Carbon optically transparent electrodes for electrogenerated chemiluminescence

This study investigates pyrolyzed photoresist film (PPF)-based carbon optically transparent electrodes (C-OTEs) for use in electrogenerated chemiluminescence (ECL) studies. Oxidative-reductive ECL is obtained with a well-characterized ECL system, C8S3 J-aggregates with 2-(dibutylamino)ethanol (DBAE) as coreactant. Simultaneous cyclic voltammograms (CVs) and ECL transients are obtained for three thicknesses of PPFs and compared to nontransparent glassy carbon (GC) and the conventional transparent electrode indium tin oxide (ITO) in both front face and transmission electrode cell geometries. Despite positive potential shifts in oxidation and ECL peaks, attributed to the internal resistance of the PPFs that result from their nanoscale thickness, the PPFs display similar ECL activity to GC, including the low oxidation potential (LOP) observed for amine coreactants on hydrophobic electrodes. Reductive-oxidative ECL was obtained using the well-studied ECL luminophore Ru(bpy)(3)(2+), where the C-OTEs outperformed ITO because of electrochemical instability of ITO at very negative potentials. The C-OTEs are promising electrodes for ECL applications because they yield higher ECL than ITO in both oxidative-reductive and reductive-oxidative ECL modes, are more stable in alkaline solutions, display a wide potential window of stability, and have tunable transparency for more efficient detection of ECL.     

New ruthenium(II) complexes functionalized with coumarin derivatives: synthesis, energy-transfer-based sensing of esterase, cytotoxicity, and imaging studies

Two new bichromophoric ruthenium(II) complexes, [Ru(bpy)(2)(bpy-CM)](PF(6))(2) and [Ru(bpy)(2)(bpy-CM343)](PF(6))(2) (bpy=2,2'-bipyridine, CM=coumarin) with appended coumarin ligands have been designed and synthesized. The energy-transfer-based sensing of esterase by the complexes has been studied by using UV/Vis and luminescence spectroscopic methods. The cytotoxicity and the cellular uptake of one of the complexes have also been investigated.     

PHI: A powerful new program for the analysis of anisotropic monomeric and exchange‐coupled polynuclear d‐ and f‐block complexes

A new program, PHI, with the ability to calculate the magnetic properties of large spin systems and complex orbitally degenerate systems, such as clusters of d‐block and f‐block ions, is presented. The program can intuitively fit experimental data from multiple sources, such as magnetic and spectroscopic data, simultaneously. PHI is extensively parallelized and can operate under the symmetric multiprocessing, single process multiple data, or GPU paradigms using a threaded, MPI or GPU model, respectively. For a given problem PHI is been shown to be almost 12 times faster than the well‐known program MAGPACK, limited only by available hardware. © 2013 Wiley Periodicals, Inc.     

Controlling the dynamics of molecular encapsulation and gating

This critical review describes mechanisms by which guest molecules enter and depart molecular capsules. The discussion focuses on presenting gated molecular encapsulation, i.e., trapping and releasing of guest molecules at rates that are controlled by conformational changes in the host's structure. Developing quantitative rules that describe the gating are, at present, a matter of scientific curiosity but could play an important role in building more effective catalysts, drug-delivery devices or membranes (105 references).     

Proof of the Fukui conjecture via resolution of singularities and related methods. II $$^{\star}$$

The present article is a direct continuation of the first part of this series. We reduce a proof of the Fukui conjecture (concerning the additivity problem of the zero-point vibrational energies of hydrocarbons) to that of a proposition related to the theory of algebraic curves, so that we can focus on the key mechanism of the additivity phenomena. Namely, by establishing what is called the Basic Piecewise Monotone Theorem (BPMT), we reduce a proof of the Fukui conjecture to that of a proposition, called the Local Analyticity Proposition, Version 1 (LAP1), which admits a proof via resolution of singularities. By LAP1, the essential part of the mechanism of the asymptotic linearity phenomena is extracted and is elucidated by using tools from the mathematical theory of algebraic curves, whose language is of vital importance in analyzing the crux of the additivity mechanism. Dedicated to the memory of Prof. Kenichi Fukui (1918–1998).     

Analysis of photoinitiated polymerization in a membrane mimetic film using infrared spectroscopy and near-IR Raman microscopy

A method has been developed to investigate the extent of polymer cross-linking that results following in situ photopolymerization of an acrylate-functionalized phospholipid assembly adsorbed onto a stabilized, membrane-mimetic film produced from a polyelectrolyte multilayer (PEM) on polytetrafluoroethylene (PTFE) grafts. The acrylate phospholipid monomer was synthesized, prepared as a unilamellar vesicle, and fused onto closed-packed acyl chains that make up the PEM membrane-mimetic barrier on the PTFE graft. Both broad band white light and 514.5 nm laser radiation were used as excitation sources for photoinitiation; eosin Y was used as the photoinitiator. The use of 514.5 nm excitation reduced the time for maximum polymerization of the acrylate lipid from 60 min to 240 s. Infrared spectroscopy was successfully used to analyze the extent of photopolymerization in simplified model acrylate lipid systems; however, this method could not be used to analyze acrylate polymerization in heterogeneous, multicomponent PEM membrane-mimetic barriers on PTFE grafts. A near-infrared Raman microscopy method based on the ratio of the integrated areas of the CC and CN vibrations was shown to provide equivalent information to the IR method for analysis of the extent of polymerization efficiency in acrylate lipids. In addition, it proved feasible to extend this near-IR Raman method to the in situ analysis of the extent of polymerization in a stabilized acrylate lipid membrane on a PEM film in a PTFE vascular graft. This work describes a new approach for generating and analyzing the robustness of a membrane-mimetic coating on biomaterial surfaces, and may improve our ability to predict the long-term stability of polymeric membrane-mimetic films on implantable medical devices.     

Study of the ESI-mass spectrometry ionization mechanism of Fischer carbene complexes

By means of deuterium-labeling experiments, we have carried out a systematic ESI-MS study to determine the mechanism of ESI ionization of alkenyl and alkynyl group 6 Fischer carbene complexes. These compounds can be ionized under ESI conditions only in the presence of additives such as hydroquinone (HQ) or tetrathiafulvalene (TTF). Our results demonstrate that in the ESI source an anion-radical is formed after the initial HQ- or TTF-mediated electron transfer to the metallic carbene complex. For alkenyl carbene complexes, this species evolves by extrusion of a hydrogen radical to form an allenylchromium anion that is detected as the [M - H](-) ion in the mass spectrum. The preference for this mechanistic pathway could be rationalized by DFT calculations. In the case of alkynyl carbene complexes, experiments combining deuterated substrate, additive, and solvent demonstrate that the previously proposed allene-anion carbene complex is not formed. Instead, the H transfer from the ethoxy group in the anion radical, followed by extrusion of a hydrogen radical, leads to an allenyl anion that is detected in the ESI-MS as [M - H - CO](-).