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1.
Mithu VS Paul S Kurur ND Madhu PK 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2011,209(2):359-363
We compare in this communication several heteronuclear dipolar decoupling sequences in solid-state nuclear magnetic resonance experiments under a magic-angle spinning frequency of 60 kHz. The decoupling radiofrequency field amplitudes considered are 190 and 10 kHz. No substantial difference was found among the sequences considered here in performance barring the difference in the optimisation protocol of the various schemes, an aspect that favours the use of swept-frequency two pulse phase modulation (SW(f)-TPPM). 相似文献
2.
An analysis of phase-modulated heteronuclear dipolar decoupling sequences in solid-state nuclear magnetic resonance 总被引:1,自引:1,他引:0
Thakur RS Kurur ND Madhu PK 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2008,193(1):77-88
The design of variants of the swept-frequency two-pulse phase modulation sequence for heteronuclear dipolar decoupling in solid-state NMR is reported, their performance evaluated, and compared with other established sequences like TPPM and SPINAL. Simulations performed to probe the role of the homonuclear (1)H-(1)H bath show that the robustness of the decoupling schemes improves with the size of the bath. In addition, these simulations reveal that the homonuclear (1)H-(1)H bath also leads to broad baselines at high MAS rates. Results from a study of the SPINAL decoupling scheme indicate that optimisation of the starting phase and phase increment improves its performance and efficiency at high MAS rates. Additionally, experiments performed on a liquid crystal display the role of the initial phase in SPINAL-64 and sequences in the SW(f)-TPPM family. 相似文献
3.
Recently, a sequence for heteronuclear dipolar decoupling in solid-state NMR, namely SWf-TPPM, was introduced by us. Under magic-angle spinning (MAS), the decoupling efficiency of the sequence was unaffected over a range of values for various experimental parameters such as the pulse length, pulse phase, and 1H resonance offset. We here demonstrate its use in multiple-quantum (MQ) and high-resolution (HR) MAS experiments. This sequence further improves the MQMAS spectra compared to the earlier reported decoupling sequences with improved immunity to any missets of the pulse length, pulse phase and decoupler offset. In contrast, for HRMAS, the simple CW scheme is as efficient as any of the decoupling schemes that were studied. 相似文献
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5.
An early solid-state NMR study of the shielding tensors in substituted fluorobenzenes had indicated the presence of the 'ortho effect'. This was confirmed recently in the liquid state from a study of cross-correlated relaxation, which gives a handle on the shielding tensor. We report here a combined experimental and computational study on substituted fluorobenzenes where the ortho substituent is varied systematically. Experimental measurements of the longitudinal relaxation of 19F indicate the cross-correlation between the chemical shift anisotropy (CSA) of fluorine and its dipolar interaction with the ortho proton, and provide a measure of the CSA orientation parameter. This parameter is obtained also from quantum chemical calculations of the 19F CSA tensor. We establish a correlation between the CSA orientation parameter and linear free energy parameters by resorting to a multi-parameter regression analysis. Excellent correlation is obtained for most of these substituents only when a parameter for the ortho effect is included. 相似文献
6.
Analysis of a TE011 mode composite sapphire-rutile dielectric resonator has been carried out to study the temperature variation of resonance
frequency, close to the Cs atomic clock hyperfine frequency of 9.192 GHz. The complementary behavior of dielectric permittivity
with temperature of the composite has been exploited to obtain the desired turning point in the resonant frequency. The frequency
of the composite structure is found to be independent of the shield diameter beyond four times the puck diameter. 相似文献
7.
Norbornene-constrained cyclic peptides with hairpin architecture: design, synthesis, conformation, and membrane ion transport 总被引:1,自引:0,他引:1
Ranganathan D Haridas V Kurur S Nagaraj R Bikshapathy E Kunwar AC Sarma AV Vairamani M 《The Journal of organic chemistry》2000,65(2):365-374
A novel family of hairpin cyclic peptides has been designed on the basis of the use of norbornene units as the bridging ligands. The design is flexible with respect to the choice of an amino acid, the ring size, and the nature of the second bridging ligand as illustrated here with the preparation of a large number of norborneno cyclic peptides containing a variety of amino acids in ring sizes varying from 12- to 29-membered, with the choice of the second bridging ligand being a rigid norbornene (11, 13a,b), an adamantane unit (7a,b and 8), or a flexible cystine residue (4a,b and 10). The presence of built-in handles (as protected COOH groups) permits the attachment of a variety of subunits as shown here with the ligation of Leu-Leu, Val-Val, or Aib-Aib pendants in 4b, 7b, and 13b, respectively. This novel class of constrained cyclic peptides are demonstrated to adopt beta-sheet- or hairpin-like conformation as shown by (1)H NMR and CD spectra. Membrane ion-transport studies have shown that the norborneno cyclic peptides 4b and 7b containing Leu-Leu or Val-Val pendants symmetrically placed on the exterior of the ring show high efficiency and selectivity in the transport of specifically monovalent cations. This property can be attributed to the hairpin-like architecture induced by the norbornene unit since the bis-adamantano peptide 15 containing two pairs of Leu-Leu pendants on the exterior is able to transport both monovalent (Na(+), K(+)) and divalent (Mg(2+)/Ca(2+)) cations. 相似文献
8.
Heteronuclear dipolar decoupling is an essential requirement for extracting structural information from the 13C NMR spectra of liquid crystals. Efficient schemes for heteronuclear dipolar decoupling in such systems are formulated here by supercycling SWf‐TPPM, a sequence introduced recently for this purpose in rotating solids. These sequences are compared with two other commonly used decoupling schemes in liquid‐crystal NMR, SPINAL‐64 and SWf‐TPPM, by analyzing the intensities of various resonances in the proton decoupled 13C spectrum of the liquid‐crystal 4‐n‐pentyl‐4′‐cyanobiphenyl (5CB). The effectiveness of the decoupling programs with respect to experimental parameters such as RF field strength, decoupler offset frequency and phase angle is also presented. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
9.
Maninder Singh Dr. Chinthalapalli Srinivas Mayukh Deb Prof. Narayanan D. Kurur 《Chemphyschem》2013,14(17):3977-3981
Long‐lived coherences (LLCs) are known to have lifetimes much longer than transverse magnetization or single quantum coherences (SQCs). The effect of paramagnetic ions on the relaxation of LLCs is not known. This is particularly important, as LLCs have potential applications in various fields like analytical NMR, in vivo NMR and MR imaging methods. We study here the behaviour of LLCs in the presence of paramagnetic relaxation agents. The stepwise increase in the concentration of the metal ion is followed by measuring various relaxation rates. The effect of paramagnetic ions is analysed in terms of the external random field’s contribution to the relaxation of two coupled protons in 2,3,6‐trichlorobenzaldehyde. The LLCs relax faster than ordinary SQCs in the presence of paramagnetic ions of varying character. This is explained on the basis of an increase in the contribution of the external random field to relaxation due to a paramagnetic relaxation mechanism. Comparison is also made with ordinary Zeeman relaxation rates like R1, R2, R1ρ and also with rate of relaxation of long‐lived states RLLS which are known to be less sensitive to paramagnetically induced relaxation. Also, the extent of correlation of random fields at two proton sites is studied and is found to be strongly correlated with each other. The obtained correlation constant is found to be independent of the nature of added paramagnetic impurities. 相似文献
10.
In this paper we propose the extension of stimulated Raman adiabatic passage, a popular technique in optics for population inversion in three-level systems, to the NMR regime. The technique employs two amplitude modulated pulses-the first connecting the final and intermediate states followed by a second partially overlapped in time with it and connecting the ground and intermediate states. We present computer simulations demonstrating the applicability of the technique in NMR although we are no longer dealing with "pure" states, unlike in optics. Double quantum population inversion in two- and three-spin scalar coupled systems provides experimental support to our proposal. 相似文献