Phenols monitoring and Hill coefficient evaluation using tyrosinase-based amperometric biosensors

Sensitive amperometric biosensors for phenols compounds, based on tyrosinase (polyphenoloxidase, PPO) immobilized on a Pt electrode in an electropolymerized poly-amphiphilic pyrrole matrix or cross-linked with glutaraldehyde, were constructed and compared. Steady-state amperometric measurements, performed at -50 mV vs. SCE in aqueous phosphate buffer containing LiClO(4) 0.1 M (pH 7) as well as in a chloroform solution containing 0.1 M C(6)H(5)CH(2)N(CH(3))(3)Cl, were used in order to compare the electroanalytical and kinetic parameters of the investigated amperometric biosensors in aqueous and nonaqueous media. It was established that the polypyrrole matrix has a higher efficiency for enzyme retention resulting in higher bioelectrode sensitivity, both in aqueous buffer (690 microA M(-1)) and in chloroform (149 microA M(-1)).     

Continuous permeation of analytes through a thin poly(dimethylsiloxane) membrane followed by sorbent trapping for their gas chromatographic monitoring

Omeprazole is a benzimidazole compound that acts as a proton-pump inhibitor. Because the metabolism of omeprazole is mainly catalyzed by cytochrome P-450 (CYP) 3A4 and CYP2C19. the genetic polymorphism of CYP2C19 could be of clinical concern in the treatment of acid-related diseases with omeprazole. Therefore, a reliable method for omeprazole phenotyping is desirable in clinical situations. This study has demonstrated the determination of omeprazole and its metabolites in human plasma by liquid chromatography-three-dimensional quadrupole mass spectrometry with a sonic spray ionization interface. The analytical column was YMC-Pack Pro C18(50x2.0 mm I.D.) using acetonitrile-50 mM ammonium acetate (pH 7.25) (1:4) at a flow-rate of 0.2 ml/min. The drift voltage was 30 V. The sampling aperture was heated at 110 degrees C and Shield temperature was 230 degrees C. In the mass spectrum, the molecular ions of omeprazole, hydroxyomeprazole and omeprazole sulfone were clearly observed as base peaks. This method is sufficiently sensitive and accurate for pharmacokinetic studies of omeprazol.     

Study of the basicity of some 1,2‐diazinium ylids

In this paper we present a study concerning the basicity of some new carbanion monosubstituted pyridazinium, 3‐methyl‐pyridazinium, 3‐(p‐halogenophenyl)‐pyridazinium and phtalazinium ylids. The pk_a values of the conjugated acids (salts) of ylids have been experimentaly determinated. Consequently, we have evaluated their basicity (k_b,) using the titration curves. The basicity depends mainly on the structure of the ylids carbanion itself, however the heterocycle's structures also has some influence on bacisity. Having in view the basicity, we have established certain correlations between basicity, structure and stability of the analised ylids.     

Self-assembled architecture based on triiron-substituted polyoxomolybdate anion and positively charged polymer

A new self-assembled multilayer architecture was constructed by successive deposition of poly(4-vinylpyridine) partially quaternized with ethylamine (B) and Keggin trilacunary polyoxomolybdate [Aα-PFe₃^III(H₂O)₃Mo₉O₃₇]⁶⁻ (PFe₃Mo₉) on the Au electrode surface, covered with 3-mercapto-1-propanesulfonic acid (MPS). Surface plasmon resonance and cyclic voltammetry measurements were performed at Au/MPS/B/PFe₃Mo₉/B interface in order to investigate the structure and the electrochemical behavior of this electrode. Due to the presence of PFe₃Mo₉, the Au/MPS/B/PFe₃Mo₉/B-modified electrode showed electrocatalytic activity towards H₂O₂ amperometric detection. Additionally, when GOx was deposited as the outermost layer on the abovementioned multilayer structure, the Au/MPS/B/PFe₃Mo₉/B/GOx-modified electrode was able to detect glucose.     

Small Time Uniform Controllability of the Linear One-Dimensional Schrödinger Equation with Vanishing Viscosity

This paper addresses the exact controllability problem of the linear one-dimensional Schrödinger equation perturbed by a vanishing viscosity term depending on a strictly positive parameter. It is shown that, for any time and for each initial datum in a suitable space, there exists a uniformly bounded family of boundary controls. Any weak limit of this family is a control for the linear Schrödinger equation.     

Simple models of firms emergence

We present a dynamical model of the emergence of firms as opposed to a flat labour market where entrepreneurs would recruit workers for each business opportunity. The model uses a preferential choice of partners based on previous collaborations experience. A sharp transition in the parameter space separates an ordered regime, where preferential links establish, from a disordered regime corresponding to a fast turnover of employees.     

Synthesis and Biological Screening of New Cyano-Substituted Pyrrole Fused (Iso)Quinoline Derivatives

Several new cyano-substituted derivatives with pyrrolo[1,2-a]quinoline and pyrrolo[2,1-a]isoquinoline scaffolds were synthesized by the [3 + 2] cycloaddition of (iso)quinolinium ylides to fumaronitrile. The cycloimmonium ylides reacted in situ as 1,3-dipoles with fumaronitrile to selectively form distinct final compounds, depending on the structure of the (iso)quinolinium salt. Eleven compounds were evaluated for their anticancer activity against a panel of 60 human cancer cell lines. The most potent compound 9a showed a broad spectrum of antiproliferative activity against cancer cell lines representing leukemia, melanoma and cancer of lung, colon, central nervous system, ovary, kidney, breast and prostate cancer. In vitro assays and molecular docking revealed tubulin interaction properties of compound 9a.     

Determination of Antioxidant Capacity by Using Xanthine Oxidase Bioreactor Coupled with Flow‐through H2O2 Amperometric Biosensor

A new flow system for antioxidant capacity (AOC) estimation, consisting of a bioreactor, containing immobilized xanthine oxidase (XOD), coupled with a H₂O₂ amperometric biosensor, based on Os‐wired horseradish peroxidase, was developed. The H₂O₂, resulting from the enzymatic reaction between xanthine (XA) and XOD, was amperometrically monitored at ?0.1 V vs. Ag/AgCl/KCl_sat, in order to avoid the electrochemical interferences. Two protocols were used to perform the AOC evaluation: “steady‐state”, when the antioxidant (AOX) was injected in the XA flow, and “transient state”, when XA and AOX were simultaneously injected in the carrier flow. The AOC of some commercial beverages were evaluated and compared with those obtained with 2,2‐diphenyl‐1‐picrylhydrazyl radical and Folin–Ciocalteu methods.     

Solution behavior of progressively quaternized poly(dimethylaminoethyl methacrylate) as a function of charge density

Hydrodynamic behavior of progressively quaternized poly(dimethylaminoethyl methacrylate) (PDMAEM) in dilute and semi-dilute salt–free aqueous solutions as a function of molar mass and charge density, which varied from 5 up to 100 mol%, was studied. The role of long range electrostatic interactions on the viscosity and on the position and value of the reduced viscosity corresponding to the peak, η_red,p, as a function of the charge density of polycation has been evaluated. The overlap concentration of polyelectrolytes, c^∗, has been evaluated as the inverse of the intrinsic viscosity determined by fitting the viscometric results on Rao equation. The values of c^∗ have been discussed as a function of polyion molar mass and charge density. The c^∗ values calculated in the frame of Odijk model for polyelectrolytes having quaternization degree ?50 were lower but comparable with those determined by viscometry, for the same molar mass.