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The oxidation of the aniline dimer, p-aminodiphenylamine (PADPA), with Trametes versicolor laccase and O2 in an aqueous solution of pH 3.5 is controlled by negatively charged AOT (sodium bis(2-ethylhexyl) sulfosuccinate) vesicles. With vesicles, a product resembling polyaniline in its emeraldine salt form (PANI-ES) is obtained, in contrast to the reaction without vesicles where no such product is formed. To understand this observation, the product distribution and structures from the reaction with and without vesicles were determined by using partially selectively deuterated PADPA as a starting material and analyzing the products with HPLC-MS. We found that in the presence of vesicles the main product is obtained in about 50% yield, which is the N-C-para-coupled PADPA dimer that has spectroscopic properties of PANI-ES, as determined by time-dependent density functional theory (TD-DFT) calculations. A secondary reaction route leads to longer PADPA oligomers that must contain a phenazine core. Without vesicles, PADPA and its products undergo partial hydrolysis, but in the presence of vesicles, hydrolysis does not occur. Because molecular dynamics (MD) simulations show that the main intermediate oxidation product is embedded within the vesicle membrane, where the water content is very low, we propose that the microenvironment of the vesicle membrane protects the oxidation products from unwanted hydrolysis.

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We report detailed calculations of the quantum wavepacket dynamics of Cl-O-O-Cl, which serves as a prototype molecule for the stereomutation dynamics of an axially chiral molecule. We include the effects both from electroweak parity violation and from the interaction with a coherent monochromatic laser field. We use the quasiadiabatic channel reaction path Hamiltonian approach to approximately solve the six-dimensional Schrödinger equation describing the vibrational motion, including rotation by an effective Hamiltonian. We calculate time-dependent wave functions based on the time-dependent Schrödinger equation. We study stereomutation dynamics due to tunneling motion and laser-induced population transfer and show results on efficient methods for selectively populating single molecular states in chiral molecules by frequency-modulated laser pulses. We also discuss laser-induced stereomutation (LISM) and a process that may be called resonance Raman induced stereomutation (RRISM). The results are discussed in relation to current experimental attempts to measure the parity violating energy difference ΔpvE between the enantiomers of chiral molecules. Furthermore, we show detailed quantitative simulations of a selection of well-defined parity levels in chiral molecules ("parity isomers") that form the basis of a possible measurement of ΔpvE by the time evolution of parity.

RESUMEN

The enzymatic polymerization of aniline to polyaniline (PANI) with Trametes versicolor laccase (TvL) as catalyst and dioxygen (O2) as oxidant was investigated in an aqueous medium containing unilamellar vesicles with an average diameter of about 80 nm formed from AOT (=sodium bis(2-ethylhexyl) sulfosuccinate). Compared to the same reaction carried out with horseradish peroxidase isoenzyme C (HRPC) as catalyst and hydrogen peroxide (H2O2) as oxidant, notable differences were found in the kinetics of the reaction, as well as in the characteristics of the PANI obtained. Under comparable optimal conditions, which are pH 3.5 for TvL/O2 and pH 4.3 for HRPC/H2O2, the reaction with TvL/O2 was much slower than with HRPC/H2O2, i.e. ≈27 days vs. 1 day reaction time to reach equilibrium with >90% yield at 25 °C. Although in both cases, aniline monomer coupling occurred mainly via the carbon atom in para position of aniline, UV-vis-NIR absorption and EPR measurements indicate that the reaction with TvL/O2 yielded mainly overoxidized products (with λ(max)=730 nm). These products had a lower amount of unpaired electrons if compared with the products obtained with HRPC/H2O2 (with λ(max)≈1000 nm, which is characteristic for the polaron state of PANI-ES, the emeraldine salt form of PANI). Similarly to previous findings with HRPC/H2O2, enzyme inactivation occurred during the polymerization also in the case of TvL/O2. Since the aqueous PANI-vesicle suspensions obtained are of high colloidal stability, they can be used directly as ink in a conventional thermal inkjet printer for printing on paper or on surface treated polyimide films. Printed PANI-ES patterns on paper changed colour from green (emeraldine salt) to blue (emeraldine base) upon exposure to ammonia gas, demonstrating the expected ammonia sensing properties.

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The feasibility of using surfactant vesicles as soft templates for the peroxidase-triggered polymerization of aniline was investigated. It was found that mixed anionic vesicles (diameter approximately 80 nm) composed of sodium dodecylbenzenesulfonate (SDBS) and decanoic acid (1:1, molar ratio) are promising templates. In the presence of the vesicles and horseradish peroxidase/hydrogen peroxide (H2O2) as initiator system, aniline polymerizes under optimized conditions at pH=4.3 to the desired conductive emeraldine form of polyaniline (PANI). The optimal polymerization conditions were elaborated, and some of the chemical and physicochemical aspects of the reaction system were investigated. After addition of aniline and peroxidase to the vesicles, aniline is only loosely associated with the vesicles, as shown by NOESY-NMR and zeta potential measurements. In contrast, the peroxidase strongly binds to the vesicle surface, as shown by fluorescence measurements using TNS (2-(p-toluidino)naphthalene-6-sulfonate) as vesicle membrane probe. This binding of the enzyme to the vesicle surface indicates that the polymerization reaction is initiated predominantly on the surface of the vesicles. Cryo-transmission electron microscopy indicates that the polymerization product remains associated with the vesicles on their surface. For short reaction times (30 s

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We review the high-resolution spectroscopic approach toward the study of intramolecular dynamics, emphasizing molecular parity violation. Theoretical work in the past decade has shown that parity-violating potentials in chiral molecules are much larger (typically one to two orders of magnitude) than anticipated on the basis of older theories. This makes experimental approaches toward small molecular parity-violating effects promising. The concepts and results of intramolecular dynamics derived from spectroscopy are analyzed as a sequence of symmetry breakings. We summarize the concepts of symmetry breakings (de facto and de lege) in view of parity violation in chiral molecules. The experimental schemes and the current status of spectroscopic experiments on molecular parity violation are established. We discuss the promises of detecting and accurately measuring parity-violating energy differences Delta(pv) E on the order of 10(11) J mol(1) (approximately 100 aeV) in enantiomers of chiral molecules with regard to their contribution to fundamental physics in the framework of the standard model of particle physics and more speculative future fundamental symmetry tests such as for the combined charge conjugation, parity, and time-reversal (CPT) symmetry violation.

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Density functional theory is used to generate local potential energy surfaces in normal coordinates for several chlorine isotopomers of trichlorofluoromethane (CCl(3)F, CFC11). An examination of predicted structures suggested that the PBE0 functional would be suitable. Anharmonic surfaces around the equilibrium geometries are reported, as determined by energies, gradients, and second derivatives. Vibrational levels for fundamentals, overtones and combination bands are reported, as well as harmonic frequencies, anharmonic constants, rotational constants, isotope shifts, and infrared intensities. These are compared with experimental information.

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In a search for efficient spectroscopic avenues toward experiments on molecular parity violation, we investigate the stereomutation tunneling processes in the axially chiral chlorine isotopomers of Cl2O2 by the quasi-adiabatic channel reaction path Hamiltonian (RPH) approach and the corresponding parity violating potentials by means of quantum chemical calculations including our recently developed Multiconfiguration linear response (MC-LR) approach to electroweak quantum chemistry. The calculated ground-state torsional tunneling splittings for all isotopomers of Cl2O2 are much smaller than the parity violating energy differences Delta(pv)E between the enantiomers of these molecules and therefore parity violation is predicted to dominate the quantum dynamics of stereomutation at low energies. We also compare these with torsional ground-state tunneling splittings and parity violating energy differences of the whole series of axially chiral HXYH(+) isotopomers (with X, Y= Cl(+), O, S, Se, Te). A comparison with our previous results for the homologous molecule Cl2S2 shows that for Cl2O2 a spectroscopic high-resolution analysis should be easier and the energy region of large tunneling splittings should be more easily accessible by IR excitation. We thus propose a scheme using "tunneling switching" with vibrational excitation in order to carry out the measurement of time-dependent parity violation in superposition states of initially well-defined parity. We discuss the advantages and drawbacks of such an experiment that can be carried out entirely in the IR spectral range (for Cl2O2 or related molecules).

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Meaninglessly small would be the effects from parity violation according to the traditional point of view on the structure and dynamics of chiral molecules; enantiomers would thus exist as symmetry-related structures, which are de facto stable because of very long tunneling times. With ClSSCl as the first example, electroweak and tunneling dynamics calculations demonstrate that the de lege asymmetry arising from the parity-violating energy difference ΔEpv between the two enantiomers ((P)- and (M)-ClSSCl, the figure shows the torsional potentials) dominates by far over the tunneling splitting in the symmetrical case. These results are of fundamental interest for our concept of molecular chirality.