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K Schmidt-Rohr

Publications and source records attributed to K Schmidt-Rohr.

28 records · Page 2Linked to original sources
PubMed2000

Pure-exchange solid-state NMR.

Three exchange nuclear magnetic resonance (NMR) techniques are presented that yield (13)C NMR spectra exclusively of slowly reorienting segments, suppressing the often dominant signals of immobile components. The first technique eliminates the diagonal ridge that usually dominates two-dimensional (2D) exchange NMR spectra and that makes it hard to detect the broad and low off-diagonal exchange patterns. A modulation of the 2D exchange spectrum by the sine-square of a factor which is proportional to the difference between evolution and detection frequencies is generated by fixed additional evolution and detection periods of duration tau, yielding a 2D pure-exchange (PUREX) spectrum. Smooth off-diagonal intensity is obtained by systematically incrementing tau and summing up the resulting spectra. The related second technique yields a static one-dimensional (1D) spectrum selectively of the exchanging site(s), which can thus be identified. Efficient detection of previously almost unobservable slow motions in a semicrystalline polymer is demonstrated. The third approach, a 1D pure-exchange experiment under magic-angle spinning, is an extension of the exchange-induced sideband (EIS) method. A TOSS (total suppression of sidebands) spectrum obtained after the same number of pulses and delays, with a simple swap of z periods, is subtracted from the EIS spectrum, leaving only the exchange-induced sidebands and a strong, easily detected centerband of the mobile site(s).

Carbon Isotopes↗
PubMed2000

Relaxation-induced dipolar exchange with recoupling-An MAS NMR method for determining heteronuclear distances without irradiating the second spin

A new magic-angle spinning NMR method for distance determination between unlike spins, where one of the two spins in question is not irradiated at all, is introduced. Relaxation-induced dipolar exchange with recoupling (RIDER) experiments can be performed with conventional double-resonance equipment and utilize the familiar pi-pulse trains to recouple the heteronuclear dipolar interaction under magic-angle spinning conditions. Longitudinal relaxation of the passive spin during a delay between two recoupling periods results in a dephasing of the heteronuclear coherence and consequently a dephasing of the magnetization detected after the second recoupling period. The information about the dipolar coupling is obtained by recording normalized dephasing curves in a fashion similar to the REDOR experiment. At intermediate mixing times, the dephasing curves also depend on the relaxation properties of the passive spin, i.e., on single- and double-quantum longitudinal relaxation times for the case of I = 1 nuclei, and these relaxation times can be estimated with this new method. To a good approximation, the experiment does not depend on possible quadrupolar interactions of the passive spin, which makes RIDER an attractive method when distances to quadrupolar nuclei are to be determined. The new method is demonstrated experimentally with (14)N and (2)H as heteronuclei and observation of (13)C in natural abundance. Copyright 2000 Academic Press.

Journal Article↗
PubMed1998

Elucidation of the chain conformation in a glassy polyester, PET, by two-dimensional NMR

The chain conformation of glassy poly(ethylene terephthalate) (PET) was characterized by two-dimensional double-quantum nuclear magnetic resonance (NMR). In amorphous carbon-13-labeled PET, the statistics of the O-13CH2-13CH2-O torsion angle were determined, on the basis of the distinct shapes of the two-dimensional NMR patterns of trans and gauche conformations. In crystalline PET, the trans content is 100 percent, but in the amorphous PET it is only 14 percent (+/-5 percent). An average gauche torsion angle of 70 degrees (+/-9 degrees) was obtained. Implications for materials properties of polyesters are discussed.

Journal Article↗
PubMed1998

Complete Dipolar Decoupling of 13C and Its Use in Two-Dimensional Double-Quantum Solid-State NMR for Determining Polymer Conformations

A multiple-pulse technique for complete dipolar decoupling of directly bonded 13C-labeled sites is described. It achieves significant spectral simplifications in a recently introduced two-dimensional double-quantum solid-state NMR experiment for determining torsion angles. Both homonuclear and heteronuclear dipolar couplings are removed by combining a 13C multiple-pulse sequence with continuous-wave irradiation on the protons. The 13C sequence has a fundamental 10-pulse cycle which is a significantly modified magic-sandwich-echo sequence. The crucial heteronuclear decoupling is achieved by breaking the 360 degrees "inner" pulses in the magic sandwich into 90 degrees pulses and spacing them by 1H 360 degrees pulse lengths. Spectral artifacts typical of multiple-pulse sequences are eliminated by phase shifts between cycles. In contrast to many other multiple-pulse decoupling sequences, the long window in the cycle is the dwell time and can be longer than the inverse dipolar coupling, which makes the sequence practical for direct detection even with long pulse ring-down times. A modification of the sequence to scale the chemical shift and increase the effective spectral width is also presented. The 1D and double-quantum 2D experiments are demonstrated on polyethylene with 4% 13C-13C spin pairs. The potential of this approach for distinguishing segmental conformations is illustrated by spectral simulations of the two-dimensional ridge patterns that correlate double-quantum and single-quantum chemical-shift anisotropies. Copyright 1998 Academic Press.

Journal Article↗
PubMed1998

Trans content in atactic polystyrene estimated by double-quantum solid-state NMR.

The conformational statistics of atactic polystyrene have been investigated by solid-state NMR, on a sample labeled with 25% 13CH2 groups. Double-quantum pulse sequences are used to select statistically formed 13C-13C spin pairs. An experiment correlating the 13C-13C internuclear vector with the 13C chemical-shift anisotropy determines the conformational statistics of a single backbone torsion angle. Double-quantum experiments correlating the 13CH2 chemical-shift anisotropies of two adjacent segments provide information on two consecutive torsion angles. The analysis of the spectra yields a trans content of 68% (+/-10%). This represents the first direct experimental estimate of the trans/gauche ratio in atactic polystyrene. The trans content found here agrees well with rotational-isomeric-state models but is inconsistent with results from more elaborate atomistic models that take packing effects into account.

Anisotropy↗
PubMed1997

Coupling amplification in 2D MAS NMR and its application to torsion angle determination in peptides.

A technique for amplifying the apparent magnitudes of 13C-1H and 15N-1H dipolar interactions in magic-angle spinning experiments is described. By inserting rotor-synchronized 180 degrees pulses in the evolution period of a 2D dipolar-chemical shift experiment, heteronuclear dipolar couplings are doubled or quadrupled relative to the spinning speed. The increased number of dipolar sidebands is desirable for retaining structural information in the indirectly detected dipolar dimension while resolving inequivalent sites in the isotropic chemical shift dimension at relatively high spinning speeds. This coupling amplification method is incorporated into an experiment that determines the peptide torsion angle phi through the relative orientation of the Calpha-Halpha and N-HN bonds. It is shown both experimentally and theoretically that the angular resolution of the measurement is enhanced significantly by the selective doubling of the N-HN coupling.

Chemical Phenomena↗
PubMed1996

Conformational constraints on the headgroup and sn-2 chain of bilayer DMPC from NMR dipolar couplings.

This paper presents new NMR constraints on the conformation of the headgroup, glycerol backbone, and sn-2 chain of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) in the liquid-crystalline bilayer. Using two-dimensional 13C-1H chemical shift correlation spectroscopy, we find significant dipolar couplings between the carboxyl carbon CO2 and the headgroup protons. This indicates that a conformation in which the DMPC headgroup and the beginning of the sn-2 chain bend toward each other is significantly populated in the fluid bilayer. The predominance of this headgroup orientation can be further confirmed by 31P-13C dipolar couplings from the literature, which constrain the glycerol G2-G3 torsion angle to be close to trans, excluding a significant presence of one of the two conformations found in the DMPC crystal. Combining and reexamining 20 known NMR couplings for the glycerol backbone and its adjacent segments of L alpha-DMPC, we find that several torsion angles and bond orientations in the core of the DMPC molecule are constrained severely and must differ from those in the crystal structure. We propose a consistent molecular model for phosphocholine lipids in the liquid-crystalline phase, with a rigid backbone in the core of the molecule, a bent-back headgroup, and increasing mobility toward the ends of the acyl chains and the headgroup.

Dimyristoylphosphatidylcholine↗
PubMed1995

Study of phospholipid structure by 1H, 13C, and 31P dipolar couplings from two-dimensional NMR.

Various motionally averaged 31P-1H, 13C-1H, 1H-1H, and 31P-13C dipolar couplings were measured for natural-abundance and unoriented phosphocholine in the L alpha phase. The couplings were obtained and assigned by a variety of advanced and partly novel two-dimensional solid-state NMR experiments. Whereas 31P-1H and 31P-13C dipolar couplings provide long-range structural constraints, geminal 1H-1H couplings and the signs of 13C-1H couplings are important new elements in a segmental order-tensor analysis of the lipid headgroup and glycerol backbone. The implications of these measured dipolar couplings for the conformational exchange of the lipid headgroup and the bending of the headgroup from the glycerol backbone are discussed. These dipolar couplings are also analyzed semiquantitatively in terms of the segmental order tensor.

Biophysical Phenomena↗
PubMedDate not supplied

High-sensitivity multinuclear NMR spectroscopy of a smectite clay and of clay-intercalated polymer.

The nuclear magnetic resonance (NMR) properties of a smectite clay low in paramagnetic ions, and NMR experiments to detect organic material near the silicate surfaces with high sensitivity, have been explored by 1H, 29Si, and 13C NMR. In oven-dried hectorite clay, 1H NMR reveals a sharp signal at 0.35 ppm that narrows significantly with spinning speed. It is assigned to the "inner" OH protons of the silicate layers. In fluorohectorite, where the OH groups are replaced by fluorines, no such 1H peak is observed. The assignment is further confirmed by the efficient cross-polarization observed in two-dimensional (2D) 1H-29Si HETCOR spectra, and by 29Si-detected REDOR experiments with 1H-dephasing in the 29Si dipolar field, which yield a 1H-29Si distance of 2.9 + 0.4 A. In these 1H-29Si experiments, the sensitivity of the 29Si signal is enhanced at least fivefold by refocusing the decay resulting from the inhomogeneous broadening of the single 29Si peak, stretching the 29Si signal out over 80 ms. The small 1H linewidth of this signal at spinning frequencies exceeding 4 kHz is attributed to the large proton-proton distances in the clay. The upfield isotropic chemical shift of the OH groups is explained by their inaccessibility to hydrogen-bonding partners, as a result of their location in hexagonal "cavities" of the clay structure. The well-resolved, easily selectable OH-proton signal and the high-sensitivity 29Si detection open excellent perspectives for NMR studies of composites of clays with organic molecules. Two-dimensional 1H-29Si and 1H-1H chemical-shift correlation experiments enable efficient detection of the 1H spectrum of organic segments near the clay surface. Combined with 1H spin diffusion, the organic segments at up to several nanometers from the clay surfaces can be probed. A 2D 1H-13C correlation experiment yields the 13C spectrum of the organic species near the clay surfaces. A mobility gradient of intercalated poly(ethylene oxide), PEO, segments is proven in 1H-3Si WISE experiments with spin diffusion.

Aluminum Silicates↗