The dynamics of water between highly oriented multilayers of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) has been studied in two time domains at different hydration levels. Incoherent quasielastic neutron scattering (QENS) and deuterium-nuclear magnetic resonance (NMR) longitudinal (T1) relaxation were employed to investigate both the high-frequency motions of water (10−9–10−11 s time scale) and their anisotropy, while 2H-NMR transverse (T2) relaxation was used for obtaining information on low frequency dynamical processes (microsecond time scale). Our results show that high frequency dynamics (picosecond-time scale) at low hydration (three to four water molecules per lipid) can be understood solely as a uniaxial rotation of the water molecules tightly bound to DPPC head groups with a correlation time τrot≊62 ps at 55 °C and a rotational radius of 1±0.1 Å, but with no detectable translational degrees of freedom. The 2H-NMR T1 data (nanosecond-time scale) can be explained satisfactorily on the basis of fast rotations with the correlation time above and a slower reorientation of the rotational axis (correlation time τ1≊6 ns).
Both QENS and 2H-NMR T1 measurements provide an apparent activation energy of Ea=32±1.0 kJ/mol for this process. Increasing the hydration level of the multilayers leaves the rotational motion essentially unchanged, but enables additional translational motion which can be considered as a jump diffusion process (diffusion coefficient D=16±1×10−10 m2/s at 44 °C and a mean residence time of τ0=2.0±0.5 ps) of nonbound water. It is interesting to note that this diffusion is completely isotropic on the characteristic length scale of this QENS experiment (≤10 Å). Temperature variation shows that the phase state of the lipids has no significant effect on the high frequency dynamics of the water molecules. Measurements of the 2H-NMR quadrupolar splitting of water (D2O) at temperatures around the phase transition temperature Tm of the oriented DPPC multilayers clearly show a coexistence of the crystalline Lβ′ phase and of the fluid Lα phase over a range of up to 4 °C at both sides of Tm. The intermediate Pβ′ (‘‘ripple’’) phase is suppressed as we worked at hydration levels below saturation. In the coexistence range, exchange of water takes place between crystalline and fluid lipid domains due to water diffusion. This exchange causes a pronounced minimum of the 2H-NMR transverse relaxation time T2 at Tm since this low frequency process satisfies approximately a critical damping condition for a two-site chemical exchange process.
We use neutron scattering to show that the low-temperature, short-range ordered spin configuration in the geometrically frustrated magnet SrCr 9p Ga12−9p O19 (p = 0.92(5)) is composed of small groups of spins whose dipole moments cancel. The local magnetic fluctuation spectrum, χ (ω), vanishes approximately in proportion to ω for hω < 0.5 meV, distinguishing this magnet from conventional spin glasses which display a featureless continuum of excited states. We argue that this behavior results from the absence of local, low-energy excitations in the zero-spin clusters from which the frozen spin configuration is composed.
The diffusion of protons in the superionic phase of CsHSO4 was investigated by quasielastic neutron scattering (QNS) on the IRIS spectrometer at the pulsed spallation neutron source ISIS, Rutherford Appleton Laboratory, UK. Two processes with different characteristic times could be distinguished: long-range translational diffusion with a diffusion coefficient D=(1.00-1.17)*10-7 cm2 s-1 (for a temperature range from 423 to 448 K) and jump rotation of HSO4 groups between two possible orientations, the corresponding nonequivalent proton sites being 2.3 AA apart.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.