsystem, although the intensity of the double quantum transitions is observed to be significantly smaller than expected. Moreover, it is shown that an efficient polarization transfer at the Hartmann–Hahn centerband matching condition as well as a broadening of the matching conditions is obtained by an appropriate partial scaling of the effective radiofrequency fields which minimizes the destructive effect of double quantum cross-polarization.