Action Spectroscopy on Dense Samples of Photosynthetic Reaction Centers of Rhodobacter sphaeroides WT Based on Nanosecond Laser-Flash 13C Photo-CIDNP MAS NMR

Photochemically induced dynamic nuclear polarization magic-angle spinning nuclear magnetic resonance (photo-CIDNP MAS NMR) allows for the investigation of the electronic structure of the photochemical machinery of photosynthetic reaction centers (RCs) at atomic resolution. For such experiments, either continuous radiation from white xenon lamps or green laser pulses are applied to optically dense samples. In order to explore their optical properties, optically thick samples of isolated and quinone-removed RCs of the purple bacteria of Rhodobacter sphaeroides wild type are studied by nanosecond laser-flash ¹³C photo-CIDNP MAS NMR using excitation wavelengths between 720 and 940 nm. Action spectra of both the transient nuclear polarization as well as the nuclear hyperpolarization, remaining in the electronic ground state at the end of the photocycle, are obtained. It is shown that the signal intensity is limited by the amount of accessible RCs and that the different mechanisms of the photo-CIDNP production rely on the same photophysical origin, which is the photocycle induced by one single photon.     

Nanosecond-Flash 15N Photo-CIDNP MAS NMR on Reaction Centers of Rhodobacter sphaeroides R26

Photochemically induced dynamic nuclear polarization (photo-CIDNP) is observed with time-resolved ¹⁵N magic-angle spinning (MAS) nuclear magnetic resonance (NMR) in uniformly ¹⁵N-labeled reaction centers (RCs) of the purple bacterium Rhodobacter (Rb.) sphaeroides R26 under illumination with nanosecond laser flashes. The ¹⁵N NMR signals enhanced by the solid-state photo-CIDNP effect are related to electron spin densities in the primary radical pair and allow for reconstruction of the electronic structure at atomic scale. New assignments for the photochemically active nitrogens are proposed based on simulations of the intensities. The ratio of electron spin densities between cofactors P _L and P _M is observed to be about 4:1. The origin of the high asymmetry is discussed.     

Modeling phase transition for compressible two-phase flows applied to metastable liquids

The seven-equation model for two-phase flows is a full non-equilibrium model, each phase has its own pressure, velocity, temperature, etc. A single value for each property, an equilibrium value, can be achieved by relaxation methods. This model has better features than other reduced models of equilibrium pressure for the numerical approximations in the presence of non-conservative terms. In this paper we modify this model to include the heat and mass transfer. We insert the heat and mass transfer through temperature and Gibbs free energy relaxation effects. New relaxation terms are modeled and new procedures for the instantaneous temperature and Gibbs free energy relaxation toward equilibrium is proposed. For modeling such relaxation terms, our idea is to make use of the assumptions that the mechanical properties, the pressure and the velocity, relax much faster than the thermal properties, the temperature and the Gibbs free energy, and the ratio of the Gibbs free energy relaxation time to the temperature relaxation time is extremely high. All relaxation processes are assumed to be instantaneous, i.e. the relaxation times are very close to zero. The temperature and the Gibbs free energy relaxation are used only at the interfaces. By these modifications we get a new model which is able to deal with transition fronts, evaporation fronts, where heat and mass transfer occur. These fronts appear as extra waves in the system. We use the same test problems on metastable liquids as in Saurel et al. [R. Saurel, F. Petitpas, R. Abgrall, Modeling phase transition in metastable liquids: application to cavitating and flashing flows, J. Fluid Mech. 607 (2008) 313–350]. We have almost similar results. Computed results are compared to the experimental ones of Simões-Moreira and Shepherd [J.R. Simões-Moreira, J.E. Shepherd, Evaporation waves in superheated dodecane, J. Fluid Mech. 382 (1999) 63–86]. A reasonable agreement is achieved. In addition we consider the six-equation model with a single velocity which is obtained from the seven-equation model in the asymptotic limit of zero velocity relaxation time. The same procedure for the heat and mass transfer is used with the six-equation model and a comparison is made between the results of this model with the results of the seven-equation model.     

Pulse-width modulation in defocused three-dimensional fringe projection

Shape measurements by fringe projection methods require high-quality sinusoidal fringes. We present a sinusoidal fringe generation technique that utilizes slightly defocused binary fringe projection. The proposed method is a spatial version of the well-known pulse-width modulation (PWM) technique of electrical engineering. PWM is easy to implement using off-the-shelf projectors, and it allows us to overcome the gamma problem (i.e., the nonlinear projector response) in the output light intensity. We will demonstrate that, with a small defocusing level--lower than with other techniques proposed in the literature--a high-quality sinusoidal pattern is obtained. Validation experiments using a commercial video projector are presented.     

Continuous time random walks and the Cauchy problem for the heat equation

We deal with anomalous diffusions induced by continuous time random walks - CTRW in ?ⁿ. A particle moves in ?ⁿ in such a way that the probability density function u(·, t) of finding it in region Ω of ?ⁿ is given by ∫_Ωu(x, t)dx. The dynamics of the diffusion is provided by a space time probability density J(x, t) compactly supported in {t ≥ 0}. For t large enough, u satisfies the equation

$$u\left( {x,t} \right) = \left[ {\left( {J - \delta } \right)*u} \right]\left( {x,t} \right)$$

, where δ is the Dirac delta in space-time. We give a sense to a Cauchy type problem for a given initial density distribution f. We use Banach fixed point method to solve it and prove that under parabolic rescaling of J, the equation tends weakly to the heat equation and that for particular kernels J, the solutions tend to the corresponding temperatures when the scaling parameter approaches 0.

     

Reversible activation of diblock copolymer monolayers at the interface by pH modulation, 2: Membrane interactions at the solid/liquid interface

A monolayer of the pH-responsive poly[2-(dimethylamino)ethyl methacrylate-block-methyl methacrylate] diblock copolymer [PDMAEMA-PMMA] was transferred from the air/water interface to a silicon substrate for evaluation as a tunable interlayer between biological material and solid substrates. Specular neutron reflectivity experiments revealed that the weak polyelectrolyte PDMAEMA chains at the solid/liquid interface can be reversibly activated by pH modulation. The thickness, scattering length density, and surface roughness of the polymer film can be systematically controlled by pH titration. As a simple model of plasma membranes, a lipid bilayer was deposited onto the polymer film. The membrane-substrate interaction was characterized by neutron reflectivity experiments, demonstrating that the membrane-substrate distance could be reversibly regulated by pH titration. These results confirm the potential of stimuli-responsive polymers for precise control of cell-surface interactions.     

Lead‐free on‐laminate laser soldering: a new module assembling concept

We demonstrate lead‐free laser soldering of standard industrial solar cells. The laser‐soldered contacts stay stable for more than 240 accelerated ageing cycles by humidity–freeze test and withstand peel forces in excess of 10 N/cm. Laser soldering is demonstrated while the cells are lying on the ethylene vinyl acetate (EVA) foil. This permits to connect the solar cells to the lead‐free tinned copper ribbons directly on the lamination materials. We also demonstrate soldering on the bottom side by lasering through the glass and the non‐polymerized EVA. With the aid of a pick and place robot it thus becomes possible to avoid all string handling. On‐laminate laser soldering (OLLS) technique, which permits a high level of automation and process control, induces little thermal and mechanical stress, reduces the handling and should thus be of particular advantage for assembling modules with very thin cells at a high yield. Copyright © 2007 John Wiley & Sons, Ltd.     

Stereoinversion of Unactivated Alcohols by Tethered Sulfonamides

The direct, catalytic substitution of unactivated alcohols remains an undeveloped area of organic synthesis. Moreover, catalytic activation of this difficult electrophile with predictable stereo‐outcomes presents an even more formidable challenge. Described herein is a simple iron‐based catalyst system which provides the mild, direct conversion of secondary and tertiary alcohols to sulfonamides. Starting from enantioenriched alcohols, the intramolecular variant proceeds with stereoinversion to produce enantioenriched 2‐ and 2,2‐subsituted pyrrolidines and indolines, without prior derivatization of the alcohol or solvolytic conditions.     

Zinc Substitution of Cobalt in Vitamin B12: Zincobyric acid and Zincobalamin as Luminescent Structural B12‐Mimics

Replacing the central cobalt ion of vitamin B₁₂ by other metals has been a long‐held aspiration within the B₁₂‐field. Herein, we describe the synthesis from hydrogenobyric acid of zincobyric acid ( Znby ) and zincobalamin ( Znbl ), the Zn‐analogues of the natural cobalt‐corrins cobyric acid and vitamin B₁₂, respectively. The solution structures of Znby and Znbl were studied by NMR‐spectroscopy. Single crystals of Znby were produced, providing the first X‐ray crystallographic structure of a zinc corrin. The structures of Znby and of computationally generated Znbl were found to resemble the corresponding Co^II‐corrins, making such Zn‐corrins potentially useful for investigations of B₁₂‐dependent processes. The singlet excited state of Znby had a short life‐time, limited by rapid intersystem crossing to the triplet state. Znby allowed the unprecedented observation of a corrin triplet (E^T=190 kJ mol^?1) and was found to be an excellent photo‐sensitizer for ¹O₂ (Φ_Δ=0.70).