The main aim of this research was to study the electrochemical behavior of novel optically active poly(amide-imide)s (PAIs). Polycondensation reactions of a 3,5-diamino-N-(4-hydroxyphenyl)benzamide with different synthetic diacid chlorides derivatives based on natural amino acids resulted in preparation of five different aromatic–aliphatic PAIs. These polymers were characterized by Fourier transform infrared, proton nuclear magnetic resonance, and elemental analyses. Also, we used electrochemical impedance spectroscopy for the evaluation of these novel optically active PAIs for the first time. Presence of p-substituted phenol groups in the structure of these polymers has been used for electrochemical investigation. Results showed that the oxidation currents in five diverse polymers were affected by their structures. In addition, the influence of carbon nanotubes on the oxidation of phenolic groups was studied using carbon paste matrix in an aqueous buffer solution (pH 7.0).
The amount of grafted poly(acrylic acid) on poly(methyl methacrylate) micro- and nanoparticles was quantified by conductometry, (13)C solid-state NMR, fluorophore labeling, a supramolecular assay based on high-affinity binding of cucurbit[7]uril, and two colorimetric assays based on toluidine blue and nickel complexation by pyrocatechol violet. The methods were thoroughly validated and compared with respect to reproducibility, sensitivity, and ease of use. The results demonstrate that only a small but constant fraction of the surface functional groups is accessible to covalent surface derivatization independently of the total number of surface functional groups, and different contributing factors are discussed that determine the number of probe molecules which can be bound to the polymer surface. The fluorophore labeling approach was modified to exclude artifacts due to fluorescence quenching, but absolute quantum yield measurements still indicate a major uncertainty in routine fluorescence-based surface group quantifications, which is directly relevant for biochemical assays and medical diagnostics. Comparison with results from protein labeling with streptavidin suggests a porous network of poly(acrylic acid) chains on the particle surface, which allows diffusion of small molecules (cutoff between 1.6 and 6.5 nm) into the network. 相似文献
The quantum phase properties of the generalized squeezed vacuum states associated with solvable quantum systems are studied by using the Pegg-Barnett formalism.Then,two nonclassical features,i.e.,squeezing in the number and phase operators,as well as the number-phase Wigner function of the generalized squeezed states are investigated.Due to some actual physical situations,the present approach is applied to two classes of generalized squeezed states:solvable quantum systems with discrete spectra and nonlinear squeezed states with particular nonlinear functions.Finally,the time evolution of the nonclassical properties of the considered systems has been numerically investigated. 相似文献
We present a semiclassical theory of spin diffusion in a ferromagnetic metal subject to a temperature gradient. Spin-flip scattering can generate pure thermal spin currents by short-circuiting spin channels while suppressing spin accumulations. A thermally induced spin density is locally generated when the energy dependence of the density of states is spin polarized. 相似文献
This paper describes the development of a tool, based on a Bayesian network model, that provides posteriori predictions of operational risk events, aggregate operational loss distributions, and Operational Value-at-Risk, for a structured finance operations unit located within one of Australia's major banks. The Bayesian network, based on a previously developed causal framework, has been designed to model the smaller and more frequent, attritional operational loss events. Given the limited availability of risk factor event information and operational loss data, we rely on the elicitation of subjective probabilities, sourced from domain experts. Parameter sensitivity analysis is performed to validate and check the model's robustness against the beliefs of risk management and operational staff. To ensure that the domain's evolving risk profile is captured through time, a formal approach to organizational learning is investigated that employs the automatic parameter adaption features of the Bayesian network model. A hypothetical case study is then described to demonstrate model adaption and the application of the tool to operational loss forecasting by a business unit risk manager. 相似文献
A modified carbon paste electrode was prepared by incorporating multi-wall carbon nanotubes with a ferrocene-based polyamide (FDADO-IPC). A mixture of fine graphite powder with 10 wt % of multi-wall carbon nanotubes was applied to the preparation of the carbon paste (by dispersing in paraffin) that was finally modified with a ferrocene polyamide complex. The electrocatalytic oxidation of captopril (CAP) was investigated on the surface of the FDADO-IPC multi-wall carbon nanotubes modified carbon paste electrode (FDADO-IPC-MCNTPE) using cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry (CHA) and chronocoloumetry (CHC). Using the modified electrode, the kinetics of CAP electrooxidation was considerably enhanced by lowering the anodic overpotential through a catalytic fashion. A linear dynamic range of 0.2–200 μM for CAP was obtained in buffered solutions at pH 7.0. The detection limit was 0.08 μM. Differential pulse voltammetry as a simple, rapid, sensitive, and selective method was developed for the determination of CAP in tablet and human urine without any treatment. 相似文献
Ab initio quantum mechanical calculations using density functional (B3LYP) method and 6-311G** basis set have been performed on two cis and trans conformers of 2,4-diphenyl thietane dioxide (DPTD), 2,4-diphenyl thietane (DPT), 2,4-diphenyl azetidine (DPA) and 2,4-diphenyl oxetane (DPO). The calculated stability energy for cis–trans isomerization in gas phase and in different solvents such as benzene, DMSO, water and methanol indicated that the cis conformer is more stable than trans in all above-mentioned compounds about 11–2 kcal mol?1. In the next step, a transition states for cis–trans inter-conversion for all four-membered heterocycles (DPTD, DPT, DPA and DPO) were proposed in methanol as solvent. Thermodynamic functions such as standard enthalpies of isomerization (?Hºiso), standard entropy of isomerization (?Sºiso) and standard Gibbs free energy of isomerization (?Gºiso) for all studied compounds were also evaluated. The calculation showed that the conversion of trans to cis isomer is exothermic and spontaneous. In all calculations, solvent effects were considered using a polarized continuum model. 相似文献
The detailed kinetics of Fischer-Tropsch synthesis over an industrial Fe/Cu/La/Si catalyst was studied in a continuous spinning basket reactor under the conditions relevant to industrial operations. Reaction rate equations were derived on the basis of Langmuir-Hinshelwood-Hougen-Watson type models for Fischer-Tropsch synthesis based on possible reactions sets originated from the carbide, enolic and combined enol/carbide mechanisms. Kinetic model candidates were evaluated by the global optimization of kinetic parameters, which were realized by first minimization of multi-response objective functions with conventional Levenberg-Marquardt method. It was found that an enolic mechanism based model could produce a good fit of the experimental data. The activation energy for paraffin formation is 95 kJ·mol?1 which is smaller than that for olefin formation (121 kJ·mol?1). 相似文献
A simple, rapid, and efficient method, dispersive liquid–liquid microextraction (DLLME) coupled with high‐performance liquid chromatography‐fluorescence detector, has been developed for the determination of guaifenesin (GUA) enantiomers in human urine samples after an oral dose administration of its syrup formulation. Urine samples were collected during the time intervals 0–2, 2–4, and 4–6 h and concentration and ratio of two enantiomers was determined. The ratio of R‐(?) to S‐(+) enantiomer concentrations in urine showed an increase with time, with R/S ratios of 0.66 at 2 h and 2.23 at 6 h. For microextraction process, a mixture of extraction solvent (dichloromethane, 100 μL) and dispersive solvent (THF, 1 mL) was rapidly injected into 5.0 mL diluted urine sample for the formation of cloudy solution and extraction of enantiomers into the fine droplets of CH2Cl2. After optimization of HPLC enantioselective conditions, some important parameters, such as the kind and volume of extraction and dispersive solvents, extraction time, temperature, pH, and salt effect were optimized for dispersive liquid–liquid microextraction process. Under the optimum extraction condition, the method yields a linear calibration curve in the concentration range from 10 to 2000 ng/mL for target analytes. LOD was 3.00 ng/mL for both of the enantiomers. 相似文献