Force constant analysis of molecular groups in apatite solids

The results of normal coordinte analyses demonstrate that the simple Urey-Bradley force field gives a reasonable representation of the potential-energy function of PO₄^3? in pyromorphite (Pb₁₀(PO₄)₆Cl₂) but is unsatisfactory for AsO₄^3? and VO₄^3? in mimetite (Pb₁₀(AsO₄)₆Cl₂) and vanadinite (Pb₁₀(VO₄)₆Cl₂). respectively. Theoretical band assignments are made for PO₄^3? in pyromorphite using simple Urey-Bradley force field and based on a good frequency fit, a physically reasonable set of molecular force constants and some experimental confirmation. The general order of magnitude and trends in force constants are physically realistic. The theoretical analysis provides additional confirmation for the assignment of the v₂ bending mode to a higher-frequency, lower-intensity band at 436 cm^?1 in the infrared. Eigenvector calculations allow determination of which internal coordinates are major contributors to the various normal modes.     

Cogwheel phase cycling

A new method for constructing phase cycles is described. The new schemes apply to experiments involving several consecutive coherence transfer steps. The radiofrequency phases of two or more irradiation blocks are incremented simultaneously, as opposed to the traditional "nested" scheme, in which the block phases are incremented independently. In many cases, the "cogwheel" phase cycles achieve the same selectivity as traditional phase cycles, using fewer steps. Significant time savings are achievable in a wide range of NMR experiments.     

Radiofrequency pulse sequences which compensate their own imperfections. 1980

Radiofrequency pulse sequences are described which have the same overall effect as a single 90° or 180° pulse but which compensate the undesirable effects of resonance offset and spatial inhomogeneity of the radiofrequency field H₁. These “composite” pulses are built up from a small number of conventional pulses which rotate the nuclear magnetization vectors about different axes in the rotating frame, while in the intervals between pulses a limited amount of free precession may be allowed to occur. Insight into the way in which pulse imperfections are compensated is obtained by computer simulation of trajectories of families of nuclear spin “isochromats” representing a distribution of H₁ intensity or resonance offset. Composite 90° pulses are suggested as a method of reducing systematic errors in spin-lattice relaxation times derived from progressive saturation or saturation-recovery experiments, and as the preparation pulse of a spin-locking experiment. A test of the effectiveness of the composite 180° pulse sequence has been made by using it for population inversion in a spin-lattice relaxation measurement, where T₁ is derived from the null point in the recovery curve, a technique known to be very sensitive to pulse imperfections.     

Reiterant speech as a test of non-native speakers' mastery of the timing of French.

The reiterant speech of ten native speakers of French was analyzed to develop baseline measures for syllable and consonant/vowel timing for a series of two-, three-, four-, and five-syllable French words spoken in isolation. Ten native speakers of English, who learned French as a second language, produced reiterant versions of both the French words and a comparable set of English words. The native speakers of English were divided into two groups on the basis of their second language experience. The first group consisted of four university-level teachers, who were relatively experienced learners of French, and the second group of six less experienced learners of French. The French reiterant imitations of the two groups of native speakers of English were compared to the native French speakers' productions. The timing patterns of the experienced group of non-native speakers did not differ significantly from those of the native French speakers, whereas there was a significant difference between these two groups and the group of six less experienced second-language learners. Deviations from the French baseline measures produced by the less experienced group are discussed in terms of the influence of the timing patterns of English and the literature on a sensitive period for second language acquisition.     

Molecular rotor measures viscosity of live cells via fluorescence lifetime imaging

The fluorescence intensity and lifetime of the 4,4'-difluoro-4-bora-5-(p-oxoalkyl)phenyl-3a,4a-diaza-s-indacene (1) show a strong correlation with the viscosity of the medium due to the viscosity-dependent twisting of the 5-phenyl group, which gives access to the dark nonemissive excited state. We propose a sensitive and versatile method for measuring the local microviscosity in biological systems, based on the determination of the fluorescence lifetime of 1. Fluorescence lifetime imaging (FLIM) performed on live cells incubated with 1 demonstrates the distinct intracellular lifetime of the molecular rotor of 1.6 +/- 0.2 ns corresponding to the intracellular viscosity of ca. 140 cP. Time-resolved fluorescence anisotropy of 1 in cells confirms insignificant binding of the fluorophore. The viscosity value obtained in the present study is considerably higher than that of water and of cellular cytoplasm. The high viscosity of intracellular compartments is likely to play an important role in vital intracellular processes, including the rate of diffusion of reactive oxygen species, causing programmed cell destruction.     

The long-lived nuclear singlet state of 15N-nitrous oxide in solution

A 15N nuclear singlet lifetime of over 26 min has been observed in a solution of 15N2O, by using a field-cycling NMR pulse sequence. This observation suggests applications of hyperpolarized 15N2O in medical imaging and for flow and diffusion studies.     

Symmetry in the design of NMR multiple-pulse sequences

The symmetry principles of NMR pulse-sequence design are summarized. The discussion is guided by an analogy with tiling schemes in the decorative arts. The symmetry operations for NMR pulse sequences are discussed in terms of excitation field modifiers and temporal modifiers. The quantum operators which describe the effect of these modifiers on the excitation field spin Hamiltonian are provided. The symmetry transformations of spin propagators, and the different types of pulse-sequence elements are discussed. The common types of symmetry expansion are treated using the propagator transformations and the Euler angles for the excitation field propagators. The selection rules associated with symmetrical pulse sequences are discussed using average Hamiltonian theory.