Regioselective alkylation of 1H-7-ethoxycarbonyl-6-methyl-3-phenyl-pyrazolo[5,1-c][1,2,4]triazole and 1H-6-methyl-3-phenyl-pyrazolo[5,1-c][1,2,4]triazole

Alkylation of 1H-6-methyl-3-phenyl-pyrazolo[5,1-c][1,2,4]triazole and 1H-7-ethoxycarbonyl-6-methyl-3-phenyl-pyrazolo[5,1-c][1,2,4]triazole using different alkylating agents leads regioselectively to 1-N-alkylated products. The hydrolysis-decarboxylation of 1,6-dimethyl-7-ethoxycarbonyl-pyrazolo[5,1-c][1,2,4]triazole yields a compound identical with that obtained by the direct methylation of 1H-6-methyl-3-phenyl-pyrazolo[5,1-c][1,2,4]triazole. The 1-N-alkylation is confirmed by NMR spectroscopy and mass spectrometry.     

Screen-printed electrode based on AChE for the detection of pesticides in presence of organic solvents

A screen-printed biosensor for the detection of pesticides in water miscible organic solvents is described based on the use of p-aminophenyl acetate as acetylcholinesterase substrate. The oxidation of p-aminophenol, product of the enzymatic reaction was monitored at 100 mV vs. Ag/AgCl screen-printed reference electrode. Miscible organic solvents as ethanol and acetonitrile were tested. The acetylcholinesterase (AChE) was immobilised on a screen-printed electrode surface by entrapment in a PVA-SbQ polymer and the catalytic activity of immobilised AChE was studied in the presence of different percentages of organic solvents in buffer solution. The sensor shows good characteristics when experiments were performed in concentrations of organic solvents below 10%. No significant differences were observed when working with 1 and 5% acetonitrile in the reaction media. Detection limits as low as 1.91x10(-8) M paraoxon and 1.24x10(-9) M chlorpyrifos ethyl oxon were obtained when experiments are carried out in 5% acetonitrile.     

Nickel(II) and palladium(II) complexes with α‐dioxime ligands as catalysts for the vinyl polymerization of norbornene in combination with methylaluminoxane,tris(pentafluorophenyl)borane,or triethylaluminum cocatalyst systems

Nickel(II) and palladium(II) complexes with α‐dioxime ligands dimethylglyoxime, diphenylglyoxime, and 1,2‐cyclohexanedionedioxime represent six new precatalysts for the polymerization of norbornene that can be activated with methylaluminoxane (MAO), the organo‐Lewis acid tris(pentafluorophenyl)borane [B(C₆F₅)₃], and triethylaluminum (TEA) AlEt₃. The palladium but not the nickel precatalysts could also be activated by B(C₆F₅)₃ alone, whereas two of the three nickel precatalysts but none of the palladium systems are somewhat active with only TEA as a cocatalyst. It was possible to achieve very high polymerization activities up to 3.2 · 10⁷ g_polymer/mol_metal · h. With the system B(C₆F₅)₃/AlEt₃, the activation process can be formulated as the following two‐step reaction: (1) B(C₆F₅)₃ and TEA lead to an aryl/alkyl group exchange and result in the formation of Al(C₆F₅)_nEt_3?n and B(C₆F₅)_3?nEt_n; and (2) Al(C₆F₅)_nEt_3?n will then react with the precatalysts to form the active species for the polymerization of norbornene. Variation of the B:Al ratio shows that Al(C₆F₅)Et₂ is sufficient for high activation. Gel permeation chromatography indicated that it was possible to control the molar mass of poly(norbornene)s by TEA or 1‐dodecene as chain‐transfer agents; the molar mass can be varied in the number‐average molecular weight range from 2 · 10³ to 9 · 10⁵ g · mol^?1. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3604–3614, 2002     

Entropy-Based Behavioural Efficiency of the Financial Market

The most known and used abstract model of the financial market is based on the concept of the informational efficiency (EMH) of that market. The paper proposes an alternative which could be named the behavioural efficiency of the financial market, which is based on the behavioural entropy instead of the informational entropy. More specifically, the paper supports the idea that, in the financial market, the only measure (if any) of the entropy is the available behaviours indicated by the implicit information. Therefore, the behavioural entropy is linked to the concept of behavioural efficiency. The paper argues that, in fact, in the financial markets, there is not a (real) informational efficiency, but there exists a behavioural efficiency instead. The proposal is based both on a new typology of information in the financial market (which provides the concept of implicit information—that is, that information ”translated” by the economic agents from observing the actual behaviours) and on a non-linear (more exactly, a logistic) curve linking the behavioural entropy to the behavioural efficiency of the financial markets. Finally, the paper proposes a synergic overcoming of both EMH and AMH based on the new concept of behavioural entropy in the financial market.     

Selective Gram–Schmidt orthonormalization for conic cutting surface algorithms

It is not straightforward to find a new feasible solution when several conic constraints are added to a conic optimization problem. Examples of conic constraints include semidefinite constraints and second order cone constraints. In this paper, a method to slightly modify the constraints is proposed. Because of this modification, a simple procedure to generate strictly feasible points in both the primal and dual spaces can be defined. A second benefit of the modification is an improvement in the complexity analysis of conic cutting surface algorithms. Complexity results for conic cutting surface algorithms proved to date have depended on a condition number of the added constraints. The proposed modification of the constraints leads to a stronger result, with the convergence of the resulting algorithm not dependent on the condition number. Research supported in part by NSF grant number DMS-0317323. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation.     

In vivo and in vitro testing of microelectronically fabricated planar sensors designed for applications in cardiology

Summary Ion-sensitive, planar micro-electrode arrays were fabricated by photolithographic microelectronics technology on a flexible polyimide substrate. The steps of the microelectronics processing are summarized. The electrodes were tested in blood serum, whole blood and in the hamstring muscle of anesthetized rabbits. The performance characteristics of planar pH-sensors are compared with commercial glass electrodes. The close correlation of the data are encouraging for further acute and later chronic applications.Dedicated to Professor Dr. Wilhelm Fresenius     

Complementary use of Fourier transform laser microprobe mass spectrometry and time-of-flight static secondary ion mass spectrometry for the study of the surface adsorption of organic dyes on silicate materials

The adsorption of organic ionic dyes on different pore size engineered silica materials with potential application for industrial wastewater treatment has been investigated using Fourier transform laser microprobe mass spectrometry (FT-LMMS) and time-of-flight secondary ion mass spectrometry (TOF-S-SIMS). The complementary use of the two methods with different information depth allowed data on the subsurface distribution and pore penetration of the adsorbed organic compounds. Macroscopic methods were employed to determine the amount adsorbed on the particles and the specific external surface area. Local MS analysis allows identification of the organic dyes exclusively at the outer particle surface when the pore size is inferior to the size of the adsorbing molecule, or at the surface of the channels inside the material. Specifically, the monolayer information depth of TOF-S-SIMS causes a signal to refer essentially to the adsorbate at the outer particle surface, which is only a fraction of the total adsorption in mesoporous materials, while FT-LMMS allowed detection of the presence of adsorbates at the outer surface as well as inside the subsurface of 10 to 50 nm depending on the material under study. The observed data open perspectives for the molecular monitoring of the adsorption behaviour of different materials at the (sub) microm scale.