@article {430, title = {Isotropic second-order dipolar shifts in the rotating frame}, journal = {Journal of Chemical Physics}, volume = {104}, year = {1996}, note = {J Chem PhysUm909Times Cited:9Cited References Count:44}, month = {Jun 1}, pages = {8258-8268}, abstract = {

An experiment is described that utilizes the truncation of the Hamiltonian in the rotating frame by a radio-frequency field designed to yield an isotropic shift for the dipolar coupling. This approach allows the measurement of a normally orientation-dependent coupling constant by a single isotropic value. The dipolar isotropic shift is closely related to the field-dependent chemical shift in solids due to the second-order dipolar perturbation observed in magic-angle spinning experiments. In the rotating frame, larger shifts of up to 1000 Hz can be observed for the case of a one-bond C-H coupling compared to a shift of a few Hertz in the laboratory-frame experiment. In addition to the isotropic shift, a line broadening due to the P-4(cos beta) terms is observed when the experiment is carried out under magic-angle sample spinning (MAS) conditions, leading to the requirement of higher-order averaging such as double rotation (DOR) for obtaining narrow lines. As an application of this new experiment the separation of CH, CH2, and CH3 groups in a 2D spectrum under MAS is demonstrated. Implemented under DOR it could be used as a technique to select carbon atoms according to the number of directly attached protons. (C) 1996 American Institute of Physics.

}, keywords = {spins}, isbn = {0021-9606}, doi = {Doi 10.1063/1.471579}, url = {://WOS:A1996UM90900008}, author = {Ernst, M. and Kolbert, A. C. and Schmidt-Rohr, K. and Pines, A.} } @article {434, title = {Rotational diffusion measurements of suspended colloidal particles using two-dimensional exchange nuclear magnetic resonance}, journal = {Journal of Chemical Physics}, volume = {104}, year = {1996}, note = {J Chem PhysTn837Times Cited:13Cited References Count:24}, month = {Jan 8}, pages = {509-520}, abstract = {

We present here an experimental and theoretical study of the application of two-dimensional exchange nuclear magnetic resonance spectroscopy (NMR) to the investigation of the rotational diffusion of colloidal particles. The theoretical discussion includes the nature of the NMR frequency time-correlation function where the NMR interaction is represented by the chemical shift anisotropy (CSA). Time-correlation functions for the isotropic rotational diffusion of a suspension of colloidal particles containing single and multiple sites are derived in addition to time-correlation functions for the rotational diffusion of a suspension of symmetric top particles containing an isotropic distribution of a single CSA interaction. Simulations of two-dimensional exchange spectra for particles undergoing isotropic rotational diffusion are presented. We performed two-dimensional exchange NMR experiments on a colloidal suspension of spherical poly(methyl methacrylate) (PMMA) particles which were synthesized with a 20\% enrichment in C-13 at the carbonyl site. Rotational diffusion time-correlation functions determined from the experimental exchange spectra are consistent with the composition of the colloidal suspension. Detailed explanations of the syntheses of the enriched methyl C-13-(carbonyl)-methacrylate monomer and the small quantities of 20\% enriched C-13-(carbonyl)-poly(methyl methacrylate) microspheres used for this study are presented. (C) 1996 American Institute of Physics.

}, keywords = {scattering}, isbn = {0021-9606}, doi = {Doi 10.1063/1.470847}, url = {://WOS:A1996TN83700009}, author = {Barrall, G. A. and Schmidt-Rohr, K. and Lee, Y. K. and Landfester, K. and Zimmermann, H. and Chingas, G. C. and Pines, A.} } @article {444, title = {Low-Power Decoupling Sequences for High-Resolution Chemical-Shift and Local-Field Nmr-Spectra of Liquid-Crystals}, journal = {Journal of Magnetic Resonance Series A}, volume = {113}, year = {1995}, note = {J Magn Reson Ser AQw158Times Cited:11Cited References Count:29}, month = {Apr}, pages = {169-176}, abstract = {

Various new and well-established multiple-pulse sequences that provide homonuclear dipolar decoupling are compared on a high-resolution spectrometer/probe configuration using low RF-irradiation powers. Proton-proton decoupled carbon-13 spectra of singly C-13-labeled benzene dissolved in a nematic liquid crystal and of the liquid crystal 152 are presented. Two classes of multiple-pulse sequences are studied that produce either broadband decoupled carbon spectra or separated local-held spectra. Several new approaches for the design of windowless sequences are demonstrated to be valuable in these heteronuclear experiments. They include implementations of the iterative MLEV scheme and the use of 270 degrees pulses. Furthermore, noncyclic propagators have been found that exhibit advantages over closely related cyclic analogues in both classes of decoupling sequences. (C) 1995 Academic Press, Inc.

}, keywords = {dipolar}, isbn = {1064-1858}, doi = {Doi 10.1006/Jmra.1995.1077}, url = {://WOS:A1995QW15800005}, author = {Nanz, D. and Ernst, M. and Hong, M. and Ziegeweid, M. A. and Schmidt-Rohr, K. and Pines, A.} } @article {451, title = {Nmr Measurement of Signs and Magnitudes of C-H Dipolar Couplings in Lecithin}, journal = {Journal of the American Chemical Society}, volume = {117}, year = {1995}, note = {J Am Chem SocQn458Times Cited:45Cited References Count:25}, month = {Mar 22}, pages = {3310-3311}, keywords = {orientation}, isbn = {0002-7863}, doi = {Doi 10.1021/Ja00116a051}, url = {://WOS:A1995QN45800051}, author = {Hong, M. and Schmidt-Rohr, K. and Pines, A.} } @article {464, title = {2-Dimensional Xe-129 Exchange Nmr Measurements of Xenon Dynamics in Na-a Zeolite}, journal = {Zeolites and Related Microporous Materials: State of the Art 1994}, volume = {84}, year = {1994}, note = {Stud Surf Sci CatalPart a-CBd02eTimes Cited:3Cited References Count:21Studies in Surface Science and Catalysis}, pages = {519-526}, abstract = {Two-dimensional (2D) exchange NMR is a powerful tool for measuring the dynamics and energetics of adsorbed xenon atoms undergoing slow exchange between the alpha-cages of Na-A zeolite. In this proceedings, we present recently published results, as well as additional discussion and data obtained, using 2D Xe-129 NMR to determine rate coefficients for intercage xenon hopping and to correlate them with adsorption and activation energies. Variable-temperature experiments establish the activation energy for hopping between alpha-cages to be 60+/-10 kJ/mol. The dependence of these kinetic and thermodynamic quantities on xenon occupancy of the alpha-cages reflects the importance of intracage interactions on the behavior of the adsorbed guest molecules.}, keywords = {cavities}, isbn = {0167-2991}, url = {://WOS:A1994BD02E00063}, author = {Janicke, M. and Chmelka, B. F. and Larsen, R. G. and Shore, J. and Schmidt-Rohr, K. and Emsley, L. and Long, H. and Pines, A.} } @article {461, title = {3-Dimensional Variable-Angle Nuclear-Magnetic-Resonance Exchange Spectroscopy without Rotor Axis Hopping}, journal = {Journal of Chemical Physics}, volume = {101}, year = {1994}, note = {J Chem PhysNy002Times Cited:12Cited References Count:48}, month = {Aug 1}, pages = {1852-1864}, abstract = {

Slow, large-amplitude chain motions play an important role in determining the macroscopic mechanical properties of polymers. Although such motions have been studied quantitatively by two-dimensional (2D) nuclear: magnetic resonance (NMR) exchange experiments, overlapping anisotropic patterns hamper spectral analysis, and limit applications. Variable angle correlation spectroscopy (VACSY) has proven useful in resolving such problems for rapidly spinning samples by separating anisotropic spectral patterns according to isotropic chemical shifts. In a previous study [J. Am. Chem. Sec. 115, 4825 (1993)], we described a three-dimensional (3D) NMR experiment that incorporates; the VACSY method and a hop of the rotor axis to correlate the isotropic chemical shifts to 2D anisotropic exchange patterns. The hop of the rotor axis, however, presents experimental difficulties and limits the range of motional rates that may be studied. We present in this paper a new 3D VACSY exchange experiment that obtains the same correlations without the need for the rotor axis hop. A series of 2D exchange spectra are recorded with the sample spinning at different rotation axis angles.\&$\#$39; Then using the scaling of the anisotropic frequency at the different angles, we construct the data onto a 3D matrix so that a Fourier transformation directly yields the desired correlations. The technique is applied to C-13 exchange NMR to study the slow molecular motion of ordered isotactic polypropylene.

}, keywords = {distributions}, isbn = {0021-9606}, doi = {Doi 10.1063/1.467696}, url = {://WOS:A1994NY00200011}, author = {Lee, Y. K. and Emsley, L. and Larsen, R. G. and Schmidt-Rohr, K. and Hong, M. and Frydman, L. and Chingas, G. C. and Pines, A.} } @inbook {466, title = {Group Theory and Nuclear Magnetic Resonance Dynamics}, booktitle = {NMR and More - In Honour of Anatole Abragam}, year = {1994}, pages = {175-199}, publisher = {Les Editions de Physique}, organization = {Les Editions de Physique}, author = {Emsley, L. and Schmidt-Rohr, K. and Pines, A.}, editor = {Porneuf, M. Goldman and M.} } @article {458, title = {Nmr Measurement of Resolved Heteronuclear Dipole Couplings in Liquid-Crystals and Lipids}, journal = {Journal of Physical Chemistry}, volume = {98}, year = {1994}, note = {J Phys Chem-UsNw531Times Cited:68Cited References Count:25}, month = {Jul 7}, pages = {6668-6670}, abstract = {

Simplified nuclear magnetic resonance (NMR) spectra of heteronuclear dipolar couplings for molecules in an anisotropic environment, such as liquid crystals and lipids, are obtained by proton-detected local-field spectroscopy. The distance-dependent dipolar interactions between spins of magnetically active nuclei can be determined directly from the spectrum because many-body effects that complicate conventional dipolar NMR spectra are avoided by selectively probing local fields produced by rare spins at the location of abundant spins. We employ the technique to resolve the carbon-proton dipolar couplings of benzene dissolved in a nematic liquid crystal and to measure phosphorus-proton couplings in lecithin in the L(alpha) phase to obtain constraints on the phosphocholine headgroup structure.

}, keywords = {solids}, isbn = {0022-3654}, doi = {Doi 10.1021/J100078a002}, url = {://WOS:A1994NW53100002}, author = {Schmidt-Rohr, K. and Nanz, D. and Emsley, L. and Pines, A.} } @article {476, title = {Nmr-Study of Xenon Dynamics and Energetics in Na-a Zeolite}, journal = {Chemical Physics Letters}, volume = {214}, year = {1993}, note = {Chem Phys LettMd614Times Cited:56Cited References Count:22}, month = {Oct 29}, pages = {220-226}, abstract = {

For xenon atoms adsorbed in Na-A zeolite, electronic interactions cause shifts in NMR frequencies, resulting in a spectrum with discrete peaks from xenon atoms in cages with different xenon occupancies. Using two-dimensional exchange NMR, it is possible to determine the microscopic rates of intercage motion and to relate them to the adsorption and activation energies of the xenon atoms. The dependence of the adsorption energies on xenon cage occupancy reflects the importance of the intercage interactions and is directly related to the cage occupancy distribution. Variable temperature measurements yield an activation energy of about 60 kJ/mol for the transfer of a xenon from one cage to another.

}, keywords = {xe}, isbn = {0009-2614}, doi = {Doi 10.1016/0009-2614(93)90085-F}, url = {://WOS:A1993MD61400015}, author = {Larsen, R. G. and Shore, J. and Schmidt-Rohr, K. and Emsley, L. and Long, H. and Pines, A. and Janicke, M. and Chmelka, B. F.} }