Electrochemical Kinetic Characterization of Redox Mediated Glucose Oxidase Reactions: A Simplified Approach

One of the main drawbacks affecting first‐generation electrochemical biosensors in the analysis of real matrices is the interference of electroactive species present in the sample under investigation. Several approaches have been attempted to overcome this problem in the past ten years but the best results were achieved by using mediated based electrochemical biosensors. Despite this, the kinetic of the redox mediators‐enzymatic proteins interaction has not been studied deeply enough. In this work we have developed a theoretical‐methodological approach for the characterization of the kinetic of interaction between redox enzymes and substrates and/or redox mediators. Particularly, the interaction of glucose oxidase (GOx) with several commercially available redox mediators has been studied by means of amperometry and cyclic voltammetry. The main kinetic parameters for different mediators were exploited and discussed with the aim of finding the best mediator for a glucose biosensor to be used on real samples.     

Rationality in families of threefolds

We prove that in a family of projective threefolds defined over an algebraically closed field, the locus of rational fibers is a countable union of closed subsets of the locus of separably rationally connected fibers. When the ground field has characteristic zero, this implies that the locus of rational fibers in a smooth family of projective threefolds is the union of at most countably many closed subfamilies.     

Three-dimensional in vivo scanning microscopy with inertia-free focus control

The acquisition of high-resolution images in three dimensions is of utmost importance for the morphological and functional investigation of biological tissues. Here, we present a laser scanning two-photon microscope with remote and motionless control of the focus position. The movement of the excitation spot along the propagation direction is achieved by shaping the laser wavefront with a spatial light modulator. Depending on the optical properties of the objective in use, this approach allows z movements in a range of tens to hundreds of micrometers with small changes of the point spread function. We applied this technique for the three-dimensional (3D) imaging of fluorescent cells in the mouse neocortex in vivo. The presented system bypasses the limitations of microscopes based on moving objectives, enabling high-resolution inertia-free 3D imaging.     

A note on congruences of semilattices with sectionally finite height

We present a bijective correspondence between congruences of semilattices with sectionally finite height (i.e., meet-semilattices whose principal downsets have finite length) and certain special subsets of their universes. We characterize these subsets from a purely order-theoretic point of view and prove that the bijection coincides with the Leibniz operator of abstract algebraic logic.     

Electromagnetic processes in a χEFT framework

Recently,we have derived a two–nucleon potential and consistent nuclear electromagnetic currents in chiral effective field theory with pions and nucleons as explicit degrees of freedom.The calculation of the currents has been carried out to include N 3 LO corrections,consisting of two–pion exchange and contact contributions.The latter involve unknown low-energy constants (LECs),some of which have been fixed by fitting the np Sand P-wave phase shifts up to 100 MeV lab energies.The remaining LECs entering the current operator are determined so as to reproduce the experimental deuteron and trinucleon magnetic moments,as well as the np cross section.This electromagnetic current operator is utilized to study the nd and n 3 He radiative captures at thermal neutron energies.Here we discuss our results stressing on the important role played by the LECs in reproducing the experimental data.     

Organic room-temperature phosphorescence from halogen-bonded organic frameworks: hidden electronic effects in rigidified chromophores

Development of purely organic materials displaying room-temperature phosphorescence (RTP) will expand the toolbox of inorganic phosphors for imaging, sensing or display applications. While molecular solids were found to suppress non-radiative energy dissipation and make the RTP process kinetically favourable, such an effect should be enhanced by the presence of multivalent directional non-covalent interactions. Here we report phosphorescence of a series of fast triplet-forming tetraethyl naphthalene-1,4,5,8-tetracarboxylates. Various numbers of bromo substituents were introduced to modulate intermolecular halogen-bonding interactions. Bright RTP with quantum yields up to 20% was observed when the molecule is surrounded by a Br⋯O halogen-bonded network. Spectroscopic and computational analyses revealed that judicious heavy-atom positioning suppresses non-radiative relaxation and enhances intersystem crossing at the same time. The latter effect was found to be facilitated by the orbital angular momentum change, in addition to the conventional heavy-atom effect. Our results suggest the potential of multivalent non-covalent interactions for excited-state conformation and electronic control.

The number and position of halogen substituents in purely organic π–π* chromophores critically affect the efficiency of phosphorescence.     

Information-based multi-assets artificial stock market with heterogeneous agents

In this paper, an artificial stock market characterized by heterogeneous and informed agents is presented. The heterogeneous agents are seen as nodes of sparsely connected graphs. The agents trade risky assets and are characterized by sentiments, amount of cash and stocks owned. Agents share information and sentiments by means of interactions determined by graphs. A central market maker (clearing house mechanism) determines the price processes for each stock at the intersection of the demand and supply curves. In this framework, the statistical properties of the univariate and multivariate process of prices and returns are studied. Importantly, concerning univariate price processes, the proposed model is able to reproduce unit root, volatility cluster and fat tails of returns. The multivariate price process exhibits both static and dynamic stylized facts, in particular the presence of static factors and common trends. Static factors are studied making reference to the cross-correlation between returns of different stocks, whereas the common trends are investigated considering the variance–covariance matrix of prices. The proposed approach allows to endogenously reproduce the multivariate stylized facts.     

Determination of elemental compositions by gas chromatography/time‐of‐flight mass spectrometry using chemical and electron ionization

Many metabolomic applications use gas chromatography/mass spectrometry (GC/MS) under standard 70 eV electron ionization (EI) parameters. However, the abundance of molecular ions is often extremely low, impeding the calculation of elemental compositions for the identification of unknown compounds. On changing the beam‐steering voltage of the ion source, the relative abundances of molecular ions at 70 eV EI were increased up to ten‐fold for alkanes, fatty acid methyl esters and trimethylsilylated metabolites, concomitant with 2‐fold absolute increases in ion intensities. We have compared the abundance, mass accuracy and isotope ratio accuracy of molecular species in EI with those in chemical ionization (CI) with methane as reagent gas under high‐mass tuning. Thirty‐three peaks of a diverse set of trimethylsilylated metabolites were analyzed in triplicate, resulting in 342 ion species ([M+H]⁺, [M–CH₃]⁺ for CI and [M]^{+ .} , [M–CH₃]^{+ .} for EI). On average, CI yielded 8‐fold more intense molecular species than EI. Using internal recalibration, average mass errors of 1.8 ± 1.6 mm/z units and isotope ratio errors of 2.3 ± 2.0% (A+1/A ratio) and 1.7 ± 1.8% (A+2/A ratio) were obtained. When constraining lists of calculated elemental compositions by chemical and heuristic rules using the Seven Golden Rules algorithm and PubChem queries, the correct formula was retrieved as top hit in 60% of the cases and within the top‐3 hits in 80% of the cases. Copyright © 2010 John Wiley & Sons, Ltd.