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HW Spiess

Publications and source records attributed to HW Spiess.

9 recordsLinked to original sources
PubMed1999

Highly Ordered Columnar Structures from Hexa-peri-hexabenzocoronenes-Synthesis, X-ray Diffraction, and Solid-State Heteronuclear Multiple-Quantum NMR Investigations.

Improved long-range ordering in the columnar mesophase of hexa(para-n-dodecylphenyl)hexabenzocoronene 1 has been achieved by inserting phenyl rings between the extended aromatic core of hexabenzocoronene and the alkyl side chains, which are needed to form liquid crystalline phases. The long-range hexagonal order of the columns is demonstrated by X-ray scattering, while the improved packing of the aromatic cores within the columns and the molecular mobility is probed by a newly developed heteronuclear multiple-quantum MAS NMR technique.

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PubMed1999

Spin counting with fast MAS

A novel magic angle spinning (MAS) multiple-quantum spin counting experiment based on the C7 recoupling sequence of Lee et al. is described. In contrast to previous approaches the new experiment is applicable at fast MAS rates and can be used to follow the multiple-quantum excitation dynamics with fine time resolution. The new method is illustrated by experiments on adamantane at spinning speeds comparable to the nonspinning dipolar linewidth. The sizes of the clusters of dipolar-coupled spins measured using the new experiment are compared to those obtained using the original nonspinning spin counting technique of Baum et al. Copyright 1999 Academic Press.

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PubMed1999

Temperature calibration under ultrafast MAS conditions

For conventional fast magic-angle spinning (MAS) frequencies (</=15 kHz), there is a known heating of the sample due to the friction between the rotor and the bearing gas. At the recently achievable ultrafast MAS frequencies of up to 35 kHz, a more dramatic heating effect is expected. Using the 119Sn NMR signal of the chemical shift thermometer Sm2Sn2O7, this frictional heating effect is quantified, and a calibration of the sample temperature under ultrafast MAS conditions is described. An empirical expression is given which allows the determination of the sample temperature as a function of the bearing gas temperature and the spinning frequency. Copyright 1999 Academic Press.

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PubMed1998

Self-Assembly of Ionically End-Capped Diblock Copolymers.

The self-assembly of ionically end-capped, symmetric polystyrene-polyisoprene diblock copolymers (PS-b-PI) has been studied. Structural data obtained from small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) were correlated with the aggregation behavior of charged chain ends as evidenced by a spin probe using electron paramagnetic resonance (EPR) spectroscopy. The resulting mesomorphic structures were shown to be determined by the chain end topology, i.e., the site where the ionic chain end has been introduced chemically: For omega-functionalized diblock copolymers (monofunctional species) microphase separation is significantly stabilized due to the presence of ionic aggregates within the respective phase separated homopolymer domains. In contrast, for salt-free alpha,omega-macrozwitterionic diblock copolymers a marked perturbation of the block copolymer superstructure was found. In this case, the formation of a network of mixed ionic aggregates creates an additional microdomain interface by joining the chemically distinct blocks at their chain ends. The alteration of the degree of microphase separation as observed for the different functionalities can be attributed to conformational changes of the copolymer chain. Chain end association in the present system is reminiscent of certain covalently joined star and graft copolymers.

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PubMed1998

Pulsed field gradient selection in two-dimensional magic angle spinning NMR spectroscopy of dipolar solids

The utility of gradient selection in MAS spectroscopy of dipolar solids is explored in two examples. In the first, rotor-synchronized gradients of appropriate strength and duration are applied to select 1H double-quantum coherences. The resulting DQ MAS spectrum of adamantane is compared with that acquired by the corresponding phase-cycling technique. As a second example, a 1H 2D exchange MAS experiment is performed on an elastomer sample. In this experiment, a gradient is applied to remove undesired coherences that would otherwise distort the spectrum for short mixing times. The diagonal-peak intensities in the resulting spectrum show a linear decrease with increasing mixing time indicating cross-relaxation by slow chain motions as the relevant process. Both types of experiments demonstrate the potential of gradient-selection techniques for MAS spectroscopy of dipolar solids. Copyright 1998 Academic Press.

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