Spectral features of electrochemiluminescence accompanying reduction of aryldiazonium salts on a copper cathode

Spectra of electrochemiluminescence (ecl) accompanying reduction of selected aryldiazonium cations (ADAC), originating from tetrafluoroborate salts, on a copper electrode were measured and compared with known fluorescence spectra of some expected products. In addition, changes of integral ecl intensity in time and its dependence on cathodic current density were investigated to shed more light on the nature of this phenomenon. With the aid of PM3 CI method it was possible to interpret ecl spectra and state that ecl occurs as a result of the recombination of two primarily formed azophenyl radicals or azophenyl and phenyl radicals – created upon N₂ elimination from the former entities.     

FLUORESCENCE AND ELECTROGENERATED CHEMILUMINESCENCE STUDIES OF SEVERAL DIMETHYL-SUBSTITUTED BENZO[a]PYRENES

Abstract— Absorption spectra, molar absorptivities, fluorescence spectra and fluorescence quantum yields of five dimethylbenzo[a]pyrenes (DMBP) in benzene solutions at room temperature are reported. Electrogenerated chemiluminescence (ecl) spectra and the relative eel intensities of these compounds to that of 9,10-diphenylanthracene in the 1:1 acetonitrile-benzene mixed solvent with tetra- n -butyl-ammonium perchlorate as a supporting electrolyte are also reported. Both fluorescence quantum yield and ecl intensity studies show that the vicinal dimethyl substitution lowers the fluorescence and eel efficiency, and this effect is more pronounced in a compound whose K-region is blocked. The compounds in which the L-region is blocked showed much higher fluorescence and eel efficiency. The fluorescence of DMBP molecules is quenched by the donor molecule, tri- p -tolylamine with a diffusion controlled rate to form an emitting exciplex. The cation radical of TPTA and the radical anion of the DMBPs are shown to form an exciplex efficiently by the eel experiments. Both quenching and eel results indicate that all DMBPs studied here are good acceptors.     

Effects of electron withdrawing and donating groups on the efficiency of tris(2,2'-bipyridyl)ruthenium(II)/tri-n-propylamine electrochemiluminescence

The effects of electron withdrawing and electron donating groups on the electrochemiluminescent (ECL) properties of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)3(2+) where bpy = 2,2'-pyridine) are reported. The electrochemistry, photophysics and ECL of (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+ (DC = 4,4'-dicarboxy-2,2'-bipyridine; DM = 4,4'-dimethyl-2,2'-bipyridine) have been studied relative to Ru(bpy)3(2+) in 50:50 (v/v) acetonitrile(CH3CN):H2O (0.1 M KH2PO4), and aqueous solutions. Furthermore, the effects of Triton X-100 (polyethylene glycol tert-octylphenyl ether) on the electrochemical, spectroscopic and ECL properties of these compounds are reported. The anodic oxidation of Ru(bpy)3(2+), (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+ produces ECL in the presence of tri-n-propylamine (TPrA) in all solvent systems. ECL efficiencies (phi(ecl), photons produced per redox event) of 0.73 and 0.84 for (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+ were obtained in aqueous buffered solution, using Ru(bpy)3(2+) as a relative standard (phi(ecl) = 1.0). Addition of 0.4 mM Triton X-100 results in a greater than 2-fold increase in ECL efficiences (i.e., 3.8, 2.4 and 2.3 for Ru(bpy)3(2+), (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+, respectively) using aqueous Ru(bpy)3(2+) containing no surfactant as standard (phi(ecl) = 1.0). ECL efficiencies of 27.4, 16.5 and 26.1 were found in 50:50 (v/v) CH3CN:H2O (0.1 M KH2PO4) for Ru(bpy)3(2+), (bpy)2Ru(DC-bpy)2+, and (bpy)2Ru(DM-bpy)2+, respectively, using aqueous Ru(bpy)3(2+) containing no surfactant as standard (phi(ecl) = 1.0). Detailed studies support adsorption of surfactant on the electrode surface, thus facilitating TPrA and ruthenium oxidation.     

Electrogenerated chemiluminescence of 9,10-diphenylanthracene, rubrene, and anthracene in fluorinated aromatic solvents

The electrogenerated chemiluminescence (ECL) of 9,10-diphenylanthracene (DPA), rubrene, and anthracene has been studied in fluorinated aromatic solvents. Mixed annihilation ECL between aromatic luminophores and quinones was observed in solvent systems containing acetonitrile and either benzene, benzotrifluoride, 3-fluorobenzotrifluoride, or 1,3-bis(trifluoromethyl)benzene. Increases in ECL efficiency (phi ecl, photons generated per redox event) correlated with decreasing solvent polarity when 1,4-benzoquinone was used as a nonemitting ECL partner. However, opposite results were observed using 1,4-naphthaoquinone (NQ) as a nonemitting partner. phi ecl also correlated with radical anion stability of NQ in these solvent systems, as indicated by reverse/forward current ratios ( I r/ I f), suggesting noncovalent interactions between the solvent and the nonemitting ECL partner. Specifically, the reaction of an aromatic luminophore with 1,4-naphthoquinone in acetonitrile/benzotrifluoride showed a 1.03-1.63-fold increases in ECL efficiency over that of acetonitrile/benzene. Slight blue shifts ( approximately 3 nm) in photoluminescence and ECL emissions were seen as solvent polarity increased. Reaction enthalpies of each system were estimated using half-wave potentials of oxidation and reduction and were found to correlate well with emission energy.     

液相色谱的交流电致化学发光检测系统的研制

讨论了由计算机控制的液相色谱交流电致化学发光检测器的研制过程,并对其性能进行了测试。     

DFT study of substitution effect on the geometry, IR spectra, spin state and energetic stability of the ferrocenes and their pentaphospholyl analogues

Optimal structures, vibrational spectra and thermochemical characteristics of ferrocenes and pentaphosphaferrocenes containing up to five methyl substituents in the cyclopentadienyl ring are found with the use of DFT computations. It is shown that the non-substituted ferrocenes and pentaphosphaferrocenes as well as the species with small number of methyl substituents adopt eclipsed conformations. Increasing the number of the methyl substituents results either in the conformational equilibria between the eclipsed and staggered forms or in complete shift to the staggered conformations. These effects, as well as elongation of CC bonds of the Cp ring and growth of Fe-Cp and Cp-P₅ distances with growing number of methyl groups can be explained by repulsive interactions of the methyl groups with each other or with phosphorus atoms of the pentaphospholyl ligands. The pentaphosphaferrocenes are predicted to be stable towards disproportionation to homoleptic sandwich complexes. This stability grows as the number of methyl substituents in cyclopentadienyl ring increases, which is a result of stronger Fe-P₅ bonding in the methyl substituted pentaphosphaferrocenes relative to the non-substituted species, and destabilization of the homoleptic ferrocenes because of Me?Me repulsion. A huge energy gap between the low- and high-spin states of the ferrocenes and pentaphosphoferrocenes is predicted, though introduction of methyl substituents causes a moderate decrease of the gap. Transition from low- to high-spin state should result in pronounced changes of geometry and IR spectra of the ferrocenes, which suggests that IR spectroscopy can be used for diagnostics of spin state of iron complexes.     

Structure of gallium(III) monofluoride phthalocyaninate: A quantum chemical study

The B3LYP/6-31G quantum chemical method is used to calculate the structural parameters of [F(PcGaF)₇]^-, [(PcGaF)₆PcGa]⁺ heptamers and the (PcGaF)_∞, polymer of gallium(III) monofluoride phthalocyaninate. The eclipsed (ecl.) configuration (D _4h point symmetry group) corresponds to the energy minimum of the [FGa(Pc)FGa(Pc)F]^- dimer. The calculated equilibrium bond lengths in the central unit of all-ecl. heptamer (GaN 1.988 Å; GaF 1.933 Å) are similar to the bond lengths in the all-ecl. polymer (GaN 1.988 Å and GaF 1.940 Å) and to the respective single crystal X-ray diffraction parameters.     

The haplotype assembly model with genotype information and iterative local-exhaustive search algorithm

The minimum error correction (MEC) model for haplotype reconstruction is efficient only when the error rate in SNP fragments is low. In order to improve reconstruction rate, additional genotype information is added into MEC model as an extension to MEC model. In this paper, we first establish a new mathematical model for haplotype assembly problem with genotype information. Several properties of the mathematical model are proved. Then an iterative local-exhaustive search algorithm is proposed based on the model and its properties. The main idea is to find the optimal pair among 2(l-1) (l denotes the number of heterozygous sites of a genotype) haplotype pairs by performing local exhaustive search for the promising haplotype pair step by step. By experiments and comparison, extensive numerical results on real data and simulated data indicate that our algorithm outperforms the other algorithms in terms of efficiency and robustness.     

The steady-state current at microcylinder electrodes modified by enzymes immobilized in conducting or non-conducting material

A diffusion-kinetic model is presented for an enzyme-modified microcylinder electrode, where the enzyme reaction generates an electro-active product. Simple, approximate expressions are derived for the steady-state current in cases where the enzyme is immobilized in a metallically conducting, or a non-conducting matrix. The model is also extended to the chemical sensor case, of a conducting polymer without enzyme. The model is used to analyze steady-state signals for glucose produced by Pt-coated carbon fibres, on which glucose oxidase has been entrapped in poly(1,2-diaminobenzene).     

Effect of charge regulation on steric mass-action equilibrium for the ion-exchange adsorption of proteins

A thermodynamic formalism is developed for incorporating the effects of charge regulation on the ion-exchange adsorption of proteins under mass-overloaded conditions as described by the steric mass-action (SMA) isotherm. To accomplish this, the pH titration behavior of a protein and the associated adsorption equilibrium of the various charged forms of a protein are incorporated into a model which also accounts for the steric hindrance of salt counterions caused by protein adsorption. For the case where the protein is dilute, the new model reduces to the protein adsorption model described recently by the authors which accounts for charge regulation. Similarly, the new model reduces to the steric mass-action isotherm developed by Brooks and Cramer which applies to mass-overloaded conditions for the case where charge regulation is ignored so that the protein has a fixed charge. Calculations using the new model were found to agree with experimental data for the adsorption of bovine serum albumin (BSA) on an anion-exchange column packing when using reasonable physical properties. The new model was also used to develop an improved theoretical criterion for determining the conditions required for an adsorbed species to displace a protein in displacement chromatography when the pH is near the protein pI.     

Solvation effect on conformations of 1,2:dimethoxyethane: charge-dependent nonlinear response in implicit solvent models

The physical content of and, in particular, the nonlinear contributions from the Langevin-Debye model are illustrated using two applications. First, we provide an improvement in the Langevin-Debye model currently used in some implicit solvent models for computer simulations of solvation free energies of small organic molecules, as well as of biomolecular folding and binding. The analysis is based on the implementation of a charge-dependent Langevin-Debye (qLD) model that is modified by subsequent corrections due to Onsager and Kirkwood. Second, the physical content of the model is elucidated by discussing the general treatment within the LD model of the self-energy of a charge submerged in a dielectric medium for three different limiting conditions and by considering the nonlinear response of the medium. The modified qLD model is used to refine an implicit solvent model (previously applied to protein dynamics). The predictions of the modified implicit solvent model are compared with those from explicit solvent molecular dynamics simulations for the equilibrium conformational populations of 1,2-dimethoxyethane (DME), which is the shortest ether molecule to reproduce the local conformational properties of polyethylene oxide, a polymer with tremendous technological importance and a wide variety of applications. Because the conformational population preferences of DME change dramatically upon solvation, DME is a good test case to validate our modified qLD model. The present analysis of the modified qLD model provides the motivation and tools for studying a wide variety of other interesting systems with heterogeneous dielectric properties and spatial anisotropy.     

Improved partition equilibrium model for predicting analyte response in electrospray ionization mass spectrometry

A previously proposed partition equilibrium model for quantitative prediction of analyte response in electrospray ionization mass spectrometry is modified to yield an improved linear relationship. Analyte mass spectrometer response is modeled by a competition mechanism between analyte and background electrolytes that is based on partition equilibrium considerations. The correlation between analyte response and solution composition is described by the linear model over a wide concentration range and the improved model is shown to be valid for a wide range of experimental conditions. The behavior of an analyte in a salt solution, which could not be explained by the original model, is correctly predicted. The ion suppression effects of 16 : 0 lysophosphatidylcholine (LPC) on analyte signals are attributed to a combination of competition for excess charge and reduction of total charge due to surface tension effects. In contrast to the complicated mathematical forms that comprise the original model, the simplified model described here can more easily be employed to predict analyte mass spectrometer responses for solutions containing multiple components. Copyright © 2008 John Wiley & Sons, Ltd.     

An elastic-plastic hybrid adhesion model for contacting rough surfaces in the presence of molecularly thin lubricant

The study of adhesion has received considerable attention in recent years, partly due to advances in the design and fabrication of micro/nano devices. Many adhesion investigations are centered on single-spherical-contact models, which include the classic Johnson-Kendall-Roberts (JKR), improved Derjaguin-Muller-Toporov (IDMT), and Maugis-Dugdale (MD) models. Based on the IDMT single-asperity model, adhesive rough surface contact models have also been developed, which are valid for elastic and elastic-plastic contact conditions. A limitation of the IDMT-based models is that they are only valid for application cases with low adhesion parameter values. In this research, a contacting rough surface adhesion model was developed by combining an extended Maugis-Dugdale (EMD) model (which is only valid for elastic contacts) with an IDMT-based elastic-plastic adhesion model. The proposed model, termed the elastic-plastic hybrid adhesion model, is valid for the entire adhesion parameter range and also for elastic-plastic contacts. The proposed model gives results similar to the EMD rough surface model when the contact is primarily elastic. Moreover, the proposed model was compared to an IDMT-based model (ISBL model) and both gave similar results for contacts with low adhesion parameter values. With high adhesion parameter values, the ISBL model fails, whereas the proposed model correctly predicts higher adhesion. Last, based on the stiffness of the external force, the instability for adhesive rough surfaces in contact was also discussed, and it was postulated that a high peak value of the external force stiffness directly relates to the unstable contact process.     

Folding mechanisms of individual beta-hairpins in a Go model of Pin1 WW domain by all-atom molecular dynamics simulations

This paper examines the folding mechanism of an individual beta-hairpin in the presence of other hairpins by using an off-lattice model of a small triple-stranded antiparallel beta-sheet protein, Pin1 WW domain. The turn zipper model and the hydrophobic collapse model originally developed for a single beta-hairpin in literature is confirmed to be useful in describing beta-hairpins in model Pin1 WW domain. We find that the mechanism for folding a specific hairpin is independent of whether it folds first or second, but the formation process are significantly dependent on temperature. More specifically, beta1-beta2 hairpin folds via the turn zipper model at a low temperature and the hydrophobic collapse model at a high temperature, while the folding of beta2-beta3 hairpin follows the turn zipper model at both temperatures. The change in folding mechanisms is interpreted by the interplay between contact stability (enthalpy) and loop lengths (entropy), the effect of which is temperature dependent.     

Effect of through-space electron transfer on infrared spectrum of amorphous selenium

In this paper we present theoretical analyses on an infrared (IR) spectrum of amorphous selenium. The system is described by a 216-atom-chain model, and a set of molecular-dynamics simulations is performed to generate vitreous structures and vibrational modes. To describe an electronic structure of the system we employ a complete neglect of differential overlap model parametrized by ab initio cluster calculations. An IR intensity is evaluated with the Berry-phase formula for an electronic polarization. The effect of the through-space electron transfer on the IR spectrum is studied by artificially changing the magnitude of matrix elements associated with the electron transfer between nonbonded atoms in the chain. We find that the through-space electron transfer leads to (i) the enhancement of the bending IR peak at 135 cm(-1) and (ii) the appearance of a new low-frequency peak around 50 cm(-1), thus resulting in a good agreement with the experiment. The mechanism is discussed by a simple dipole model.     

A density functional theory formulation of the reaction field model of solvent effects

It is possible to reformulate the reaction field (RF ) model of continuum solvent effects, by considering an approximate expression describing the energy changes from one ground state to another, in the frame of density functional theory (DFT ). The energy functional for an arbitrary electronic system coupled to a spin-independent electrostatic external perturbation is used to derive the well-known Born expression giving the electrostatic component of the solvation energy of an atomic ion. The approximate RF –DFT model is illustrated for a series of representative singly positive and negatively charged atomic ions. A Kohn–Sham (KS )-like formalism is then proposed to compute solvation energies within a self-consistent field scheme. The extension of the RF -DFT model to molecular systems is also outlined. © 1995 John Wiley & Sons, Inc.     

Estimation of residual stresses in SiC/Ti 15-3 composites and their relaxation during a fatigue test. Part I: Presentation of the models

Different models for the calculation of residual stresses induced by cooling down from elaboration process in SiC/Ti-15-3 composite were presented. First of all, an analytical model (derived from those of Eshelby and of Mikata and Taya) already used for ceramic matrix composites is explained. It is a suitable method for elementary composites but we present an extension of this model to real (1D) composites. Then, we also briefly present the finite model using MARC anc MENTAT softwares. Finaly, an analytical model to predict the evolution of TRS during a fatigue test is detailed. The part II of the paper will present the results obtained using all these differents models.     

Mechanism of the thermal stabilization of poly(vinyl chloride) with metal carboxylates and epoxy plasticizers

The chemical reactions responsible for the retardation of thermal discoloration in poly(vinyl chloride) (PVC) stabilized with a combination of an epoxy plasticizer and a heavy metal soap mixture of Group IIa and IIb metals have been studied. Allylic chlorides (a mixture of 4-chlorohexene-2 and 2-chlorohexene-3) are used as prototypes for the degrading segment of the polymer chain. The results confirm earlier reports that, when a mixture of a covalent and ionic metal soap is used as the stabilizer, the covalent moiety (e.g., Cd and Zn soaps) functions to esterify the allylic site of the degrading PVC model. A synergistic effect displayed by the ionic soap (e.g., Ca or Ba) is caused by a transfer of carboxylate ligands from the ionic soap to the depleting covalent species, which has been largely converted to the corresponding chloride. When an epoxy plasticizer model (cyclohexene oxide) is used in conjunction with the metal soap stabilizer, the preferred reaction is esterification. After a considerable build-up of ester, an α-chloroether, 2-hexenyl 4-(2-chlorocyclohexyl) ether, is formed by the reaction of cyclohexene oxide with the PVC model. This reaction was found to be catalyzed by cadmium chloride. The esterification and etherification reactions provide an explanation for the synergism observed in the stabilization of PVC containing a combination of an epoxy plasticizer with a covalent and an ionic metal soap.     

Mathematical Simulation of Plasma-Chemical Coal Conversion

A mathematical model that describes the conversion of a coal-dust flow in a cylindrical plasma reactor is presented. The model describes a two-phase (coal particles + air) chemically reacting flow, which propagates in a channel with or without an internal heat source (an electric arc, a plasmatron torch, or exothermic chemical reactions). The model is based on the assumption that the process is quasi-stationary and one-dimensional; coal particles are taken isothermal, and ash is assumed an inert component. The model represents the composition of coals by their organic and mineral constituents. The model was implemented as a program for personal computers; calculations performed with the use of this program are in satisfactory agreement with experimental data.