Dynamic control of surface energy and topography of microstructured conducting polymer films

Microstructured polymer surfaces, including conducting and insulating polymers, have been prepared to achieve electrochemical control of the surface energy and topography. The reported surface switches include pillar- and mesh-like surface patterns of polypyrrole (PPy), poly(3,4-ethylene-dioxythiophene) (PEDOT), and photoresists. The structures have been evaluated by contact angle measurements and optical and scanning electron microscopy to determine the surfaces characteristics. These microstructured polymer surface switches can be electrochemically modified from dewetting to wetting conditions, with a maximum associated change of the water contact angle from 129 degrees to 44 degrees . This contact angle switching was observed for samples in which dynamic control of the surface topography and surface tension was coupled. Control of topography was achieved with a dynamic height-switching range of more than 3 mum. In addition, dynamic control of anisotropic wetting is reported. Our experiments were carried out under conditions that are suitable for a biointerface, implying potential application in biotechnology and cell science. In particular, switching of the energy, chemistry, and topography of the surface, along with their associated orientation, are interesting features for dynamic (electronic) control of the seeding and proliferation for living cells. The technology reported promises for electronically controlled cell-growth within Petri dishes, well plates, and other cell-hosting tools.     

Valence-band electronic structure of iron phthalocyanine: an experimental and theoretical photoelectron spectroscopy study

The electronic structure of iron phthalocyanine (FePc) in the valence region was examined within a joint theoretical-experimental collaboration. Particular emphasis was placed on the determination of the energy position of the Fe 3d levels in proximity of the highest occupied molecular orbital (HOMO). Photoelectron spectroscopy (PES) measurements were performed on FePc in gas phase at several photon energies in the interval between 21 and 150 eV. Significant variations of the relative intensities were observed, indicating a different elemental and atomic orbital composition of the highest lying spectral features. The electronic structure of a single FePc molecule was first computed by quantum chemical calculations by means of density functional theory (DFT). The hybrid Becke 3-parameter, Lee, Yang and Parr (B3LYP) functional and the semilocal 1996 functional of Perdew, Burke and Ernzerhof (PBE) of the generalized gradient approximation (GGA-)type, exchange-correlation functionals were used. The DFT/B3LYP calculations find that the HOMO is a doubly occupied π-type orbital formed by the carbon 2p electrons, and the HOMO-1 is a mixing of carbon 2p and iron 3d electrons. In contrast, the DFT/PBE calculations find an iron 3d contribution in the HOMO. The experimental photoelectron spectra of the valence band taken at different energies were simulated by means of the Gelius model, taking into account the atomic subshell photoionization cross sections. Moreover, calculations of the electronic structure of FePc using the GGA+U method were performed, where the strong correlations of the Fe 3d electronic states were incorporated through the Hubbard model. Through a comparison with our quantum chemical calculations we find that the best agreement with the experimental results is obtained for a U(eff) value of 5 eV.     

An easily accessible isoindigo-based polymer for high-performance polymer solar cells

A new, low-band-gap alternating copolymer consisting of terthiophene and isoindigo has been designed and synthesized. Solar cells based on this polymer and PC(71)BM show a power conversion efficiency of 6.3%, which is a record for polymer solar cells based on a polymer with an optical band gap below 1.5 eV. This work demonstrates the great potential of isoindigo moieties as electron-deficient units for building donor-acceptor-type polymers for high-performance polymer solar cells.     

Experimental and theoretical multiple kinetic isotope effects for an SN2 reaction. An attempt to determine transition-state structure and the ability of theoretical methods to predict experimental kinetic isotope effects

The secondary alpha-deuterium, the secondary beta-deuterium, the chlorine leaving-group, the nucleophile secondary nitrogen, the nucleophile (12)C/(13)C carbon, and the (11)C/(14)C alpha-carbon kinetic isotope effects (KIEs) and activation parameters have been measured for the S(N)2 reaction between tetrabutylammonium cyanide and ethyl chloride in DMSO at 30 degrees C. Then, thirty-nine readily available different theoretical methods, both including and excluding solvent, were used to calculate the structure of the transition state, the activation energy, and the kinetic isotope effects for the reaction. A comparison of the experimental and theoretical results by using semiempirical, ab initio, and density functional theory methods has shown that the density functional methods are most successful in calculating the experimental isotope effects. With two exceptions, including solvent in the calculation does not improve the fit with the experimental KIEs. Finally, none of the transition states and force constants obtained from the theoretical methods was able to predict all six of the KIEs found by experiment. Moreover, none of the calculated transition structures, which are all early and loose, agree with the late (product-like) transition-state structure suggested by interpreting the experimental KIEs.     

Diffusion in an inhomogeneous system: NMR studies of diffusion in highly concentrated emulsions

In this study the self-diffusion of different species in highly concentrated water-in-oil emulsions was investigated by means of the NMR diffusometry approach. The emulsions contained 96% aqueous solutions of salt or other additives; heptane was used as the oil phase. The surfactants, used to stabilize the emulsion, were soybean phosphatidylcholine and C(12)EO(4). The water drops were about 1.5 microm in diameter according to diffusion measurements performed on water. Diffusion of tetramethyl ammonium ions and glucose between the emulsion droplets was found to be negligible on the relevant time-scale (<1 s). On the contrary, acetic acid/acetate ions diffused between the droplets and had exchange times which were a function of pH.     

On the convergence of supercritical general (C-M-J) branching processes

Summary Convergence in probability of Malthus normed supercritical general branching processes (i.e. Crump-Mode-Jagers branching processes) counted with a general characteristic are established, provided the latter satisfies mild regularity conditions. If the Laplace transform of the reproduction point process evaluated in the Malthusian parameter has a finite x log x-moment convergence in probability of the empirical age distribution and more generally of the ratio of two differently counted versions of the process also follow.Malthus normed processes are also shown to converge a.s., provided the tail of the reproduction point process and the characteristic both satisfy mild regularity conditions. If in addition the x log x-moment above is finite a.s. convergence of ratios follow.Further, a finite expectation of the Laplace-transform of the reproduction point process evaluated in any point smaller than the Malthusian parameter is shown to imply a.s. convergence of ratios even if the x log x-moment above equals infinity.Straight-forward generalizations to the multi-type case are available in Nerman (1979).     

Exciton dynamics in alternating polyfluorene/fullerene blends

Exciton dynamics in alternating copolymer/fullerene solar cell blends have been investigated using femtosecond transient absorption spectroscopy. The acceptor concentrations have been varied over a wide range. Experimental data, kinetic modeling and simulations, all indicate that the efficiency of exciton conversion to charges is 100% even at acceptor concentrations as low as 20 wt%. The reported dependence of solar cell efficiency on fullerene concentration may thus arise from other factors. However, there exists an acceptor concentration threshold (5 wt%) below which a substantial fraction of the excitations remain unquenched. The results, we believe are very relevant to optimization of performance efficiency by clever manipulation of morphology. We have also observed exciton–exciton energy transfer in these blends at low acceptor concentrations.     

Arsenic speciation by coupling high-performance liquid chromatography with inductively coupled plasma mass spectrometry

Summary An ICP-MS detector in combination with HPLC has been evaluated for the analysis of six arsenic compounds. The influence of the presence of an organic modifier in the mobile phase on arsenic response and the quality parameters of the analysis are discussed. Detection limits for arsenic species under study range from 10 to 30 pg. The determination of arsenic compounds in solutions simulating fish or sediment extracts has been used to demonstrate the applicability of this technique.