Laser field induced charge transfer: Para-nitroaniline coupled to a quantum mechanical radiation field

Summary We present a preliminary model for describing a solvated intramolecular charge transfer reaction coupled to a quantum mechanical radiation field. Actual calculations of energies and couplings were performed with a recently developed self-consistent reaction field response method. The representation of dressed molecular states is used for calculating state populations for various laser fields. The state populations are sensitive to the properties of the laser field.     

Evaluations of solid electrodes for use in voltammetric monitoring of heavy metals in samples from metallurgical nickel industry

Evaluation of different solid electrode systems for detection of zinc, lead, cobalt, and nickel in process water from metallurgical nickel industry with use of differential pulse stripping voltammetry has been performed. Zinc was detected by differential pulse anodic stripping voltammetry (DPASV) on a dental amalgam electrode as intermetallic Ni–Zn compound after dilution in ammonium buffer solution. The intermetallic compound was observed at –375 mV, and a linear response was found in the range 0.2–1.2 mg L^–1 (r²=0.98) for 60 s deposition time. Simultaneous detection of nickel and cobalt in the low g L^–1 range was successfully performed by use of adsorptive cathodic stripping voltammetry (AdCSV) of dimethylglyoxime complexes on a silver–bismuth alloy electrode, and a good correlation was found with corresponding AAS results (r²=0.999 for nickel and 0.965 for cobalt). Analyses of lead in the g L^–1 range in nickel-plating solution were performed with good sensitivity and stability by DPASV, using a working electrode of silver together with a glassy carbon counter electrode in samples diluted 1:3 with distilled water and acidified with H₂SO₄ to pH 2. A new commercial automatic at-line system was tested, and the results were found to be in agreement with an older mercury drop system. The stability of the solid electrode systems was found to be from one to several days without any maintenance needed.     

Conformation of glycomimetics in the free and protein-bound state: structural and binding features of the C-glycosyl analogue of the core trisaccharide alpha-D-Man-(1 --> 3)-[alpha-D-Man-(1 --> 6)]-D-Man

The conformational properties of the C-glycosyl analogue of the core trisaccharide alpha-D-Man-(1 --> 3)-[alpha-D-Man-(1 --> 6)]-D-Man in solution have been carefully analyzed by a combination of NMR spectroscopy and time-averaged restrained molecular dynamics. It has been found that both the alpha-1,3- and the alpha-1,6-glycosidic linkages show a major conformational averaging. Unusual Phi ca. 60 degrees orientations for both Phi torsion angles are found. Moreover, a major conformational distinction between the natural compound and the glycomimetic affects to the behavior of the omega(16) torsion angle around the alpha-1 --> 6-linkage. Despite this increased flexibility, the C-glycosyl analogue is recognized by three mannose binding lectins, as shown by NMR (line broadening, TR-NOE, and STD) and surface plasmon resonance (SPR) methods. Moreover, a process of conformational selection takes place, so that these lectins probably bind the glycomimetic similarly to the way they recognize the natural analogue. Depending upon the architecture and extension of the binding site of the lectin, loss or gain of binding affinity with respect to the natural analogue is found.     

Correction of Gauge Factor for Strain Gauges Used in Polymer Composite Testing

Strain gauges are used together with the corresponding gauge factor to relate the relative electrical resistance change of the strain gauge with the strain of the underlying material. The gauge factor is found from a calibration on a stiff material - steel. Nevertheless, the gauge factor depends on the stiffness of the calibration material and ideally the calibration should be done on a similar material as tested. In practice, the gauge factor found by the strain gauge manufacturer is often used. The paper documents that even for moderately stiff materials such as glass-fibre composites a significant error is found on the strain measurements obtained by the strain gauges. This is documented both experimentally and numerically. A stiffness, also test sample and strain gauge geometry dependent correction coefficient of the gauge factor is proposed. A correction coefficient covers material stiffnesses ranging from 1 GPa to 200 GPa.     

Solar Thermal Energy Storage in a Photochromic Macrocycle

The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA–DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF–VHF). A stepwise energy release over two sequential ring‐closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long‐term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release.     

Experimental investigation of three-dimensional flow instabilities in a rotating lid-driven cavity

The swirling flow between a rotating lid and a stationary cylinder is studied experimentally. The flow is governed by two parameters: the ratio of container height to disk radius, h, and the Reynolds number, Re, based on the disk angular velocity, cylinder radius and kinematic viscosity of the working liquid. For the first time, the onset of three-dimensional flow behavior is measured by combining the high spatial resolution of particle image velocimetry and the temporal accuracy of laser Doppler anemometry. A detailed mapping of the transition scenario from steady and axisymmetric flow to unsteady and three-dimensional flow is investigated for 1 ≥ h ≥ 3.5. The flow is characterized by the development of azimuthal modes of different wave numbers. A range of different modes is detected and critical Reynolds numbers and associated frequencies are identified. The results are compared to the numerical stability analysis of Gelfgat et al. (J Fluid Mech 438:363–377, 2001). In most cases, the measured onset of three-dimensionality is in good agreement with the numerical results and disagreements can be explained by bifurcations not accounted for by the numerical stability analysis.     

Investigation of a wake decay behind a circular disk in a hydro channel at high Reynolds numbers

LDA and PIV techniques were used to study the decay of an axisymmetrical turbulent wake originated downstream an immobile disk in a water flume for Reynolds numbers Re = 1.5?2.4?10⁵. Data were compared with experiments performed with a set of thermo-anemometers behind a disk in a wind tunnel at lower Reynolds numbers (Re = 1.3?2.6?10⁴). Observations for a new range of Reynolds number confirmed that the velocity distribution in the disk wake keeps self-similarity. The decay of a wake by the power law ?2/3 in the presented experiments remains until the maximum deficit of velocity becomes comparable with the turbulent pulsation level in the free-stream (less than 2 %).