Fluorescence intensities of chromophores in front of a thin metal film

The fluorescence intensity from a planar multilayered system with a chromophore separated from a gold film by a dielectric spacer is measured quantitatively. The direction of excitation and the spacer thickness are varied and the angular distribution of the emission is recorded as well as its polarization. The experimental data are compared to the predictions obtained from classical electromagnetic theory, taking into account the refractive indices of the layer system as well as the nonradiative decay rate and the relative orientation of absorption and emission dipole moments of the dye. Excellent agreement is found for a spacer thickness above 15 nm if proper values for these parameters are used. Samples with thinner spacer layers show significant deviations from classical theory.     

Probing the limit of weak host-guest interactions: insertion compounds of mercury(II) halides with microporous SiO(2) hosts

Mercury(II) halides HgX(2) (X=Cl, Br, I) were inserted into the voids of the crystalline microporous SiO(2) modifications deca-dodecasil 3R (short term: DDR), silica-theta-1 (TON), silica-ferrierite (FER) and silicalite-1 (MFI) by vapour phase loading. The properties of the occluded guest species were studied by X-ray absorption spectroscopy (X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis), UV/Vis spectroscopy, and IR and Raman spectroscopy. The methods reveal the presence of HgX(2) molecules in the insertion compounds. The interactions between these electroneutral guest molecules and the electroneutral surrounding SiO(2) framework are weak. In addition, no indication of any significant guest-guest interaction between the embedded molecules was found, in contrast to the analogous iodine insertion compounds, where these become more important with increasing pore dimensionality (G. Wirnsberger et al., Angew. Chem. 1996, 108, 2951-2953; Angew. Chem. Int. Ed. Engl. 1996, 35, 2777). Analysis of the HgL(3) EXAFS confirms a coordination number of two for Hg and gives HgX bond lengths of 2.26 +/- 0.02, 2.38 +/- 0.02 and 2.57 +/- 0.02 A for the trapped HgCl(2), HgBr(2) and HgI(2) molecules, respectively. These values are very close to those of the corresponding molecules in the vapour phase and are the shortest determined for HgX(2) molecules in solid-state compounds to date (a comparably short distance only appears in the recently reported [Cu(2-pyrazinecarboxylato)(2)HgI(2)] x HgI(2) with d(Hg[bond]I)=2.577(2) A; Dong et al., Angew. Chem. 2000, 112, 4441-4443; Angew. Chem. Int. Ed. 2000, 39, 4271). Thus, there emerges a picture of almost unperturbed HgX(2) molecules, similar to those in the vapour phase or in non-coordinating solvents, in a solid crystalline matrix of high temperature stability, a very unusual state of matter. Despite the weakness of the host-guest interactions, investigations on small crystallites of the HgX(2)-TON composites using a Raman microscope show a strong polarization dependence, providing evidence for an orientational alignment of the HgX(2) molecules inside the one-dimensional pore system of this host. For these reasons, the host matrices used in this study can be viewed as orienting solid solvents, coordinating only very weakly to the inserted HgX(2) guest molecules, but exhibiting a strong geometrical template function for their alignment. The concept of using electroneutral SiO(2) modifications as host components for a modular construction of new host-guest compounds thus allows the designed construction of ordered guest assemblies, with the pore systems of the rigid host matrices acting as space-confining and ordering templates for the guest components.     

PHASE: a new engine for pharmacophore perception, 3D QSAR model development, and 3D database screening: 1. Methodology and preliminary results

We introduce PHASE, a highly flexible system for common pharmacophore identification and assessment, 3D QSAR model development, and 3D database creation and searching. The primary workflows and tasks supported by PHASE are described, and details of the underlying scientific methodologies are provided. Using results from previously published investigations, PHASE is compared directly to other ligand-based software for its ability to identify target pharmacophores, rationalize structure-activity data, and predict activities of external compounds.     

Estimation of dielectric function of biotin-capped gold nanoparticles via signal enhancement on surface plasmon resonance

Biotin-capped gold nanoparticles assembled on flat gold with volume fraction f are studied by surface plasmon resonance (SPR) spectroscopy and atomic force microscopy (AFM) in order to estimate the dielectric function of the gold nanoparticles based on the Maxwell-Garnett (MG) theory. The complex dielectric function (epsilon',epsilon') of the spherical nanoparticles at three representative wavelengths in the vis-near-IR region, i.e., lambda = 543, 632.8, and 1152 nm, is estimated for a surface homogeneously covered with nanoparticles in order to discuss the wavelength dependence of the dielectric function. The SPR response of a surface covered with particles in 2D aggregates is also analyzed. The experimental SPR curve of the particle aggregates deviates from the theoretical predictions, suggesting dipole interactions between particles.     

High-density arrays of titania nanoparticles using monolayer micellar films of diblock copolymers as templates

Highly dense arrays of titania nanoparticles were fabricated using surface micellar films of poly(styrene-block-2-vinylpyridine) diblock copolymers (PS-b-P2VP) as reaction scaffolds. Titania could be introduced selectively within P2VP nanodomains in PS-b-P2VP films through the binary reaction between water molecules trapped in the P2VP domains and the TiCl(4) vapor precursors. Subsequent UV exposure or oxygen plasma treatment removed the organic matrix, leading to titania nanoparticle arrays on the substrate surface. The diameter of the titania domains and the interparticle distance were defined by the lateral scale present in the microphase-separated morphology of the initial PS-b-P2VP films. The typical diameter of titania nanoparticles obtained by oxygen plasma treatment was of the order of approximately 23 nm. Photoluminescence (PL) properties were investigated for films before and after plasma treatment. Both samples showed PL properties with major physical origin due to self-trapped excitons, indicating that the local environment of the titanium atoms is similar.     

Methyl radical addition to methyl ethyl ketone

From relative rates of acetone formation in the azomethane sensitized decomposition of methyl ethyl ketone at 290 °C, log₁₀(k/cm³mol^–1s^–1)=5.3±0.4 for the methyl radical addition to methyl ethyl ketone has been determined.

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290°C, , . lg₁₀(^{3 –1–1})=5,3±0,4.

     

Properties of polyaniline/carbon nanotube multilayer films in neutral solution and their application for stable low-potential detection of reduced beta-nicotinamide adenine dinucleotide

A conducting polymer, polyaniline (PANI), was successfully assembled with commercially available poly(aminobenzenesulfonic acid)-modified single-walled carbon nanotubes (PABS-SWNTs) via the simple layer-by-layer method. PABS-SWNTs inside the multilayer film can dope PANI effectively and shift its electroactivity to a neutral pH environment, pointing to their potential biological applications. The obtained PANI/PABS-SWNTs multilayer films are very stable and show a high electrocatalytic ability toward the oxidation of reduced beta-nicotinamide adenine dinucleotide (NADH) at a much lower potential (about +50 mV vs Ag/AgCl), which makes it an ideal substrate for NADH detection and offers great promise for developing dehydrogenase-based biosensors depending on NADH as a cofactor. For a six-bilayer sample, the detection limit can go down to 1 x 10(-6) M as detected by the simple cyclic voltammetry method, with a linear detection range for NADH at concentrations between 5 x 10(-6) and 1 x 10(-3) M. The substrate can be used repeatedly for consecutive detection cycles of NADH with a very stable signal.     

Comparison of galactomannan crosslinking with organotitanates and borates

Water-soluble polymers crosslinked with metal ions form stable gels that are used in oil and gas production processes. We present an investigation of the chemistry of the binding between guar galactomannans and both borates and titanates using NMR and dynamic light scattering. The two monosaccharides comprising guar — methyl--D-galactopyranoside and methyl--D-mannopyranoside — have been studied as model compounds. High resolution¹³C NMR detected complexation of the sugars with borate but displayed no sign of complexation with either of the two titanates even at high titanate concentrations. Dynamic light scattering studies demonstrated the existence of colloidal titanium dioxide particles for both titanate crosslinkers. The loss of free titanium to the colloidal particles reduces the concentration of titanium crosslinking sites to below the detectable limits of NMR. The role of colloidal titanium dioxide colloids in these crosslinking reactions has not been reported previously. Data are presented following the growth of these particles with time as a function of pH and salt concentration. The observed particle growth kinetics explains the observed sensitivity of the guar gelation process to these variables.