Coupling artificial actin cortices to biofunctionalized lipid monolayers

We report the assembly of protein supramolecular structures at an air-water interface and coupling of artificial actin cortices to such structures. The coupling strategies adopted include electrostatic binding of actin to monolayers doped with lipids, exposing positively charged poly(ethylene glycol) headgroups; binding of biotinylated actin to lipids carrying biotin headgroups through avidin; binding of actin to membranes through biotinylated hisactophilin (a cellular actin-membrane coupler) using an avidin-biotin linkage; and coupling of actin to membranes carrying chelating lipids through a 15-nm-diameter protein capsid (bacterial lumazine synthase or LuSy) exhibiting histidine tags (which bind both to actin and to the chelating lipid). The distribution of the proteins in a direction normal to the interface was measured by neutron reflectivity under different conditions of pH and ionic strength. In the case of the first three binding methods, the thickness of the actin film was found to correspond to a single actin filament. Multilayers of actin could be formed only by using the multifunctional LuSy couplers that exhibit 60 hexahistidine tags and can thus act as actin cross-linkers. The LuSy-mediated binding can be reversibly switched by pH variations.     

Calculation of absorption spectra for light-harvesting systems using non-Markovian approaches as well as modified Redfield theory

For an ensemble of B850 rings of the light-harvesting system LH2 of purple bacteria the linear absorption spectrum is calculated. Using different Markovian and non-Markovian, time-dependent and time-independent methods based on second-order perturbation theory in the coupling between the excitonic system and its surrounding environment as well as the modified Redfield theory, the influence of the shape of the spectral density on the linear absorption spectrum is demonstrated for single samples and in the ensemble average. For long bath correlation times non-Markovian effects clearly show up in the static absorption line shapes. Among the different spectral densities studied is one of the purple bacterium Rhodospirillum molischianum obtained by a molecular-dynamics simulation earlier. The effect of static disorder on its line shapes in the ensemble average is analyzed and the results of the present calculations are compared to experimental data.     

Brewster-angled chirped mirrors for broadband pulse compression without dispersion oscillations

We use Brewster-angled chirped mirrors for dispersion compensation of a noncollinear optical parametric amplifier. This novel mirror design virtually eliminates spurious surface reflections and resultant dispersion ripple. The absence of compression artifacts is demonstrated by the generation of clean 5.6 fs pulses, with what is believed to be an unprecedented low ripple-induced satellite content for a nonadaptive scheme. In addition, the 270 THz spectral coverage allows generation of widely tunable visible pulses of 8 to 15 fs duration.     

Combined coherent anti-Stokes Raman spectroscopy and linear Raman spectroscopy for simultaneous temperature and multiple species measurements

The simultaneous application of pure rotational coherent anti-Stokes Raman spectroscopy (CARS) and vibrational linear Raman spectroscopy (LRS) for the measurement of temperature and species concentrations in combustion systems is demonstrated. In addition to the standard rotational CARS experimental setup, only one detection system (spectrometer and intensified CCD camera) for the collection of the LRS signals was applied. The emission of the broadband dye laser used for CARS was shifted to the deep red to avoid interferences with the LRS signals located in the visible region. First experimental results from a vaporizing propane spray using an engine injection system are shown.     

The 15N chemical shifts in mixed NB2Si and NBSi2 environments of Si3B3N7--a theoretical investigation

Nuclear magnetic resonance (NMR) chemical shifts in solids may be calculated by ab initio methods approximating the solid state by molecular clusters. We employed this technique to obtain estimates of (15)N chemical shifts in NB(2)Si and NBSi(2) environments in the solid state. Such nitrogen environments are found in amorphous (Si/B/N-)ceramics which exhibit very interesting features such as high thermal and mechanical stability. We based our calculations on cutouts of hypothetical Si(3)B(3)N(7) crystals suggested by Kroll and Hoffmann [Silicon boron nitrides: hypothetical polymorphs of Si(3)B(3)N(7), Angew. Chem. Int. Ed. 37 (1998) 2527]. Taking the systematic errors of our calculations into account we expect the chemical shifts in NBSi(2) environments around -293+/-5ppm. Chemical shifts in NB(2)Si environments are expected at -272+/-6ppm. The range of the calculated chemical shifts in NBSi(2) environments coincides with experimental chemical shifts in molecular compounds. Experimental chemical shifts of NB(2)Si nitrogen in molecules appear at lower field than our calculated chemical shifts in the solid state.     

Performance of cryogenic probes as a function of ionic strength and sample tube geometry

The pursuit for more sensitive NMR probes culminated with development of the cryogenic cooled NMR probe. A key factor for the sensitivity is the overall resistance of RF circuitry and sample. Lowering the coil temperature to approximately 25 K and the use of superconducting coil material has greatly reduced the resistance contribution of the hardware. However, the resistance of a salty sample remains the same and evolves as the major factor determining the signal-to-noise ratio. Several approaches have been proposed to reduce the resistance contribution of the sample. These range from encapsulating proteins in a water cavity formed by reverse micelles in low viscosity fluids to the optimal selection of low mobility, low conductivity buffer ions. Here we demonstrate that changing the sample diameter has a pronounced effect on the sample resistance and this results in dramatic improvements of the signal-to-noise ratio and shorter pi/2 pulses. We determined these parameters for common 5 mm NMR tubes under different experimental conditions and compared them to the 2, 3 and 4 mm tubes, in addition, 5mm Shigemi tubes were included since these are widely used. We demonstrate benefits and applicability of studying NMR samples with up to 4M salt concentrations in cryogenic probes. Under high salt conditions, best results in terms of short pi/2 pulses and high signal-to-noise ratios are obtained using 2 or 3mm NMR tubes, especially when limited sample is available. The 4 mm tube is preferred when sample amounts are abundant at intermediate salt conditions.     

On retardation,radiation and Liénard–Wiechert type potentials in electrodynamics and elastodynamics

The aim of this paper is to investigate the fundamental problems of retardation and radiation caused by non-uniformly moving point sources using the theories of electrodynamics and elastodynamics. This paper investigates and compares the retarded electromagnetic fields and the retarded elastodynamic fields. For the non-uniform motion of a general point source, the Liénard–Wiechert type potentials and the radiation and nonradiation fields are derived for a point charge and for a point force.     

Simultaneous Measurements of Temperature and CO Concentration in Stagnation Stabilized Flames

An impinging jet burner was developed to investigate flame-wall interactions (FWI) using laser based diagnostics. CO concentrations were measured with two-photon laser-induced fluorescence (LIF) in combination with coherent anti-Stokes Raman spectroscopy (CARS) gas phase temperature measurements. Besides being the principal factor in chemical kinetics, temperature data is required to correct the CO LIF data for various factors like density variation, quenching and variation in the Boltzmann population. Phosphor thermometry was used to determine surface temperatures of the wall and to estimate the heat flux. In an parameter study Reynolds numbers and fuel equivalence ratio were varied.     

A Study of Microscale Gas Trapping Using Etched Silicon Micromodels

Immobilization and trapping of carbon dioxide (CO₂) enhances the security of geological storage. Trapping mechanisms have been characterized in four groups: structural, residual, dissolution, and mineralization. While structural trapping acts immediately when injection starts and is well investigated, the contribution of residual and dissolution trapping increases over storage time and these contributions need to be better understood for better predictions. This paper focuses on an experimental pore-scale investigation of residual and capillary trapping. CO₂?Cwater imbibition experiments were conducted in micromodels whose homogenous pore space is geometrically and topologically similar to Berea sandstone. Microvisual data, photographs and video footage, describes the trapping mechanism and, especially, the disconnection and shrinkage of the CO₂ phase. Results show that depending on the flow rate of the imbibing water different trapping mechanisms are observed. Lower flow rates, comparable to the trailing edge of a CO₂ plume, lead to more snap-off events and greater trapped residual saturation, whereas rates comparable to the near wellbore area during enhanced sequestration showed displacement of gas bubbles and greater dissolution that ultimately leads to very low or zero gas saturations. Furthermore, complete dissolution events showed that homogenous as well as heterogeneous dissolution occurs. Whereas the latter is subdivided into microbubble formation and dissolution on crevices or pore roughness, the former occurs without the influence of pore walls. Based on the observations we suggest that the type of rock and its roughness as well as the fines present at the CO₂ brine interface are important factors determining the dissolution mechanism.