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.

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.

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.

NDDO-based CI methods for the prediction of electronic spectra and sum-over-states molecular hyperpolarization

NDDO-based (AM1) configuration interaction (CI) calculations have been used to calculate the wavelength and oscillator strengths of electronic absorptions in organic molecules and the results used in a sum-over-states treatment to calculate second-order-hyperpolarizabilities. The results for both spectra and hyperpolarizabilities are of acceptable quality as long as a suitable CI-expansion is used. We have found that using an active space of eight electrons in eight orbitals and including all single and pair-double excitations in the CI leads to results that agree well with experiment and that do not change significantly with increasing active space for most organic molecules. Calculated second-order hyperpolarizabilities using this type of CI within a sum-over-states calculation appear to be of useful accuracy.

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.

Synthesis, spectral characterisation and single-crystal structure of a bicyclic tetraphosphapentazane tetraoxide, N5P4ET5O4(OC6H3Me2-2,6)2

Reaction of the bicyclic phosphazane N5P4Et5Cl2 with 2,6-dimethylphenol and subsequent oxidation of the product by aqueous hydrogen peroxide yields N5P4Et5O4(OC6H3Me2-2,6)2 in 85% yield. Its structure has been established by NMR spectroscopy and single-crystal X-ray diffraction. The compound crystallises in the monoclinic space group C2/c with a= 21.245(5), b= 10.879(2), c= 16.450(6)Å, ?= 123.94(2)°, Z= 4, R= 0.066. The structural features are compared with those of bicyclic ?5-phosphazenes of type N5P4R3(NR1R2)5(NHR3)(R1,R3= Me or Et, R2= H or Me). The observed conformation of the N3P3 rings in the present compound is mainly dictated by the maximisation of the stabilising influence of �negative hyperconjugative interactions� between the nitrogen lone pairs and the adjacent P�X ?* orbitals.

Synthesis, structure and redox properties of (?-oxo)bis(?-carboxylato)diruthenium(III) complexes containing three different terminal ligands

Blue coloured, unstable, essentially diamagnetic and non-electrolytic diruthenium(III) complexes of the formation [Ru2O(O2CR)4(en)2(PPh3)2] were prepared by reacting [Ru2O(O2CR)4(PPh3)2] with 1,2-diaminoethane (en) in CH2Cl2 (R = C6H4-p-X; X = H, Me and OMe). The molecular structure of the complexes is proposed as [{(?1-O2CR)(?1-en)(PPH3)Ru}2(?-O)(?-O2CR)2] based on the 1H NMR spectral data. The electronic spectra of the complexes display a band near 569 nm with a shoulder at 630 nm. In CH2Cl2-0.1 M [Bun4N]ClO4, the complexes exhibit redox couples Ru2III,III/Ru2III,IV and Ru2III,IV/Ru2IV,IV near 0.1 and 1.2 V (vs SCE), respectively. The potentials are the lowest among diruthenium(III) complexes with a similar core structure.

Amino acid selective unlabeling for sequence specific resonance assignments in proteins

Sequence specific resonance assignment constitutes an important step towards high-resolution structure determination of proteins by NMR and is aided by selective identification and assignment of amino acid types. The traditional approach to selective labeling yields only the chemical shifts of the particular amino acid being selected and does not help in establishing a link between adjacent residues along the polypeptide chain, which is important for sequential assignments. An alternative approach is the method of amino acid selective `unlabeling' or reverse labeling, which involves selective unlabeling of specific amino acid types against a uniformly C-13/N-15 labeled background. Based on this method, we present a novel approach for sequential assignments in proteins. The method involves a new NMR experiment named, {(CO)-C-12 (i) -N-15 (i+1)}-filtered HSQC, which aids in linking the H-1(N)/N-15 resonances of the selectively unlabeled residue, i, and its C-terminal neighbor, i + 1, in HN-detected double and triple resonance spectra. This leads to the assignment of a tri-peptide segment from the knowledge of the amino acid types of residues: i - 1, i and i + 1, thereby speeding up the sequential assignment process. The method has the advantage of being relatively inexpensive, applicable to H-2 labeled protein and can be coupled with cell-free synthesis and/or automated assignment approaches. A detailed survey involving unlabeling of different amino acid types individually or in pairs reveals that the proposed approach is also robust to misincorporation of N-14 at undesired sites. Taken together, this study represents the first application of selective unlabeling for sequence specific resonance assignments and opens up new avenues to using this methodology in protein structural studies.

1H NMR study of molecular dynamics and phase transition in (NH4)2ZnBr4

The proton second moment (M2) and spin-lattice relaxation time (T1) have been measured in (NH4)2ZnBr4 in the range 77-300 K. The room-temperature spectrum shows a structure which disappears around 243 K. The signal is strong and narrow even at 77 K. Proton T1 shows a maximum at 263 K, caused by spin rotation interaction and decreases with decreasing temperature till 235 K, where it shows a sudden increase. Below 235 K, again it decreases and shows a slope change around 216.5 K (reported Tc). From 216.5 K, T1 decreases continuously without exhibiting any minimum down to 77 K. The narrow line at 77 K, and absence of a T1 minimum down to 77 K indicate the possibility of quantum mechanical tunnelling in this system. Motional parameters such as activation energy and pre-exponential factor have been evaluated for the reorientational motion of the NH+4 ion.

Conformation of polymerizable diacetylenic lecithin, DC8,9PC, by 1H-NMR spectroscopy

Diacetylenic phospholipid, 1,2 bis-(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine (DC8,9PC), forms helices and tubules in addition to liposomes. The diacetylenic moiety responsible for the transformation is probed by 2-D NMR correlated spectroscopy. Chemical shift assignments and the analysis of 2D-COSY measurements were done on the lipid in chloroform-d solution. Based on this analysis, a model for the lipid is proposed. The geometry of the headgroup, glycerol backbone and acyl chains up to three methylenes from glycerol backbone [-(CH2)(3)-] is similar to that of dipalmitoyl phosphatidylcholine. The estimated torsional angle for methylene groups adjacent to diacetylenic moieties suggested an overall tilt of the diacetylenic lipid molecule from the bilayer axis of 25-30 degrees. This tilt could be negative or positive depending on the handedness of the resultant microstructures.