Chaotic switching in a two-person game

We study robust long-term complex behaviour in the Rock-Scissors-Paper game with two players, played using reinforcement learning. The complex behaviour is connected to the existence of a heteroclinic network for the dynamics. This network is made of three heteroclinic cycles consisting of nine equilibria and the trajectories connecting them. We provide analytical proof both for the existence of chaotic switching near the heteroclinic network and for the relative asymptotic stability of at least one cycle in the network, leading to some trajectories paying alternate visits to only two nodes while others follow a complicated sequence of visits to all nodes in the network. Our results are obtained by making use of the symmetry of the original problem, a new approach in the context of learning, and they provide an explanation of numerical results previously obtained by other authors.     

Theoretical and Experimental Study of the Homogeneous Catalytic Oxidation of Nicotinamide Adenine Dinucleotide (NADH) at Spherical Gold Electrodes Using Linear Sweep Voltammetry and Chronopotentiometry

The homogeneous catalytic oxidation of coenzyme nicotinamide adenine dinucleotide (NADH) with dopamine at a thiolactic acid modified gold spherical electrode of radius 0.0128 cm has been studied in aqueous phosphate media (pH 7.0) using linear sweep voltammetry and chronopotentiometry with power time and exponential time currents. We have proved that, under the conditions of this study, the steady state is reached, in such a way that the expressions for the I?E and dI/dE?E responses are simplified and become independent of time and the electrochemical technique employed. Therefore, the experimental I?E and dI/dE?E curves obtained in chronopotentiometry and linear sweep voltammetry are practically superimposable and, from easy expressions for the peak parameters of the dI/dE?E curves deduced in this paper, values of the chemical and electrochemical rate constants have been obtained.     

Are the five natural DNA/RNA base monomers a good choice from natural selection?: A photochemical perspective

In order to prevent the damaging effects of sun radiation in the genetic material, its constituent chromophores, the five natural DNA/RNA nucleobases cytosine, thymine, uracil, adenine, and guanine, should be able to efficiently dissipate absorbed radiation, UV specifically, avoiding as much as possible photoreactions leading to lesions. It has been established experimentally and theoretically that efficient internal conversion channels, still open and relevant in the oligomer-stacked strands, exist in the monomers allowing an effective waste of the initial energy. Previous evidences cannot explain, however, why minor differences in the molecular structure modify drastically the photochemistry of the systems, leading for many derivatives to slower decays, sometimes to intense fluorescence, and also to reactivity. Using the accurate CASPT2//CASSCF quantum chemical method and the Photochemical Reaction Path Approach it is determined that the five natural nucleobases display barrierless paths from the allowed excited state toward accessible conical intersection seams with the ground state. Such features are known to be the funnels for efficient energy decay and fluorescence quenching. Modified nucleobases, except the methylated ones, are predicted less photostable because they display energy barriers along lowest-energy paths and hence restricted accessibility of the internal conversion channel. This specificity speaks in favor of the choice of the biological nucleobases by natural selection based on their resistance to photochemical damage. Whereas natural and methylated nucleobases, also frequent in the genetic code, are photostable and cannot be photochemically discarded, other non-natural nucleobases may have been eliminated at early stages of the natural selection process.     

Investigation of the Interaction Between Lidocaine and the Components of Hyaluronic Acid Using Frontal Analysis Continuous Capillary Electrophoresis

The frontal analysis continuous capillary electrophoresis (FACCE) technique was used for the characterziation of the interaction between lidocaine-HCl (Lido) and components of Na-hyaluronic acid (HA). N-Acetylglucosamine (GlcNAc) and glucuronic acid (GluA) were the components of Na-hyaluronic acid. For the investigations fused silica capillaries were used. The FACCE method was compared to affinity capillary electrophoresis (ACE). The association constants between lidocaine-HCl and the components of Na-hyaluronic acid were determined using FACCE. It was observed that only an interaction between Lido and GluA exhibited. The association constant (K _lido-GluA) between Lido and GluA was 26 ± 0.3 L mol^?1.     

Headspace sorptive extraction using silicone tubes for the determination of chlorobenzenes in water

A new approach for headspace sorptive extraction is presented and demonstrated for the determination of 12 chlorobenzenes in water samples. It consists of a silicone tube (15-mm length) arranged around a stainless steel rod. This device is fixed on a septum cap and exposed to the headspace of 50 mL of a salt-saturated water sample. After extraction (60-min optimized extraction time), thermodesorption is carried out by direct insertion of the silicone tube into the thermodesorption-gas chromatography-mass spectrometry system. Desorption of the analytes is performed at 250 °C for 5 min with a gas flow of 50 mL/min. Repeatability (relative standard deviation 5–10%), extraction yields (9–46%), enrichment factors (129–657), and detection limits (0.002–0.012 μg/L) were determined and four real water samples were analyzed with the headspace tube extraction. The results were verified by standard addition. A comparison of headspace tube extraction with other headspace enrichment techniques underlined the high extraction capacity of the proposed method. A big advantage of tube extraction is the low cost of the silicone material. The tubes can be discarded after single use, avoiding carryover problems and cross-contamination. Figure Scheme of the HS-tube extraction and thermodesorption system     

Evolution of hypersurfaces in \Bbb RN {\Bbb R}^N by Gaussian curvature

In this paper we first prove short time existence of a classical solution for the problem which describes the evolution by Gaussian curvature of a strictly convex hypersurface in . Then we give a proof of the existence of a viscosity solution for this problem in such a way as to define a generalized motion existing for each time. Received November 24, 1997     

Influence of sialic acid and bacterial sialidase on differential adhesion of Pseudomonas aeruginosa to epithelial cells

Epithelial cell lines from several tissues show a differential sensitivity to Pseudomonas aeruginosa adherence. A549 (lung), HepG2 (liver) and Caco-2 (colon) cells presented an adhesion index of about 3, 1.5 and 5 CFU/cell, respectively, whereas Mz-Ch cell lines (gallbladder cholangiocytes) presented adhesion indexes up to 35. These variations could be associated with the variable amount of sialic acid in cell surface glycoconjugates. Moreover, the presence of free sialic acid in culture media induces the secretion by P. aeruginosa of a sialidase which is able to hydrolyze glycoconjugate-linked sialic acid. As shown with A549 cells, this specific hydrolysis increases bacterial adhesion, probably by unmasking new binding sites onto the cell surface.     

Theoretical insight into the spectroscopy and photochemistry of isoalloxazine, the flavin core ring

The electronic singlet-singlet and singlet-triplet electronic transitions of the isoalloxazine ring of the flavin core are studied using second-order perturbation theory within the framework of the CASPT2//CASSCF protocol. The main features of the absorption spectrum are computed at 3.09, 4.28, 4.69, 5.00, and 5.37 eV. The lowest singlet (S1) and triplet (T1) excited states are found to be both of pi character with a singlet-triplet splitting of 0.57 eV. On the basis of the analysis of the computed spin-orbit couplings and the potential energy hypersurfaces built for the relevant excited states, the intrinsic mechanism for photoinduced population of T1 is discussed. Upon light absorption, evolution of the lowest singlet excited state along the relaxation pathway leads ultimately to the population of the lowest triplet state, which is mediated by a singlet-triplet crossing with a state of npi* type. Subsequently a radiationless decay toward T1 through a conical intersection takes place. The intersystem crossing mechanism and the internal conversion processes documented here provide a plausible route to access the lowest triplet state, which has a key role in the photochemistry of the flavin core ring and is mainly responsible for the reactivity of the system.     

Guanidinate-stabilized monomeric hafnium amide complexes as promising precursors for MOCVD of HfO2

Novel guanidinato complexes of hafnium [Hf{eta2-(iPrN)2CNR2}2(NR2)2] (R2 = Et2, 1; Et, Me, 2; Me2, 3), synthesized by insertion reactions of N,N'-diisopropylcarbodiimide into the M-N bonds of homologous hafnium amide complexes 1-3 and {[mu2-NC(NMe2)2][NC(NMe2)2]2HfCl}2 (4) using a salt metathesis reaction, are reported. Single-crystal X-ray diffraction analysis revealed that compounds 1-3 were monomers, while compound 4 was found to be a dimer. The observed fluxional behavior of compounds 1-3 was studied in detail using variable-temperature and two-dimensional NMR techniques. The thermal characteristics of compounds 1-3 seem promising for HfO2 thin films by vapor deposition techniques. Metal-organic chemical vapor deposition experiments with compound 2 as the precursor resulted in smooth, uniform, and stoichiometric HfO2 thin films at relatively low deposition temperatures. The basic properties of HfO2 thin films were characterized in some detail.