Demixing of severely overlapped H-1 NMR resonances and interpretation of anomalous intensity pattern of dipolar coupled A(3) spins in a weakly aligning medium

We report a single C-13 spin edited selective proton-proton correlation experiment to decipher overcrowded 13C coupled proton NMR spectra of weakly dipolar coupled spin systems. The experiment unravels the masked C-13 satellites in proton spectrum and permits the measurement of one bond carbon-proton residual dipolar couplings in I3S and for each diastereotopic proton in I2S groups. It also provides all the possible homonuclear proton-proton residual couplings which are otherwise difficult to extract from the broad and featureless one dimensional H-1 spectrum, in addition to enantiodifferentiation in a chiral molecule. Employment of heteronuclear (C-13) decoupling in the evolution period results in complete demixing of overlapped signals from enantiomers. The observed anomalous intensity pattern in strongly dipolar coupled methyl protons in methyl selective correlation experiment has been interpreted using polarization operator formalism. (C) 2010 Elsevier Inc. All rights reserved.

An Investigation Of Alkali Aluminosilicate Glasses By Si-29 And Al-27 Magic-Angle-Spinning Nmr-Spectroscopy

Alkali aluminosilicate glasses prepared by the gel and the melt routes have been investigated by Si-29 and Al-27 MAS NMR spectroscopy. It is found that Al has a tetrahedral coordination in the gel glasses modified with equivalent proportions of alkalis unlike in a pure aluminosilicate glass where Al has both four and six coordinations. Silicon is present as Q4 units in all the 5M2O 5Al2O3 9OSiO2 ( M = Li, Na and K) gel glasses studied whereas it is present in Q2 or Q3 species in the lithium aluminosilicate glasses of compositions 40Li2O x Al2O3 (1-x)SiO2 (1 less-than-or-equal-to x less-than-or-equal-to 15) and xLi2O 10Al2O3 (1-x)SiO2 (20 less-than-or-equal-to x less-than-or-equal-to 40). The combination of Q2 and Q3 is also found in certain sodium aluminosilicate glasses, but they change to Q2 and Q1 as the concentration of SiO2 decreases.

1, 2-Bis (diphenylphosphino) etane bridged dinuclear copper (I) complexes: Investigations of solid state and solution structures by CP/MAS31P NMR spectroscopy, X-ray crystallography, IR spectroscopy and solution 31P NMR and 63Cu NMR spectroscopy

Three different complexes of copper (I) with bridging 1, 2-bis(diphenylphosphino)ethane (dppe), namely [Cu2 (mu-dppe) (CH3CN)6] (ClO4)2 (1), [Cu2 (mu-dppe)2 (CH3 CN)2] (ClO4)2 (2), and [Cu2 (mu-dppe) (dppe)2 (CH3CN)2] (ClO4)2 (3) have been prepared. The structure of [Cu2 (mu-dppe) (dPPe)2 (CH3CH)2] (ClO4)2 has been determined by X-ray crystallography. It crystallizes in the space group PT with a=12.984(6) angstrom, b=13.180(6) angstrom, c=14.001(3) angstrom, alpha=105.23(3), beta=105.60(2), gamma=112.53 (4), V=1944 (3) angstrom3, and Z=1. The structure was refined by least-squares method with R=0.0365; R(w)=0.0451 for 6321 reflections with F0 greater-than-or-equal-to 3 sigma (F0). The CP/MAS P-31 and IR spectra of the complexes have been analysed in the light of available crystallographic data. IR spectroscopy is particularly helpful in identifying the presence of chelating dppe. P-31 chemical shifts observed in solid state are very different from those observed in solution, and change significantly with slight changes in structure. In solution, complex 1 remains undissociated but complexes 2 and 3 undergo extensive dissociation. With a combination of room temperature H-1, Cu-63, and variable temperature P-31 NMR spectra, it is possible to understand the various processes occurring in solution.

A Simple Programmable 2-Pulse Generator for Pulsed NMR NQR Applications

Programmable pulse generator (PPG) circuits using programmable interval timer chips are normally based on a PC or a microprocessor. We describe here a simple low cost programmable two-pulse generator using Intel 8253s in a stand-alone mode, eliminating the need for a PC or a microprocessor, though our design also can be operated via a PC or a microprocessor.

Carbon-13 NMR studies of lipid mobilization pattern in germinating groundnut (Arachis hypogaea L.) seeds

The products of lipid mobilization in groundnut (Arachis hypogaea L.) seeds as a function of time immediately after imbibition are monitored by 13C NMR. Different parts of the embryonic axis, namely,the radicle, hypocotyl, and plumule, exhibit characteristic time dependent 13C NMR spectra observed at 24-h intervals after imbibition. The various stages in the transformation of storage lipids present in different parts of the embryonic axis are clearly demonstrated. The transformaton of storage lipids is completed first in the radicle followed by the hypocotyl and finally the plumule. A mechanism of the transformation of the storage lipids is discussed.

CD and NMR studies on the aggregation of amphotericin-B in solution

We report in this paper the aggregation properties of amphotericin-B (amp-B) in solution using CD and 1H-NMR techniques. Our results indicate that the preferred structure of amp-B in dimethylsulfoxide is a monomer at low concentrations (10−4M and below) and a stable dimer at higher concentrations (range 5 · 103 M to 10−2M). In a DMSO/ethanol mixture (1:1 (v/v)), the antibiotic is monomeric, irrespective of the concentration within the range studied. We propose a head-to-tail model based on NMR data. An understanding of the head-to-tail dimer, is, we believe important, particularly in view of the recent report wherein it is proposed that the drug inserts into bilayers as head-to-tail oligomers.

Chiral polyhydroxylated tetrahydrothiophene derivatives: novel synthesis and structural elucidation by X-ray crystallography, NMR spectroscopy and molecular mechanics calculations

The dideoxygenation reaction of 1,3;4,6-di-O-alkylidene-2,5-di-S-methylthiocarbonyl-D-mannitol derivatives under Barton-McCombie reaction conditions gave the hexahydrodipyranothiophenes 4 and 7 instead of the expected 2,5-dideoxy products. Structural and conformational information on these novel derivatives has been obtained by NMR spectroscopy, single-crystal X-ray crystallography and molecular mechanics calculations.

1H NMR Study of Molecular Motions and Phase Transitions in Methyl Ammonium Hexabromo Selenate [(CH3NH3)2SeBr6]

The temperature dependence of 1H spin-lattice relaxation time, T1, and that of the second moment, M2, are analysed in the temperature range 390 K to 77 K. A plot of T1 vs inverse temperature shows three phase transitions at 250 K, 167 K and 111 K. At 167 K, T1 displays a large jump while it shows changes in slope at 250 K and 111 K. In the high temperature phase (> 167 K), the correlated motion of CH3 and NH3 groups is found to cause the relaxation while their uncorrelated motion takes over in the low temperature phases (< 167 K). The unusual T1 behaviour in phase II (250 K-167 K) is ascribed to the small angle torsion of the cation. A constant M2 value of ∼ 9.7 G2, throughout the range of temperature studied, indicates the presence of reorientation of CH3 and NH3 groups.

High Pressure NMR Study of Ammonium Thiocyanate

Wide-line proton NMR spectra of ammonium thiocyanate have been recorded at 77 K as a function of external hydrostatic pressure. Contrary to expectations the line-width and the second moment decrease with the increase of pressure. This, however, is in accordance with the anomalous behaviour observed in other magnetic resonance studies of this compound and can be understood in terms of the change of electron density around the nitrogen atom of the SCN- group.

Investigation of the (PEG)xLiCl system using conductivity, DSC and NMR techniques

Electrolytes based on polyethylene glycol (PEG, mol.wt.8000) and LiCl of compositions, (PEG)(x)LiCl, x=4, 6, 8, 10, 12, 40, 60, where x is the O/Li ratio, were prepared by solution casting from methanol solutions. FTIR studies indicate that the ether oxygens of the polymer chain participate in Li+ ion conduction. The presence of a salt-polymer complex that melts around 190 degrees C was evidenced by DSC measurements for the electrolytes with compositions x<12. The highest conductivity was obtained at the composition x=10 which was attributed to the presence of a mostly amorphous compound. NMR measurements indicated two regions of motional narrowing, one attributable to the glass transition and another to translational diffusion.

Proton NMR study of molecular dynamics in ammonium tribromo stannate (NH4SnBr3)

The proton second moment M2 and spin-lattice relaxation time T1 have been measured in ammonium tribromo stannate (NH4SnBr3) in the temperature range 77–300 K, to determine the ammonium dynamics. The continuous wave signal is strong and narrow at 77 and 300 K but has revealed an interesting intensity anomaly between 210 and 125 K. T1 shows a maximum (13 s) around 220 K. No minimum in the T1 vs 1000/T plot was observed down to 77 K. M2 and T1 results are interpreted in terms of NH+4 ion dynamics. The activation energy Ea for NH+4 ion reorientation is estimated to be 1.4 kcal mol−1.

Pulsed NMR study of molecular motions and phase transitions in [N(CH3)4]PbX3 (X=Cl, Br, I)

Proton spin—lattice relaxation time (T1) is measured in [N(CH3)4]PbX3 (X=Cl, Br, I) from 300-77 K at 9.75 MHz. All the compounds show discontinuous changes in T1 values (at 256, 270 and 277 K, respectively), indicating phase transitions. Single T1 minimum is observed in all the cases and the T1 variation is explained in terms of [N(CH3)4] and CH3 group dynamics. The activation energy Eα decreases from chloride to iodide (from 4 to 2 kcal/mol). In bromide and iodide, T1 is found to decrease with increase in temperature at higher temperatures, indicating the presence of spin—rotation interaction.

Solvent-solute and solute-solute interactions from NMR in nematic phases

The use of NMR spectroscopy of molecules oriented in liquid-crystalline media to study solvent-solute and solute-solute interactions in π-systems such as benzene-chloroform and in charge transfer complexes, for example pyridineiodine, is illustrated. Changes in molecular order and chemical shifts as a result of complexation are employed in such studies. The extraordinary symmetry of C60 has also been investigated by using a mixture of liquid crystals of opposite diamagnetic anisotropies indicating, thereby, negligible solvent-solute/solute-solute interactions.

Quantification of enantiomeric excess by H-1-detected heteronuclear refocusing and homonuclear multiple quantum NMR experiments

The omega(1)-heterodecoupled-C-13-filtered proton detected NMR experiments are reported for the accurate quantification of enantiomeric excess in chiral molecules embedded in chiral liquid crystal. The differential values of both H-1-H-1 and C-13-H-1 dipolar couplings in the direct dimension and only H-1-H-1 dipolar couplings in the indirect dimension enable unraveling of overlapped enantiomeric peaks. The creation of unequal C-13-bound proton signal for each enantiomer in the INEPT block and non-uniform excitation of coherences in homonuclear multiple quantum experiments do not yield accurate quantification of enantiomeric excess. In circumventing these difficulties, a coupling dependent intensity correction factor has been invoked. (C) 2010 Elsevier B.V. All rights reserved.