Inelastic incoherent neutron scattering measurements of intact cells and tissues and detection of interfacial water

We have previously used inelastic incoherent neutron scattering spectroscopy to investigate the properties of aqueous suspensions of biomolecules as a function of hydration. These experiments led to the identification of signals corresponding to interfacial (hydration) water at low water content. A prediction from these studies was that in the crowded environment inside living cells, a significant proportion of the water would be interfacial, with profound implications for biological function. Here we describe the first inelastic incoherent neutron scattering spectroscopy studies of living cells and tissues. We find that the interfacial water signal is similar to that observed for water interacting with purified biomolecules and other solutes, i.e., it is strongly perturbed in the librational and translational intermolecular optical regions of the spectrum at 20-150 meV. The ratio of interfacial water compared to total water in cells (approximately 30%) is in line with previous experimental data for hydration water and calculations based on simple assumptions.     

Wavelet filtering to study mixing in 2D isotropic turbulence

This paper presents the application of coherent vortex simulation (CVS) filtering, based on an orthogonal wavelet decomposition of vorticity, to study mixing in 2D homogeneous isotropic turbulent flows. The Eulerian and Lagrangian dynamics of the flow are studied by comparing the evolution of a passive scalar and of particles advected by the coherent and incoherent velocity fields, respectively. The former is responsible for strong mixing and produces the same anomalous diffusion as the total flow, due to transport by the coherent vortices, while mixing in the latter is much weaker and corresponds to classical diffusion.     

Quantitative information about the hydrogen bond strength in dilute aqueous solutions of methanol from the temperature dependence of the Raman spectra of the decoupled OD stretch

We have obtained quantitative information about the hydrogen bond strength in pure water and in dilute aqueous solutions of methanol by analyzing the temperature dependence of Raman spectra of the decoupled OD stretch from 21 to 160 degrees C with the hydrogen bond energy dispersion method. A minimum at 2440 cm(-1) assigned to strong icelike hydrogen bonds and a maximum at 2650 cm(-1) due to maximally (but not completely) broken hydrogen bonds result in all cases. The energy of the minimum decreases upon addition of methanol due to formation of stronger water-methanol hydrogen bonds, whereas the energy of the maximum increases because water hydrogen atoms in the vicinity of the methyl group might participate in "more broken" hydrogen bonds than in bulk water.     

A hierarchy of global coupling induced cluster patterns during the oscillatory H2-electrooxidation reaction on a Pt ring-electrode

We report experimental results on spatiotemporal pattern formation during the oscillatory hydrogen electrooxidation reaction on a Pt ring-electrode under negative (desynchronizing) global coupling (GC). Spatially one-dimensional profiles of the interfacial potential drop along the angular direction of the ring electrode are recorded by means of a potential probe. The dynamics is investigated as a function of two control parameters, the applied voltage U and the strength of the global coupling. The latter is adjusted either by varying the distance between the working electrode (WE) and the reference electrode (RE) or by inserting a negative impedance device in series with the WE. In the absence of global coupling, uniform oscillations were destabilized by migration coupling, and electrochemical turbulence developed at large values of U (H. Varela, C. Beta, A. Bonnefont and K. Krischer, Phys. Rev. Lett., 2005, 94, 174104; ). Already low global coupling strengths sufficed to suppress turbulence. Instead, regular two-phase clusters formed. At higher coupling strength, a second type of two-phase cluster was observed as well as two types of irregular cluster patterns, which were connected with an irregular motion of the cluster boundaries and the emergence and disappearance of clusters through splitting and merging of the boundaries, respectively. Upon increasing the coupling strength even further, five-phase clusters were stabilized and at the highest coupling strength applied the cluster patterns transformed into strongly modulated pulses. The two types of two-phase clusters and the five-phase clusters are analyzed employing several signal processing techniques.     

Inelastic neutron scattering and infrared spectroscopic study of furan adsorption on alkali-metal cation-exchanged faujasites.

Inelastic neutron scattering (INS) as well as infrared (IR) transmission and diffuse reflection infrared Fourier transform (DRIFT) spectra of furan adsorbed on Li-LSX, NaY, NaX, K-LSX, and CsNaX zeolites have been measured in the range 2000-200 and 4000-1300 cm(-1), respectively. On the basis of an assignment of normal modes of furan taken from the literature and our own quantum chemical calculations of vibrational frequencies, the observed frequency shifts between bulk furan and furan adsorbed on the zeolites mentioned above have been interpreted in view of the interactions between furan and zeolite. For an explanation of frequency shifts of CH out-of-plane bendings, CH stretchings and some ring vibrations, it has to be assumed that in addition to the interaction between furan and the corresponding cation of the zeolite, a further interaction between the CH bonds and lattice oxygen atoms exists.     

Adsorption structures of water in NaX studied by DRIFT spectroscopy and neutron powder diffraction

Diffuse reflectance infrared Fourier transform spectroscopic (DRIFTS) measurements (4000-1500 cm(-1)) and the results of neutron powder diffraction have been combined to study the structure of adsorption complexes of water in a NaX zeolite at different water loadings (25, 48, 72, and 120 water molecules per unit cell, respectively). Sharp bands corresponding to non-hydrogen-bonded OH groups of water molecules and broad associate bands due to hydrogen-bonded molecules are observed in the DRIFT spectra. We observe a remarkable downshift of the high-frequency associate band in a narrow temperature interval when the water amount decreases from 120 to 72 molecules per unit cell, which could signify some kind of "phase transition" for the water inside the zeolite cavities. Neutron powder diffraction results show that water molecules are predominantly localized in or near the 12-ring windows. Water molecules with hydrogen-bonded and non-hydrogen-bonded OH groups were found, in agreement with the observation of sharp and broad bands in the DRIFT spectra. We find strong evidence for the formation of cyclic hexamers of water molecules localized in the 12-ring windows, which are further stabilized by hydrogen bonds to framework oxygen atoms.     

Characterization of Extra-framework Cations in Zeolites. A temperature-programmed desorption (TPD) study

We have investigated the interaction of a few 5-ring organic compounds (cyclopentane, cyclopentene, furan, 2-methylfuran, 2,5-dihydrofuran and tetrahydrofuran) with alkali-metal cation-exchanged faujasites (LSX, X and Y types) by means of temperature-programmed desorption (TPD). The desorption behavior at higher temperatures of all probe molecules on the sodium ion containing faujasites with different Si/Al ratios reflects the higher cation content of zeolites with greater aluminum content. Only the desorption profiles of tetrahydrofuran and 2,5-dihydrofuran show, depending on the kind of cation, additional desorption features at higher temperatures. Using a regularization method, desorption energy distribution functions for furan and tetrahydrofuran were calculated. The calculated desorption energy distributions clearly illustrate the very different adsorption behavior of furan and tetrahydrofuran which leads to large differences in the binding energies between the corresponding adsorption complexes. This revised version was published online in July 2006 with corrections to the Cover Date.     

Transitions to electrochemical turbulence

We report experimental evidence of transitions from limit cycle oscillations through a phase turbulent regime to space-time defect turbulence in a spatially (quasi-)one-dimensional electrochemical system with nonlocal coupling. The transitions are characterized in terms of the defect density, the Karhunen-Loève decomposition dimension, and a measure of the degree of spatial correlation in the data. Furthermore, these quantities give the first experimental confirmation that the spatial coupling range in electrochemical systems indeed depends on the distance between the working and the counterelectrode.     

Test elements in pro-<Emphasis Type="Italic">p</Emphasis> groups with applications in discrete groups

Let G be a group. An element g ∈ G is called a test element of G if for every endomorphism ? : G → G, ?(g) = g implies ? is an automorphism. We prove that for a finitely generated profinite group G, g ∈ G is a test element of G if and only if it is not contained in a proper retract of G. Using this result we prove that an endomorphism of a free pro-p group of finite rank which preserves an automorphic orbit of a nontrivial element must be an automorphism. We give numerous explicit examples of test elements in free pro-p groups and Demushkin groups. By relating test elements in finitely generated residually finite-p Turner groups to test elements in their pro-p completions, we provide new examples of test elements in free discrete groups and surface groups. Moreover, we prove that the set of test elements of a free discrete group of finite rank is dense in the profinite topology.