A Simple Strategy to Improve the Accuracy of the Injection Step in Batch Injection Analysis Systems with Amperometric Detection

In this study, we describe for the first time the application of an internal standard method to compensate for random errors associated with the injection procedure in batch injection analysis (BIA) systems with multiple pulse amperometric detection. A sequence of potential pulses was selected in such a way that the internal standard (IS) compound was detected individually at one potential pulse and both the IS and analyte, were detected at another potential pulse. The current ratio (I_IS+analyte/I_IS) was used in the construction of the calibration curve and then to compensate for random errors. The use of disposable syringes or manual pipettes in BIA systems increases the robustness of the method and dispenses with skilled operators.     

Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

Uniqueness of limit cycles bounded by two invariant parabolas

In this paper we consider a class of cubic polynomial systems with two invariant parabolas and prove in the parameter space the existence of neighborhoods such that in one the system has a unique limit cycle and in the other the system has at most three limit cycles, bounded by the invariant parabolas.     

Local–global multiscale model reduction for flows in high-contrast heterogeneous media

In this paper, we study model reduction for multiscale problems in heterogeneous high-contrast media. Our objective is to combine local model reduction techniques that are based on recently introduced spectral multiscale finite element methods (see [19]) with global model reduction methods such as balanced truncation approaches implemented on a coarse grid. Local multiscale methods considered in this paper use special eigenvalue problems in a local domain to systematically identify important features of the solution. In particular, our local approaches are capable of homogenizing localized features and representing them with one basis function per coarse node that are used in constructing a weight function for the local eigenvalue problem. Global model reduction based on balanced truncation methods is used to identify important global coarse-scale modes. This provides a substantial CPU savings as Lyapunov equations are solved for the coarse system. Typical local multiscale methods are designed to find an approximation of the solution for any given coarse-level inputs. In many practical applications, a goal is to find a reduced basis when the input space belongs to a smaller dimensional subspace of coarse-level inputs. The proposed approaches provide efficient model reduction tools in this direction. Our numerical results show that, only with a careful choice of the number of degrees of freedom for local multiscale spaces and global modes, one can achieve a balanced and optimal result.     

Experimental NMR and MS study of benzoylguanidines. Investigation of E/Z isomerism

Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI‐MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (¹H‐¹³C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple‐Bond Correlation (HMBC), ¹H‐¹⁵N HMBC, ¹H‐¹H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p‐Cl and p‐Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p‐NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd.