Ab initio characterization of electron transfer coupling in photoinduced systems: generalized Mulliken-Hush with configuration-interaction singles

To calculate electronic couplings for photoinduced electron transfer (ET) reactions, we propose and test the use of ab initio quantum chemistry calculation for excited states with the generalized Mulliken-Hush (GMH) method. Configuration-interaction singles (CIS) is proposed to model the locally excited (LE) and charge-transfer (CT) states. When the CT state couples with other high lying LE states, affecting coupling values, the image charge approximation (ICA), as a simple solvent model, can lower the energy of the CT state and decouple the undesired high-lying local excitations. We found that coupling strength is weakly dependent on many details of the solvent model, indicating the validity of the Condon approximation. Therefore, a trustworthy value can be obtained via this CIS-GMH scheme, with ICA used as a tool to improve and monitor the quality of the results. Systems we tested included a series of rigid, sigma-linked donor-bridge-acceptor compounds where "through-bond" coupling has been previously investigated, and a pair of molecules where "through-space" coupling was experimentally demonstrated. The calculated results agree well with experimentally inferred values in the coupling magnitudes (for both systems studied) and in the exponential distance dependence (for the through-bond series). Our results indicate that this new scheme can properly account for ET coupling arising from both through-bond and through-space mechanisms.     

Synthesis and characterization of side-chain liquid crystalline polysiloxanes containing oligooxyethylene spacers and benzyl ether based mesogenic groups

The synthesis of side-chain liquid crystalline polysiloxanes containing oligooxyethylene spacers and 4-methoxyphenyl benzyl ether and 6-cyano-2-naphthyl benzyl ether based mesogenic groups is presented. The phase behavior of both monomeric and polymeric liquid crystals was characterized by differential scanning calorimetry and optical polarized microscopy. All synthesized polysiloxanes present smectic mesomorphism. The insertion of oxygen atoms into the flexible aliphatic spacers leads to decrease in both glass transition and isotropization temperatures of the resulting side-chain liquid crystalline polymers.     

Derivation of analytical expressions for the electrical potential distribution in lipid structures

The electrical potential inside a lipid structure, which is described by a modified Poisson-Boltzmann equation in the literature (Borukhov et al. Electrochim. Acta 2000, 46, 221), is solved, taking into account the effects of ionic sizes. Here, a micelle comprises an ionic surfactant layer and an aqueous core; the dissociation of the former yields a charged surface. The governing equation, which was solved numerically in a previous study for spherical geometry (Hsu et al. J. Phys. Chem. B 2003, 107, 14429), is solved analytically in this study for planar, cylindrical, and spherical geometries. The analytical results obtained are readily applicable for the evaluation of the spatial distributions of counterions inside a lipid structure. We show that if the linear size of a reverse micelle is fixed, the degree of dissociation of the surfactant layer follows the order planar > cylindrical > spherical.     

Synthesis and electrogenerated chemiluminescence of donor-substituted phenylethynylcoumarins

Two series of donor-bearing phenylethynylcoumarins have been synthesized, and their photophysical properties have been evaluated. Chemiluminescence was observed through the annihilation of their electrogenerated radical ions and was found to be only slightly affected by the presence of various donor groups on the phenyl moiety linked through the C-C triple bond. The overall properties of the two series of compounds are discussed with respect to their structures. The observed electronic absorption properties are explained with the help of computational studies.     

Constituents of Ilex Species I. On the Leaves of Ilex Cornuta Lindl

Phytochemical examination on the leaves of Ilex cornuta Lindl. (Aquifoliaceae) resulted in the isolation and identification of lupeol (I), 3β-hydroxylup-20(29)-en-30-al (II), oleanolic acid (III), and β-sitosterol-β-D-glucoside (IV).     

Identification and quantitation of trenbolone in bovine tissue by gas chromatography-mass spectrometry

Identification and quantitation of trace amounts of trenbolone in bovine tissue by capillary gas chromatography-mass spectrometry-selected-ion monitoring (GC-MS-SIM) has been developed. Three-phase liquid-liquid extraction using a mixture of water-acetonitrile-dichloromethane-hexane was utilized for the sample extraction from tissue. Target compounds were extracted from the tissue into the acetonitrile layer. The residue from this extraction was then subjected to solid-phase extraction by C18 and silica gel disposable cartridges using methanol-water and benzene-acetone as eluents. To overcome extensive matrix interferences, preparative reversed-phase high-performance liquid chromatographic separation was used with an octadecyl-bonded column using methanol-water as mobile phase for sample clean-up prior to GC-MS analysis. A structural analogue of trenbolone, 19-nortestosterone, was chosen as the internal standard for quantitation by GC-MS. The sample was co-injected with N,O-bis (trimethylsilyl) trifluoroacetamide-1-(trimethylsilyl) imidazole (95:5, v/v) for flash heater derivation. Identification and quantitation were simultaneously carried out by SIM of characteristic ions of the trimethylsilyl derivatives of trenbolone and 19-nortestosterone. The limit of detection for trenbolone and epitrenbolone was 0.5 ppb in muscle and liver tissue. A comparison of sensitivity and specificity between GC-MS under electron ionization in addition to positive- and negative-ion chemical ionization conditions using methane reagent gas is also discussed.     

Electron transfer reactions to electroactive polymers

In the electrochemical reduction of an electroactive polymer several thousand electrons may be transferred to a single molecule. For polymers with noninteracting centers, recently developed theory indicates that the current—potential response would be identical with that of the corresponding molecule solvation, structural change, and variation in ionic environment, and may be used to probe these factors. A series of model compound of poly(vinylbenzophenone) and of poly(vinylbenzophenone-co-styrene) were prepared and investigated. In this study samples of various constant chain length with differing spacing of electroactive centers were employed. The current—potential measurements corresponded to the ideal theoretical case. This indicates that the behavior of the electroactive groups attached to the polymer chain was not influenced by the macromolecular environment or by neighboring group interaction.     

Colorimetric detection of morphine in a molecularly imprinted polymer using an aqueous mixture of Fe and [Fe(CN)6]

In this work, a molecularly imprinted polymer (MIP) of morphine (MO) was prepared through thermal radical copolymerization of methacrylic acid (MAA) and ethylene glycol dimethacrylate (EDMA) in the presence of MO templates, and a molecularly imprinted sorbent assay (MIA) based on a colorimetric reporter was developed to determine the adsorption isotherm of MO-MIP binding. In practice, the MO-bound MIP was brought into contact with an aqueous mixture of Fe³⁺ and [Fe(CN)₆]³⁻ so that the 3-phenolic group of MO was oxidized and Fe³⁺ was reduced to Fe²⁺. As a result, the MO-bound MIP was stained with Prussian blue (PB), which was attributed to the instant co-precipitation of Fe²⁺ and [Fe(CN)₆]³⁻ (K_sp=10⁻⁴⁰). Accordingly, MO-MIP binding of the blue dye could be detected by visible spectroscopy. In addition, such staining could successfully distinguish MO from codeine. Upon data analyses, a two-site binding isotherm with two dissociation constants of 6.00×10⁻⁵ and 1.03×10⁻³ M was found for MO-MIP binding. MIAs for non-MIP were also performed. In addition, the results of flow-system characterizations and the particle size effect are also described in this paper.     

Diastereoselective Cyanation of α‐Keto Amides Derived from N‐Phenyl Camphorpyrazolidinone and Camphorsultam

The diastereoselective cyanation of α‐keto amides using trimethylsilyl cyanide in the presence of a Lewis acid is described. The corresponding O‐acetylated cyanohydrins are obtained in good to high levels of stereoselectivities. The predominance of products with the S absolute configuration at the newly generated stereogenic center was deduced from single crystal X‐ray analysis. ¹³C NMR data suggest that a preferential s‐cis conformation was formed by the chelation of a Lewis acid to the dicarbonyl oxygen atoms.     

Transforming large scale product documents into multimedia trainingmanuals

Current authoring tools have limitations in creating large-scale product training documents in a timely manner because of labor-intensive and time-consuming authoring processes. We present an automated authoring method based on a formal specification for dynamically generating ISO DSSSL document styles. From the generated styles, we transform the existing storage-based product documents into large-scale presentation-based product training manuals