Diffusion,Adsorption and Electrode Kinetics of Electro‐oxidatons on a Stationary Solid Electrode

The i‐E oxidation curves, obtained using a boron doped diamond electrode, for studies of oxidations of two piperazine derivatives ARIP (I) and PIRI (II), resulted in a sharp increase of current in the range of the oxidation potentials. After reaching a value, depending on concentration of I or II, the current remains practically constant up to +1.6 V. Such limiting currents i₁ are a linear function of concentrations and depend on the v^1/2. Hence it is diffusion controlled, shifts of the oxidation potentials indicate, that the monoprotonated forms are oxidized. At more negative potentials a limiting current i₂ occurs, due to the oxidation of the diprotonated form. Current i₂ increases with decreasing pH in a shape of a part of a dissociation curve. Diffusion control reflects the large size of molecules I and II. The two‐electron oxidations yield a C=N bond in the piperazine ring. It seems to be the first reported diffusion controlled oxidation curves obtained on a stationary solid electrode.     

Comparative study for voltammetric investigation and trace determination of pramipexole at bare and carbon nanotube-modified glassy carbon electrodes

A sensitive, simple, and reproducible method was developed in this study for the determination of pramipexole, and in doing that, a glassy carbon electrode modified with –COOH-functionalized multi-walled carbon nanotube was utilized. The modified electrode was compared with a bare glassy carbon electrode in order to prove the sensitivity of the developed sensor. Cyclic, differential pulse, and adsorptive stripping differential pulse voltammetric techniques were used to investigate the oxidation behavior and stripping techniques were used for the determination of pramipexole. Based on optimum experimental conditions, calibration and partial validation studies were realized for bare and modified electrodes. As a result, the values of limit of detection and quantification were determined as be 2.38 × 10⁻¹⁰ and 7.93 × 10⁻¹⁰ M for bare and 1.06 × 10⁻¹⁰ and 3.52 × 10⁻¹⁰ M for modified glassy carbon electrodes, respectively. The applicability of the bare and modified electrodes was demonstrated for the determination of pramipexole in pharmaceutical dosage forms. The selectivity of the developed method was considered in the presence of Ca²⁺, Na⁺, K⁺, and glucose, ascorbic acid, uric acid, and dopamine. Interfering agents except uric acid did not affect pramipexole determination considerably.

     

Fast and Tight Boronate Formation for Click Bioorthogonal Conjugation

A new click bioorthogonal reaction system was devised to enable the fast ligation (k_ON≈340 m ^?1 s^?1) of conjugatable derivatives of a rigid cyclic diol (nopoldiol) and a carefully optimized boronic acid partner, 2‐methyl‐5‐carboxymethylphenylboronic acid. Using NMR and fluorescence spectroscopy studies, the corresponding boronates were found to form reversibly within minutes at low micromolar concentration in water, providing submicromolar equilibrium constant (K_eq≈10⁵–10⁶ m ^?1). Efficient protein conjugation under physiological conditions was demonstrated with model proteins thioredoxin and albumin, and characterized by mass spectrometry and gel electrophoresis.     

Minimum-error method for scattering problems in quantum mechanics: Two stable and efficient implementations

We examine here, by using a simple example, two implementations of the minimum error method (MEM), a least-squares minimization for scattering problems in quantum mechanics, and show that they provide an efficient, numerically stable alternative to Kohn variational principle. MEM defines an error-functional consisting of the sum of the values of (HPsi - EPsi)2 at a set of grid points. The wave function Psi, is forced to satisfy the scattering boundary conditions and is determined by minimizing the least-squares error. We study two implementations of this idea. In one, we represent the wave function as a linear combination of Chebyshev polynomials and minimize the error by varying the coefficients of the expansion and the R-matrix (present in the asymptotic form of Psi). This leads to a linear equation for the coefficients and the R-matrix, which we solve by matrix inversion. In the other implementation, we use a conjugate-gradient procedure to minimize the error with respect to the values of Psi at the grid points and the R-matrix. The use of the Chebyshev polynomials allows an efficient and accurate calculation of the derivative of the wave function, by using Fast Chebyshev Transforms. We find that, unlike KVP, MEM is numerically stable when we use the R-matrix asymptotic condition and gives accurate wave functions in the interaction region.     

Electrochemical Detection of Vascular Endothelial Growth Factor by Molecularly Imprinted Polymer

In this study, we report the development of a sensitive label‐free impedimetric sensor based on molecularly imprinted polymer (MIP) as biomimetic receptor coupled with screen‐printed electrodes (SPEs) for the detection of vascular endothelial growth factor (VEGF). Firstly, electropolymerization of o‐phenylenediamine (o‐PD) in the presence of VEGF molecule by cyclic voltammetry was performed onto graphite screen‐printed electrodes. The solvent extraction of the target was then carried out. The MIP based sensor was characterized by electrochemical techniques and scanning electron microscopy (SEM). Using optimized experimental conditions, the single‐use MIP‐based sensor showed a good analytical performance for VEGF detection from 20 to 200 pg mL^?1 with limit of detection of 0.08 pg mL^?1. Finally, the developed MIP‐based sensor in human serum samples was also tested.     

Application of multilevel analysis in animal sciences

Multilevel modeling is considerably useful way to analyze hierarchical data sets. The main purpose of this paper is to apply multilevel analysis in animal science and also show that this modeling technique is appropriate to analyze this kind of data. Thus multilevel modeling technique is used to analyze the milk yield data which has hierarchical structures, sires nested within cows. As a result of the analysis done in this paper, it is obvious that multilevel modeling is needed to use for analyzing this data. This illustrates that it is a convenient way to use multilevel analysis for the data which obtained from animals when the data have hierarchies.     

Voltammetric behavior and determination of antidepressant drug paroxetine at carbon-based electrodes

Ionics - Simple, rapid, sensitive, and reproducible methods were developed for the assay of paroxetine in tablets. The electrooxidative behavior and determination of paroxetine on boron-doped...