Analysis of ultrafast X-ray diffraction data in a linear-chain model of the lattice dynamics

We present ultrafast X-ray diffraction (UXRD) experiments which sensitively probe impulsively excited acoustic phonons propagating in a SrRuO₃/SrTiO₃ superlattice and further into the substrate. These findings are discussed together with previous UXRD results (Herzog et al. in Appl. Phys. Lett. 96, 161906, 2010; Woerner et al. in Appl. Phys. A 96, 83, 2009; v. Korff Schmising in Phys. Rev. B 78, 060404(R), 2008 and in Appl. Phys. B 88, 1, 2007) using a normal-mode analysis of a linear-chain model of masses and springs, thus identifying them as linear-response phenomena. We point out the direct correspondence of calculated observables with X-ray signals. In this framework the complex lattice motion turns out to result from an interference of vibrational eigenmodes of the coupled system of nanolayers and substrate. UXRD in principle selectively measures the lattice motion occurring with a specific wavevector, however, each Bragg reflection only measures the amplitude of a delocalized phonon mode in a spatially localized region, determined by the nanocomposition of the sample or the extinction depth of X-rays. This leads to a decay of experimental signals although the excited modes survive.     

Increased imaging speed and force sensitivity for bio-applications with small cantilevers using a conventional AFM setup

In this study, we demonstrate the increased performance in speed and sensitivity achieved by the use of small AFM cantilevers on a standard AFM system. For this, small rectangular silicon oxynitride cantilevers were utilized to arrive at faster atomic force microscopy (AFM) imaging times and more sensitive molecular recognition force spectroscopy (MRFS) experiments. The cantilevers we used had lengths between 13 and 46μm, a width of about 11μm, and a thickness between 150 and 600nm. They were coated with chromium and gold on the backside for a better laser reflection. We characterized these small cantilevers through their frequency spectrum and with electron microscopy. Due to their small size and high resonance frequency we were able to increase the imaging speed by a factor of 10 without any loss in resolution for images from several μm scansize down to the nanometer scale. This was shown on bacterial surface layers (s-layer) with tapping mode under aqueous, near physiological conditions and on nuclear membranes in contact mode in ambient environment. In addition, we showed that single molecular forces can be measured with an up to 5 times higher force sensitivity in comparison to conventional cantilevers with similar spring constants.     

1H-1,2,4-Triazole as solvent for imidazolium methanesulfonate

The solvation effect of 1H-1,2,4-triazole towards imidazolium methanesulfonate was studied by blending imidazolium methanesulfonate and 1H-1,2,4-triazole. Upon addition of 1H-1,2,4-triazole, the melting point of imidazolium methanesulfonate was lowered to less than 100 °C while maintaining the high ionic conductivity for a wide composition range of the blend. The ionic conductivity of the blend can be adequately described by using the Vogel-Fulcher-Tamman equation. A vehicle mechanism is postulated to govern the proton conduction for the blend. The contribution of protons to the ionic conductivity was corroborated electrochemically. The blend exhibited electrochemical activities for H(2) oxidation and O(2) reduction at a Pt electrode, as well as a wide electrochemical window. Therefore, suitable blends can possibly serve as electrolytes for polymer electrolyte membrane fuel cells operating under non-humidifying conditions. The solvation effect studied herein suggests a promising approach to a wider application area of protic ionic liquids.     

Spectroscopic characterizations on the N,N′-bis-alkyl derivatives of 1,4,6,8-naphthalenediimide charge-transfer complexes

Charge-transfer (CT) complexes formed from the reactions of two N,N′-bis-alkyl derivatives of 1,4,6,8-naphthalenediimide such as N,N′-bis-[2-hydroxyethyl]-1,4,6,8-naphthalenediimide (BHENDI) and N,N′-bis-[2-N,N-dimethylaminoethyl]-1,4,6,8-naphthalenediimide (BDMAE NDI) with DDQ, CHL, TCNQ, DCQ and DBQ as π-acceptors have been studied spectrophotometrically in chloroform and/or methanol at 25 °C. The photometric titration curves for the reactions indicated that the data obtained refer to 1:1 charge-transfer complexes of [(BHENDI)(DDQ)], [(BDMAENDI)(DDQ)], [(BHENDI)(CHL)], [(BDMAENDI)(CHL)], [(BHENDI)(TCNQ)], [(BDMAENDI)(TCNQ)], [(BHENDI)(DCQ)], [(BDMAENDI)(DCQ)], [(BHENDI)(DBQ)] and [(BDMAENDI)(DBQ)] were formed. Benesi–Hildebrand and its modification methods were applied to the determination of association constant (K), molar extinction coefficient (?). The solid CT complexes have been synthesized and characterization by different spectral methods.     

Orientation of the axial ligands and magnetic properties of the hemes in the cytochrome c7 family from Geobacter sulfurreducens determined by paramagnetic NMR

Geobacter sulfurreducens is a sediment bacterium that contains a large number of multiheme cytochromes. The family of five c(7) triheme periplasmic cytochromes from Geobacter sulfurreducens shows structural diversity of the heme core. Structural characterization of the relative orientation of the axial ligands of these proteins by (13)C-paramagnetic NMR was carried out. The structures in solution were compared with those obtained by X-ray crystallography. For some hemes significant differences exist between the two methods such that orientation of the magnetic axes obtained from NMR data and the orientation taken from the X-ray coordinates differ. The results allowed the orientation of the magnetic axes to be defined confidently with respect to the heme frame in solution, a necessary step for the use of paramagnetic constraints to improve the complete solution structure of these proteins.     

Dynamic measurement of the height and volume of migrating cells by a novel fluorescence microscopy technique

We propose a new technique to measure the volume of adherent migrating cells. The method is based on a negative staining where a fluorescent, non-cell-permeant dye is added to the extracellular medium. The specimen is observed with a conventional fluorescence microscope in a chamber of uniform height. Given that the fluorescence signal depends on the thickness of the emitting layer, the objects excluding the fluorescent dye (i.e., cells) appear dark, and the decrease of the fluorescent signal with respect to the background is expected to give information about the height and the volume of the object. Using a glass microfabricated pattern with steps of defined heights, we show that the drop in fluorescence intensity is indeed proportional to the height of the step and obtain calibration curves relating fluorescence intensity to height. The technique, termed the fluorescence displacement method, is further validated by comparing our measurements with the ones obtained by atomic force microscopy (AFM). We apply our method to measure the real-time volume dynamics of migrating fish epidermal keratocytes subjected to osmotic stress. The fluorescence displacement technique allows fast and precise monitoring of cell height and volume, thus providing a valuable tool for characterizing the three-dimensional behaviour of migrating cells.     

Energy spectra and bubble velocity distributions in pseudo-turbulence: Numerical simulations vs. experiments

Direct numerical simulations (DNS) are performed to study the behavior of a swarm of rising air bubbles in water, employing the front tracking method, which allows to handle finite-size bubbles. The swarms consist of monodisperse deformable 4 mm bubbles with a gas fraction of 5% and 15%. This paper focuses on the comparison of the liquid energy spectra and bubble velocity probability density functions (PDFs) with experimental data obtained by phase-sensitive constant-temperature anemometry (CTA) and three-dimensional particle tracking velocimetry (PTV), respectively.     

Water and aqueous solutions: simple non-speculative model approach

Different ways of molecular modeling of water are analyzed and their similarities and differences identified. An up-to-date summary of achievements of a general approach to common rigid site-site interaction models of molecular fluids applied to water and aqueous solutions is then presented and discussed. The method is based on considering only a short-range part of a total realistic potential (such as SPC/E or TIPxP) which determines the structure of water (and fluids in general). A simplification of the interactions at short intermolecular separations leads then to simple models, called primitive models. Quite accurate results in an analytic form for the thermodynamic properties of the models are obtained using the thermodynamic perturbation theory. It is shown that the properly constructed primitive models reproduce, qualitatively, anomalies of pure water and basic characteristics of hydrophobic hydration. The concept of an extended excluded volume, based on pseudo-hard bodies, is introduced and exemplified by considering the partial molar volume of apolar solutes. Potential future development towards a theory of water based on the primitive models as a reference with the long-range contributions added as a perturbation is discussed.     

Ultrafast carotenoid band shifts correlated with ChlZ excited states in the photosystem II reaction center: are the carotenoids involved in energy transfer?

We show a correlation between the electronic excitation of the peripheral chlorophylls (Chls(Z)) of the photosystem II reaction center and a shift of the S(2) absorption bands of β-carotene, and suggest that the carotenoids may enhance the excitation energy transfer rate from these chlorophylls to the central cofactors.